5th Asia-Paciﬁc Symposiumon Radiochemistry

APSORC 13

22-27 September 2013
Kanazawa, Japan5th Asia Pacific Symposium on Radiochemistry

APSORC 13
Kanazawa, JAPAN
September 22 – 27, 2013

Book of Abstracts

Organizing Committee
Co-chairpersons
Y. Nagame (Tokai, JAEA)
M. Yamamoto (Kanazawa, Kanazawa University)
Secretaries
A. Yokoyama (Kanazawa, Kanazawa University)
M. Watanabe (Tokai, JAEA)
Members of the Organizing Committee
R. Amano (Kanazawa, Kanazawa University), M. Ebihara (Tokyo, Tokyo
Metropolitan University), M. K. Kubo (Tokyo, International Christian University),
N. Momoshima (Fukuoka, Kyushu University), S. Nagao (Kanazawa, Kanazawa
University), W. Sato (Kanazawa, Kanazawa University), A. Shinohara (Osaka,
Osaka University), Y. Yamada (Kanazawa, Hokuriku University)

Kanazawa Symposium Committee
T. Nakanishi (Kanazawa, Kanazawa University), M. Inoue (Kanazawa, Kanazawa
University), Y. Hamajima (Kanazawa, Kanazawa University), K. Washiyama(Kanazawa, Kanazawa University), K. Yasuike (Kanazawa, Hokuriku University)

International Advisory Committee (IAC)
J. Bennett (Australia), N. Beresford (UK), P. Bode (The Netherlands), Y. H. Chung(Korea), S. B. Clark (USA), S. Dmitriev (Russia), C. E. Düllmann (Germany), M.
Ebihara (Japan), E. A. De Nadai Fernandes (Brazil), H. Geckeis (Germany), K. A.
Higley (USA), Q. Hua (Australia), J. John (Czech Republic), V. Kolotov (Russia), S.
Lahiri (India), M. Garcia-Leon (Spain), D. Moir (Canada), N. Momoshima (Japan), A.
Mutalib (Indonesia), S. -I. Nakayama (Japan), Y. Nagame (Japan), H. Nitsche(USA), Y. Ohkubo (Japan), A. V. R. Reddy (India), Z. Révay (Hungary), E. Simoni(France), K. S. Song (Korea), A. Türler (Switzerland), J. H. Wang (China), M.
Yamamoto (Japan), S. D. Zhang (China), Y. L. Zhao (China)

Program Chairperson
N. Momoshima (Fukuoka, Kyushu University)（ 2 ）Scientific Topics (Abbrev.)
1. Fukushima issues (FK)
2. Education in nuclear and radiochemistry (ED)
3. Nuclear forensics (NF)
4. Nuclear energy chemistry (NE)
5. Nuclear chemistry (NC)
6. Actinide chemistry (AC)
7. Environmental radiochemistry (EN)
8. Radiopharmaceutical chemistry and Nuclear medicine (RP)
9. Nuclear probes for materials science (NP)
10. Activation analysis (AA)
11. Application of nuclear and radiochemical techniques (AP)（ 3 ）Sunday, 22 September
Robby
Time
09:00-09:10
09:10-09:20
09:20-09:30
09:30-09:40
09:40-09:50
09:50-10:00
10:00-10:10
10:10-10:20
10:20-10:30
10:30-10:40
10:40-10:50
10:50-11:00
11:00-11:10
11:10-11:20
11:20-11:30
11:30-11:40
11:40-11:50
11:50-12:00
12:00-12:10
12:10-13:20
13:20-13:30
13:30-13:40
13:40-13:50
13:50-14:00
14:00-14:10
14:10-14:20
14:20-14:30
14:30-14:40
14:40-14:50
14:50-15:00
15:00-15:10
15:10-15:20
15:20-15:30
15:30-15:40
15:40-15:50
15:50-16:00
16:00-16:10
Registration Desk
16:10-16:20
OPEN
16:20-16:30
16:30-16:40
16:40-16:50
16:50-17:00
17:00-17:10
17:10-17:20
17:20-17:30
17:30-17:40
17:40-17:50
17:50-18:00
Welcome Reception
18:00-18:10
18:10-18:20
18:20-18:30
18:30-18:40
18:40-18:50
18:50-19:00
19:00-19:20
19:20-19:40
19:40-20:00
20:00-

9:00

9:30

Monday, 23 SeptemberHall
Meeting Room
Arrangement for presentation

Opening Ceremony

10:00

11:40

12:10
13:20

PL-01

9:30

PL-04

10:20

Coffee BreakPlenary

PL-02

M. Yamamoto
Plenary
I. McKinley

Lunch Time
API-01

Invited

API-02

H. Harada
Invited

FKI-01

Invited

FKI-02

H. Tsuruta
Invited

14:20

FKI-03

Y. Takahashi (388)
Invited

14:50

FKI-04

M. Aoyama
Invited

13:50

PL-03

B. Grambow

15:20

APO-01
APO-02
APO-03

Y.L. Zhao
GeneralT. M. Nakanishi
General
S.H. Jung
GeneralM. Anvia

Coffee Break

15:40

FKO-01

16:00

FKO-02

16:20

FKO-03

16:40

FKO-04

17:00

FKO-05

17:20

FKO-06

17:40

FKO-07

18:00

FKO-08GeneralA. Shimada
GeneralY. Miyake
GeneralT. Ohta
GeneralY. Muramatsu
GeneralY. Satou
GeneralM. C. Honda
General
Z.J. Zhang
General
D.R. Neville

NCO-01
NCO-02
NCO-03
NCO-04
NCO-05
NFO-01
NFO-02
NFO-03GeneralZ. QinGeneralW.M. Kerlin
General
Y.K. Ha
GeneralI. Laszak
GeneralY. Xu
GeneralY. Miyamoto
GeneralN. Gharibyan
GeneralR. Sudowe

ENI-01

ENO-01

11:10

ENO-02

11:30

ENO-03

11:50

ENO-04

12:10
13:20

ENO-05

13:40

ENO-06

14:00

ENO-07

14:20

ENO-08

14:40

ENO-09

15:00

ENO-10

15:20

NCI-01

Invited

H. Foerstendorf
General
NCI-02
Z.J. Guo
GeneralH. Tuovinen
NCI-03General
M.-C. Wu
General
NCO-06
T. Ohnuki
Lunch Time
General
NCO-07
S. Sachs
General
NCO-08Y. Iwahana
General
NCO-09J. Krmela
GeneralNCO-10K. Masumoto
GeneralNCO-11
H.W. Gaeggeler
GeneralNCO-12
A. Sakaguchi

16:10

ENO-11

16:30

ENO-12

16:50

ENO-13

17:10

FKI-05

17:40

FKO-0918:00

FKO-10Invited
J.V. Krtaz
GeneralJ.H. Park
GeneralJ. Zheng
GeneralI. Milanovic
InvitedK. Minato
GeneralY. OuraGeneralK. Hirose

PL-05

9:30

PL-06

Invited

10:20

RPI-01

10:50

RPI-02

Ch.E. Duellmann
Invited

11:20

RPO-01

11:40

RPO-02

H. Haba
GeneralV. Pershina
GeneralD. Rudolph
GeneralA. Yakushev
GeneralJ. EvenGeneralH. Nitsche
GeneralR. Eichler
General
T.K. Sato

12:00

13:40

14:40

15:20

NEI-02

16:00

FKO-11

16:20

FKO-12

A. Goswami
General
16:40
E. Loefstroem-Engdahl
General
17:00
Y. Tomobuchi
General
17:20
F. Poineau
GeneralA. Braatz
17:50
GeneralR. Chen
18:30

18:50

18:50
Poster Session

18:50
Poster Session

20:00

20:00

（ 4 ）

JNRS M

15:00

Z.F. Chai
InvitedNEO-05Y

14:20

RPO-03NEO-04

E

14:00

15:40

NEO-03DJNRS Genera(For Member

InvitedNEO-02M.

13:20

NEI-01

NEO-01We
Ha

J.

S. Dmitriev
InvitedCoffee BreakENI-02

9:00

10:00

Coffee Break

10:50

15:40

A. Tuerler
Plenary
S. Nagao

10:00
Hevesy Award Ceremony
R. S. Dybczyński

11:00
11:10

9:00

Tuesday, 24 SeptemberHall
Meeting RoomPlenary

20:00

FKO-13
FKO-14

L. S

E.

K

T.

D

JNRS Award(Open S
T. Kimeting Room

9:00

PL-05

Wednesday, 25 SeptemberHall
Meeting RoomPlenary

9:30

PL-06

M. A. Denecke
Plenary
J. Hatazawa

10:00
InvitedS. Dmitriev
InvitedCh.E. Duellmann
Invited
H. Haba
GeneralV. Pershina
GeneralD. Rudolph
GeneralA. Yakushev
GeneralJ. EvenGeneralH. Nitsche
GeneralR. Eichler
General
T.K. Sato

10:20

10:50

Invited

RPI-02

D. S. Wilbur
Invited

11:20

RPO-01

11:40

RPO-02

12:00
13:20
13:40

ACI-01

Invited

ACI-02

J. Li
InvitedS. Lahiri
General
ACO-01
E. Aneheim
General
ACO-02
Y. Hatsukawa
Group Photo (Hall)
Lunch Time

PL-07

9:30

PL-08

Y. Kitatsuji
GeneralA. Kirishima
GeneralH. Hayashi

10:20

NPI-01

NPO-01

11:10

NPO-02

11:30

NPO-03

11:50

NPO-04

10:20

AAO-01

10:40

AAO-02

11:00

AAO-03

11:20

AAO-04

11:40

AAO-05JNRS Meeting
Excursion(Shirakawa-go)
Coffee BreakInvited

15:40

RPO-03

Z.F. Chai
Invited

16:00

FKO-11

16:20
A. Goswami
General
16:40
Loefstroem-Engdahl
General
17:00
Y. Tomobuchi
General
17:20
F. Poineau
GeneralA. Braatz
17:50
GeneralR. ChenFKO-12
FKO-13
FKO-14GeneralL. Safavi-Tehrani
GeneralE. Rasmussen
GeneralK. Minami
GeneralT. Kawamoto
GeneralD. Parajuli

ACO-03
ACO-04
NCO-13
NCO-14
NCO-15GeneralT.H. Park
GeneralN. Aoyagi
General
A. Toyoshima
GeneralP. Steinegger
GeneralR. Tripathi

17:00

Coffee BreakJNRS Award Presentation(Open Session)
T. Kimura

18:30
18:50
Poster Session

T. Miura

J. JohnInvited

19:00
Banquet

20:00

（ 5 ）

W. Wu
InvitedA. Yokoyama
GeneralS. B. Sarmani

12:00
13:20

APO-04

14:10

APO-05

14:30

APO-06

15:10

GeneralJ.H. Moon
GeneralY. TohGeneralK. Ninomiya
GeneralM. Fukushima
GeneralN. Shirai
Lunch Time

API-03

13:50

14:50

A. Chatt
InvitedCoffee BreakInvited

14:20

15:20

AAI-02

EDI-01

InvitedJNRS General Assembly(For Member of JNRS))

15:00

9:30

W. SatoGeneral
EDI-02
K. Nomura
GeneralJ. Wang
EDI-03GeneralS. Nakashima
General
EDO-01
G. Yoshida
Lunch Time

14:00

14:40

9:00

Friday, 27 September
Meeting Room
AAI-01
Invited

10:00

Coffee Break

10:50

12:10
13:00

S. B. Clark
Plenary
H. Ueno10:00

Coffee Break
RPI-01

9:00

Thursday, 26 SeptemberHall
Meeting RoomPlenary

InvitedY. Hamajima
GeneralC. Gautier
GeneralT.Yoshimura
GeneralJ.D. Despotopulos
Coffee BreakClosing CeremonyTime
09:00-09:10
09:10-09:20
09:20-09:30
09:30-09:40
09:40-09:50
09:50-10:00
10:00-10:10
10:10-10:20
10:20-10:30
10:30-10:40
10:40-10:50
10:50-11:00
11:00-11:10
11:10-11:20
11:20-11:30
11:30-11:40
11:40-11:50
11:50-12:00
12:00-12:10
12:10-13:20
13:20-13:30
13:30-13:40
13:40-13:50
13:50-14:00
14:00-14:10
14:10-14:20
14:20-14:30
14:30-14:40
14:40-14:50
14:50-15:00
15:00-15:10
15:10-15:20
15:20-15:30
15:30-15:40
15:40-15:50
15:50-16:00
16:00-16:10
16:10-16:20
16:20-16:30
16:30-16:40
16:40-16:50
16:50-17:00
17:00-17:10
17:10-17:20
17:20-17:30
17:30-17:40
17:40-17:50
17:50-18:00
18:00-18:10
18:10-18:20
18:20-18:30
18:30-18:40
18:40-18:50
18:50-19:00
19:00-19:20
19:20-19:40
19:40-20:00
20:00-APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

PROGRAM OF APSORC13
Sunday, 22 September 2013
Lobby, Kanazawa Bunka Hall
15:00-

Registration

17:30-18:30

Welcome reception

Monday, 23 September 2013
Hall & Meeting Room, Kanazawa Bunka Hall
09:00-

Registration (continued)

09:30-10:00

Opening Ceremony - Welcome addressHall

Y. Nagame, APSORC13 co-chair, Japan Atomic Energy Agency, JapanT. Kishikawa, APSORC chair, Kumamoto University, Japan

10:00-11:00

Hevesy Medal Award Ceremony

Hall

Chair : A. Chatt
HMA-01R. S. Dybczyński, Institute of Nuclear Chemistry and Technology, Poland
50 years of adventures with neutron activation analysis with the special
emphasis on radiochemical separations

11:00-11:10

Coffee Break

11:10-12:10

Plenary Session
Fukushima issues
Chairs : N. Momoshima and H. NitscheHall
11:10-11:40

PL-01

11:40-12:10

PL-02

M. Yamamoto, LLRL, Kanazawa University, Japan
Overview of the Fukushima Dai-ichi nuclear power plant (FDNPP) accident
with amounts and nuclear compositions of the released radionuclides
I. McKinley, MCM Consulting, Switzerland
Fukushima challenges in perspective

12:10-13:20

Lunch

13:20-18:20

Parallel session
Fukushima issues (continued)
Chairs : S. Nagao and I. McKinleyHall
13:20-13:50

FKI-01

H. Tsuruta, M. Takigawa, T. Nakajima, The University of Tokyo, Japan,

Japan Agency for Marine-Earth Science and Technology, Japan

Atmospheric transport of radioiodine and radiocesium released in the early（ 6 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

13:50-14:20

14:20-14:50

14:50-15:20

FKI-02phase by the Fukushima Daiichi Nuclear Power Plant accident from fieldmeasurements and a simulation model
Y. Takahashi, Q. Fan, Y. Togo, A. Sakaguchi, K. Tanaka, Hiroshima

FKI-03Migration of radiocesium and radioiodine released by FDNPP accident in theterrestrial environment and its interpretation by their speciation analyses
M. Aoyama, Y. Hamajima, Meteorological Research Institute, Japan,

FKI-04

15:20-15:40

16:00-16:20

16:20-16:40

16:40-17:00

17:00-17:20

17:20-17:40

Kanazawa University, Japan

Oceanic and coastal dispersion of 134Cs and 137Cs released from the TEPCO
Fukushima NPP1 accident: past present and prediction
B. Grambow, Université de Nantes, France
Interactions between nuclear fuel and water at the Fukushima Daiichi
Reactors
Coffee Break
Fukushima issues (continued)
Chairs : M. Yamamoto and B. Grambow

Hall
15:40-16:00

University, Japan, National Institute of Advanced Industrial Science &Technology, Japan

FKO-01

A. Shimada, K. Sakatani, Y. Kameo, K. Takahashi, Japan Atomic Energy

FKO-02

Determination of 129I in the accumulated radioactive water and processing
water of Fukushima Daiichi Nuclear Power Plant
Y. Miyake, H. Matsuzaki, T. Fujiwara, T. Saito, T. Yamagata, M. Honda, The

FKO-03

Measurement of Iodine-129 in surface soil collected near the Fukushima
Daiichi Nuclear Power Plant accident site
T. Ohta, T. Kutoba, Y. Mahara, H. Matsuzaki, T. Igarashi, Hokkaido

FKO-04

Speciation of 137Cs and 129I in surface soil in Kanto loam layer after the
Fukushima NPP accident
Y. Muramatsu, T. Ohno, N. Inagawa, K. Oda, M. Sato, H. Matsuzaki,

FKO-05

Transfer of radiocesium and radioiodine in the environment following the
Fukushima nuclear accident
Y. Satou, K. Sueki, K. Sasa, J. Kitagawa, S. Ikarashi, University of Tsukuba,

FKO-06

Agency, Japan

University of Tokyo, Japan, Nihon University, Japan

University, Japan, Kyoto University, Japan, The University of Tokyo, Japan

Gakushuin University, Japan, Fukushima Agricultural Technology Centre,
Japan, The University of Tokyo, Japan

Japan, High Energy Accelerator Research Organization and J-PARC Center,
Japan
States of existence of the cesium and silver radionuclides at the sandy beachin Iwaki city, Fukushima
M. C. Honda, H. Kawakami, S. Watanabe, T. Saino, S. Nagao, K. Buesseler,
C. German, S. Manganini, Japan Agency for Marine-Earth Science andTechnology, Japan, Kanazawa University, Japan, Woods Hole Oceanographic
Institution, USA
17:40-18:00

FKO-07

Vertical transport of FNPP1-derived radiocesium by settling particles in theWestern North Pacific
Z. J. Zhang, S. Kakitani, K. Ninomiya, N. Takahashi, Y. Yamaguchi, T.
Yoshimura, T. Saito, K. Kita, H. Tsruta, S. Higaki, A. Shinohara, Osaka

University, Japan, Shokei Gakuin University, Japan, Ibaraki University,
Japan, The University of Tokyo, Japan
Strontium-90 determination in air dust filter using solid phase extraction
after the accident of FD-NPS（ 7 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

18:00-18:20

FKO-08D. R. Neville, A. J. Phillips, K. A. Higley, Oregon State University, USA
Dosimetric implications of the Fukushima release for Pacific albacore in the
Northern California Current

18:20-18:50

Mounting of posters

18:50-20:00

Poster session 1

13:20-18:20

Parallel session

Meeting
Room

Application of nuclear and radiochemical techniques
Chairs : T. Yoshimura and C. Gautier

13:20-13:50

API-01

13:50-14:20

API-02

14:20-14:40

APO-01

H. Harada, Japan Atomic Energy Agency, Japan
ANNRI at J-PARC
Y. L. Zhao, W. Q. Shi, L. Y. Yuan, Z. F. Chai, Institute of High Energy

Physics, China, National Center for Nanosciences and Technology, Chaina

Nanomaterial and nanotechnology in nuclear energy chemistry
T. M. Nakanishi, N. I. Kobayashi, A. Hirose, T. Saito, R. Sugita, H. Suzuki, R.
Iwata, K. Tanoi, The University of Tokyo, Japan, National Institute ofRadiological Sciences, Japan, Tohoku University, Japan
14:40-15:00

15:00-15:20

APO-02Development of real-time radioisotope imaging system to study plant
nutrition
S. H. Jung, J. G. Park, J. B. Kim, J. H. Moon, C. H. Kim, Korea Atomic

APO-03

MCNP study on the development of industrial SPECT in terms of a radiation
measurement design and void influence in multiphase media
M. Anvia, S. A. Brown, Australian Nuclear Science and Technology

Energy Research Institute, Korea, Hanyang Universuty, Korea

Organization Minerals and The University of Sydney, Australia, The
University of Sydney, Australia
Tracking the deportment of uranium chain daughters during alkalineleaching of an Australian monazite

15:20-15:40

Coffee BreakMeeting
Room

Nuclear chemistry
Chairs : A. Yokoyama and Z. F. Chai

15:40-16:00

NCO-01

16:00-16:20

NCO-02

Z. Qin, F.-L. Fan, Y. Wang, F.-Y. Fan, X.-L. Wu, J. Bai, X.-J. Yin, L.-L. Tian,
W. Tian, Z. Li, C.-M. Tan, Institute of Modern Physics, China
Nuclear chemistry and radiochemistry studies at IMP
W. M. Kerlin, F. Poineau, P. M. Forster, A. P. Sattelberger, K. R. Czerwinski,

16:20-16:40

NCO-03

Preparation of low valent technetium metal-metal bonded species via
solvothermal reduction of pertechnetate salts
Y.-K. Ha, S.-D. Park, Y.-S. Park, J.-S. Kim, K. Song, Korean Atomic Energy

16:40-17:00

NCO-04

University of Nevada Las Vegas, USA, Argonne National Laboratory, USA

Research Institute, Korea

The status of chemical characterization of a spent nuclear fuelI. Laszak, J. P. Degros, C. Gautier, P. Fichet, F. Goutelard, J. N. Saas, A.
Vian, J. F. Valéry, CEA Saclay, France, AREVA, France
Determination of 93Zr from intermediate level radioactive effluent（ 8 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

17:00-17:20

NCO-05Y. L. Xu, S. Y. Kim, T. Ito, H. Tokuda, T. Tada, K. Hitomi, K. Ishii, Tohoku

University, Japan

Selective separation of cesium from simulated high level liquid waste using asilica-based (Calix[4] + Dodecanol)/SiO2-P adsorbent
Meeting
Room

Nuclear forensics
Chairs : A. Yokoyama and Z. F. Chai

17:20-17:40

NFO-01

Y. Miyamoto, F. Esaka, D. Suzuki, M. Magara, Japan Atomic Energy Agency,

17:40-18:00

NFO-02Age determination of a single Pu and Pu/U mixed oxide particle
N. Gharibyan, K. J. Moody, T. A. Brown, J. D. Despotopulos, J. M. Gostic, R.
A. Henderson, E. Tereshatov, S. J. Tumey, D. A. Shaughnessy, LawrenceJapan

Livermore National Laboratory, USA, Air Force Technical Applications
Center, USA
18:00-18:20

NFO-03

Radiochemical measurement of 10-15 MeV proton induced fission yields for
U-238
R. Sudowe, E. M. Bond, A. R. Dailey, D. R. Mclain, A. R. Roman, University of

Nevada Las Vegas, USA, Los Alamos National Laboratory, USA

Effect of interferences on actinide and strontium separations in unusual
matrices
18:20-18:50

Mounting of posters

18:50-20:00

Poster session 1（ 9 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Tuesday, 24 September 2013
Hall & Meeting Room, Kanazawa Bunka Hall
09:00-10:00

Plenary Session
Nuclear chemistry (continued) & Environmental radiochemistry
Chairs : Y. Muramatsu and M. Schädel

Hall
09:00-09:30

PL-03

09:30-10:00

PL-04

A. Türler, Paul Scherrer Institut & University of Bern, Switzerland
Advances in the production and chemistry of the heaviest elements
S. Nagao, Kanazawa University, Japan
Study on transport of particulate organic matter in river and coastal marine
systems using radiocarbon

10:00-10:20

Coffee Break

10:20-18:30

Parallel session
Environmental radiochemistry (continued)
Chairs : H. Tsuruta and W. S. Wu

Hall
10:20-10:50

ENI-01

10:50-11:10

ENO-01

11:10-11:30

ENO-02

H.

Foerstendorf,

K.

Gückel,N.Jordan,A.

Rossberg,

V.

Brendler,

Helmholtz-Zentrum Dresden-Rossendorf, Germany, Rossendorf Beamline atthe European Synchrotron Radiation Facility (ESRF), France

Surface speciation of dissolved radionuclides on mineral phases – A vibrational
and X-ray absorption spectroscopic study
Z. J. Guo, Z. Y. Chen, Q. Jin, W. S. Wu, Lanzhou University, China
Adsorption of Eu(III) and Am(III) on granite
H. Tuovinen, E. Pohjolainen, D. Vesterbacka, C. Kirk, D. Read, D. Solatie, J.
Lehto, University of Helsinki, Finland, Geological Survey of Finland,

Loughborough University, UK, Finnish Radiation and Nuclear Safety
Authority, Finland
11:30-11:50

11:50-12:10

ENO-03

ENO-04Behaviour of radionuclides and secondary mineral formation in the Talvivaara
mining process
C.-P. Lee, M.-C. Wu, C.-Y. Liu, C.-H. Pan, T.-L. Tsai, H.-J. Wei, L.-C. Men,

National Cheng Kung University, Tainan, National Central University,
Taiwan, Institute of Nuclear Energy Research, Taiwan
Evaluation of HTO and selenium diffusion behavior in compacted bentonite
with different lenghths
T. Ohnuki, N. Kozai, F. Sakamoto, Japan Atomic Energy Agency, Japan
Sorption behavior of Dy(III) and Np(V) on microbial consortia

12:10-13:20

Lunch
Environmental radiochemistry (continued)
Chairs : M. Aoyama and H. Foerstendorf

Hall
13:20-13:40

13:40-14:00

ENO-05

S. Sachs, A. Heller, G. Bernhard, Helmholtz-Zentrum Dresden-Rossendorf,

ENO-06

Interaction of Eu(III) with mammalian cells as a function of Eu(III)concentration and nutrient composition
Y. Iwahana, Y. Koike, M. Kitano, T. Nakamura, Meiji University, Japan
Monitoring and elution characteristics of radioactive Cs in incinerator fly
ashes of municipal solid waste

Germany（ 10 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

14:00-14:20

ENO-07

14:20-14:40

ENO-08

J. Krmela, Ústav Jaderného Výzkumu Řež a.s., The Czech Republic
The issue of separation of uranium from drinking water in the Czech Republic
K. Masumoto, A. Toyoda, H. Matsumura, T. Kunifuda, High Energy

14:40-15:00

ENO-09Air-born contamination caused in a high-energy proton accelerator room
H. W. Gäggeler, L. Tobler, M. Schwikowski, Paul Scherrer Institut,

15:00-15:20

ENO-10Accelerator Research Organization, Japan, Tokyo Nuclear Service, Japan
Switzerland

Application of 210Pb in Glaciology
A. Sakaguchi, A. Kadokura, P. Steier, Y. Takahashi, K. Shizuma, T. Nakakuki,
M. Yamamoto, Hiroshima University, Japan, University of Vienna, Austria,

Kanazawa University, Japan

Depth distributions of uranium-236 and cesium-137 in the Japan Sea; toward
the potential use as a new oceanic circulation tracer
15:20-15:40

Coffee Break
Environmental radiochemistry & Fukushima issues (continued)
Chairs : S. Nakayama and R. Sudowe

Hall
15:40-16:10

ENI-02

16:10-16:30

ENO-11J. V. Kratz, Johannes Gutenberg-University of Mainz, Germany
Ultratrace Analysis of Long-lived Radionuclides by Resonance Ionization
Mass Spectrometry (RIMS)
J.-H. Park, S. Lee, Y.-G. Ha, S. A Lee, K. Jeong, K. Song, Korea Atomic Energy

ENO-12The bulk analysis with TIMS measurements preformed in KAERI for nuclear
safeguards
W. Bu, J. Zheng, Q. Guo, T. Aono, K. Tagami, S. Uchida, Peking University,

16:30-16:50

16:50-17:10

ENO-13

17:10-17:40

FKI-04

17:40-18:00

FKO-09Research Institute, Korea

China, National Institute of Radiological Sciences, Japan

Determination of plutonium isotopes at ultratrace level in seawater samples
by sector-field ICP-MS combined with chromatographic separation
I. Milanović, Ž. Grahek, Ruđer Bošković Institute, Croatia
Semi-automated procedure for the determination of 89,90Sr in environmental
samples by Cherenkov counting
K. Minato, Japan Atomic Energy Agency, Japan
Research and development towards decommissioning of Fukushima Daiichi
Nuclear Power Plants
Y. Oura, M. Ebihara, H. Tsuruta, T. Nakajima, T. Ohara, M. Ishimoto, Y.
Katsumura, Tokyo Metropolitan University, Japan, The University of Tokyo,

Japan, National Institute for Environmental Studies, Japan

18:00-18:20

FKO-10

Determination of atmospheric radiocesium on filter tapes used at automated
SPM monitoring stations for estimation of transport pathways ofradionuclides from Fukushima Daiichi Nuclear Power Plant
K. Hirose, Sophia University, Japan
Two-years trend of monthly Cs-137 deposition observed within 300 km of the
Fukushima Dai-ichi Nuclear Power Plant

18:20-18:50

Mounting of posters

18:50-20:00

Poster session 2

10:20-15:20

Parallel session（ 11 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Meeting
Room

Nuclear chemistry (continued)
Chairs : H. Kudo and H. W. Gäggeler

10:20-10:50

NCI-01

10:50-11:20

NCI-02

11:20-11:50

NCI-03

11:50-12:10

NCO-06

12:10-13:20

Lunch

MeetingRoom
13:20-13:40

S. Dmitriev, The Flerov Laboratory of Nuclear Reactions, Russia
Synthesis and study of properties of superheavy elements: status, problems,and prospects
Ch. E. Düllmann, Johannes Gutenberg University of Mainz, Germany
The search for new chemical elements and the possibilities to synthesize
transactinide "chemistry" isotopes
H. Haba, RIKEN, Japan
Production and decay studies of transactinide nuclides with GARIS at RIKEN
V. Pershina, GSI Helmholtzzentrum für Schwerionenforschung, Germany
Theoretical predictions of the electronic structure and properties of theheaviest elements

Nuclear chemistry (continued)
Chairs : Y. Nagame and S. Dmitriev
NCO-07

D. Rudolph, U. Forsberg, P. Golubev, L. G. Sarmiento, A. Yakushev, L.-L.
Andersson, Ch. E. Düllmann, J. M. Gates, K. E. Gregorich, F. P. Heßberger,
R.-D. Herzberg, J. Khuyagbaatar, J. V. Kratz, K. Rykaczewski, M. Schädel, S.
Åberg, D. Ackermann, M. Block, H. Brand, B. G. Carlsson, D. Cox, X. Derkx,
A. Di Nitto, K. Eberhardt, J. Even, C. Fahlander, J. Gerl, C. J. Gross, E. Jäger,B. Kindler, J. Krier, I. Kojouharov, N. Kurz, B. Lommel, A. Mistry, C. Mokry,
H. Nitsche, J. P. Omtvedt, P. Papadakis, I. Ragnarsson, J. Runke, H.
Schaffner, B. Schausten, P. Thörle-Pospiech, T. Torres, A. Türler, A. Ward, D.
Ward, N. Wiehl, Lund University, Sweden, GSI Helmholtzzentrum für

Schwerionenforschung, Germany, Helmholtz Institute Mainz, Germany,
Johannes Gutenberg-University of Mainz, Germany, Lawrence Berkeley
National Laboratory, USA, University of Liverpool, Oak Ridge National
Laboratory, USA, Japan Atomic Energy Agency, Japan, Paul Scherrer Institut,
Switzerland
13:40-14:00

NCO-0814:00-14:20

NCO-09Spectroscopy of element 115 decay chains
A. Yakushev, GSI Helmholtzzentrum für Schwerionenforschung, Germany
Chemistry at one-atom-per-week level
J. Even, A. Yakushev, Ch. E. Düllmann, H. Haba, M. Asai, T. Sato, H. Brand,
A. Di Nitto, R. Eichler, F. Fangli, W. Hartmann, M. Huang, E. Jäger, D. Kaji, J.
Kanaya, Y. Kaneya, J. Khuyagbaatar, B. Kindler, J. V. Kratz, J. Krier, Y.
Kudou, N. Kurz, B. Lommel, S. Miyashita, K. Morimoto, K. Morita, Y.
Nagame, H. Nitsche, K. Ooe, M. Schädel, J. Steiner, T. Sumita, K. Tanaka, A.
Toyoshima, K. Tsukada, A. Türler, I. Usoltsev, Y. Wakabayashi, Y. Wang, N.
Wiehl1, S. Yamaki, Q. Zhi, Helmhotz-Institut Mainz, Germany, GSI

Helmholtzzentrum für
Schwerionenforschung, Germany, Johannes
Gutenberg-University of Mainz, Germany, RIKEN, Japan, Japan Atomic
Energy Agency, Japan, University of Bern, Switzerland, Paul Scherrer
Institut, Switzerland, Institute of Modern Physics, China, University ofCalifornia, USA, Lawrence Berkeley National Laboratory, USA, Niigata
University, Japan, Saitama University, Japan
14:20-14:40

NCO-10Sg(CO)6 - The first organometallic transactinde complex opening a window to
a new compound class
H. Nitsche, G. K. Pang, J. M. Gates, K. E. Gregorich N. E. Esker, O. R, Gothe,

University of California, USA, Lawrence Berkeley National Laboratory , USA
Superheavy element Z and A measurements at the Berkeley Gas-Filled（ 12 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

14:40-15:00

NCO-11

Separator
R. Eichler, I. Usoltsev, J. P. Omtvedt, O. V. Petrushkin, D. Piguet, A. V.
Sabel’nikov, A. Türler, G. K. Vostokin, A. V. Yeremin, Paul Scherrer Institute,

Switzerland, University of Bern, Switzerland, The Flerov Laboratory of
Nuclear Reactions, Russia, University of Oslo, Norway
15:00-15:20

NCO-12

Intermetallic actinide compounds for SHE production targets
T. K. Sato, M. Asai, N. Sato, Y. Kaneya, K. Tsukada, A. Toyoshima, S.
Miyashita, Y. Nagame, M. Schädel, A. Osa, S. Ichikawa, K. Ooe, T. Stora, J. V.
Kratz, Japan Atomic Energy Agency, Japan, Ibaraki University, Japan,

RIKEN, Japan, Niigata University, Japan, ISOLDE, CERN, Switzerland,
Johannes Gutenberg-University of Mainz, Germany
The first successful observation of mass-separated lawrencium (Lr, Z = 103)
ions with ISOL technique
15:20-15:40

Coffee BreakMeeting
Room

Nuclear energy chemistry
Chairs : Z. Yoshida and S. Clark

15:40-16:10

NEI-01

16:10-16:40

NEI-02

16:40-17:00

NEO-01Z. F. Chai, Institute of High Energy Physics, China
Nuclear energy chemistry in China: present status and future perspectives
A. Goswami, Bhabha Atomic Research Centre, India
Evaluation of new extractants relevant to the back-end of nuclear fuel cycle
E. Löfström-Engdahl, E. Aneheim, C. Ekberg, H. Elfversson, G. Skarnemark,NEO-02

Hexanoic acid as alternative diluent in a GANEX process based on TBP and
CyMe4-BTBP
Y. Tomobuchi, Y. Tachibana, M. Nomura, T. Suzuki, Nagaoka University of

17:00-17:20

17:20-17:40

NEO-03

Chalmers University of Technology, Sweden

Technology, Japan, Tokyo Institute of Technology, Japan

Effect of alcohols on separation behavior of rare earth elements using
benzimidazole-type anion-exchange resin in nitric acid solutions
F. Poineau, P. Weck, B. P. Burton-Pye, A. Maruk, G. Kirakosyan, I. Denden,
D.. B. Rego, E. V. Johnstone, W. Kerlin, E. Kim, M. Ferrier, A. P. Sattelberger,
W. Lukens, M. Fattahi, L. C. Francesconi, K. E. German, K. R. Czerwinski,

University of Nevada Las Vegas, USA, Sandia National Laboratories, USA,
Hunter college of the City University of New York, USA, A. N. FrumkinInstitute of Physical Chemistry and Electrochemistry, Russia, Ecoles desMines de Nantes, France, Argonne National Laboratory, USA, Lawrence
Berkeley National Laboratory, USA
17:40-18:00

NEO-0418:00-18:20

NEO-05Speciation and reactivity of heptavalent technetium in concentrated acids
A. Braatz, M. Nilsson, University of California, Irvine, USA
Fluorescence studies of complex stoichiometry of metal ions in extraction
systems combining dibutyl phosphoric acid and tri-n-butyl phosphate
R. Chen, H. Tanaka, M. Asai, C. Fukushima, T. Kawamoto, M. Ishizaki, M.
Kurihara, M. Arisaka, T. Nankawa M. Watanabe, National Institute ofAdvanced Industrial Science and Technology, Japan, Yamagata University,
Japan, Japan Atomic Energy Agency, Japan
Column study on electrochemical separation of cesium ions from wastewaterusing copper hexacyanoferrate film
18:20-18:50

Mounting of posters

18:50-20:00

Poster session 2（ 13 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Wednesday, 25 September 2013
Hall & Meeting Room, Kanazawa Bunka Hall
09:00-10:00

Plenary Session
Actinide chemistry & Radiopharmaceutical chemistry and Nuclear medicine
Chairs : T. Yaita and E. Simoni

Hall
09:00-09:30

PL-05

09:30-10:00

PL-06

M. A. Denecke, University of Manchester, UK
Actinide speciation using synchrotron-based methods
J. Hatazawa, Osaka University, Japan
Radionuclides in diagnostic nuclear medicine

10:00-10:20

Coffee Break

10:20-12:00

Parallel session
Radiopharmaceutical chemistry and Nuclear medicine (continued)
Chairs : J. Hatazawa and A. Türler

Hall
10:20-10:50

RPI-01D. S. Wilbur, D. K. Hamlin, M.-K. Chyan, E. Balkin, J. M. Pagel, O. W. Press,
B. M. Sandmaier, University of Washington, USA, Fred Hutchinson Cancer

Research Center, USA
10:50-11:20

RPI-02

11:20-11:40

RPO-01

11:40-12:00

RPO-02

Addressing challenges in preparation of 211At-labeled biomolecules for use intargeted alpha therapy
M. Maiti, S. Lahiri, Indian Institute of Technology Roorkee, India, Saha

Institute of Nuclear Physics, India

Generation of nuclear data for the production of 97Ru from 12C + 89Y reaction
E. Aneheim, S. Lindegren1, H. Jensen, Sahlgrenska Academy at Gothenburg
University, Sweden, Cyclotron and PET Unit, Denmark
Towards an automatic procedure for the production of astatinated antibodies
Y. Hatsukawa, K. Hashimoto, K. Tsukada, T. Sato, M. Asai, A. Toyoshima, Y.
Nagai, T. Tanimori, S. Sonoda, S. Kabuki, H, Saji, H. Kimura, Japan Atomic

Energy Agency, Japan, Kyoto University, Japan, Tokai University, Japan
Production of 95mTc for compton camera imaging
12:00-13:20

Group photo (Hall) and Lunch

10:20-12:00

Parallel session

Meeting
Room

Actinide chemistry (continued)
Chairs : M. Watanabe and A. Goswami

10:20-10:50

ACI-01

10:50-11:20

ACI-02

11:20-11:40

ACO-01

11:40-12:00

ACO-02

J. Su, J. Li, Tsinghua University, China
Relativistic quantum chemical studies on electronic structures andphotoelectron spectra of actinide complexes
Y. Kitatsuji, Japan Atomic Energy Agency, Japan
Flow electrolysis of actinide ions utilizing electrocatalysis
A. Kirishima, N. Sato, Tohoku University, Japan
Determination of the thermodynamic quantities of U(VI) complexation with“aliphatic” and “aromatic” di-carboxylic acids by calorimetry
H. Hayashi, M. Akabori, K. Minato, Japan Atomic Energy Agency, Japan
Electrochemical behavior of americium in NaCl-2CsCl melt
（ 14 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201312:10-13:20

Group photo (Hall) and Lunch

13:20-15:20
Hall

Japan Society of Nuclear and Radiochemical Sciences (JNRS) General
Assembly for Member of JNRS

13:20-14:20

JNRS General Assembly

14:20-15:20

JNRS Meeting

15:20-15:40

Coffee Break

15:40-17:20

Parallel session

RPO-03

Radiopharmaceutical chemistry and Nuclear medicine & Fukushima issues(continued)
Chairs : T. Ohnuki and D. S. Wilbur
L. Safavi-Tehrani, G. E. Miller, M. Nilsson, University of California Irvine,

FKO-11

Production of high specific activity radiolanthanides for medical purposes
using the UC Irvine TRIGA Reactor
S. LaZar, E. Rasmussen, P. Stamets, Department of Energy (DOE), USA, SanHall
15:40-16:00

16:00-16:20

16:20-16:40

FKO-12

USA

Diego State University, USA, Fungi Perfecti Research Laboratories, USA

Mycoremediation:
fungus-based
soil
remediationofradioisotope
contamination
K. Minami, T. Funabashi, R. Kamimura, T. Yasutaka, H. Tanaka, A.
Kitajima, H. Ogawa, T. Kawamoto, National Institute of Advanced Industrial

Science and Technology, Japan, Tokyo Power Technology Ltd., Japan
16:40-17:00

FKO-13

Automatic Cs-uptake device for radioactive-Cs evaluation in environmental
water
K. Minami, H. Ogawa, H. Tanaka, A. Takahashi, T. Uchida, A. Kitajima, D.
Parajuli, T. Kawamoto, M. Yamaguchi, M. Osada, N. Otake, S. Sato, R.
Kamimura, Y. Hakuta, The National Institute of Advanced Industrial Scienceand Technology, Japan, Tokyo Power Technology Ltd., Japan
17:00-17:20

FKO-14

Pilot plant for volume reduction of Cs-contaminated combustible materials
D. Parajuli, H. Tanaka, S. Fukuda, R. Kamimura, T. Kawamoto, The National

Institute of Advanced Industrial Science and Technology, Japan, Tokyo PowerTechnology Ltd., Japan
Decontamination of radioactive cesium from ash and soil

15:40-17:20

Parallel session

Meeting
Room

Actinide chemistry & Nuclear chemistry (continued)
Chairs : H. Haba and Ch. E. Düllmann

15:40-16:00

ACO-03

16:00-16:20

ACO-04

T.-H. Park, Y. S. Choi, J.-H. Park, J.-Y. Kim, S.-E. Bae, Y.-H. Cho, J.-W. Yeon,
K. Song, Korea Atomic Energy Research Institute, Korea
Rapid radioanalytical determination of U, Pu, and Am in radioactive wastes
via extraction chromatography, alpha spectrometry, and thermal ionization
mass spectrometry
N. Aoyagi, M. Watanabe, A. Kirishima, N. Sato, T. Kimura, Japan Atomic

Energy Agency, Japan, Tohoku University, Japan

Luminescence spectroscopy of uranium complexes in non-aqueous media（ 15 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

16:20-16:40

NCO-13

A. Toyoshima, S. Miyashita, M. Asai, T. K. Sato, Y. Kaneya, K. Tsukada, Y.
Kitatsuji, Y. Nagame, M. Schädel, H. V. Lerum, J. P. Omtvedt, Y. Oshimi, K.
Ooe, Y. Kitayama, A. Yokoyama, A. Wada, Y. Oura, H. Haba, J. Kanaya, M.
Huang, Y. Komori, T. Yokokita, Y. Kasamatsu, A. Shinohara, V. Pershina, J. V.
Kratz, Japan Atomic Energy Agency, Japan, University of Oslo, Norway,

Niigata University, Japan, Kanazawa University, Japan, Tokyo Metropolitan
University, Japan, RIKEN, Japan, Osaka University, GSI Helmholtzzentrum
für Schwerionenforschung, Germany, Johannes Gutenberg-University ofMainz, Germany
16:40-17:00

NCO-1417:00-17:20

NCO-15Chemical studies of Mo and W in preparation of a seabogrium (Sg) reduction
experiment using MDG, FEC, and SISAK
P. Steinegger, R. Dressler, R. Eichler, A. Türler, Paul Scherrer Institute,
Switzerland , University of Bern, Switzerland
Diamond detectors for isothermal vacuum chromatography
R. Tripathi, S. Sodaye, K. Mahata, P. K. Pujari, Bhabha Atomic ResearchCentre, India

Angular distribution of projectile like fragments in 16O + 89Y reaction
17:20-17:50

Coffee Break

17:50-18:30

Plenary session

Hall
17:50-18:30

JNRSAward

JNRS Award Presentation (Open session)
Chair : T. Sasaki
T. Kimura, Japan Atomic Energy Agency, Japan
Studies on solution chemistry of actinides and lanthanides by time-resolved
laser-induced fluorescence spectroscopy

18:30-18:50

Mounting of posters

18:50-20:00

Poster session 3（ 16 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Thursday, 26 September 2013
Hall & Meeting Room, Kanazawa Bunka Hall
09:00-10:00

Plenary Session

Hall
09:00-09:30

PL-07

09:30-10:00

PL-08

Education in nuclear and radiochemistry & Nuclear probes for materialscience
Chairs : K. Kubo and J. John
S. B. Clark, Washington State University, USA
Preparing the next generation of radiochemists for global challenges
H. Ueno, RIKEN, Japan
Researches with stopped radioisotopes at the RIKEN RIBF facility

10:00-10:20

Coffee Break

10:20-12:10

Parallel session
Nuclear probes for material science (continued)
Chairs : Y. Yamada and Y. Kobayashi

Hall
10:20-10:50
10:50-11:10

11:10-11:30

NPI-01

W. Sato, S. Komatsuda, Y. Yamada, Y. Ohkubo, Kanazawa University, Japan,

NPO-01

Local structure at the In impurity site in ZnO probed by the TDPAC technique
K. Nomura, P. de Souza, S. Hirai, N. Kojima, The University of Tokyo, Japan,

NPO-02

Mössbauer analysis of iron ore and rapidly reduced iron ore bymicro-discharge
J. Wang, A. I. Rykov, K. Nomura, Dalian Institute of Chemical Physics, China,

11:30-11:50

NPO-03

11:50-12:10

NPO-04

Tokyo University of Science, Japan, Kyoto University, Japan

University of Tasmania, Australia, Tokyo Toshi University, JapanThe University of Tokyo, Japan

Three ways to fix Cs in prussian blues
M. Kaneko, H. Dote, S. Nakashima, Hiroshima University, Japan
Theoretical study on Mössbauer parameters of iron assembled complexes
G. Yoshida, K. Ninomiya, M. Inagaki, T. U. Ito, W. Higemoto, T. Nagatomo, P.
Strasser, N. Kawamura, K. Shimomura, Y. Miyake, T. Miura, M. K. Kubo, A.
Shinohara, Osaka University, Japan, Japan Atomic Energy Agency, Japan,

High Energy Accelerator Research Organization, Japan, International
Christianity University, Japan
Study on muon capture process for gaseous molecules containing C and O
atoms
12:10-13:00

Lunch

10:20-12:10

Parallel session

MeetingRoom
10:20-10:50

Education in nuclear and radiochemistry (continued)
Chairs : A. Shinohara and Y. H. Chung
EDI-01

J. John, V. Čuba, M. Němec, T. Retegan, C. Ekberg, G. Skarnemark, J. Lehto,
T. Koivula, P. J. Scully, C. Walther, J.-W. Vahlbruch, N. Evans, D. Read, E.
Ansoborlo, B. Hanson, L. Skipperud, B. Salbu, J. P. Omtvedt, Czech Technical

University in Prague, Czech Republic, Chalmers University of Technology,
Sweden, University of Helsinki, Finland, University of Hanover, Germany,
Loughborough University, Great Britain, Commissariat à l’énergie atomiqueet aux énergies alternatives, France, Leeds University, UK, Norwegian（ 17 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

University of Life Sciences, Norway, University of Oslo, Norway
10:50-11:20

EDI-02

11:20-11:50

EDI-03

11:50-12:10

EDO-01

CINCH-II Project - Next step in the coordination of education in nuclear andradiochemistry in Europe
W. S. Wu, Z. F. Chai, Lanzhou University, China, Institute of High Energy

Physics, China

Fostering of personnel for nuclear and radiochemistry according to China's
NPP prospects after Fukushima Daiichi accident
A. Yokoyama, Kanazawa University, Japan
Post-Fukushima situation on radiation awareness activities and nuclear andradiochemistry education in JapanS. B. Sarmani, R. B. Yahaya, M. S. Yasir, A. Ab. Majid, K. S. Khoo, I. A.
Rahman, F. Mohamed, Universiti Kebangsaan, Malaysia
Radiochemistry course in the undergraduate nuclear science program at
Universiti Kebangsaan Malaysia

12:10-13:00

Lunch

13:00-17:30

Excursion : Shirakawa-go

19:00-21:00

Banquet at Kanazawa Excel Hotel Tokyu（ 18 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Friday, 27 September 2013
Meeting Room, Kanazawa Bunka Hall
09:00-10:00
Meeting
Room

Activation analysis
Chairs : M. Ebihara and J. H. Moon

09:00-09:30

AAI-01

09:30-10:00

AAI-02W. M. Sanchez, Y. Shi, A. Chatt, Dalhousie University, Canada
Simultaneous analysis for As, Sb, and Se species in water by chemical
separation and neutron activation
T. Miura, R. Okumura, Y. Iinuma, S. Sekimoto, K. Takamiya, M. Ohata, A.
Hioki, National Metrology Institute of Japan, Japan, Kyoto University

Research Reactor Institute, Japan

Precise determination of bromine in PP resin pellet by instrumental neutron
activation analysis using internal standardization
10:00-10:20

Coffee Break

10:20-12:00
MeetingRoom
10:20-10:40

10:40-11:00

Activation analysis (continued)
Chairs : T. Miura and A. Chatt
AAO-01

AAO-02J. H. Moon, B. F. Ni, R. M. Theresia, N. A. Abd. Salim, B. Arporn, C. D. Vu,

Korea Atomic Energy Research Institute, Korea, China Institute of Atomic
Energy, China, National Nuclear Energy Agency, Indonesia, Malaysian
Nuclear Agency, Malaysia, Thailand Institute of Nuclear Technology,
Thailand, Vietnam Atomic Energy Agency, Vietnam

Analysis of most popular and/or consumed fish species by neutron activation
analysis in six Asian countries
Y. Toh, M. Ebihara, K. Hara, A. Kimura, H. Harada, S. Nakamura, M.
Koizumi, K. Furutaka, F. Kitatani, Japan Atomic Energy Agency, Japan,

Tokyo Metropolitan University, Japan
11:00-11:20

AAO-03Current status and future perspective on time-of-flight prompt gamma-ray
analysis combined with gamma-ray coincidence technique development
K. Ninomiya, M. K. Kubo, T. Nagatomo, G. Yoshida, M. Inagaki, A. Shinohara,
T. Suzuki, N. Kawamura, P. Strasser, K. Shimomura, Y. Miyake, Y. Kobayashi,
K. Ishida, W. Higemoto, S. Sakamoto, T. Saito, Osaka University, Japan,

International Christianity University, Japan, High Energy Accelerator
Research Organization, Japan, RIKEN, Japan, Japan Atomic Energy Agency,
Japan, National Museum of Japanese History, Japan
11:20-11:40

11:40-12:00

AAO-04

Simultaneous and multielemental analysis by muonic X-rays for inside
Japanese bronze and gold coin
M. Fukushima, A. Chatt, Y. Nakamura, M. Haga, S. Hoshi, T. Sakata,

AAO-05

Rapid analysis for selenium in urine samples using the 17.4-s neutron
activation product 77mSe
N. Shirai, Y. Hidaka, S. Sekimoto, M. Ebihara, H. Kojima, Tokyo Metropolitan

Ishinomaki Senshu University, Japan, Dalhousie University, Canada, Meiji
Co., Ltd., Japan, Shokei Gakuin University, Japan

University, Japan, Kyoto University Research Reactor Institute, Japan,
National Institute of Polar Research, Japan, Graduate University for
Advanced Sciences, Japan（ 19 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Neutron activation analysis of iron meteorite
12:00-13:20

Lunch

Meeting
Room

Application of nuclear and radiochemical techniques (continued)
Chairs : W. Sato and Y. L. Zhao

13:20-13:50

API-03

13:50-14:10

APO-04

14:10-14:30

APO-05

Y. Hamajima, Kanazawa University, Japan
What has been revealed in the low-level radioactivity measurement? - lowlevel gamma-ray counting in Ogoya underground laboratory

C. Gautier, M. Coppo, C. Caussignac, I. Laszak, P. Fichet, F. Goutelard, CEA

Saclay, France

Zr and U determination at trace level in simulated deep groundwater by Q
ICP-MS using TRU-based and TODGA-based extraction chromatography
T. Yoshimura, H. Ikeda, A. Ito, E. Sakuda, N. Kitamura, T. Takayama T.
Sekine, A. Shinohara, Osaka University, Japan, Hokkaido University, Japan,

Daido University, Japan, Tohoku University, Japan
14:30-14:50

APO-06

Photoluminescence of five- and six-coordinate tetracyanidonitridotechnetium(V) and -rhenium (V) complexes
J. D. Despotopulos, N. Gharibyan, R. A. Henderson, W. Kerlin, K. J. Moody, D.
A. Shaughnessy, E. Tereshatov, R. Sudowe, Lawrence Livermore National

Laboratory, USA, University of Nevada Las Vegas, USA

Studies of flerovium and element 115 homologs with macrocyclic extractants
14:50-15:10

Coffee Break

15:10-15:30

Closing Ceremony

MeetingRoom

M. Yamamoto, APSORC13 co-chair, Kanazawa University, Japan
Student Poster Award（ 20 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Monday, 23 September 2013, Poster Session
23-FKP-01

137Cs accumulation enhanced by potassium starvation in lotus japonicus

J. Furukawa1, H. Noda2, R. Sugita3, K. Tanoi3, T. M. Nakanishi3, S. Satoh1
1Facultyof Life and Environmental Sciences, University of Tsukuba, 2Graduate School of Life andEnvironmental Sciences, University of Tsukuba, 3Graduate School of Agricultural and Life Sciences, The
University of Tokyo

23-FKP-02

Decontamination of the contaminated water on severe nuclear accidents by titanium oxide adsorption
Y. Takahatake1, M. Nakamura1, A. Shibata1, K. Nomura1, Y. Koma1, Y. Nakajima1
1Japan Atomic Energy Agency

23-FKP-03

Iodine-129 in the aquatic environment adjacent to a spent nuclear fuel reprocessing plant, Rokkasho, Japan
S. Ueda1, H. Kakiuchi1, H. Hasegawa1 N. Akata1, H. Kawamura2, S. Hisamatsu1
1Departmentof Radioecology, Institute for Environmental Sciences, Japan,
Evaluation Association, Japan

23-FKP-04

2Kyushu

Environmental

Specific activity and time dependence of radionuclides in soils affected by the accident of the Fukushima
Dai-ichi nuclear power plant (Part 2).
T. Shimasaki1, Y. Shiraishi1, O. Kawahara1, K. Goto1, M. Shimamoto1, A. Kojima1, S. Okada2

1Institute of Source Development and Analysis, Kumamoto University, 2Center for AIDS Research, Kumamoto

University

23-FKP-05

Differences between year 2011 and 2012 in Cs-137 concentration in brown rice grown in Fukushima
Prefecture
S. Fujimura1,2, Y. Sakuma1, T. Yamauchi1, K. Niitsuma1, N. Sato3, M. Sato1, T. Saito1, K. Yoshioka1
1Fukushima

Town, Japan

23-FKP-06

Agricultural Technology Centre, 2NARO Tohoku Agricultural Research Center, 3InawashiroSize-distribution of airborne radioactive particles from the Fukushima accident
H. Muramatsu1, K. Kawasumi1, T. Kondo1, and K. Matsuo2

1Department of Chemistry, Faculty of Education, Shinshu University, Japan, 2Graduate School of Education,

Shinshu University, Japan

23-FKP-07

Long-term effects of radionuclides originating from the Fukushima nuclear power plant accident in airborne
particulate matters in Kawasaki
K. Nakamachi1, H. Matsuno1, T. Honda1, Y. Kikawada2
1Graduate

University

23-FKP-08

School of Engineering, Tokyo City University, 2Faculty of Science and Technology, Sophia

Measurement of Iodine-129 concentration in water samples in relation with Fukushima Daiichi Nuclear
Power Plant accident
H. Matsuzaki1, H. Tokuyama1, Y. Miyake1, M. Honda2, T. Yamagata3, Y. Muramatsu4
1Departmentof Nuclear Engineering and Management, School of Engineering, The University of Tokyo,
Japan, 2Graduate School of Integrated Basic Sciences, Nihon University, Japan, 3College of Humanities andSciences, Nihon University, Japan, 4Department of Chemistry, Gakushuin University, Japan

23-FKP-09

Observed radioactivities and activity ratios in aerosols from April 2011 at the geological survey of Japan,
Tsukuba, Japan
Y. KANAI1
1Geological Survey of Japan, National Institute of Advanced Industrial and Technology

23-FKP-10

Chemical forms of radioactive Cs in soils originated from Fukushima Dai -ichi nuclear power plant accident, as
studied by extraction experiments
M. Hirose1, Y. Kikawada1, A. Tsukamoto2, T. Oi1, T. Honda2, K. Hirose1, H. Takahashi3
1Facultyof Science and Technology, Sophia University, 2Graduate School of Engineering, Tokyo City
University, 3Graduate School of Engineering, Tohoku University

23-FKP-11

Thermal Oxidation of Cesium Loaded Prussian Blue as a Precaution for Exothermic Phase Change in Extreme
Conditions（ 21 ）

��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

D. Parajuli, H. Tanaka, A. Takahashi, T. Kawamoto

Nanosystem Research Institute, AIST, Japan

23-FKP-12

Analysis of 134Cs and 137Cs distribution in soil of Fukushima prefecture and their specific adsorption on clay
mineralsA. Maekawa1, N. Momoshima2, S. Sugihara2, R. Ohzawa1, A. Nakama1
1Graduate School of Sciences, Kyushu University, Japan, 2Radioisotope Center, Kyushu University, Japan

23-FKP-13

Distribution of radionuclides in seabed sediments off Ibaraki coast after the Fukushima Daiichi Nuclear
Power Plant accident
M. Nagaoka1, H. Yokoyama1, H. Fujita1, M. Nakano1, H. Watanabe1, S. Sumiya1
1Nuclear Fuel Cycle Engineering Laboratories, Japan Atomic Energy Agency

23-FKP-14

Radiocesium concentration change in tree leaves before and after defoliation
S. Uchida1, K. Tagami

1Office of Biospheric Assessments for Waste Disposal, National Institute of Radiological Sciences

23-FKP-15

Distributions and concentrations of radionuclides in giant butterbur after the Fukushima Nuclear Power
Plant Accident
K. Tagami1, S. Uchida1
1Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences, Japan

23-FKP-16

The Behavior of Cs adsorption of microcapsule beads nano-prussian blue
A. Kitajima1, H. Ogawa1, K. Yoshino2, M. Takasaki2, H. Tanaka1, T. kawamoto1

1Nanosystem Research Institute, Japan, 2Kanto Chemical Company Inc., Japan

23-FKP-17

Transfer of radiocesium from soil to cut flowers
Y. Suzuki1,2, H. Munakata1, Y. Yajima1, Y. Tooyama3, H. Suzuki1, H. Tsukada4, K. Inubushi2

1Fukushima Agricultural Technology Centre , 2 Graduate School of Horticulture, Chiba University ,3Ken-poku District Agriculture and Forestry Office, Japan, 4Fukushima University

23-FKP-18

CLEVASOL, a novel radiation hard cation exchanger suitable for treatment of liquid radioactive waste withhigh salinity
A. Yakushev1, A. Türler2, Z. Dvorakova3, K. von Bremen2

1GSI Helmholtzzentrum für Schwerionenforschung GmbH, 2University of Bern, 3Neplachova 17, 37004 Ceske

Budejovice

23-FKP-19

Estimation of I-131/I-129 ratios and vertical distribution of radioiodine in soil collected from Fukushima
Prefecture
N.Inagawa1, Y. Muramatsu1, T. Ohno1, T. Toyama1, C. Satou2, M. Outsuki3, T. Matsuzaki4

1Gakushuin University, 2Fukushima Agricultural Technology Centre, 3Tohoku University, 4University ofTokyo

23-FKP-20

Effects of soil types on the transfer of radiocesium to plant
K. Oda1, Y. Muramatsu1, T. Ohno1, T. Kobayashi2, S. Fujimura2

1Gakushuin University, 2Fukushima Agricultural Technology Centre

23-FKP-21

Temporal distribution of plutonium isotopes in marine sediments off Fukushima and Ibaraki after the
Fukushima Dai-ichi Nuclear Power Plant accident
W. Bu1,2, J. Zheng*2, T. Aono2, S. Otosaka3, K. Tagami2, Q. Guo1, S. Uchida2
1Schoolof Physics, Peking University, 2National Institute of Radiological Sciences, Japan, 3Japan Atomic
Energy Agency

23-FKP-22

Evaluation of Iodine-129 mobility and deposition amount in the soil contaminated by the Fukushima Daiichi
nuclear power plant accident
M. Honda1, H. Matsuzaki2, T. Yamagata 3, Y. (S.) Tuchiya2, C. Nakano2, Y. Matsushi4, Y. Maejima5, H. Nagai3

1Graduate School of Integrated Basic Sciences, Nihon university, Japan, 2Department of Nuclear Engineeringand Management, School of Engineering, The University of Tokyo, Japan, 3College Humanities and Sciences,
Nihon University, Japan, 4Disaster Prevention Research Institute, Kyoto University, Japan, 5National
Institute for Agro-Environmental Sciences, Japan（ 22 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

23-FKP-23

Vertical distribution of the Fukushima-derived radiocesium in the western North Pacific in January andFebruary 2011
Y. Kumamoto1, A. Murata1, T. Kawano1, M. Aoyama2
1Japan Agency for Marine-Earth Science and Technology, Japan, 2Meteorological Research Institute, Japan

23-FKP-24

Effect of application timing of potassium fertilizer on root uptake of 137Cs in brown rice
T. Saito1, K. Takahashi1, T. Makino2, H. Tsukada3,4, M. Sato1, K. Yoshioka1

1Fukushima Agricultural Technology Centre, 2National Institute for Agro-Environmental Sciences, 3Institutefor Environmental Sciences, 4Fukushima University

23-FKP-25

Low levels of 134Cs and 137Cs in bottom sediments along the Japanese archipelago side of the Sea of Japan after
the Fukushima Dai-ichi NPP accident
M. Inoue1,*, S. Ochiai1, T. Murakami1, S. Oikawa2, M. Yamamoto1, S. Nagao1, Y. Hamajima1, H. Kofuji1, J.
Misonoo2
1Low Level Radioactivity Laboratory, Kanazawa University, 2Marine Ecology Research Institute, Japan

238
238
238
248
23-NCP-01 The heavy-ion reactions U + U and U + Cm and actinide production close to the barrier revisited

J.V. Kratz1a, M. Schädel1b, H.W. Gäggeler1c
1Gesellschaft

für Schwerionenforschung mbH, acurrently at Institut für Kernchemie, Johannes
Gutenberg-Universität, Germany, bcurrently at Advanced Science Research Center, Japan Atomic Energy
Agency, Japan, ccurrently at Paul Scherrer Institute, Switzerland

23-NCP-02 Mechanism of Mo-99 adsorption and Tc-99m elution from zirconium-based material in Mo-99/Tc-99m
generator column using neutron-irradiated natural molybdenum
R. Awaludin1, A. H. Gunawan1, H. Lubis1, Sriyono1, Herlina1, A. Mutalib1, A. Kimura2, K. Tsuchiya2, M.
Tanase3, M. Ishihara2
1Center for Radioisotope and Radiopharmaceutical, National Nuclear Energy Agency of Indonesia, 2Neutron

Irradiation and Testing Reactor Center, Oarai Research and Development Center, Japan Atomic Energy
Agency, 3Chiyoda Technol Corporation, Japan

23-NCP-03 Startup of a new gas-filled recoil separator GARIS-II

D. Kaji1, K. Morimoto1, H. Haba1, Y. Wakabayashi1, Y. Kudou1, M. Huang1, S. Goto2, M. Murakami2, N. Goto2,
T. Koyama2, N. Tamura2, S. Tsuto2, T. Sumita3, K. Tanaka3, M. Takeyama4, S. Yamaki5, K. Morita1
1Nishina

Center for Accelerator Based Science, RIKEN, 2Niigata University, Japan, 3Tokyo University of
Science, Japan, 4Yamagata University, 5Saitama University, Japan

23-NCP-04 Purification of scintillation cocktails containing the alpha emitters americium and plutonium

E. Löfström-Engdahl*, G. Skarnemark, K. El Tayara, J. Eriksson, N. Halldin, J. Halleröd, M. Malmberg, J.
Mattiasson Bjugren

Nuclear chemistry, Department of Chemical and Biological Engineering, Chalmers University of Technology,
Sweden23-NCP-05 Formation and stability of sulfides of the superheavy elements Cn and Fl
N.M. Chiera1,2, R. Eichler1,2*, A. Türler 1,2

1Department of Chemistry & Biochemistry, University of Berne, Switzerland, 2Laboratory for Radiochemistry

and Environmental Chemistry, Paul Scherrer Institute, Switzerland

23-NCP-06 Development of a batch-type solid-liquid extraction apparatus for repetitive extraction experiment of element

104, Rf
Y. Kasamatsu1, T. Yokokita1, A. Kino1, K. Nakamura1, K. Toyomura1, Y. Komori1, N. Takahashi1, H. Haba2, J.
Kanaya2, M. Huang2, Y. Kudou2, T. Yoshimura3, A. Shinohara1
1Graduate

School of Science, Osaka University, 2Nishina Center for Accelerator-Based Science, RIKEN,

3Radioisotope Research Center, Osaka University

23-NCP-07 Coprecipitation of Zr, Hf and Th with Sm hydroxide for chemical study of Rf

K. Toyomura1, Y. Kasamatsu1, N. Shiohara1, T. Yokokita1, Y. Komori1, K. Nakamura1, N. Takahashi1, T.
Yoshimura2, H. Haba3, Y. Kudou3, H. Kikunaga4, T. Ohtsuki4, K. Takamiya5, T. Mitsugashira6, and A.
Shinohara1
1Graduate School of Science, Osaka University, 2Radioisotope Research Center, Osaka University, 3Nishina

Center for Accelerator-Based Science, 4Research Center for Electron Photon Science, Tohoku University,
5Research Reactor Institute, Kyoto University, 6International Research Center for Nuclear Materials Science,（ 23 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Institute for Material Research, Tohoku University

23-NCP-08 Development of modified epoxy paint films to reduce the volatile iodine source term in the containments of
LWRs during severe nuclear accidents
S. Tietze1

1Severe Nuclear Accident Chemistry, Nuclear Chemistry Department, Department of Chemical and BiologicalEngineering, Chalmers University of Technology, Sweden

23-NCP-09 New insights into the formation and stability of molybdenum carbonyl compounds
I. Usoltsev1,2, Wang Yang3, R. Eichler1,2, A. Türler1,2, Qin Zhi3

1Department of Chemistry & Biochemistry, University of Berne, Switzerland, 2Laboratory for Radiochemistry

and Environmental Chemistry, Paul Scherrer Institut, Switzerland, 3Institute of Modern Physics Lanzhou;
Chinese Academy of Sciences, China

23-NCP-10 Adsorption behavior of super-heavy elements (Z ≥ 112) on metal and inert surfaces
J. Anton1, T. Jacob1, V. Pershina2

1Institut für Elektrochemie, Universität Ulm, Germany, 2Gesellschaft für Schwerionenforschung, Germany

23-ACP-01

Structural studies of the Eu(III) and U(VI) interactions with pentapeptides
A. Jeanson1, J. Roques1, S. Safi1, E. Simoni1, D. Aitken2

1IPN Orsay UMR 8608 - Université Paris Sud, France, 2ICMMO - Université Paris Sud, France

23-ACP-02

Solubility of amorphous UO2 and NpO2 in nitrate media containing platinum catalyst
A. Kitamura1, S. Shimoda2
1Japan Atomic Energy Agency, 2Mitsubishi Materials Corporation, Japan

23-ACP-03

Apparent formation constants of actinide complexes with humic substances determined by solvent extraction
T. Sasaki1, Y. M. Kulyako2, K. Müller3, T. Kobayashi1, M. Samsonov2, B. F. Myasoedov2

1Department of Nuclear Engineering, Kyoto University, Japan, 2V.I.Vernadsky Institute of Geochemistry andAnalytical Chemistry, Russia, 3Helmholtz-Zentrum Dresden-Rossendorf e.V., Institute of Resource Ecology,
Germany

23-ACP-04

The solubility of Np(IV) under alkaline and anoxic conditions
G. Källvenius1, S. Allard2, C. Ekberg2

1AB SVAFO, SE-611 23 Nyköping, Sweden, 2Chalmers University of Technology, Nuclear Chemistry, Sweden

23-ACP-05

Separation of Am and Cm by using TODGA and DOODA(C8) adsorbents with hydrophilic ligand-nitric acidsolution
S. Usuda1, K. Yamanishi1, H. Mimura1, Y. Sasaki2, A. Kirishima3, N. Sato3, Y. Niibori1
1Departmentof Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku
University, 2Research Group for Aqueous Separation Chemistry, Japan Atomic Energy Agency, 3Institute ofMultidisciplinary Research for Advanced Materials, Tohoku University

23-ACP-06

Growth of uranyl hydroxide nanowires and nanotubes with electrodeposition method
L. Wang, L.-Y. Yuan, Z.-F. Chai, W.-Q. Shi*

Key Laboratory of Nuclear Analysis Techniques, Institute of High Energy Physics, Chinese Academy of
Sciences, China

23-ACP-07

Adsorption behavior of neptunium ions on pyridine resin in hydrochloric acid solutions
Y. Tachibana1, Y. Tomobuchi1, M. Inaki1, Y. Yamazaki1, T. Suzuki1, T. Yamamura2
1Departmentof Nuclear System Engineering, Nagaoka University of Technology, 2Institute of Material
Research, Tohoku University

23-ACP-08

A method for 237Np determination with liquid scintillation counting in the experiment of neptunium sorption
onto bentonite
L. Ping, L. Zhi, G. Zhijun, W. Wangsuo*

Radiochemistry Laboratory, School of Nuclear Science and Technology, Lanzhou University, China

23-ACP-09

Determination of stability constants for the thorium iminodiacetic acid complexes
D. Rama Mohana Rao, R. M. Sawant, B. S. Tomar.

Radioanalytical Chemistry Division, Bhabha Atomic Research Centre, India（ 24 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-ACP-03

Time-resolved laser fluorescence spectroscopy combined with parallel factor analysis: a robust speciation
technique for UO22+
T. Saito1, N. Aoyagi2, T. Kimura2
1Nuclear

Professional School, School of Engineering, The University of Tokyo, 2Nuclear Science andEngineering Directorate, Japan Atomic Energy Agency
55
89,90Sr in liquid samples using Sr and/or Pb resins for the mutual separation of Fe
23-ENP-01 Determination of Fe andand Sr
M. Nodilo, I. Milanović, Ž. Grahek

Division for marine and environmental research, Rudjer Bošković Institute, Croatia
90
23-ENP-02 Implementation of dry cow dung powder for biosorption of Sr(II) from simulated radioactive waste

R. P. Khilnani, H. K. Bagla

Department of Nuclear and Radiochemistry, K. C. College, India

23-ENP-03 Application of simplified desorption method to sorption study: (1) sorption of americium (III) on bentonite andits major components
N. Kozai1, T. Ohnuki1

1Japan Atomic Energy Agency, Japan

23-ENP-04 Effect of aging on availability of iodine in grassland soil collected in Rokkasho, Japan
A. Takeda, H. Tsukada, Y. Takaku, S. Hisamatsu

Department of Radioecology, Institute for Environmental Sciences
14
23-ENP-05 Study on C spatial distribution around Qinshan nuclear power plant in China

Z. Wang1, D. Hu2, Q. Guo1

1State Key Laboratory of Nuclear Physics and Technology, Peking University, China, 2Radiation Monitoring

Technical Center of Ministry of Environmental Protection, China

7
210
134
40
23-ENP-06 Atmospheric deposition of radionuclides ( Be, Pb, Cs, and K) during 2000–2012 at Rokkasho, Japan, andimpact of the Fukushima Dai-ichi Nuclear Power Plant accident
N. Akata1, H. Hasegawa1, H. Kawabata1, H. Kakiuchi1, Y. Chikuchi2, N. Shima3, T. Suzuki4, S. Hisamatsu1
1Institutefor Environmental Sciences, Japan, 2Aomori JGC PLANTECH, Japan, 3Fukushima University,

Japan, 4Yamagata University, Japan

23-ENP-07 Effect of aging on water extractability of radioactive iodine and cesium from soil
H. Tsukada, A. Takeda, S. Hisamatsu

Department of Radioecology, Institute for Environmental Sciences, Japan

23-ENP-08 Background internal dose rates of earthworm and arthropod species in the forests of Aomori, Japan
Y. Ohtsuka, Y. Takaku, S. Hisamatsu

Department of Radioecology, Institute for Environmental Sciences, Japan

23-ENP-09 An EXAFS study on the effect of natural organic matter and mineralogy composition on cesium mobility inenvironment
Q. Fan, M. Tanaka, Y. Takahashi

Department of Earth and Planetary Systems Science, Graduate School of Science, Hiroshima University
90
23-ENP-10 Using factorial design to the robustness analysis of the classic sample preparation method for Sr

determination in tea leaf
C.-C. Liu1*, W.-H. Tsai1, M.-C. Horng1, C.-C. Huang1, Y.-W. Wu2

1Radiation Monitoring Center, AEC, Taiwan, ROC, 2Department of Chemical Engineering, I-Shou University,

Taiwan, ROC

23-ENP-11 A simple method for dehydrogenase assay of soil microorganisms to evaluate the biospheric behavior of C -14
originated in transuranic waste
K. Iwata, N. Ishii, K. Tagami, S. Uchida

Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences（ 25 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

23-ENP-12 Effect of humic acid on the sorption of selenium (VI) on ferric oxide hydrate
N. Guo, Z. L. Niu, Y. L. Ye, R. Zhang, Z. J. Guo

School of nuclear science and technology, Lanzhou University, China

23-ENP-13 Uranyl ions adsorption to Na-GMZ and interactions with FA adsorption: experiments and modeling
Y. Yuanlv, G. Zhijun*, W. Wangsuo

Radiochemistry Laboratory, School of Nuclear Science and Technology, Lanzhou University, China

23-ENP-14 Foliar uptake and translocation of stable cesium and iodine by radish

H. Hasegawa1, H. Tsukada1, H. Kawabata1, Y. Takaku1, S. Hisamatsu1
1Institute for Environmental Sciences, Japan

23-ENP-15 The rapid determination of radiostrontium from large amount of seawater (within 72hrs) for the emergency
situation
H. Kim1*, K.-H. Chung1, H.-K. Park1, J.-M. Lim1, M.-J. Kang1

1Environmental Radioactivity Assessment Team, Korea Atomic Energy Research Institute, Korea
222
220
23-ENP-16 Peak tailing correction in measurement of Rn/ Rn activity concentration with α spectrum method

L. Zhang1, Q. Guo2, R. Ma2, L. Guo2

1Solid Dosimetric Detector and Method Laboratory, China, 2State Key Laboratory of Nuclear Physics andTechnology, School of Physics, Peking University, China

23-ENP-17 Underwater analysis of sediment chemistry using an autonomous platform
J. Breen1, P. de Souza1,2,3, G. Timms3, R. Ollington1
1Schoolof Computing and Information Systems, University of Tasmania, Australia, 2Vale Institute ofTechnology, Brazil, 3Intelligent Sensing and Systems Laboratory, ICT Centre, CSIRO, Australia

23-RPP-01

Development of the in-line multiple elution cartridge-based radioisotope concentrator device for increasing
99mTc and 188Re concentration of commercial radionuclide generator eluates
Van S. Le 1,2*; N. Morcos,1 J. McBrayer1, Z. Bogulski1, C. Buttigieg1, G. Phillips1
1CYCLOPHARM Ltd, Australia, 2MEDISOTEC, Australia

23-RPP-02

Production and preclinical evaluation of diagnostic and therapeutic radionuclides in tumor-bearing mice:recent developments at Paul Scherrer Institute
A. Türler1,2, M. Behe3, M. Bunka1,2, H. Dorrer1,2, A. Hohn3, K. Johnston4, U. Köster5, C. Müller3, J. Reber3, R.
Schibli3, N.T. van der Walt6, K. Zhernosekov1,2
1Laboratoryof Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, Switzerland,

2Laboratory of Radiochemistry and Environmental Chemistry, University of Bern, Switzerland, 3Center forRadiopharmaceutical Sciences ETH-PSI-USZ, Paul Scherrer Institute, Switzerland, 4Physics Department,
ISOLDE/CERN, Switzerland, 5Institut Laue-Langevin, France, 6Faculty of Applied Sciences, Cape Peninsula
University of Technology, South Africa

23-RPP-03

99Mo production by 100Mo(n,2n)99Mo using accelerator neutrons

N. Sato1, M. Kawabata1, Y. Nagai1, K. Hashimoto1, Y. Hatsukawa1, H. Saeki1, S. Motoishi1, T. Kin2, C. Konno3,
K. Ochiai3, K. Takakura3, F. Minato4, O. Iwamoto4, N. Iwamoto4, S. Hashimoto4
1Nuclear Engineering Research Collaboration Center, Japan Atomic Energy Agency, 2Faculty of Engineering

Sciences, Kyushu University, 3Fusion Research and Development Directorate, Japan Atomic Energy Agency,
4Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

23-RPP-04

Production and separation of 64Cu and 67Cu using 14 MeV neutrons
M. Kawabata1, K. Hashimoto1, H. Saeki1, N. Sato1, S. Motoishi1, K. Takakura2, C. Konno2 and Y. Nagai1

1Nuclear Engineering Research Collaboration Centre, Japan, 2Fusion Research and Development Directorate,

Japan Atomic Energy Agency

23-RPP-05

Novel radiochemical separation of arsenic from selenium for 72Se/72As generator.
E. Chajduk1, H. Polkowska-Motrenko1, A.Bilewicz1
1Institute of Nuclear Chemistry and Technology, Poland

23-RPP-06

Training program of synthesizing a radiopharmaceutical in KAERIS. Yang1, Y. H. Chung2
1Advanced

Radiation Technology Institute, Korea Atomic Research Institute, Korea,（ 26 ）

2DepartmentofAPSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Chemistry, Hallym University, Korea

23-RPP-07

Synthesis of 64Cu-labeled MARSGL peptide as an imaging probe for HER2/neu overexpressing tumors
Y. Sugo, I. Sasaki, S. Watanabe, Y. Ohshima, N. S. Ishioka

Quantum Beam Science Directorate, Japan Atomic Energy Agency

23-RPP-08

Molybdenum isotope fractionation in ion exchange reaction by using anion exchange chromatography
M. Inaki1, Y. Tachibana1, M. Nomura2 T. Suzuki1

1Department of Nuclear System Safety Engineering, Nagaoka University of Technology, 2Reserch Laboratory

for Nuclear Reactors, Tokyo Institute of Technology

23-APP-01

The mechanism of oxidized multi-walled carbon nanotubes across placental barrier and its effects on pregnany
Q. Wei1, B. Juanjuan1, W. Jing1, L.Zhan2, L. Peng1, W. Wangsuo1*
1Radiochemical Laboratory, Lanzhou University, China, 2Institute of Modern Physics, Chinese Academy of

Sciences, Lanzhou, China

23-APP-02

Prompt gamma test of a large volume lanthanum bromide detector
A. A. Naqvi*1, M. A. Gondal1, M. Raashid1, Khateeb-ur-Rehman1, M. Dastegeer1

1Department of Physics, King Fahd University of Petroleum and Minerals, Saudi Arabia

23-APP-03

Radiation-induced reactions in D, L-α-alanine adsorbed in solid surfaces
E. Aguilar, A. Negrón-Mendoza, C. Camargo

Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Mexico

23-APP-04

36Cl determination in steel radioactive waste

F. Goutelard1, P. Perret1, C. Hamon1, R. Brennetot1, C. Andrieu2
1Operator

SupportAnalyses
Laboratory,
AtomicEnergyCommission,
CEA
Saclay,DEN/DANS/DPC/SEARS/LASE, France, 2Electricité de France, EDF – CIDEN / Département Etudes Division Déconstruction/Groupe Inventaire et Agréments, France

23-APP-05

Naturally occurring radioactive materials (NORM) in malaysian oil sludge samples
B.A. Teiara Mohamed1, S. B. Sarmani2

1Department of Physics, University of Al-Zaituna, Tarhruna, Libya, 2School of Chemical Sciences and Food

Technology, Faculty of Science and Technology, Universiti Kebangsaan, Malaysia

23-APP-06

On the use of 233U and 237Np as radiotracers for redox potential measurements
S. Holgersson

Chalmers University of Technology, Department of Chemical and Biological Engineering, Nuclear Chemistry,
Sweden23-APP-07

Analysis of 129I/127I ratios from underground fluids collected in Japan
N. Okabe1, Y. Muramatsu1, M. Arai1, H. Matsuzaki2, M. Takahashi3, K. Kazahaya3
1Gakushuin University, Japan, 2University of Tokyo, 3AIST, Japan

23-APP-08

Radiocarbon dating of ancient Japanese calligraphy sheets: checks with ancient documents of known age andits application to kohitsugire calligraphies
H. Oda1, K. Ikeda2, H.i Yasu3, S. Sakamoto4
1Center for Chronological Research,

Nagoya University, 2Faculty of Letters, Chuo University, 3Taga HighSchool, 4Degital Archives Research Center, Ryukoku University

23-APP-09

μ-XRF study on Wiangkalong pottery
K. Won-in1, S. Tancharakorn2, W. Tanthanuch2, P. Dararutana3
1Departmentof Earth Sciences, Faculty of Science, Kasetsart University, Thailand, 2Synchrotron Light
Research Institute, Thailand, 3The Royal Thai Army Chemical School of the Royal Thai Army Chemical
Department, Thailand（ 27 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Tuesday, 24 September 2013, Poster Session
24-FKP-01

Determination of short-lived 241Pu in environmental samples by inductively coupled plasma mass
spectrometry
Jian Zheng*, Keiko Tagami, Shigeo Uchida

Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences

24-FKP-02

Numerical evaluation of Cs adsorption in PB column by extended Langmuir formula and one -dimensional
adsorption model
Hiroshi Ogawa, Akiko Kitajima, Hisashi Tanaka, and Tohru Kawamoto

Nanosystem Research Institute, Advanced Industrial Science and Technology (AIST), Tsukuba, 305-8568,
Japan

24-FKP-03

Secular distribution of radioactive concentration in the atmosphere at Fukushima, Hitachi and Marumori
ZiJian Zhang1, Shunsuke Kakitani1, Kazuhiko Ninomiya1, Naruto Takahashi1, Yoshiaki Yamaguchi2, Takashi
Yoshimura2, Kazuyuki Kita3, Akira Watanabe4, Atsushi Shinohara1
1Graduate School of Science, Osaka University, 2Radioisotope Research Center, Osaka University, 3Faculty ofSymbiotic Systems Science, Fukushima University, 4College of Science, Ibaraki University

24-FKP-04

Concentration of 137Cs in atmospheric coarse and fine particles collected in Fukushima
Kyo Kitayama1, Hirofumi Tsukada1, Kenji Ohse1, Chika Suzuki1, Akira Kanno1, Kencho Kawatsu1,
1Fukushima University Future Center for Regional Revitalization

24-FKP-05

Electrochemical cesium sorption under coexisting other ions using nanoparticle film of copper
hexacyanoferrate
Hisashi Tanaka1, Rongzhi Chen1, Miyuki Asai1, Chikako Fukushima1, Tohru Kawamoto1, Manabu Ishizaki2,
Masato Kurihara1,2, Makoto Arisaka3, Takuya Nankawa3 and Masayuki Watanabe3
1Nanosystem Research Institute, AIST, Japan , 2Department of Material and Biological Chemistry, Yamagata
University, Japan, 3Japan Atomic Energy Agency, Japan

24-FKP-06

Determination of 129I in Fukushima soil samples by ICP-MS
Takeshi Ohno1, Yasuyuki Muramatsu1, Hiroyuki Matsuzaki2
1Faculty of Science, Gakushuin University, 2School of Engineering, The University of Tokyo

24-FKP-07

Measurement of soil-to-crop transfer factor of tellurium for estimation of potential radiotellurium ingestion
from crops
Guosheng Yang, Keiko Tagami*, Jian Zheng, Shigeo Uchida

Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences

24-FKP-08

Retention of radiocesium incorporated in tree leaves contaminated by fallout of the radionuclides emitted fromthe Fukushima Daiichi Nuclear Power Plant
Kazuya Tanaka1, Hokuto Iwatani2, Aya Sakaguchi2, Yoshio Takahashi2, Yuichi Onda3
1Institute for Sustainable Sciences and Development, Hiroshima University, Japan , 2Department of Earth andPlanetary Systems Science, Hiroshima University, Japan , 3Graduate School of Life and Environmental

Sciences, University of Tsukuba, Japan

24-FKP-09

Decontamination of radioactive cesium in the soil
Makoto Yanaga, Ayumi Oishi

Department of Chemistry, Graduate School of Science, Shizuoka University, Japan

24-FKP-10

Altitude distribution of radioactive cesium at Mt. Fuji due to Fukushima No.1 nuclear power plant accident
T. Saito1, Y. Kurihara2, Y. Koike2, I. Tanihata3, M. Fujiwara3, H. Sakaguchi3, A. Shinohara4, H. Yamamoto5
1Faculty of Comprehensive Human Sciences, Shokei Gakuin University , 2School of Science and Technology,

Meiji University
3Research Center for Nuclear Physics, Osaka University , 4Graduate School of Science, Osaka University,
5Department for the Administration of Safety and Hygiene, Osaka University

24-FKP-11

Isotope compositions of strontium in environmental samples in Fukushima Prefecture
Y. Shibahara1, S. Fukutani1, T. Fujii1, T. Kubota1, M. Yoshikawa2, T. Shibata2, T. Ohta3, K. Takamiya1, N.
Sato1, M. Tanigaki1, Y. Kobayashi1, R. Okumura1, H. Yoshinaga1, H. Yoshino1, A. Uehara1, S. Mizuno4, T.

（ 28 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Takahashi1, and H. Yamana1

1Research Reactor Institute, Kyoto University, 2Institute for Geothermal Sciences, Kyoto University, 3Facultyof Engineering, Hokkaido University, 4Nuclear Power Safety Division, Fukushima Prefectural Government

24-FKP-12

Distribution of radioactive caesium in the North Pacific one year and a half after the Fukushima Dai -ichi
Nuclear Power Plant accident
K. Tsujita1, A. Hasegawa1, N. Harada2, T. Yamagata2, H. Nagai2, M. Aoyama3
1Graduate School of integrated Basic Sciences, Nihon University, 2College of Humanities and Sciences, Nihon
University, 3Geochemical Research Department, Meteorological Research Institute, Japan

24-FKP-13

Image analysis for the study of radiocesium distribution in coniferous trees: two years after the Fukushima
Daiichi Nuclear Power Plant accident
Haruka Minowa

Radioisotope Research Facility, The Tokyo Jikei University School of Medicine, Japan

24-FKP-14

Distribution of Iodine-129 in off Fukushima and the North Pacific one year and a half after the Fukushima
Dai-ichi Nuclear Power Plant accident
A. Hasegawa1, T. Yamagata2, H. Nagai2, M. Aoyama3, H. Matsuzaki4
1Graduate School of integrated Basic Sciences, Nihon University , 2College of Humanities and Sciences, Nihon
University, 3Geochemical Research Department, Meteorological Research Institute, 4School of Engineering,

The University of Tokyo

24-FKP-15

Agricultural implications for Fukushima nuclear accident
Tomoko M. Nakanishi

Graduate School of Agricultural and Life Sciences, The University of Tokyo

24-FKP-16

Concentration of radiocesium in rice, vegetables, and fruits cultivated in evacuation area at Okuma town,
Fukushima
Kenji Ohse1, Kyo Kitayama1, Seiich Suenaga2, Kiyoyuki Matsumoto2, Akira Kanno1, Chika Suzuki1, Kencho
Kawatsu1, Hirofumi Tsukada1
1Fukushima Future Center for Regional Revitalization, Fukushima University , 2Okuma Government Office,Japan

24-FKP-17

Isotopic U, Pu, Am and Cm signatures in environmental samples from the Fukusima Dai -ichi Nuclear Power
Plant accident
Masayoshi Yamamoto1, Aya Sakaguchi2, Shinya Ochiai1,Takahiro Takada1, Seiya Nagao1, Peter Steier3
1Low Level Radioactivity Laboratory, Kanazawa University, Japan , 2Graduate School of Science, Hiroshima
University, Japan, 3VERA-Laboratory, University of Vienna, Austria

24-FKP-18

Influence of the Fukushima Daiichi nuclear disaster on the tritium concentration in the precipitation of
Kanazawa city
Yoshimune Yamada1, Kaeko Yasuike1, Toshiyuki Kawabata2, Akihiro Fujii2, Hitoshi Kakimoto2
1Faculty of Pharmaceutical Sciences, Hokuriku University, Japan , 2Ishikawa Prefectural Institute of Public

Health and Environmental Science, Japan

24-FKP-19

Sediment transport processes in reservoir-catchment system inferred from sediment trap observation andfallout radionuclides
Shinya Ochiai1, Seiya Nagao1, Masayoshi Yamamoto1, Taeko Itono2, Kenji Kashiwaya3
1Low

Level Radioactivity Laboratory, Institute of Nature and Environmental Technology, Kanazawa
University, Japan, 2Graduate School of Natural Science & Technology, Kanazawa University, Japan,
3Institute of Nature and Environmental Technology, Kanazawa University, Japan

24-FKP-20

Transfer of radiocesium to crops cultivated in Fukushima
Shinji Sugihara1, Toshio Hara2, Akihiro Maekawa3, Noriyuki Momoshima1
1Radioisotope Center, Kyushu University, Japan, 2Molecular Engineering Institute, Kinki University, Japan,
3Graduate School of Sciences, Kyushu University, Japan

24-FKP-21

Dynamics of radiocesium in bamboo forests after the accident of Fukushima Daiichi nuclear power plant
Tsutomu Kanasashi, Mitsutoshi Umemura, Yuki Sugiura , Chisato Takenaka

Graduate School of Bioagricultural Sciences, Nagoya University, Japan（ 29 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-22

Reaction behavior of uranium and zirconium oxides in oxidative and reductive conditions
Nobuaki Sato, Kohei Fukuda and Akira Kirishima

Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Japan

24-FKP-23

Radiocesium in zooplankton in seawaters off Miyagi, Fukushima, and Ibaraki Prefectures
H. Takata1, M. Kusakabe2, S. Oikawa1
1Central Laboratory, Marine Ecology Research Institute , 2Head Office, Marine Ecology Research Institute24-FKP-24

Plutonium isotopes and 241Am in surface sediments off the coast of the Japanese islands after the Fukushima
accident
S. Oikawa1, T. Watabe2, H. Takata1, J. Misonoo2, M. Kusakabe2
1Central Laboratory, Marine Ecology Research Institute , 2Head Office, Marine Ecology Research Institute24-NEP-01 A theoretical study of actinide and lanthanide extraction with carbamoylmethylphosphine oxide ligands
Cong-Zhi Wang , Jian-Hui Lan , Yu-Liang Zhao , Zhi-Fang Chai , Wei-Qun Shi*

Nuclear Energy Nano-Chemistry Group, Key Laboratory of Nuclear Analytical Techniques and Key
Laboratory For Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics,
Chinese Academy of Sciences, China

24-NEP-02 The role of microorganisms during the wet nuclear fuel storage in Slovak Republic
Martin Pipíška1, Lenka Tišáková2, Miroslav Horník1, Jozef Augustín1
1Departmentof Ecochemistry and Radioecology, University of SS Cyril and Methodius, Slovak Republic ,2Institute of Molecular Biology, Slovak Academy of Sciences, Slovak Republic

24-NEP-03 Single centrifugal contactor test of a proposed group actinide extraction process for partitioning andtransmutation purposes
Emma Aneheim1,2, Christian Ekberg1, Giuseppe Modolo3, Andreas Wilden3
1Nuclear

Chemistry, Department of Chemical- and Biological Engineering, Chalmers University ofTechnology, Sweden, 2Targeted Alpha Therapy group, Department of Radiation Physics, Sahlgrenska
Academy at Gothenburg University, Sweden, 3Forschungszentrum Jülich GmbH (FZJ), Institut für Energieund Klimaforschung, Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Germany

24-NEP-04 Application of flow analytical methods for determination of radionuclides in cooling water and wastes from
nuclear plants
Anna Bojanowska-Czajka1, Kamila Kołacińska1, Marek Trojanowicz1
1Institut of Nuclear Chemistry and Technology, Poland

99
24-NEP-05 Determination of low level Tc in the primary coolant water by ICP-MS. Analysis of potential interferences

Ewelina Chajduk1, Sylwia Witman-Zając1, Halina Polkowska-Motrenko1
1Institute of Nuclear Chemistry and Technology, Poland

24-NCP-01 Extraction of homologous elements of dubnium and seaborgium from HCl solution

T. Yokokita1, K. Nakamura1, A. Kino1, Y. Komori1, K. Toyomura1, Y. Kasamatsu1, N. Takahashi1, T.
Yoshimura2, K. Ooe3, Y. Kudou4, K. Takamiya5, A. Shinohara1
1Graduate School of Science, Osaka University, 2Radioisotope Research Center, Osaka University, 3Faculty of
Science, Niigata University, 4Nishina Center for Accelerator Based Science, RIKEN, 5Research Reactor

Institute, Kyoto University

24-NCP-02 Evaluation of stopping powers of superheavy ions in Al and U
Y. H. Chung

Department of Chemistry, Hallym University, Korea
99
24-NCP-03 Separation of tungsten from LEU fission-produced Mo solution to improve technological performance in boththe processes of 99Mo and 99mTc generator production
Van So Le1 , Cong Duc Nguyen2
1Medisotec, NSW, Australia, 2ChoRay Hospital, HCM, Vietnam

24-NCP-04 Effecting separation of fission products from the actinides by direct reaction with diketones
Daniel B. Rego, Paul M. Forster, Kenneth R. Czerwinski

University of Nevada, Las Vegas, USA（ 30 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-NCP-05 Muonic atom formation by muon transfer process in C6H6 / C6H12 + CCl4 mixtures

M. Inagaki1, K. Fujihara1, G. Yoshida1, K. Ninomiya1, Y. Kasamatsu1, A. Shinohara1, M. K. Kubo2, W.
Higemoto3, Y. Miyake4, T. Miura5
1Graduate School of Science, Osaka University, 2Colleage of Liberal Arts, International Christian University ,3Advanced Science Research Center, Japan Atomic Energy Agency , 4Institute of Materials Structure Science,High Energy Accelerator Research Organization (KEK), 5Radiation Science Center, High Energy Accelerator

Research Organization (KEK)24-NCP-06 Research for fusion reaction mechanisms with deformed nuclei

S. Ueno1, K. Toda1, A. Asano1, N. Takahashi2, Y. Kasamatsu2, T. Yokokita2, A. Yokoyama3,
1Graduate School of Natural Science and Technology, Kanazawa Univ ., 2Graduate School of Science, Osaka
Univ.
3Institute of Science and Engineering, Kanazawa Univ.

24-NCP-07 Extraction behavior of Nb and Ta in HF solutions with tributyl phosphate

M. Murakami1,2, S. Tsuto1, K. Ooe1, H. Haba2, J. Kanaya2, S. Goto1, and H. Kudo1
1Departmentof Chemistry, Faculty of Science, Niigata University, Japan ,Accelerator-Based Science, RIKEN, Japan

2Nishina

Center for

24-NCP-08 A modified method for synthesis of [γ-32P] labeled adenosine triphosphate

Wira Y Rahman1*, Endang Sarmini1, Herlina1, Triyanto1, Rien Ritawidya1, Abdul Mutalib1 and Santi
Nurbaiti2
1Center for Radioisotope and Radiopharmaceuticals (PRR) - BATAN, 2Biochemistry Research Division, facultyof Mathematics and Natural Sciences, Institut Teknologi Bandung, Indonesia

88170
24-NCP-09 Production of Nb and Ta for chemical studies of element 105 Db using the GARIS gas-jet system

M. Huang,1 M. Asai,2 H. Haba,1 D. Kaji,1 J. Kanaya,1 Y. Kasamatsu,3 H. Kikunaga,4 Y. Kikutani,3 Y. Komori,3
H. Kudo,5 Y. Kudou,1 K. Morimoto,1 K. Morita,1 M. Murakami,5 K. Nakamura,3 K. Ozeki,1 R. Sakai,1 A.
Shinohara,3 T. Sumita,1 K. Tanaka,1 A. Toyoshima,2 K. Tsukada,2 Y. Wakabayashi1 and A. Yoneda2
1Nishina Center for Accelerator-Based Science, RIKEN, 2Advanced Science Research Center, JAEA, 3Graduate
School of Science, Osaka University, 4Research Center for Electron Photon Science, Tohoku University,
5Department of Chemistry, Niigata University

724-NCP-10 Half-life measurement of Be in several materials

T. Ohtsuki

Research Center for Electron Photon Science, Tohoku University, Japan

24-ENP-01 Verification of anticlockwise gyre in the semi-closed water area of Lake Nakaumi, southwest Japan, by using
224Ra/228Ra activity ratios

Ritsuo Nomura1,* Mutsuo Inoue2, Hisaki Kofuji3 and Shota Ikeda1
1Foraminiferal

Laboratory, Faculty of Education, Shimane University, Japan, 2Institute of Nature andEnvironmental Technology, Kanazawa University, Japan, 3Mutsu Marine Laboratory, Japan Marine Science
Foundation

24-ENP-02 Effect of hydroxylated fullerene on U(VI) adsorption onto oxidized multi -walled carbon nanotubes
Jing Wang1, Zhan Li2, Peng Liu1, Wei Qi1, Juanjuan Bi1, Wangsuo Wu1*

1Radiochemistry Laboratory, School of Nuclear Science and Technology, Lanzhou University, China , 2Instituteof Modern Physics, Chinese Academy of Sciences, China

24-ENP-03 Corrosion of copper in water and colloid formation under intense radiation field

Kotaro Bessho1, Yuichi Oki2, Naoya Akimune3, Hiroshi Matsumura1, Kazuyoshi Masumoto1, Shun Sekimoto2,
Naoyuki Osada4, Norikazu Kinoshita5, Hideaki Monjushiro1, Seiichi Shibata2
1Radiation Science Center, High Energy Accelerator Research Organization (KEK) , 2Research Reactor
Institute, Kyoto University (KURRI), 3Graduate School of Engineering, Kyoto University, 4Graduate School ofEngineering, Tohoku University, 5Institute of Technology, Shimizu Corporation, Japan

24-ENP-04 Study on unattached fraction of radon progeny and its environmental influence factors
Lu Guo1, Lei Zhang2, Qiuju Guo1
1StateKey Laboratory of Nuclear Physics and Technology, Peking University, China , 2Solid Dosimetric
Detector and Method Laboratory, China（ 31 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

24-ENP-05 Preliminary study on measuring radon progeny concentration using alpha/beta spectroscopic method
Abdumomin Kadir1, Lei Zhang2, Qiuju Guo1, and Juncheng Liang3

1State Key Laboratory of Nuclear Physics and Technology, School of Physics, Peking University, China , 2Solid

Dosimetric Detector and Method Laboratory, China , 3Ionizing Radiation and Medical Science, National
Institute of Metrology, China

134
137
24-ENP-06 The measurement comparability of Cs and Cs in foodstuff samples in Japan - result of inter-laboratory

experiment for certification of certified reference material
Tsutomu Miura1, Yoshitaka Minai2, Shoji Hirai3, Hiroshi Iwamoto4, Chushiro Yonezawa5, Yoshinobu
Uematsu6, Akira Okada7, Masami Shibukawa8, Koichi Chiba1, Kiyoshi Kitamura9, Takahiro Yamada10,
Kazutoshi Kakita11, Isao Kojima11, 1National Metrology Institute of Japan, AIST, 2Musashi University, 3Tokyo
City University, 4Environmental Technology Service Co, Ltd., 5Japan Institute of International Affairs,
6Japan Accreditation Board, 7TERM, 8Saitama University, 9Japan Chemical Analysis Center, 10Japan
Radioisotope Association, 11The Japan Society for Analytical Chemistry

24-ENP-07 Synthesis and Characterization of Volatile Technetium Compound
Bradley C. Childs1, Frederic Poineau2, Ken R. Czerwinski2

1University of Nevada Las Vegas, Las Vegas, Nevada 89154, USA

24-ENP-08 Time variation of concentrations of radioactive cesium -134, 137 and iodine-129 in the Ohori River, Chiba

Prefecture, Japan
Nao Shibayama1, Keisuke Sueki2, Kimikazu Sasa2,3, Yukihiko Satou1, Tsutomu Takahashi3, Masumi
Matsumura3, Hiroyuki Matsuzaki4, Michio Murakami5, Rey Yamashita6, Mahua Saha6, Hideshige Takada6,
Yukio Koibuchi7, Soulichan Lamxay7, Taikan Oki8
1Graduate School of Pure and Applied Sciences, Univ. of Tsukuba , 2Faculty of Pure and Applied Sciences,
Univ. of Tsukuba, 3Research Facility Center for Science and Technology, Univ. of Tsukuba, 4MALT, The Univ.
of Tokyo, 5”Wisdom of Water”(Suntory), The Univ. of Tokyo, 6Tokyo Univ. of Agri. & Tech., 7Graduate School of

Frontier Sciences, The Univ. of Tokyo, 8Insitute of Industrial Science, The Univ. of Tokyo

24-ENP-09 Ra isotopes in Na-Cl type groundwater in Japan

Junpei Tomita1,a, Takahiro Takada1, Seiya Nagao1, Masayoshi Yamamoto1
1Low

Level Radioactivity Laboratory, Institute of Nature and Environmental Technology, Kanazawa
University, Japan, aDepartment of Radiation Protection, Nuclear Science Research Institute, Japan Atomic
Energy Agency, Japan
210
210
24-ENP-10 A new method to estimate Po/ Pb activity ratio in atmospheric aerosol by alpha spectrometry

N. Momoshima1, S. Nishio2, K. Hibino2, S. Sugihara1
1Radioisotope Center, Kyushu University, Japan , 2Graduate School of Science and Technology, Kumamoto

University, Japan

210
137
24-ENP-11 Sedimentary environment inferred from sedimentation rates by Pb and Cs and their inventories in Mutsu

Bay, Japan
Kazuhito Hamataka1, Seiya Nagao1, Michio Kato2, Isao Kudo3, Masayoshi Yamamoto1
1Low Level Radioactivity Laboratory, KINET, Kanazawa University, Japan , 2Graduate School of Science,
Kanazawa University, Japan, 3Graduate School of Fisheries Sciences, Hokkaido University, Japan

24-ENP-12 Distribution of radiocarbon in Japanese agricultural soils
Nobuyoshi Ishii, Keiko Tagami, Shigeo Uchida

Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences
228
228
228
226
24-ENP-13 Lateral distributions of Th/ Ra and Ra/ Ra ratios in surface waters of the Sea of Japan and their

physical implications
Y. Furusawa1, M. Inoue1, S. Nagao1, M. Yamamoto1, Y. Hamajima1, H. Kofuji1, K. Yoshida1, Y. Nakano1, K.
Fujimoto2, A. Morimoto3, T. Takikawa4, Y. Isoda5
1Low Level Radioactivity Laboratory, Kanazawa University , 2Fisheries Research Agency, National ResearchInstitute of Fisheries Science, 3Hydrospheric Atmospheric Research Center, Nagoya University, 4National
Fisheries University, 5Graduate School of Fisheries Sciences, Hokkaido University

228
226
24-ENP-14 Vertical profiles of Ra and Ra activities in the Sea of Japan and their implications for water circulation

M. Inoue1, M. Minakawa2,*, K. Yoshida1, Y. Nakano1, H. Kofuji1, S. Nagao1, M. Yamamoto1, Y. Hamajima1
1Low Level Radioactivity Laboratory, Kanazawa University , 2Fisheries Research Agency, National Research（ 32 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Institute of Fisheries Science

24-ENP-15 Induced radioactivity in air and water at medical accelerators

K. Masumoto1, K. Takahashi1, H. Nakamura1, A. Toyoda1, K. Iijima1, K. Kosako2, K. Oishi2, F. Nobuhara3
1High Energy Accelerator Research Organization (KEK) , 2Shimizu Co., Japan, 3Tokyo Nuclear Service Co.,

Japan

14
3
24-ENP-16 Radioactivity determination of C and H in solid waste samples by liquid scintillation counter

Jong-Myoung Lim1*, Mun-Ja Kang1, Kun-Ho Chung1, Chang-Jong Kim1, Geun-Sik Choi1

1Environmental Radioactivity Assessment Team, Korea Atomic Energy Research Institute, Korea

24-ENP-17 Preparation of pure TiO2 sorption material

Irena Špendlíková, Jakub Raindl, Mojmír Němec

Czech Technical University in Prague, Department of Nuclear Chemistry, Czech Republic

24-NPP-01

Mössbauer study of iron carbide nanoparticles produced by sonochemical synthesis
R. Miyatani1, Y. Yamada1, Y. Kobayashi2,31Department of Chemistry, Tokyo University of Science, 2Department of Engineering Science, The University
of Electro-Communications, 3RIKEN

24-NPP-02

Mössbauer study of iron fluoride films produced by pulsed laser deposition
K. Shiga1, Y. Yamada1, Y. Kobayashi2,31Department of Chemistry, Tokyo University of Science, 2Department of Engineering Science, The University
of Electro-Communications, 3RIKEN

24-NPP-03

Iron sulfide particles synthesized in liquid phase
R. Shimizu1, Y. Yamada1, Y. Kobayashi2,31Department of Chemistry, Tokyo University of Science, 2Department of Engineering Science, The University

of Electro-Communications, 3RIKEN, Japan

24-NPP-04

Mössbauer and XRD studies of NiCuZn ferrites by Sol-Gel auto-combustion
Chenglong Lei1, Qing Lin1,2*, Haifu Huang3, Hui Zhang1, Yun He1
1Collegeof Physics and Technology, Guangxi Normal University, China , 2Department of Information
Technology, Hainan Medical College, China, 3Nanjing National Laboratory of Microstructures and Jiangsu
Provincial Laboratory for NanoTechnology,,Department of Physics, Nanjing University, China

24-NPP-05

Thermal stability of locally-associated Al and In impurities in zinc oxide
S. Komatsuda1, W. Sato1,2, and Y. Ohkubo3
1Graduate

School of Natural Science and Technology, Kanazawa University , 2Institute of Science andEngineering, Kanazawa University, 3Research Reactor Institute, Kyoto University

24-NPP-06

Structure and antimony-121 Mössbauer spectra of hypervalent antimony compounds with an antimony –goldbond in equatorial position
Masashi Takahashi, Asumi Sato, Shiro Matsukawa

Department of Chemistry, Toho University, Japan

24-NPP-07

Local structure of 57Mn/57Fe implanted into lithium hydride
Jun Miyazaki1, Takashi Nagatomo2, Yoshio Kobayashi3, 4, Michael K. Kubo5, Yasuhiro Yamada6, Mototsugu
Mihara7, Wataru Sato8, Kazuya Mae5, Shinji Sato9, Atsushi Kitagawa9
1College of Industrial Technology, Nihon University , 2J-PARC Center, High Energy Accelerator Research
Organization, 3Department of Engineering Science, The University of Electro-Communications, 4RIKEN
Nishina Center for Accelerator-Based Science, RIKEN, 5The Division of Arts and Sciences, International
Christian University, 6Department of Chemistry, Tokyo University of Science , 7Department of Physics, Osaka
University, 8Institute of Science and Engineering, Kanazawa University, 9Department of Accelerator andMedical Physics, National Institute of Radiological Sciences

24-NPP-08

Evaluation of vacancy-type defects in ZnO by the positron annihilation lifetime spectroscopy
R. Ono1, T. Togimitsu1, and W. Sato1,2
1Graduate School of Natural Science and Technology, Kanazawa University , 2Institute of Science andEngineering, Kanazawa University（ 33 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

24-AAP-01

Determination of ultratrace-levels of 99Tc using ICP-QMS in the low level radioactive waste samples
Te-Yen Su, Tsuey-Lin Tsai, Hsin-Chieh Wu, Lee-Chung Men

Chemistry Division, Institute of Nuclear Energy Research, Taiwan, R.O.C.

24-AAP-02

Development of an automatic prompt gamma-ray activation analysis system
Takahito Osawa1

1Neutron Imaging and Quantum Beam Analysis Group, Quantum Beam Science Directorate, Japan Atomic

Energy Agency

24-AAP-03

Concentration of heavy metal elements in Chinese medicine by INAA
S. Ishihara1, E. Furuta2, N. Iwasaki1, Y. Yoshihara3, R.Okumura4, Y.Iinuma4
1Ochanomizu University, Facility of Sciences , 2Ochanomizu University, Graduate School of Humanities andSciences, 3Ochanomizu University, Facility of Human Life and Environmental Sciences , 4Kyoto University,

Research Reactor Institute

24-AAP-04

Application of instrumental neutron activation analysis to assess dietary intake of selenium in Korean adults
from meat and eggs
Jong-Hwa Moon1, Sun-Ha Kim1, Yong-Sam Chung1, Ok-Hee Lee2
1Korea Atomic Energy Research Institute, Korea , 2Dept of Food Science and Nutrition, Yongin University,

Korea

24-AAP-05

Evaluation of hypoxia at dredged trenches in Tokyo Bay by determination of redox sensitive elements in thesediments
T. Yamagata1, K. Shozugawa1, R. Okumura2, K. Takamiya2, M. Matsuo1
1Graduate School of Arts and Sciences, The Univ. of Tokyo, 2Research Reactor Institute, Kyoto Univ.

24-AAP-06

Determination of ultra trace amounts of Mn in iron meteorites by preconcentration neutron activation
analysisY. Tanaka1, Y. Arai1, T. Imamura1, Y. Oura1
1Department of Chemistry, Tokyo Metropolitan University

24-AAP-07

Instrumental photon activation analysis of geological and cosmochemical samples
Naoki Shirai1, Shun Sekimoto2, Mitsuru Ebihara1
1Tokyo Metropolitan University, 2Kyoto University Research Reactor Institute

24-AAP-08

Monte carlo calculation of chloride diffusion in concrete
A. A. Naqvi1, Khateeb-ur-Rehman1, M. Maslehuddin2, O.S.B. Al-Amoudi3 and M. Raashid1
1Department of Physics, 2Center for Engineering Research, and 3Department of Civil and Environmental

Engineering King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia

24-APP-01

Catalysis induced by radiation in fatty acids adsorbed on clay minerals
A. Negron-Mendoza1*, S. Ramos-Bernal1, M. Colin-Garcia2 and F.G. Mosqueira3

1Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, México , 2Instituto de Geología,

Universidad Nacional Autonoma de Mexico, México , 3Dirección General de Divulgación de la Ciencia,
Universidad Nacional Autonoma de Mexico, México

24-APP-02

Preliminary study for highly sensitive airborne radioiodine monitor
Yoshimune Ogata1, Tadashi Yamasaki2, Ryuji Hanafusa3
1Nagoya University, 2CEPCO, Japan, 3Fuji Electric, Japan

24-APP-03

Radiation synthesis and cesium removal of cellulose microsphere based hybrid adsorbent
Long Zhao1*, Yanliang Chen1, Yuezhou Wei1
1School of Nuclear Science and Engineering, Shanghai Jiao Tong University, China

24-APP-04

Study about separation mechanism of endohedral metallofullerenes with Lewis acid
K. Chiba1, T. Hamano1, E. Takeuchi1, K. Akiyama1, S. Kubuki1, and H. Shinohara2
1Department of Chemistry, Tokyo Metropolitan University, Japan , 2Graduate School of Science, Nagoya

University, Japan

24-APP-05

Crystal structure and1,3-bis(4-Pyridyl)Propane)

spin

state

of

mixed-crystals（ 34 ）of

Fe(NCS)x(NCBH3)2-x(bpp)2

(bpp

=

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Haruka Dote1, Hiroki Yasuhara1, Satoru Nakashima2
1Graduate

School of Science, Hiroshima University, 2Natural Science Center for Basic Research andDevelopment (N-BARD), Hiroshima University

24-APP-06

Analysis of fragments of a roman mask using Mössbauer spectroscopy
Paulo de Souza1,2, G. Klingelhöfer3, P Gütlich3, M. Egg4
1University of Tasmania, Australia , 2Commonwealth Scientific and Industrial Research Organisation,
Australia, 3Johannes Gutenberg-Universität Mainz, Germany, 4Römisch-Germanisches Zentralmuseum,

Germany

24-APP-07

Synthesis of 14C labeled C60 with higher specific activity
T. Tadai1, K. Akiyama1, H. Aoshima2, R. Ibuki2, S. Kubuki1
1Department of Chemistry, TokyoJapan

24-APP-08

Metropolitan University, Japan, 2Vitamin C60 BioResearch Corporation,

Adsorption behavior of Zr and Hf to TTA-resin in microcolumn for determining the forming ability of Rf
monofluoride complex
Y. Kitayama1, Y. Shigeyoshi1, A. Yokoyama2, A. Toyoshima3, K. Tsukada3, K. Ooe4, E. Maeda1, H. Kimura1, H.
Kikunaga5, Y. Kudou6, J. Kanaya6, M. Huang6, and H. Haba6

Graduate School of Natural Science and Technology, Kanazawa University, 2 Institute of Science andEngineering, Kanazawa University, 3 Japan Atomic Energy Research Institute, 4 Institute of Science andTechnology, Niigata University, 5 Research Center for Electron Photon Science, Tohoku University, 6 Nishina
Center for Accelerator-Based Sience, RIKEN
1（ 35 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Wednesday, 25 September 2013, Poster Session
25-FKP-01

235U/238U isotopic ratio in environmental samples at the Fukushima area

Y. Shibahara1, T. Fujii1, S. Fukutani1, T. Kubota1, R. Okumura1, T. Ohta2, K. Takamiya1, N. Sato1, M.
Tanigaki1, Y. Kobayashi1, H. Yoshinaga1, H. Yoshino1, A. Uehara1, S. Mizuno3, T. Takahashi1, and H. Yamana1

1Research Reactor Institute, Kyoto University, 2Faculty of Engineering, Hokkaido University, 3Nuclear Power

Safety Division, Fukushima Prefectural Government

25-FKP-02

Particulates of Ag and Pu radioisotopes released from Fukushima Daiichi nuclear power plants
H. Kimura1, M. Uesugi2, A. Muneda2, R. Watanabe1, A. Yokoyama3, T. Nakanishi4

1Grad. School Nat. Sci. Tech., Kanazawa Univ., 2Col. Sci. Eng., Kanazawa Univ., 3Inst. Sci. Eng., Kanazawa

Univ., 4Adv. Sci. Res. Cent., Kanazawa Univ.

25-FKP-03

The measurement of 14C/12C ratios in Japanese plant samples affected by anthropogenic sources
R. Hashimoto1, A. Inoue1, Y. Muramatsu1, H. Matsuzaki2

1Depertment of Chemistry, Gakushuin University, 2School of Engineering, The University of Tokyo

25-FKP-04

Radiocesium and stable cesium in edible wild plants (Sansai) collected from forests in Fukushima Prefecture
M. Sugiyama1, Y. Muramatsu1, T.Ohno1, M. Sato 2
1Gakushuin University, Japan, 2Fukushima Agricultural Technology Center

25-FKP-05

Annual variation of radioactivity in marine biota in the Pacific off Fukushima after TEPCO's Fukushima
Daiichi Nuclear Power Station accident
T. Aono 1, S. Yoshida1, T. Saotome 2,T. Mizuno 2, Y. Ito3, J. Kanda3, T. Ishimaru 3
1National Institute of Radiological Sciences, 2Fukushima prefecture

University of Marine Science and Technology

25-FKP-06

fisheries experimental station, 3Tokyo

Migration behavior of 134Cs and 137Cs in the Niida River water in Fukushima Prefecture, Japan during
2011-2012
S. Nagao1, M. Kanamori2, S. Ochiai1, M. Yamamoto1
1Low

Level Radioactivity Laboratory, Kanazawa University, 2Graduate School of Natural Science andTechnology, Kanazawa University

25-FKP-07

Migration behavior of radiocesium released from Fukushima Daiichi Nuclear Power Plant accident
T. Ohnuki1, N. Kozai1, F. Sakamoto1
1Japan Atomic Energy Agency, Japan

25-FKP-08

Research on atmospheric radionuclides from the Fukushima Nuclear Accident at the MRI, JapanY. Igarashi1, K. Adachi 1, T. Tanaka1, M. Kajino1, T. Sekiyama1, T. Maki1, Y. Zaizen1, M. Mikami1
1Meteorological Research Institute, Japan

25-FKP-09

Presuming techniques of radioactive cesium concentration in muscle for beef cattle
T. Ohtsuki1, F. Koga2, M. Uchida2, Y. Ishikawa2, T. Takase3, K. Kawatsu3, M. Mogi4 S. Murayama4, Y. Izumi4,
H. Kikunaga1, T. Tachiya5, Y. Shiraishi2, K. Endo2
1ResearchCenter for Electron Photon Science, Tohoku University, 2Fukushima Agricultural Technology
Center Livestock Industry Research Center, Fukushima Prefecture, 3Faculty of Symbiotic System Science,
Fukushima University, 4Japan Environment Research Co., LTD, 5Comtec Eng. Co., LTD, Fukushima

25-FKP-10

Spatio-temporal distribution of atmospheric radiocesium at monitoring stations for suspended particulatematter in Fukushima area released from the TEPCO Fukushima Daiichi Nuclear Power Plant accident
H. Tsuruta1, Y. Oura2, M. Ebihara2, M. Ishimoto3, Y. Katsumura3, T. Ohara4, T. Nakajima1
1Atmosphereand Ocean Research Institute, The University of Tokyo, Japan, 2Department of Chemistry,
Tokyo Metropolitan University, Japan, 3Center for Regional Environmental Research, National Institute forEnvironmental Studies, 4Nuclear Professional School, The University of Tokyo, Japan

25-EDP-01

Education of nuclear and radiochemistry in Hallym University, Korea
Y. H. Chung

Department of Chemistry, Hallym University, Korea

25-EDP-02

Use of small 68Ge/68Ga generators in experiments for the education of radioisotope-related fields as well as of（ 36 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

natural and social sciences in general
T. Nozaki,1 K. Ogawa2

1School of Sciences, Kitasato University, 2School of Allied Health Sciences, Kitasato University, Japan

25-NFP-01

Application of alpha spectrometry to the measurement of a single plutonium particle for nuclear safeguards
K. Yasuda, D. Suzuki, F. Esaka and M. Magara

Research group for analytical chemistry, Japan Atomic Energy Agency

25-NEP-01 High LET radiolytic degradation studies of separation processes for spent nuclear fuelJ. Pearson and M. Nilsson

University of California – Irvine, USA, Department of Chemical Engineering and Materials Science

25-NEP-02 Effects of helium retention and lithium depletion on tritium behaviors in Li 2TiO3

M. Kobayashi1, H. Uchimura1, K. Toda1, M. Sato1, K. Tatunuma2, Y. Oya1 and K. Okuno1

1Radioscience Research Laboratory, Faculty of Science, Shizuoka University, Japan, 2Kaken Co. Ltd., Japan

25-NEP-03 Adsorptivity of various metal ions onto benzo-18-crown-6 and dibenzo-18-crown-6 resins
M. Nogami1, T. Haratani1, Y. Tachibana2, T. Kaneshiki3, M. Nomura3, T. Suzuki2

1Department of Electric and Electronic Engineering, Kinki University, 2Department of Nuclear System Safety

Engineering, Nagaoka University of Technology, 3Research Laboratories for Nuclear Reactors, Tokyo Instituteof Technology

25-NEP-04 Cesium adsorption ability and stability of metal hexacyanoferrate irradiated with gamma -rays
M. Arisaka1, M. Watanabe1, M. Ishizaki2, M. Kurihara2, R. Chen3, H. Tanaka3
1Research Group for Radiochemistry, Nuclear Scienceand Engineering Directorate, Japan Atomic Energy
Agency, 2Department of Material and Biological Chemistry, Faculty of Science, Yamagata University,
3Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology, Japan

25-NEP-05 Residual actinides separation from the DIAMEX/SANEX secondary waste and decontamination of the spent
DIAMEX solvent from the “difficult-to-strip” elements
J. John, F. Šebesta, K. V. Mareš, F. Klimek, M. Vlk

Czech Technical University in Prague, Department of Nuclear Chemistry, Czech Republic

25-NEP-06 Thorium based molten salt fuel cycle

Q.-N. Li*, L. Zhang, W.-X. Li, G.-Z. Wu

Shanghai Institute of applied physics, Chinese Academy of Sciences, China

25-NEP-07 Study on electrochemical behaviors of rare earth elements in FLINAK eutectic salt
L.-F. Tian, W. Huang, F. Jiang, C.-F. She, H.-Y. Zheng, D.-W. Long*, Q.-N. Li

Shanghai Institute of applied physics, Chinese Academy of Sciences, China

25-NCP-01 Measurement of cosmogenic nuclides in meteorites by well -type Ge detector in Ogoya Underground
Laboratory - correction of coincidence sum effect for Al-26,Co-56,Na-22 and Co-60 Y. Hamajima

LLRL, Kanazawa Univ., Japan

25-NCP-02 Development of multipurpose neutron irradiation apparatus at KUR

K. Takamiya1, Y. Yoshida2, H. Tanaka1, T. Fujii1, S. Fukutani1, T. Sano1, H. Yoshino1, Y. Iinuma1, R.
Okumura1, S. Shibata1
1Research Reactor Institute, Kyoto University, 2Graduate School of Engineering, Kyoto University

25-NCP-03 Development of a new continuous dissolution apparatus with a hydrophobic membrane for superheavy

element chemistry
K. Ooe1,2, K. Tsukada2,M. Asai2, T. K. Sato2, A. Toyoshima2, S. Miyashita2, Y. Nagame2, M. Schädel2, Y.
Kaneya3, H. V. Lerum4, J. P. Omtvedt4, J. V. Kratz5, H. Haba6, A. Wada7, Y. Kitayama8
1Institute of Science and Technology, Niigata University, 2Japan Atomic Energy Agency, 3Graduate School of

Science and Engineering, Ibaraki University, 4Department of Chemistry, University of Oslo, 5Institut für
Kernchemie, Universität Mainz, 6Nishina Center for Accelerator-Based Science, RIKEN, 7Department ofChemistry, Tokyo Metropolitan University, 8Graduate School of Natural Science and Technology, Kanazawa
University

25-NCP-04 Cross-section measurements of high energy neutron-induced reactions for Cu and Nb（ 37 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

K. Ninomiya1, T. Omoto1, R. Nakagaki1, N. Takahashi1, Y. Kasamatsu1, A. Shinohara1, S. Sekimoto2, H.
Yashima2, S. Shibata2, T. Shima3, H. Matsumura4, M. Hagiwara4, Y. Iwamoto5, D. Satoh5, M. W. Caffee6, K.
Nishiizumi7
1Graduate

School of Science, Osaka University, 2Research Reactor Institute, Kyoto University, 3ResearchCenter of Nuclear Physics, Osaka University, 4Radiation Research Center, High Energy Accelerator
Organization, 5Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, 6Department of
Physics, Purdue University, 7Space Sciences Laboratory, University of California

25-NCP-05 Development of a rapid solvent extraction technique with flow injection analysis for superheavy element
chemistry
T. Koyama1, N. Goto1, M. Murakami1,2, K. Ooe1, H. Haba2, J. Kaneya2, S. Goto1, and H. Kudo1
1Departmentof Chemistry, Faculty of Science, Niigata University, Japan,
Accelerator-Based Science, RIKEN, Japan

2Nishina

Center for

25-NCP-06 Solid-liquid extraction of Mo and W by Aliquat 336 from HF and HCl solutions towards extraction

chromatography experiments of Sg
Y. Komori1, T. Yokokita1, K. Toyomura1, K. Nakamura1, Y. Kasamatsu1, H. Haba2, J. Kanaya2, M. Huang2, Y.
Kudou2, A. Toyoshima3, N. Takahashi1, A. Shinohara1
1Graduate

School of Science, Osaka University, 2Nishina Center for Accelerator-Based Science, RIKEN,

3Advanced Science Research Center, Japan Atomic Energy Agency

25-NCP-07 Off-line isothermal gas chromatography of Zr and Hf compounds
Y. Oshimi, S. Goto, T. Taguchi, T. Tomitsuka, K. Ooe, H. Kudo

Department of Chemistry, Faculty of Science, Niigata University, Japan

25-NCP-08 Chemical studies of Rf and Db in liquid-phases using automated rapid chemical separation apparatuses at

JAEA
K. Tsukada1, A. Toyoshima1, M. Asai1, Y. Kasamatsu2, Z. J. Li3, Y. Ishii1, H. Haba4, T. K. Sato1, Y. Nagame1,
M. Schädel1
1JapanAtomic Energy Agency, 2Graduate School of Science, Osaka University, 3Institute of High Energy
Physics, Chinese Academy of Science, China, 4Nishina Center for Accelerator Based Science, RIKEN, Japan

25-NCP-09 Solvent extraction of hexavalent Mo and W using 4-isopropyltropolone (Hinokitiol) for Seaborgium (Sg)reduction experiment
S. Miyashita1, A. Toyoshima1, K. Ooe2, M. Asai1, T. K. Sato1, K. Tsukada1, Y. Nagame1, M. Schädel1, Y.
Kaneya3, H. Haba4, J. Kanaya4, M. Huang4, Y. Kitayama5, A. Yokoyama5, A. Wada6, Y. Oura6 J. V. Kratz7, H.
V. Lerum8 and J. P. Omtvedt8
1Advanced

Science Research Center, Japan Atomic Energy Agency, 2Institute of Science and Technology,
Niigata University, 3Graduate School of Science and Engineering, Ibaraki University, 4Nishina Center for
Accelerator-Based Science, RIKEN, 5College and Institute of Science and Engineering, Kanazawa University,
6Graduate School of Science and Engineering, Tokyo Metropolitan University, 7Institut für Kernchemie,
Universität Mainz, Germany, 8Department of Chemistry, University of Oslo, Norway

25-NCP-10 Development of surface ionization ion-source for determination of the first ionization potentials of heavy
actinides
Y. Kaneya1,2, T. K. Sato2, M. Asai2, K. Tsukada2, A. Toyoshima2, S. Miyashita2, Y. Nagame1,2, M. Schädel2, N.
Sato3, K. Ooe4, A. Osa5, S. Ichikawa2,6, T. Stora7, J. V. Kratz8
1Graduate School of Science and Engineering, Ibaraki University, Japan, 2Advanced Science Research Center,

Japan Atomic Energy Agency, 3Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency,
4Institute of Science and Technology, Niigata University, Japan, 5Department of Research Reactor andTandem Accelerator, Japan Atomic Energy Agency, 6Nishina Center for Accelerator Based Science, RIKEN,
Japan, 7ISOLDE, CERN, Switzerland, 8Institut für Kernchemie, Universität Mainz, Germany

25-NCP-11 Comparison of the decay constants of 51Cr with various valence states
H. Kikunaga1, K. Takamiya2, K. Hirose1*, T. Otsuki1
1ResearchCenter for Electron Photon Science, Tohoku University, 2Research Reactor Institute, Kyoto
University, *Present address: Advanced Science Research Center, Japan Atomic Energy Agency

25-NCP-12 Selective separation of strontium (II) from nitric acid solution by a macroporous silica-based DtBuCH18C6
adsorbent modified with surfactants
Y. Wu, Z. Chen, Y. Wei*

（ 38 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

School of Nuclear Science and Engineering, Shanghai Jiao Tong University, China

25-NCP-13 Exploring the synthesis and characterization of binary technetium chlorides and bromides

E. Johnstone1, F. Poineau1, P. M. Forster1, P. Weck,2 C. D. Malliakas3, E. Kim4, M. G. Kanatzidis3, B. L. Scott5,
A. P. Sattelberger6, and K. R. Czerwinski1
1Department of Chemistry, University of Nevada Las Vegas, Las Vegas, USA, 2Sandia National Laboratories,

USA, 3Department of Chemistry, Northwestern University, USA, 4Department of Physics and Astronomy,
University of Nevada, USA, 5Materials Physics and Applications Division, Los Alamos National Laboratory,
USA, 6Energy Engineering and Systems Analysis Directorate, Argonne National Laboratory, USA

25-ACP-01

Solvent extraction of americium(III) and europium(III) using hydroxyoctanoic acid and n-heteroaromaticcompound
M. Seike1, M. Eguchi1, A. Shinohara1, T. Yoshimura2
1Graduate School of Science, Osaka University, 2Radioisotope Research Center, Osaka University

25-ACP-02

Stability of uranyl peroxo-carbonato complex ions in the presence of metal oxide in carbonate media
D.-Y. Chung1, M.-S. Park1, K.-Y. Lee1, H.-B. Yang1, E.-H. Lee1, K.-W. Kim1, J.-K. Moon1
1Korea Atomic Energy Research Institute, Korea

25-ACP-04

Raman spectroscopic study on uranyl and neptunyl complexes in highly concentrated calcium chloride
T. Fujii1, A. Uehara1, Y. Kitatsuji2, and H. Yamana1

1Division of Nuclear Engineering Science, Research Reactor Institute, Kyoto University, 2Nuclear Science andEngineering Directorate, Japan Atomic Energy Agency

25-ACP-05

Electrode reaction of actinide ions in a weak acidic solution
Y. Kitatsuji1, H. Otobe1, T. Kimura1

1Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

25-ACP-06

Biomineralization of uraninite and uranyl phosphate controlled by organic acids
Y. Suzuki1, N. Kozai2, T. Ohnuki2
1Graduate School of Bionics, Tokyo University of Technology,

Japan Atomic Energy Agency, Japan

25-ACP-07

Japan, 2Advanced Science Research Center,

Comparison of the spectroscopic characteristics of uranium species when U(III) in a LiCl -KCl molten salt isleached out with water and ionic liquid
H.-J. Im, K. Song

Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, Korea

25-ACP-08

Distribution of Neptunium in PUREX streams
N. Rawat, A. Kar, M.A. Mahajan, N.B. Khedekar, R.M. Sawant, B. S. Tomar and K. L. Ramakumar

Radioanalytical Chemistry Division, Bhabha Atomic Research Centre, India

25-ACP-09

α-radiation effect on solvent extraction of minor actinide
Y. Sugo1, Y. Sasaki2, M. Taguchi1, N. S. Ishioka1
1Quantum

Beam Science Directorate, Japan Atomic Energy Agency, 2Nuclear Science and Engineering
Directorate, Japan Atomic Energy Agency

25-ENP-01 Retardation and release study of U(VI) on phlogopite at conditions relevant to uranium contamination inenvironment
D. Pan1,2, Z. Wang2, W. S. Wu1

1Radiochemistry Laboratory, Lanzhou University, China, 2Pacific Northwest National Laboratory, USA

25-ENP-02 Application of simplified desorption method to sorption study: (2) sorption of neptunium (V) on
montmorillonite-based mixtures
N. Kozai1, T. Ohnuki1

1Japan Atomic Energy Agency, Japan

25-ENP-03 Continuous measurement of radon exhalation rate of soil in Beijing
L. Zhang1,2, K. S.2, Q. Guo2

1Solid Dosimetric Detector and Method

Laboratory, China, 2State Key Laboratory of Nuclear Physics andTechnology, School of Physics, Peking University, China（ 39 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-ENP-04 Dosimetric evaluation of thoron exposure in three typical rural indoor environments in China
L. Zhang1, Q. Guo2, S. Wang1

1Solid Dosimetric Detector and Method Laboratory,

China, 2State Key Laboratory of Nuclear Physics andTechnology, School of Physics, Peking University, China

25-ENP-05 Binary technetium phosphide synthesis at low temperature conditions
B. C. Childs1, W. M. Kerlin1, K. R. Czerwinski1
1University of Nevada Las Vegas, USA

25-ENP-06 Dissolution behavior of 137Cs absorbed on the green tea leaves

Y. Oya1, H. Uchimura1, K. Toda1, T. Ikka2, A. Morita2, K. Okuno1

1Graduate School of Science, Shizuoka University, 2Graduate School of Agriculture, Shizuoka University

25-ENP-07 Characterization on the radioactive aerosols dispersed during plasma arc cutting of radioactive metal piping
T. Shimada1, T. Tanaka1

1Nuclear Safety Research Center, Japan Atomic Energy Agency, Japan

25-ENP-08 A passive collection method for whole size fractions of suspended river materials

T. Matsunaga1, T. Nakanishi1, M. Atarashi-Andoh1, E. Takeuchi1, K. Tsuduki1, S. Nishimura1, J. Koarashi1, S.
Otosaka1, T. Sato2, S. Nagao3
1Nuclear

Science and Engineering Directorate, Japan Atomic Energy Agency, 2Division of Sustainable
Resources Engineering, Graduate School of Engineering, Hokkaido University, Japan, 3Low Level
Radioactivity Laboratory, Institute of Nature and Environmental Technology, Kanazawa University, Japan

25-ENP-09 Study of factors controlling organic pollution in Lake Kiba
Y. Kawano1, S. Nagao1, S. Ochiai1, M. Yamamoto1

1Low Level Radioactivity Laboratory, Kanazawa Univ., Japan

25-ENP-10 Rapid monitoring particulate radiocesium with nonwoven fabric cartridge filter and application to field
monitoring
H. Tsuji1, Y. Kondo2, S. Kawashima2, T. Yasutaka1

1National Institute of Advanced Industrial Science and Technology, 2 Japan Vilene Company. Ltd.

25-ENP-11 In-situ measurement of 134Cs and 137Cs in seabed by underwater γ-spectrometry systems and application forthe survey to the Fukushima Dai-ichi NPP accident
H. Kofuji

Japan Marine Science Foundation, Japan

25-ENP-12 Radiocarbon dating of molluscan shells and its application
Y. Miyata1, 2, 3, H. Matsuzaki2
1The

Low Level Radioactivity Laboratory (LLRL), Institute of Nature and Environmental Technology,
Kanazawa University, Japan, 2The College of Liberal Arts, International Christian University, Japan,
3National Museum of Japanese History, Japan, 4Department of Nuclear Engineering and Management, Schoolof Engineering (MALT), The University of Tokyo, Japan

25-ENP-13 Concentration of uranium on TiO-PAN and NaTiO-PAN composite absorbers
A. Motl, F. Šebesta, J. John, I. Špendlíková, M. Němec

Czech Technical University in Prague, Department of Nuclear Chemistry, Czech Republic

25-ENP-14 Use of radon to characterise surface water recharge to groundwater

N Hermanspahn,1 M Close,1 M Matthews,1 L Burbery,1 P Abraham,1

1Institute of Environmental Science and Research (ESR), Christchurch, New Zealand

25-RPP-01

Production and utilization of radioactive astatine isotopes in the 7Li + natPb reaction
I. Nishinaka1, A. Yokoyama2, K. Washiyama2, R. Amano2, E. Maeda2, N. Yamada2, H. Makii1, A. Toyoshima1,
S. Watanabe1, N. S. Ishioka1, K. Hashimoto1
1Japan Atomic Energy Agency (JAEA), 2Kanazawa University

25-RPP-02

Production of actinium-225 from natural thorium irradiated with protons
A. N. Vasiliev1, V. S. Ostapenko1, R. A. Aliev1, S. N. Kalmykov1, E. V. Lapshina2, S. V. Ermolaev2 and B. L.

（ 40 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Zhuikov2

1Chemisrtry Department, Lomonosov Moscow State University,

Russian Academy of Sciences, Russia

25-RPP-03

Russia, 2Institute for Nuclear Research ofDevelopment of 99Mo-99mTc domestic production with high-density MoO3 pellets by (n, γ) reaction
K. Tsuchiya1, M. Tanase2, T. Shiina2, A. Ohta2, M. Kobayashi3, A. Yamamoto3, Y. Morikawa3, M. Kaminaga1,
H. Kawamura1
1Japan Atomic Energy Agency, 2Chiyoda Technol Corporation, Japan, 3FUJIFILM RI Pharma Co. Ltd., Japan

25-RPP-04

Preparation of 99Mo–99mTc by using spallation neutron
Y. Hayashi*1, N. Takahashi1, K.Nakai1, H. Ikeda2, G. Horitsugi2, T. Watabe2, Y. Kanai2, H. Watabe2, E.
Shimosegawa2, Y. Miyake2, J. Hatazawa2, M. Fukuda3, K. Hatanaka3, K. Takamiya4, S. Yamamoto5, Y.
Kasamatsu1, A. Shinohara1
1Graduate School of Science, Osaka University, 2Graduate School of Medicine, Osaka University, 3ResearchCenter for Nuclear Physics, Osaka University, 4Kyoto University Research Reactor Institute, 5Graduate
School of Medicine, Nagoya University

25-RPP-05

Development of automated measurement system for radioactive intensities of sealed small radiation sources(Iodine-125 seed source) for brachytherapy
M. Sakama,1 H. Ikushima,2 T. Saze,3 Y. Nagano,4 T. Yamada,5 T. Ichiraku,5 H. Takai,5 Y. Kuwahara,6 S.
Nakayama7
1Departmentof Radiological Science (also Advanced Radio-Analytical Chemistry, Division of Biomedical
Information Sciences, Institute of Health Biosciences, The University of Tokushima, Japan, 2Department ofRadiation Therapy Technology, Division of Biomedical Information Sciences, Institute of Health Biosciences,
The University of Tokushima, 3Otsuka Pharmaceutical Factory, Japan, 4Department of Radiological Science,
Division of Biomedical Information Sciences, Institute of Health Biosciences, The University of Tokushima,
5Dairyu Co. Ltd., Japan, 6Radioisotope Center, The University of Tokushima, 7Department of Nuclear Science,
Institute of Socio-Arts and Sciences, The University of Tokushima, Japan

25-RPP-06

Extraction of astatine isotopes for development of radiopharmaceuticals
E. Maeda1, A.Yokoyama2, T. Taniguchi1, K. Washiyama3 I. Nishinaka4

1Grad. School Nat. Sci., Tech. Kanazawa Univ., 2Inst. Sci. Eng., Kanazawa Univ., 3Sch. of Health Sci., Collegeof Med., Pharma. Health Sci., Kanazawa Univ., 4ASRC, Japan Atomic Energy Agency

25-RPP-07

Lutetium-177 complexation of DOTA and DTPA in the presence of competing metals
S. Watanabe1, K. Hashimoto1, N. S Ishioka1

1Medical Radioisotope Application Group, Quantum Beam Science Directorate, Japan Atomic Energy Agency

25-NPP-01

Hyperfine fields at 140Ce in He-doped Fe
Y. Ohkubo1, A. Taniguchi1, Q. Xu1, M. Tanigaki1, K. Sato1 and M. Tsuneyama2

1Research Reactor Institute, Kyoto University, 2Grauduate School of Science, Kyoto University

25-NPP-02

Mössbauer studies of lanthanum doped Ni0.4Cu0.2Zn0.4Fe2O4 ferrites by sol-gel autocombustion
Q. Lin1,2, C. Lei1*, H. Huang3, H. Zhang1, Y. He1
1Collegeof Physics and Technology, Guangxi Normal University, China, 2Department of Information
Technology, Hainan Medical College,China, 3Nanjing National Laboratory of Microstructures and Jiangsu
Provincial Laboratory for NanoTechnology, Department of Physics, Nanjing University, China

25-NPP-03

Analysis of corrosion products formed on anti-weather steel
M. Oyabu1, R. Satoh1, K. Nomura2

1Math & Science Division, Kanazawa Institute of Technology, Japan, 2The University of Tokyo

25-NPP-04

Study of the spin-crossover phenomena in 1D coordination polymers, [FeII(NH2-triazole)3](CnH2n+1SO3)2, by
Fe-K edge XAFS and 57Fe Mössbauer spectroscopy
H. Kamebuchi1, A. Nakamoto1, M. Enomoto2, T. Yokoyama3, N. Kojima1
1Graduate School of Arts and Sciences, The University of Tokyo, 2Department of Chemistry, Tokyo Universityof Science, 3Department of Materials Molecular Science, Institute for Molecular Science, Japan

25-NPP-05

Mössbauer spectroscopic and powder X-ray diffraction studies on incorporation of gaseous organic molecules
into intermolecular nano-voids of mixed-valence trinuclear iron pentafluorobenzoate complex
Y. Sakai1, S. Onaka1, R. Ogiso1, M. Takahashi2, T. Nakamoto3, and T. Takayama1（ 41 ）APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013
1DaidoUniversity,Japan, 2Toho University, Japan, 3Toray Research Center, Japan

25-NPP-06

Dynamic perturbation to 111Cd(←111Ag) doped in AgI nanoparticles
W. Sato1,2, R. Mizuuchi2, N. Irioka3, S. Komatsuda2, S. Kawata4, A. Taoka1,2, and Y. Ohkubo5
1Instituteof Science and Engineering, Kanazawa University, 2Graduate School of Natural Science andTechnology, Kanazawa University, 3School of Chemistry, Kanazawa University, 4Department of Chemistry,
Faculty of Science, Fukuoka University, 5Research Reactor Institute, Kyoto University

25-AAP-01

A prototype of a simple collection system for the determination of 14C
T.-H. Chuang, T. –L. Tsai, H. –J. Wei, L. –C. Men

Chemistry Division, Institute of Nuclear Energy Research, Taiwan, ROC

25-AAP-02

Elemental analysis of Korean adult toenail using of instrumental neutron activation analysis
S. –H. Kim1, J. –H. Moon1, Y. –S. Chung1, O.-H. Lee2

1Korea Atomic Energy Research Institute, 2Dept of Food Science and Nutrition, Yongin University, Korea

25-AAP-03

Determination of vanadium at ppb levels in relatively high-salt biological materials without chemical
separation and using neutron activation coupled to compton suppression gamma-ray spectrometry
W. Zhang and A. Chatt

Trace Analysis Research Centre, Department of Chemistry, Dalhousie University, Canada

25-AAP-04

Radiochemical neutron activation analysis of halogens (Cl, Br and I) in geological and cosmochemical samples
M. Ebihara1 and S. Sekimoto2
1Tokyo Metropolitan University, 2Kyoto University Research Reactor Institute

25-AAP-05

Multielement analysis of KIGAM reference samples by INAA, ICP-AES and ICP-MS
N. Shirai1, M. Toktaganov2, H. Takahashi1, Y. Yokozuka1, S. Sekimoto3, M. Ebihara1

1Tokyo Metropolitan University, 2National Nuclear Center Republic of Kazakhstan Institute of Atomic Energy
3Kyoto University Research Reactor Institute

25-AAP-06

Comparison of calculated results with NTD measured data for establishment of burned core model for montecarlo simulation of HANARO reactor
D.-K. Cho and M.-S. Kim

Korea Atomic Energy Research Institute, Korea

25-AAP-07

Neutron activation analysis of JCFA-1, JCu-1 and JZn-1
S. Sekimoto1, Y. Homura1, R. Okumura1, N. Shirai2

1Kyoto University Research Reactor Institute, 2Tokyo Metropolitan University

25-AAP-08

Prompt gamma-ray analysis of chloride concentration in blended cement concretes
A. A. Naqvi1*, M. Maslehuddin2, O.S.B. Al-Amoudi3, Khateeb-ur-Rehman1, M. Raashid1
1Departmentof Physics, 2Center for Engineering Research, and 3Department of Civil and Environmental
Engineering, King Fahd University of Petroleum and Minerals, Saudi Arabia

25-AAP-09

Cold neutron and thermal neutron PGAA facilities at The HANARO research reactor
G.M. Sun1, E.J. Lee1, B.G. Park1, J.H. Moon1

1Neutron Utilization Technology Division, Korea Atomic Energy Research Institute, Korea

25-AAP-10

Exposing dogs to uranium contained in commercial diets
Camila Elias,1 Elisabete A. De Nadai Fernandes,1 Márcio A. Bacchi,1 Peter Bode2
1 University of São Paulo, Nuclear Energy Center for Agriculture, Brazil

2 Reactor Institute Delft, Delft University of Technology, The Netherlands（ 42 ）

Oral Presentations
Monday, 23 September 2013
Hall & Meeting Room, Kanazawa Bunka HallTime
09:00-09:10
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19:40-20:00
20:00-

9:00

9:30

Monday, 23 SeptemberHall
Meeting Room
Arrangement for
presentation
Opening Ceremony

10:00
Hevesy Award Ceremony
R. S. Dybczyński

11:00
11:10

Coffee Break
PL-01
Plenary

11:40

PL-02

M. Yamamoto
Plenary

12:10
13:20

FKI-01

I. McKinley
Lunch Time
Invited
API-01

Invited

13:50

FKI-02

H. Tsuruta
Invited

API-02

H. Harada
Invited

14:20

FKI-03

Y. Takahashi
InvitedAPO-01

14:50

FKI-04

M. Aoyama
Invited
B. Grambow

15:20

APO-02
APO-03

Y.L. Zhao
GeneralT. M. Nakanishi
General
S.H. Jung
GeneralM. Anvia

Coffee Break

15:40

FKO-01

16:00

FKO-02

16:20

FKO-03

16:40

FKO-04

17:00

FKO-05

17:20

FKO-06

17:40

FKO-07

18:00

FKO-08GeneralA. Shimada
GeneralY. Miyake
GeneralT. Ohta
GeneralY. Muramatsu
GeneralY. Satou
GeneralM. C. Honda
General
Z.J. Zhang
General
D.R. Neville

NCO-01
NCO-02
NCO-03
NCO-04
NCO-05
NFO-01
NFO-02
NFO-03

18:50
Poster Session
20:00

－1－

GeneralZ. QinGeneralW.M. Kerlin
General
Y.K. Ha
GeneralI. Laszak
GeneralY. Xu
GeneralY. Miyamoto
GeneralN. Gharibyan
GeneralR. Sudowe

HMA-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

50 Years of Adventures with Neutron Activation Analysis with the Special
Emphasis on Radiochemical Separations�����������������������

Laboratory of Nuclear Analytical Techniques, Institute of Nuclear Chemistry and Technology, 03-195 Warszawa,
POLANDr.dybczynski@ichtj.waw.plRadiochemical separations are the key element of

the basis for selective separation and determination ofanalytical methods based on radiochemical neutron

La,Sc, Ga and Hf by NaI(Tl) spectrometry in refractory

activation analysis (RNAA). At the same time, the work inmaterials. Complex separation schemes involving some

this area is the best reference to the heritage of George

cation and anion exchange columns were devised for theHevesy who received Nobel Prize in Chemistry 1943 "fordetermination of impurities in platinum and rhodium metals

his work on the use of isotopes as tracers in the study of

by RNAA. Traces of cesium in mineral salts (down tochemical processes". In this paper author’s activities in

8x10-9% ) were determined by pre-irradiation isolating

devising new systems for the separation of inorganic ions,cesium on phenolsulfonic resin followed by post-irradiation

determination of trace elements by RNAA, but also purely

purification and measurement of short-lived 134mCs with

instrumental NAA (INAA), are reviewed. In the early

very thin NaI(Tl) crystal. Pre-irradiation separation

years of atomic era, only non-selective radiation detectors

together with post-irradiati���������������������-raysuch as Geiger-Müller or proportional counters were

spectrometry was used for the determination of noble

available, so except of some special cases , the analysis

metals in geological materials as well as all lanthanides in

had to rely on chemical separations. Radiochemical

biological materials. The uses of INAA included inter alia

separation retained much of its significance even with theanalysis of meteorites, human hair ( for forensic,

advent of scintillation spectrometry. After Ge(Li) andenvironmental and biomedical purposes), analysis of fly

HPGe detectors became available, most of analyses wereashes (together with investigation of leaching of trace

done by �-ray spectrometry ( INAA) but in several

elements by water and acid rain), study on homogeneity of

instances group separation was necessary. There werecertified reference materials (CRMs), and contribution toalways two philosophies in radiochemical separations

the certification of new CRMs. The idea of “definitive

intended for RNAA. First, relied on addition of inactive

methods” by RNAA was proposed, the essence of which iscarriers for the radionuclides to be quantified, isolation of

the combination of neutron activation with selective anda portion of an element in the state of sufficientquantitative post-irradiation separation of the desiredradiochemical purity, followed by radioactivity

radionuclide by column chromatography followed ����-ray

measurement and determination of chemical yield. Second,

spectrometric measurement. A set of rules which should beassumed that sufficiently selective and practicallyobserved when constructing definitive methods , as well as

quantitative separation of radionuclides into groups orcriteria which must be fulfilled to acknowledge theindividual species can be attained by properly designed andanalytical result as obtained by definitive method, were

tested chromatographic procedures , thus obviating theformulated. The methods elaborated by us , e.g. those forneed for the determination of chemical yield. This second

the determination of Co, Se or Fe in biological materials ,approach was mostly used in author’s laboratory. New

with their expanded uncertainties of 2.7-3.4% areanion exchange system for the separation of rare earth

comparable to those by ID-MS. Definitive methods byelements (REE) as complexes with EDTA was devised and

RNAA are the only methods of such class, possible forused for the determination of traces of Lu, Ho and Dy inmonoisotopic elements. In accordance with the ISO/IEC

Er2O3 as well as La in Pr6O11. Fundamental study

Guide 99:2007, definitive methods by RNAA may be

performed on the effect of temperature and resin cross-termed: Ratio primary reference measurement procedures

linking was helpful in optimization of the separation(RPRMPs). Such methods are intended for verification ofprocedure. Ion exchange behavior of several elements inaccuracy of other methods of trace analysis andcertification of the candidate reference materials.

+

the system: Dowex50WX2[H ] – HBr was studied and was－2－

PL-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Overview of the Fukushima Dai-ichi nuclear power plant (FDNPP) accident, with amounts andnuclear compositions of the released radionuclides
Masayoshi Yamamoto

Low Level Radioactivity Laboratory, KINET, Kanazawa University, Nomi, Ishikawa 923-1224, Japan
Since release of artificial radionuclide into the environment
was first initiated in 1945 at Alamogordo, New Mexico, theemission developed through the World War II of Hiroshima
and Nagasaki, and continued with nuclear weapons testings,
which finished in 1980. Furthermore, accidental releases ofradioactivities have occurred through the events such as thefall of nuclear-fueled satellites, and accident in nuclear power
plants and the related facilities (Windscale (Sellafield), Three
Mile Island, Chernobly, etc.). The Japanese also experienced
tragedies of the Fifth Fukuryu-Maru accident at Bikini atoll(1954) and the JCO criticality accident at Tokai-mura (1999).
This time, as widely recognized, the M 9.0 earthquake off
the Pacific coast of Japan on 11 March 2011 and thesubsequent tsunami induced an accident in the FDNPP. Total
loss of electric power happed and the cooling systems ofsome of the reactor units 1-3 failed, resulting in hydrogen
explosion in the reactor buildings and venting of gases, withsignificant releases of radionuclides into the atmosphere. In
addition, highly contaminated water with large amounts ofradionuclides was directly leaked or discharged into theNorth Pacific. Public health actions to reduce the negative
consequence of this event were taken by government; a 20km evacuation zone was put in place around the site, with asheltering zone between 20 and 30 km. The Japanese
Government and various prefectural governments started
emergency monitoring of radioactivity to assess theenvironmental and human effects by the FDNPP accident.
The details of the FDNPP accident have been already opened
in a report by the Japanese Government to the IAEA (IAEA
2011, NISA, 2011, Japanese Government 2011). The
Fukushima accident was classified on the INES (International
Nuclear and Radiological Event Scale) scale at the maximum
level of 7, being the same as that of the Chernobyl nuclear
power plant (CNPP) accident (April 26, 1986). Compared to
the CNPP accident, the FDNPP accident presents a much
more difficult situation, since various reactor cores and spent
fuel pools may have contributed to the emissions.
Several atmospheric radionuclide releases occurred mainly
during the periods from March 12 through March 23, 2011.
The air contaminated by the released radionuclides,
especially noble gas (133Xe, etc.) and volatile nuclides such as
131 134
I, Cs and 137Cs, eventually spread over large distances,and were observed at monitoring stations (IMS by CTBTO)
throughout the world. In Japan, the radionuclide fallout
resulted in a track of contaminated land that expanded
approximately 50 km to the northwest of the FDNPP andlater in a larger, lower level area of contamination mostly tothe south and southwest. Total estimated atmospheric releasesof 131I and 137Cs by government are around 160 and 15 PBq,
respectively, although exact amount of radionuclides emitted
are still being argued. These levels are lower for 131I and 137Cs
by about a factor of 12 and 7, respectively, compared withthose of the CNPP accident. More than 70% of the released
radionuclides into the atmosphere were deposited over the
North Pacific. Thus, by broad survey and early investigations,whole picture about levels and spreading areas ofcontaminants, especially 134Cs and 137Cs, has been becoming
clear, together with the situation of the plant. For radioiodine
released, this nuclide consists of gaseous and particulate
forms, therefore, its behavior seems to be very difficult,resulting in large variation of 131I/137Cs ratios measured in airand soil. Since 1311 is a short half-life (8 d), its reconstructionin the initial stage by 129I is attempted to evaluate the impact
of human health from radioiodine. For other possible released
radionuclides, radiostrontium (89Sr and 90Sr) and transuranic
nuclides, which have attracted much scientific and potential
radiological concern, are poorly investigated, mainly becauseof the difficulties of analyzing and measuring these beta- andalpha-emitting radionuclides. These nuclides are much lessvolatile than other fission products such as cesium and iodine
isotopes. TEPCO published a 90Sr/137Cs ratio in soils 10-3.
Actual environmental measurements showed variability in the90
Sr/137Cs ratios for different locations, ranging of 10-2-10-4 insurface soils within the 50 km area from the FNPP. On theother hand, in addition to the limited data of Pu isotopes insoil and litter samples, 236U, Pu isotopes (238Pu, 239Pu and240
Pu), 241Am and Cm isotopes (242Cm and 243,244Cm) havebeen measured by us for roadside dust collected at the
Fukushima areas heavily contaminated. When the ratios
among these nuclides measured are compared with those offuel compositions in the FDNPP estimated by Nishihara et al(2012) of the JAEA group, fairly good agreement was found,indicating that traces of U and transuranic nuclides, probably
with forms of fine particles, were released into theenvironment without their large fractionation. In any event,such measurements may allow us to give information (burnup, conditions of fuel during the release phase, etc.) on theon-site situation, which may be difficult to receive otherwise.
In this presentation, I have two main objectives as follows:
first, I will show the overview of the accident, second, I wantto present the amounts and isotopic signatures of the released
radionuclides, especially transuranic nuclides. We hope that
this special session on Fukushima accident promotes further
investigations about radiological impact of the accident andtransport dynamics.

－3－

PL-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Fukushima Challenges in Perspective
1

Ian G. McKinley1, Susie M. L. Hardie1, Elizaveta Klein1

MCM Consulting, Täfernstrasse 11, 5405 Baden-Dättwil, Switzerland

Keywords – Fukushima, decontamination, radioactive waste,knowledge transfer, communication

The accident at the Fukushima Dai-ichi nuclear power plant
was undoubtedly a local industrial disaster that has had aglobal impact on the “nuclear renaissance”, which was
beginning to blossom in 2011. Nevertheless, from a purely
radiochemical perspective, the environmental consequencesof the core meltdowns were significantly less than a worst
case scenario and much can be learnt from this. A key
factor was containment of most of the radioactivity fromthe fuel melt within the reactor buildings, releases being
limited to volatile elements, which were either vented to theatmosphere or picked up by cooling waters. This will makedecommissioning of the heavily contaminated parts of units
1-4 tricky, but the overall situation is certainly lessproblematic than Chernobyl.

being virtually non-existent. This indicates that, despite thepervasive nature of background radiation and thewidespread use of radionuclides in medicine, industry andresearch, radiochemists need to take a more active role inpublic education, to help replace non-technical audiences’
visceral fear of anything radioactive with a real
understanding of the issues involved.
REFERENCES[1]

The most significant radionuclides off-site were isotopes of
I and Cs, possibly the best understood of all environmental
radionuclides due to the huge knowledge base built up
since the middle of the last century [1]. Evacuation, issue ofiodine tablets and limitation of consumption ofcontaminated foodstuffs has ensured that radiological risks
to the general public have been negligible. Subsequent
remediation actions will complement decay and “selfcleaning” to ensure that most of the evacuated populations
can safely return home and resume normal lifestyles in thenear future. Nevertheless, a huge volume of radioactive
waste will result, which needs to be managed in a safe andefficient manner.
For the international community, there are two issues to beconsidered – how can experience from other locations beutilised to support recovery in Fukushima and how can theexperience gained from this incident be taken over toreduce the risk of something similar happening elsewhere
and also to increase the effectiveness of any similar largescale clean-up operations, for example in military legacy
sites? Here modern “knowledge management” technology
can facilitate the process of capture and transfer of such
experience.
Apart from such technical considerations, a special
challenge after the accident was communicating
information on extent of contamination and progress withcleanup to the general public. This is an international
concern and is complicated by campaigns of disinformation
by nuclear opponents and the tone of reporting by agenerally critical mass media. The nuclear industry,
government organisations and professional bodies have all
performed poorly here - the response to public concerns－4－

McKinley, I.G., Grogan, H.A., McKinley, L.E., Fukushima:
Overview of relevant international experience. J. Nuclear Fuel Cycle
and Environment, 18, 89-99 (2011)

FKI-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Atmospheric transport of radioiodine and radiocesium released in the early phaseby the Fukushima Daiichi Nuclear Power Plant accident from field measurements
and a simulation model
1

Haruo Tsuruta1, Masayuki Takigawa2, Teruyuki Nakajima1

Atmosphere and Ocean Research Institute, The University of Tokyo, Kashiwa, Chiba 277-8568, Japan
2
Japan Agency for Marine-Earth Science and Technology, Yokohama, Kanagawa 236-0001, Japan

Abstracts – The continuous measurements of atmosphericconcentration of 131I and 137Cs at ten stations in the Kanto area
located 120km south from Fukushima, showed that 131I/137Cs andthe ratio of particulate 131I to the sum of particulate 131I andgaseous 131I significantly changed in the periods when thepolluted air masses were transported, compared with those in theother periods. A numerical model well simulated the transport ofthe polluted air masses to the Kanto and Fukushima area, while
any field data did not suggest the transport to Fukushima on
March 20-21due to no precipitation.
Keywords – FD1NPP accident, gaseous and particulate 131I, 137Cs,
I/ Cs, atmospheric concentration

131 137I.

INTRODUCTION

A large amount of radioactive materials was released
into the atmosphere after the accident of the Fukushima
Daiichi Nuclear Power Plant (FD1NPP) caused by the
Tohoku Earthquake and Tsunami on March 11, 2011, andwas transported and deposited to the land surface in aregional scale. Many datasets have been opened such as theroutine monitoring of radiation dose rate and fallout by
MEXT, and the regional map of radionuclides deposited to
the land surface by MEXT, and by aircraft monitoring by
MEXT and DOE. In contrast, continuous monitoring of
atmospheric radionuclides in an early phase after theaccident, was made only in the Kanto area located morethan 120km south from the Fukushima prefecture, although
it is critical for evaluation of the internal exposure dose,reconstruction of time-dependent release rate ofradionuclides, and for validation of numerical simulations
by atmospheric transport models. The purpose of this paper
is to summarize new findings on atmospheric 131I and 137Csfrom the field measurements, and to discuss the results oftransport pathways by a numerical model.
II. MATERIALS AND METHODSIn the Kanto area, ten research groups independently
measured radionuclides in the atmosphere just after theaccident, and their results and/or datasets were alreadyreported, and most of them have been summarizedelsewhere[1]. Furthermore, gaseous 131Ig and particulate
131
Ia were separately measured at a few stations. The
datasets were used for an analysis of time series ofatmospheric concentration of 131I and 137Cs, 131I/137Cs (=R1),
and 131Ia/(131Ia+131Ig) (=R2). A numerical simulation ofradioactive materials in the atmosphere was performed byusing an atmospheric transport model for radionuclides
based on a regional chemical transport model of

WRF/Chem[2]. In the model, the radionuclide of 131I and137
Cs was taken into account, and their release rates werebased on the estimate by Katata et al.[3].
III.

RESULTS AND DISCUSSION

According to the field measurements in the Kanto area,
high concentrations of 131I and 137Cs (>100 Bq m-3) were
measured during March 15-16 (the first period) and March
20-23 (the second period), and 131I was much higher than137
Cs. A numerical simulation by the atmospheric transportmodel showed that the polluted air masses with high 131I
and 137Cs were directly transported to the Kanto area fromthe FD1NPP in the morning of both periods bynortheasterly wind, in good agreement with the results ofthe field measurements. The model also simulated thetransport of the polluted air masses to the Fukushima areain the afternoon to the midnight in both periods. The
radiation dose rates and deposition rates in the Fukushima
area increased only in the first period with precipitation,
supporting the transport. On the contrary, they did not show
any increase in the second period due to no precipitation.
The recent analysis for stored filters on which atmosphericaerosols in the early phase were collected, revealed the highconcentration of 137Cs in both periods[4,5], validating the
calculated transport of the polluted air masses by the model.
The time series of R1 at all the stations showed that R1
was around or less than 10 when the plume with highradionuclides from the FD1NPP was transported in the
Kanto area, which was almost equal to the ratio in a
calculated core inventory on March 11, 2011[6]. In contrast,
R1 was around 100 in the other periods. On the morning ofMarch 22 when the polluted air masses were alsotransported to the Kanto area, R1 increased to around 100,much higher than that in the previous day, suggesting thepossible change in the release condition in the reactor units.
The ratio of R2 was 0.4-0.8 when the plume was directlytransported, while it was 0.1-0.3 in the other periods. Hence,
the ratio of R1 and R2 at the time when the radionuclides
were released into the atmosphere possibly suggests any
change in conditions of the reactor units.
[1]
[2]
[3]
[4]
[5]
[6]

－5－

Tsuruta et al. (2012), Proceedings of the 1st NIRS Symposium on
Reconstruction of Early Internal Dose in the TEPCO Fukushima
Daiichi Nuclear Power station accident, Chiba, Japan
Takigawa (2012), Proceedings of 92nd American MeteorologicalSociety, New Orleans, US.
Katata et al. (2012), J. Environ. Radioactiv., 109, 103-113.
Oura et al. (2013), A paper in the APSORC’2013.
Tsuruta et al. (2013). A paper in the APSORC’2013.
Nishihara et al. (2012), Transactions of Atomic Energy Society ofJapan, 12, 13-19.

FKI-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Migration of Radiocesium and Radioiodine released by FDNPP accident in theterrestrial environment and its interpretation by their speciation analyses
Yoshio Takahashi,1 Qiaohui Fan,1 Yoko S. Togo,2 Aya Sakaguchi,1 and Kazuya Tanaka1
1

Graduate School of Science, Hiroshima University, Higashi-Hiroshima, 739-8526, Japan
National Institute of Advanced Industrial Science & Technology (AIST), Tsukuba, Ibaraki 305-8567, Japan

2

Abstract – Distribution of radiocesium and radioiodine suchas vertical profile in soil layer, particulate matter-water
distribution in river water, and size distributions in sediments
were studied to understand their migration in the terrestrial
environment in Fukushima area. In addition, speciation
studies on cesium and iodine focusing on (i) the surface
complex structure of cesium on clay minerals and (ii)formation of organoiodine in soil have been conducted,
which can clearly explain the possible chemical processes
that control the behavior of these radionuclides in theterrestrial environment.
Keywords – FDNPP accident, radiocesium, radioiodine, clay
mineral, humic substances, X-ray absorption fine structure

I. INTRODUCTIONRadionuclides such as radiocesium and radioiodine were
emitted from the Fukushima Daiichi Nuclear Power Plant(FDNPP) accident caused by the Great East Japan Earthquake
and Tsunami on March 11, 2011. Highly contaminated areas
spread in the northwest direction from FDNNP in Fukushima
Prefecture, which mainly resulted from the distribution of thewet deposition on March 15 [1]. After the deposition, they
have migrated in the terrestrial environment depending on
their chemical properties and interactions with various
components in the soil, sediment, and water. In thispresentation, we report our results on the distributions ofradiocesium and radioiodine in soil, river water, andsediments in Fukushima coupled with speciation studies ofcesium and iodine in the systems that should be important tounderstand their behaviors in the terrestrial environment.
II. EXPERIMENTAL
Distributions of radiocesium in the soil layer, river water,and river sediments mainly in Fukushima Prefecture were
determined. Vertical profile in soil was also obtained forradioiodine. Sequential extraction studies have been also
conducted for radiocesium and radioiodine to estimate mainchemical species of the radionuclides. On the other hand,interactions of radiocesium with various clay minerals in theabsence and presence of humic acid were examined by X-ray
absorption fine structure (XAFS) to interpret the behavior ofradiocesium in the soil-water and river water-sediment
systems. Formation of organoiodine species were also
examined using XAFS in laboratory and natural systems.

III. RESULTS AND DISCUSSION
After the deposition of radiocesium and radioiodine, their
vertical profiles in soil in Fukushima showed that more than
90% of radiocesium and radioiodine have been retained
within 5 cm from the surface [2]. Leaching experiment of thesoil sample showed that radiocesium is strongly bound to soil
particles. Size distribution analyses for particulate mattersand sediment particles in rivers in the region showed thatradiocesium is enriched in finer particle fractions. These
results suggested that radiocesium has a high affinity for soil
particles, in particular for clay minerals. Thus, XAFS
spectroscopy has been used to characterize structure ofsurface complex of cesium to solid phase [3]. It was foundthat cesium forms inner-sphere complex to 2:1 phyllosilicate
with medium interlayer distance such as vermiculite andweathered illite. In the presence of humic substances,
however, formation of inner-sphere complex was inhibited
because of the blocking effect of humic substances on theadsorption of cesium into the interlayer. This result also
showed that direct complexation between radiocesium andhumic substances is not important. These results are
consistent with sequential extraction analysis of soil samples
and clay mineral-humic substances hybrid containing cesium.
As for radioiodine, about 30% of radioiodine leached by
NaOH solution (pH 10.5) from the soil collected one monthafter the accident [2]. When the extracted solution wasacidified, more than 60% of radioiodine was precipitatedpossibly with humic materials that can bind iodine in thepolyorganic structure. This leaching-precipitation behavior
suggests that a part of iodine is in the organic form in the soil,
which can be a reason for the retention of radioiodine in thesoil surface. The formation of organic iodine in natural soil
has been suggested by XAFS using X-ray microbeam [4],which can proceed in a relatively short period, such as withina week or a month. Thus, the formation of organoiodine islikely for radioiodine in the soil.
As seen above, speciation studies of cesium and iodine can
explain the chemical processes controlling migration
behaviors of radiocesium and radioiodine in Fukushima area.
[1] N. Yoshida and Y. Takahashi, Elements 8 (1012) 201.
[2] K. Tanaka et al., Geochem. J. 46 (2012) 73.
[3] Q. Fan et al., submitted to Geochim. Cosmochim. Acta.
[4] Y. Shimamoto et al., Environ. Sci. Technol. 45 (2011)
2086.

－6－

FKI-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Oceanic and coastal dispersion of 134Cs and 137Cs released from the TEPCO
Fukushima NPP1 accident: past, present and prediction
Michio AOYAMA1, Yasunori HAMAJIMA2

1Meteorological Research Institute, Tsukuba, 305-0052 Japan
2 Low Level Radioactivity Laboratory,Kanazawa University, Nomi, Ishikawa 923-1224, Japan
Abstract: The bulk of the anthropogenic radionuclide 137Cspresent in the oceans today was injected about five decades
ago from atmospheric nuclear weapons tests. In the North
Pacific Ocean 137Cs inventory was 290 ± 30 PBq in 1970
and it was 69 PBq just before the TEPCO Fukushima Daiichi Nuclear Power Plant (FNPP1) accident. An impact of
FNPPP1 accident to the North Pacific Ocean in terms of
inventory was estimated to be 10 – 13 PBq by atmosphericdeposition and 3.5 ± 0.7 PBq by direct discharge, therefore
the total 137Cs inventory in the North Pacific Ocean
increased by up to 20 – 23%.Fukushima released
radiocaesium already subducted in 2011/2012 winter andformed subsurface maximum at a densities of Central Mode
Water (CMW), and Subtropical Mode Water (STMW).

Key words: 137Cs, Pacific Ocean, inventory, subduction,
radioactive plumeI. INTRODUCTION
On 11 March 2011, an extraordinary earthquake ofmagnitude 9.0 centered about 130 km off the Pacific coastof Japan’s main island, at 38.3 ºN, 142.4 ºE, was followed
by a huge tsunami with waves reaching up to 40 m heightin Iwate region and about 10 m in Fukushima region. The
station blackout developed into a disaster that left three ofthe six FNPP1 reactors heavily damaged, meltdown of core,and caused radionuclides to be discharged into the air andocean[1, 2].
II. SAMPLING AND METHODS
We collected 2 litre surface seawater samples at morethan 300 stations. The samples were treated by an improved
ammonium phosphomolybdate, AMP, procedure [3, 4].
III.RESULTS
134
Cs and 137Cs activities in surface water at Hasaki, acoastal station 180 km south of the Fukushima Dai-ichi
Nuclear Power Plant (FNPP1) accident site, were observedin April to December 2011 [5]. The maximum inradiocaesium activity at Hasaki was observed in June 2011,
representing a delay of two months from the corresponding
maximum in April 2011 at FNPP1. Directly discharged
134
Cs and 137Cs were transported dominantly southward
along the coastline of north eastern Honshu, at least in May
and June 2011.
Before the FNPP1 accident, 137Cs was already exist
which was originated from the nuclear weapon tests
conducted in the late 1950s and in the early 1960s [4, 6]. In
the western North Pacific Ocean, 90Sr and 137Cs activities insurface water was 10 – 100 Bq m-3 in the late 1950s and in
the early 1960s, then it decreased gradually and the 137Cs
activity in surface water decreased to around a few Bq m-3
just before FNPP1 accident as shown in Figure 1[6, 7].

Figure1. 60 years trend of 90Sr and 137Cs in surface water in the North
Pacific Ocean and decay corrected accumulative deposition inTokyo/Tsukuba, Japan.

The 137Cs inventory in the North Pacific Ocean was 290± 30 PBq in January 1970 based on 10 º by 10 º mesh dataof the 137Cs deposition [7]. In 2003, 137Cs inventory in the
North Pacific Ocean was 86 PBq by the model study [8]and 85 PBq by the observation [9], then it decreased to 69
PBq in 2011 because due to decay [9].
The horizontal distribution of FNPP1 derived 134Cs in
the western North Pacific Ocean except just in front of the
FNPP1 site showed that the high concentration area locatedclose to the FNPP1 accident site which might have received
both atmospheric deposition – showing good consistency
with previous atmospheric transport model study [10] – anddirect discharge [2] from the FNPP1 site. During the winterbetween 2011/2012, Fukushima derived radiocaesium
subducted and formed subsurface maximum at a densities
of Central Mode Water (CMW) of which depth is about
400 meters depths and Subtropical Mode Water (STMW)
of which depth is about 150 meters depths due to cooling at
sea surface. This implies that a speed of main body ofFukushima derived radiocaesium will be decreased muchbecause of less wind driven force at subsurface layers
rather than those at surface layers which was 8 cm s-1 as
the average speed of radioactive plume at sea surface statedpreviously. [6]REFERENCES

1. Chino, M., et al., Journal of Nuclear Science and Technology, 48(7), p.
1129-1134, 2011.
2. Tsumune, D., et al., J Environ Radioact, 111, p. 100-108, 2012.
3. Hirose, K., et al., Journal of Radioanalytical and Nuclear Chemistry,
263(2), p. 349-353, 2005.
4. Aoyama, M. and K. Hirose, Radiometric determination ofanthropogenic radionuclides in seawater, in Radioactivity in theEnvironment, P.P. Pavel, Editor. 2008, Elsevier. p. 137-162.
5. Aoyama, M., et al., Geochem. J, 46, p. 321-325, 2012.
6. Aoyama, M., et al., Progress In Oceanography, 89(1-4), p. 7-16, 2011.
7. Aoyama, M., K. Hirose, and Y. Igarashi, Journal of Environmental
Monitoring, 8(4), p. 431-8, 2006.
8. Tsumune, D., et al., Progress In Oceanography, 89(1-4), p. 38-48,
2011.
9. Aoyama, M., D. Tsumune, and Y. Hamajima, Journal ofRadioanalytical and Nuclear Chemistry, p. 1-5, 2012.
10. Honda, M.C., et al., Geochem. J, 46, p. e1-e9, 2012.

－7－

FKI-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Interactions between nuclear fuel and water at the Fukushima Daiichi Reactors
1

Bernd Grambow1

SUBATECH (Ecole des Mines de Nantes, University of Nantes, IN2P3-CNRS)
4 rue Alfred Kastler, 44307 Nantes, France,
Grambow@subatech.in2p3.fr

The rapid increase in temperature in the cores of the
Fukushima reactors was caused by the loss of coolant in theaftermath of the damage from the tsunami. Hightemperatures caused partial melting of not only the UO2 in
the fuel but also the zircaloy cladding and steel, forming aquenched melt, termed corium. Substantial amounts ofvolatile fission products, such as Xe, Cs and I, werereleased during melting, but the less volatile fission
products and the actinides (probably >99.9%) wereincorporated into the corium as the melt cooled and wasquenched. The corium still contains these radionuclides,
which leads to a very large long-term radiotoxicity of themolten reactor core. Access by water to the core may
constitute an important vector for transfer of radioactivity.
The challenge for radiochemists is to assess the long-term
interactions between water and the mixture of corium andpotentially still-existing unmelted fuel, particularly if themolten reactor core is left in place and covered with asarcophagus for hundreds of years. Part of the answer tothis question can be found in the knowledge that has been
gained from research into the disposal of spent nuclear fuelin a geologic repository.
Comparison of radionuclide release during the accident
from the reactors with the radionuclide inventories
remaining in the reactor and estimation of corium–waterinteraction from known spent fuel–water interaction
provide important insight for developing assessment andmanagement strategies for the molten fuel in the reactor
cores. Furthermore, analyzing the radiochemical analysesof the temporal evolution of the radioactive elements in thecooling water of the accidental reactors provide valuable
information on the chemical state of the corium andpotential phase separations. Models for corium stability
and for radionuclide release from corium upon contact withwater will have to be developed based on (1) analyses ofradionuclide activities in actual cooling waters, (2)chemical modeling of the analytical results in the context of
the kinetics and thermodynamics of actinide and fission
product release (solubility constraints, redox states, etc.),and (3) comparison with spent fuel behavior andexperimental corium databases. Such models may be very
useful in developing appropriate corium management
strategies.

－8－

FKO-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of 129I in the Accumulated radioactive water and processing waterof Fukushima Daiichi Nuclear Power Plant
Asako Shimada1,2, Keiichi Sakatani1, Yutaka Kameo1,2, Kuniaki Takahashi1
1

Nuclear Cycle Backend Directorate, Japan Atomic Energy Agency
2
Fukushima Project Team, Japan Atomic Energy Agency

Abstract – Accumulated radioactive water (AW) and processing
water (PW) were sampled from some positions of the
Accumulated Radioactive Water Processing Facility (ARWPF) at
Fukushima Daiichi Nuclear Power Plant (FDNPP) to estimate theradioactivity of the secondary waste such as zeolite and sludge
which adsorbed radioactive material. Separation method of Ifrom the radionuclides using solid phase extractant, Anion-SR,
was developed. After the chemical separation, the concentrationof 129I in the sampled water was determined by Inductively
Coupled Plasma Mass Spectrometry with dynamic reaction cell
(DRC-ICP-MS).
Keywords – 129I, Accumulated radioactive water, Fukushima
Daiichi Nuclear Power Plant, Anion-SR

I.

INTRODUCTION

In the early stage of the handling to cool down thereactor core of FDNPP, seawater was poured in theseverely damaged reactor buildings. Highly contaminatedwater was leaked and accumulated in the reactor andturbine buildings. The ARWPF were installed todecontaminate the radioactive materials and to desalinate.
Highly contaminated sludge was generated from theseapparatus as the secondary waste. To estimate theradioactivity of the waste, AW and PW were sampled fromthe inflow and outflow of the apparatus.
Because of the long half-life, 129I is one of the importantnuclide to assess the safety of radioactive waste disposal.
The present study focuses the development of separation
method of I- and determination of 129I in the sampled water.
Separation method of I- with Anion-SR was optimized to
improve the detection limit of 129I and to reduceradioactivity of the analyte. After separation, the ratio of127
I and 129I were determined by DRC-ICP-MS to reducethe influence of 129Xe.
II. EXPERIMENTAL
Samples
The AW and PW were sampled at � reactor/turbine
building, � , � outflow of Cs adsorption apparatus, �outflow of decontamination instruments, �outflow of Cs
adsorption apparatus, �outflow of desalination apparatus,�concentrated sea water tank, �processed water tank �outflow of evaporative concentration apparatus, as shownin Fig.1.
Separation of I with Anion-SR
Anion-SR disk was assembled suction filtration
apparatus. The disk was conditioned by passing solutions
as follows; 1. 10 ml acetone, 2. 10 ml methanol, 3. 5 ml

Fig.1 Sampling point of the AW and PW

ultrapure water, 4. 5 ml of 1 M HNO3, 5. 10 ml ultrapure
water, 6. 15 ml of 1 M NaOH (ultrapure), 7. 3 times of 15
ml ultrapure water. After then, sample solution was passed
through the disk and the disk was washed with ultrapure
water. The extracted I- was recovered with 9.5 ml of 1 M
HNO3 in the 10 ml measuring flask, and 50 �� NaClO wasadded to oxidize I- to IO3-. Finally, 1 ml of 1 M HNO3 wasadded untill the total volume became 10 ml. The ratio of127
I and 129I was determined by DRC-ICP-MS.
III. RESULTS AND DISCUSSION
Because sample volume of the AW and PW was 0.1 ml,
they were needed to be diluted by appropriate solution tocarry out the separation of I- with Anion-SR. Before
analysis of the water samples, the dilutant was optimized.
Five ml of 3 M NaOH (ultrpure), 3 M NaOH (97%), 2.7 M
tetramethyl ammonium hydroxide (TMAH, ultrapure), and
3 M Na2CO3 (99.8%) solutions were examined as thediluent to obtain high recovery of I- and low contamination
for the DRC-ICP-MS measurement. Approximately 90%
recovery was accomplished by all the examined dilutant,whereas the lowest back ground count from blank operation
was obtained for ultrapure 3 M NaOH solution. Therefore,
it was used for the analysis of AW and PW samples.
Iodide in AW and PW solution was analyzed with andwithout known amount of 127I spike, and the concentration
was calculated with the ratio of 127I and 129I. Table 1 shows
the concentration of 129I in the AW and PW samples. It was
found that 129I was decontaminated by desalination andevaporation
apparatus.
Resultsofperiodicallymeasurements and development of analysis of IO3- with Iwill be delivered on the presentation.
Table 1 Concentration of 129I in the AW and PW samples

Concentration of 129I /Bq·g-1
� 0.25±0.002
� 0.085±0.001
� 0.18±0.002
� 0.083±0.002
� 0.13±0.001
� <0.021
� 0.27±0.003
� <0.021
� 1.3±0.03－9－APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

FKO-02

Measurement of Iodine-129 in surface soil collected near the Fukushima Daiichi
nuclear power plant accident site
Yasuto Miyake1, Hiroyuki Matsuzaki1, Takeshi Fujiwara2, Takumi Saito2, Takeyasu Yamagata3
and Maki Honda3
1

Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, Japan
2
Nuclear Professional School, School of Engineering, The University of Tokyo, Japan
3
Nihon University, Japan

Abstract – Iodine-129 in soil around Fukushima Daiichi nuclear
power plant were measured by Accelerator Mass Spectrometry
and isotopic ratio of radioiodine was estimated. Surface
deposition amount of Iodine-129 resulted in 6.7 to 5500mBq/m2.
The mean isotopic ratio between Iodine-129 and Iodine-131 at theaccident was estimated that 129I/131I = 26 ± 6 as of March 11 2011.
This result was compared to the calculation result of ORIGEN2
code to test the validity of this estimation.

In order to check the validity of analytical result, it wascompared to the calculation result of ORIGEN2 code [3].
In Fig. 1, 134Cs/137C data were plotted against 129I/131I data.
Each of nuclides was decay-corrected as of March 11, 2011.
Not only observation results but also calculation data of
isotopic ratio of Unit 1, Unit 2, and Unit 3 were shown here.

Keywords – FDNPP accident, Iodine-129, Accelerator Mass
Spectrometry, soil, isotopic ratio

I.

INTRODUCTION

A lot of radioactive materials were released into theenvironment owing to the Fukushima Daiichi nuclear
power plant (FDNPP) accident. Among them, Iodine-131
has already decayed out and cannot be detected now. On
the other hand, Iodine-129, which is the isotope of Iodine131, has long half-life and can be measured by Accelerator
Mass Spectrometry. If isotopic ratio of radioactive iodine(129I/131I) at the initial stage at the accident is obtained,
distribution of Iodine-131 at the accident can bereconstructed by measuring Iodine-129 in soil. In this study,
Iodine-129 was measured in soils, which were collected
within 60km distance from FDNPP on April 2011.
II. METHOD
50 soil samples were collected within 60km distancefrom FDNPP on April 20, 2011. Sampling strategy was
shown in other paper [1]. Iodine-131 and otherradionuclides have already been determined by gamma ray
measurement [1]. In order to extract Iodine from soil,
homogenization, combustion, solvent extraction, and backextraction were conducted [2]. After making AgI
precipitation, samples were pressed into a cathode for AMS
and 129I was measured at MALT (Micro Analysis
Laboratory, Tandem accelerator), The University of Tokyo.
Iodine-127 in soil was measured by ICP-MS at the
University of Tokyo.

Fig. 1. Comparison of isotopic ratio of radioiodine andradio cesium between observation results and calculation
result of ORIGEN2 code

In Fig. 1, average of observation results is located close
to center of calculation and this average seems to beaffected by Unit 1. This suggests contribution of Unit 1
might be larger than expected or there are other reasons.
Problems are still under debate.

III. RESULTS AND DISCUSSION
Surface deposition amount of Iodine-129 resulted in
between 6.7 to 5500mBq/m2 within the area 60km distantfrom FDNPP. These values were corresponding to Iodine129 concentration between 7.8E7 to 5.9E10atoms/g.
Iodine-127 concentration was distributed from 1 to 16ppm.
The mean isotopic ratio of 129I/131I =26 ± 6 on March 11,2011 was obtained.
－ 10 －

IV. REFERENCE[1] Fujiwara et al., J. Environ. Radioact., 113, 37 – 44 (2012).
[2] Miyake et al., Geochemical Journal, vol. 46, 327 – 333 (2012).
[3] Nishihara et al., JAEA-Data/Code, 2012-018 (2012).

FKO-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Speciation of 137Cs and 129I in surface soil in Kanto loam layer
after the Fukushima NPP accident
Tomoko Ohta1, Takumi Kutoba2, Yasunori Mahara3,
Hiroyuki Matsuzaki4, Toshifumi Igarashi1
1Faculty of Engineering, Hokkaido University
Research Reactor Institute, Kyoto University
3
Professor Emeritus, Kyoto University
4
School of Engineering, The University of Tokyo
2

Abstract
We measured chemical speciation of 137Cs and 129I in the surface
soil of Kanto loam after Fukushima nuclear disaster. We observed
the behavior of 137Cs and 129I in soil samples of the Kanto loam
layer: more than 90% of 137Cs was fixed by organically bound andresidual fractions, while 129I was mainly fixed by Fe-Mn oxidationand organically bound.
Keywords –Cs-137, I-129, Fukushima nuclear disaster, Kanto loam,
Solid-phase extraction, leaching

Introduction
Sequential extraction has been proven to be a useful andpractical technique for the speciation analysis ofradionuclides in the soil and sediment samples (Desideri, etal., 2001; Desideri et al., 2002 ; Oughton et al., 1992; Riise etal.,1990; Tessier et al., 1979). We extracted 137Cs and 129I
from surface soil samples from the Kanto-loam layer ineastern Tokyo metropolitan area.
Methods
The two soil samples of depths of 0�2.5cm were reduced bycone and quartering to approximately 10 g. Approximately 10
g of the samples were used in the sequential-extraction
experiment. A solution/sample ratio of 5 (v/w) was used forextraction in each step (Fraction 1, 2, 3, 4, 5 and residue).
Fraction 1: Ultrapure water was added to the soil sample, andthe sample was shaken for 24 h at room temperature. The
sample was stored overnight. This fraction represents watersoluble species. The remaining solid on the filter paper was
combined with the residue for the leaching in the next step.
Fraction 2: 1 M of NaAc was added to the residue fromFraction 1. The sample was shaken for 12 h at room
temperature and stored overnight. This fraction represents
exchangeable species.
Fraction 3: 1-M NaAc�HAc (pH 5) was added to the residue
from Fraction 2, and the sample was shaken for 12 h at room
temperature. This fraction represents carbonate-bound species.
Fraction 4: 0.04-M NH2OH�HCl in 25% (v/v) HAc (pH 2)
was added to the residue from the fraction and stirred in a
hot-water bath at 80 °C for 4 h. This fraction represents
species associated with solids via chemical-sorption

mechanisms which can be released into the extraction
solution with a weak reducing agent, and they mainly include
species bound to Fe/Mn oxides.
Fraction 5: 30% H2O2 was added to the residue, in which
HNO3 had already been added to adjust the final pH to 2, andthe sample was agitated for 2 h at 85 °C. After the sample
solution was cooled to room temperature, 1.8-M NH4Ac in
11% HNO3 (v/v) was added, and the extraction continued for
30 mins at room temperature. This fraction is associated withorganic matter.
After extraction, each solution was separated from the soil
residue by centrifugation at 2000 rpm for 5 mins. The
solution was filtered through a filter paper with a pore size of������������������������������������������������ U-8 vessel,
137
Cs was measured by gamma-ray spectrometry (Hokkaido
University). I-129 was measured by AMS (Tokyo University).
Result
The amount of 137Cs leached into water (F1) from the
Kanto-loam soil was below the detection limit. The rate of137
Cs exchange from the two soil samples was less than 1%,
with 50–60% of 137Cs remaining in the residue.
Approximately more than 90 % of 137Cs was adsorbed onorganic matter and the residue, while 129I was mainly fixed by
Fe-Mn oxidation and organically bound.

[1]
[2]
[3]
[4]
[5]

－ 11 －

References

Desideri, D., et al., 2001. Speciation of natural and anthropogenic
radionuclides in different sea sediment samples. J. Radioanal. Nucl.
Chem. 248, 727–33.
Desideri, D., et al., 2002. Geochemical partitioning of actinides, 137Cs
and 40K in a Tyrrhenian sea sediment sample: comparison to stableelements. J. Radioanal. Nucl. Chem. 251, 37–41.
Oughton, D.H., et al., 1992. Radionuclide mobility and bioavailability
in Norwegian and Soviet soils. Analyst. 117, 481–6.
Riise, G., et al., 1990. A Study on Radionuclide Association with Soil
Components using a Sequential Extraction Procedure. J. Radioanal.
Nucl. Chem. 142, 531–8.
Tessier, A., et al., 1979. Sequential extraction procedure for the
speciation of particulate trace metals. Anal. Chem. 51, 844–50.

FKO-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Transfer of radiocesium and radioiodine in the environment following the
Fukushima nuclear accident
Yasuyuki Muramatsu1, Takeshi Ohno1, Naoya Inagawa1, Kazumasa Oda1, Mamoru Sato2, Hiroyuki
Matsuzaki3
1

Gakushuin University, 2Fukushima Agricultural Technology Centre, 3The University of Tokyo

Abstract- Following the Fukushima accident, intensive studies
have been carried out regarding the distribution and transfer ofradionuclides that have been released into the environment. In
this paper, the following two topics related to this theme arepresented: (1) The importance of translocation pathways tounderstand the transfer of radiocesium into some crops such as
tealeaves and citrus fruit. (2) The reconstruction of I-131
deposition in different places in Fukushima Prefecture throughthe analysis of long-lived I-129.

months and there were not enough data toconstruct a deposition map for I-131. Since along-lived I-129 (half-life: 15.7 million years)
was also released from the accident, we haveanalyzed it for reconstructing I-131 deposition.

Keywords – Radiocesium transfer to plant, translocation pathway,
I-129 analysis for the reconstruction of I-131 deposition

Concentrationsofradiocesium
weredetermined with a Ge-detector in crop samples
collected in Fukushima following the accident.
For I-129 analysis, iodine fractions wereseparated from soil samples to make a AgI target
for the determination of this nuclide by AMS.

I.

INTRODUCTION

Among radionuclides released from theaccident of Fukushima Daiichi Nuclear Power
Plant, radioiodine and radiocesium are very
important from the viewpoint of environmental
safety. Shortly after the accident, high I-131
concentrations were observed in leafy vegetables
in Fukushima and in the surrounding Prefectures.
The levels of I-131 in vegetables decreased
markedly with time due to its short half-life (8days), as a consequence more attention has been
paid to the longer-lived radiocaesium (Cs-134
and Cs-137) deposited in soil. Results of themonitoring for agricultural crops harvested
during spring to autumn in 2011 showed thatmost of crops had not exceeded the provisionalguideline for radiocaesium of 500 Bq/kg for 2011.
(After 2012 the guideline was changed to 100
Bq/kg.) However, values higher than theguideline were found in some crops such asbamboo shoots, some fruits (e.g. Japanese citron‘Yuzu’) and new tealeaves. These high values
could not be explained solely by root-uptake,which was previously assumed to be the primarypathway.
In this study we analyzed radiocesium
concentrations in a variety of crops and studied
the mechanisms of radiocesium transfer. Apartfrom radiocesium, we have studied the
distribution of I-131 (half-life: 8 days) depositedin Fukushima Prefecture. Due to the short halflife of I-131, most of it decayed away after someII. EXPERIMENTALS

III. RESULTS AND DISCUSSION

The distribution of radiocesium in an entire
tea tree (old leaves, new leaves, bark, roots andsoil) was studied and it was found that the newtealeaves that had not appeared until March 2011
also showed high values for this nuclide. It was
found that translocation pathway from thecontaminated old leaves and bark should be
important to understand the high values observedin new leaves. Higher concentrations foundin ’Yuzu’ were also explained by thetranslocation pathway. The levels in tealeavesand ‘Yuzu’ harvested in the second year
decreased significantly. High radiocesium
concentrations found in bamboo shoots should be
the effect of both translocation and root-uptake
pathways.
Soil samples that had been determined for I131 were analyzed for I-129 to estimate I-131/I129 ratio. Amounts of I-131 deposition indifferent areas were reconstructed through theanalysis of I-129 together with the obtained I131/I-129 ratio.

－ 12 －

FKO-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

States of existence of the Cesium and Silver radionuclides at the sandy beachin Iwaki city, Fukushima
Yukihiko SATOU1, Keisuke SUEKI1, Kimikazu SASA1 , Jun-ichi KITAGAWA1,2, Satoshi IKARASHI1
1

Graduate school of Pure and Applied Sciences, University of Tsukuba
Radiation Science Center, High Energy Accelerator Research Organization and J-PARC Center

2

Abstract
We have made an investigation that shows the states of existence ofradionuclides from the Fukushima Dai-ichi nuclear power plant(FDNPP) accident on the sandy beach in Iwaki city, Fukushima
Prefecture, Japan. The 137Cs and 110mAg were observed different
behavior along the depth distribution of sand layer. As a result of
the checking of the imaging plate photograph, 137Cs from the
FDNPP were attached to the granular spots. In addition, it issuggested that 110mAg and 137Cs were independent for the same layer.

relatively large amount of 137Cs. The granular radioactive
nuclides were observed, and it seems that granular spots wereconsist on 137Cs from the FDNPP resulting gamma ray
spectrometry. In Figure 1(c), shows the fraction activity of
110m
Ag and 137Cs in each sample. From the above
observational results can be shown that 137Cs and 110mAg wereindependent. In order to make clear for relationship between
137
Cs and 110mAg, additional chemical experiments required.

Keywords
110m
Ag, 137Cs, Sandy beach, Depth distribution, Particle

I.

INTRODUCTION

The Fukushima Daiichi nuclear power plant (FDNPP)
disaster occurred in March 2011, various radionuclides were
emitted from the FDNPP and deposited to a wide area of thenortheastern Japan associated with precipitation. We alreadyreported the fall out radionuclides were easily penetrated
deeper layer in the sandy beach at the Iwaki city [1].
However, the cause of such a phenomenon is not yet
understood clearly. For this reason, we have made a researchthat shows behavior and dynamics of months or longer halflife radionuclides such as 134Cs, 137Cs, and 110mAg in the
sandy beach.
II. MATERIALS AND METHODSCore soil sample (depth 30cm, D 5.0 cm) was collected at
Yotsukura district, Iwaki city (E140.993, N37.1074) on 2
June 2011. Radionuclides in the sample were measured by a
HPGe. More than one year has elapsed from the initialsample measurement, we have took the imaging plate
photographs of the layer of more had accumulated 137Cs incore sample. In addition, include soil sample of 110mAg was
divided into 7 samples. Further were these samples measured
radionuclides by using a HPGe detector.
III. RESULTS AND DISCUSSION
Figure 1(a) shows the depth distribution of radionuclides
from the FDNPP. 137Cs, 129mTe, and 131I were distributed
broadly. On the other hand, 110mAg are predominantly
confined in the 5-6 cm layer from top. Figure 1(b) shows
imaging plate (IP) photograph of the sample containing a

Figure 1 (a) Depth distribution of radioactivity inventories in the sandy beachcore sample, (b) Imaging plate photograph in layer 4 from top level,(c) Fraction activity of 7 samples. Fraction activities are expressed as apercentage of the total activity (%)

REFERENCES[1]－ 13 －

Satou, Y., et al., J. Rad. Nucl. Sci. 12 Suppl. 116, 2011(Japanese)

FKO-06

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Vertical transport of FNPP1-derived radiocesium by settling particles in the Western
North Pacific
Makio C. Honda1, Hajime Kawakami1, Shuichi Watanabe1, Toshiro Saino1, Seiya Nagao2,
Ken Buesseler3, Chris German3, Steven Manganini3
1

Japan Agency for Marine-Earth Science and Technology 2Kanazawa University 3Woods Hole Oceanographic Institution
Keywords – FNPP1, radiocesium, Western North Pacific, settling particle, sediment trap

Introduction
On March 2011, the 2011 Tohoku-Oki Earthquake occurred.
This earthquake and the tsunami seriously damaged the
Fukushima Daiichi Nuclear Power Plant (FNPP1). As a result,large quantities of radionuclides were emitted. About one monthafter the FNPP1 accident, FNPP1-derived radiocesium wasdispersed to broad area in the Western North Pacific (WNP).
Based on mathematical simulation, it was suspected thatradiocesium detected in the WNP originated from not only
contaminated water directly discharged, but also eolian input(Honda et al., 2012). It is well known that biogenic and lithogenic
materials in the surface ocean are quickly transported to the oceaninterior by settling particles. At the time of the FNPP1 accident,
settling particles’ collectors (sediment traps) had already been
deployed at time-series stations in the WNP. We measured
radiocesium (134Cs, 137Cs) in settling particles collected by
sediment traps and verified how FNPP1-derived radiocesium wastransported to the ocean interior.
Methods
Sediment traps were deployed at 500 m and 4810 m oftime-series stations K2 (47°N/160°E, ca. 2000 km from FNPP1)
and S1 (30°N/145°N, ca. 1000 km from FNPP1) in July 2010and successfully collected settling particles before and after the
FNPP1 accident. In July 2011, 4 months after the accident,
sediment traps were also deployed at 500 m and 1000 m of F1(36-30°N/141-30°E, ca. 100 km from FNPP1) and started
collection of settling particles. After recovery, collected samples <1 mm were dried and pulverized. Specific activities (activities) of134
Cs and 137Cs were measured by gamma spectrometry with a
Ge detector.
Results and discussion
At stations K2 and S1, radiocesium was detected at 4810 m bymiddle April 2011 (Fig. 1 a, b). The sinking velocity was estimatedto be 8 – 36 m day-1 between surface and 500 m, and > 180 m
day-1 between 500 m and 4810 m. At 4810 m of K2, maximum134
Cs flux and activity were observed in June 2011 and, thereafter,134
Cs flux and activity decreased gradually. At 4810 m of S1, thehighest 134Cs flux was observed in early May 2011. It was notablethat the maximum 134Cs activity and relatively higher flux was
observed in late November and early December 2011. Total 137Cs
flux (137Cs inventory) at 4810 m was about 3 Bq m-2 at K2 and 2
Bq m-2 at S1. These corresponded to about 0.7% and 0.3% of 137Cs

eolian input to respective stations by one month after FNPP1
accident. The 134Cs was detected, at the earliest, by April 2012 at
K2 and by February 2012 at S1. At 500 m of F1, the highest 134Cs
activity was observed in late August 2011 and 134Cs activity
decreased thereafter (Fig. 1 c). However 134Cs activity temporary
increased in March 2012 and 134Cs flux was the maximum at thattime during observation. 137Cs inventory at 500 m of F1 duringobservation was about 60 Bq m-2 and 20 – 30 times higher thanthat at 4810 m of K2 and S1. It might be attributed to much higher
137
Cs inventory to surface around F1 (30000 – 40000 Bq m-2 byJune 2011. Buesseler et al., 2011). In addition, lithogenic materials
were pre-dominant in settling particle collected at F1 whilebiogenic materials such as biogenic opal and CaCO3 werepre-dominant at K2 and S1. Station F1 was located on thecontinental shelf slope and the “nepheloid layer” was observed
around 600 m depth and near seafloor. Lateral transport ofradiologically contaminated clay minerals from/near the land
might also contribute the higher 137Cs inventory at sediment trap
depth at F1.
References
Buesseler et al. (2011) Proc. Natl. Acad. Sci. 109, 5984-5988.
Honda et al. (2012) Geochem. J. 46, e1-e9.
(a)

(b)

(c)

Fig.1 134Cs fluxes (bar graphs) and activities (line graphs) at (a) 4810 m ofK2, (b) 4810 m of S1 and (c) 500 m of F1 (after Honda et al. submitted to
Biogeosciences). Note that vertical scale is different between figures.

－ 14 －

FKO-07

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Strontium-90 determination in air dust filter using solid phase extraction after theaccident of FD-NPS
ZiJian Zhang1, Shunsuke Kakitani1, Kazuhiko Ninomiya1, Naruto Takahashi1, Yoshiaki Yamaguchi2,
Takashi Yoshimura2, Takashi Saito3, Kazuyuki Kita4, Haruo Tsruta5, Shogo Higaki6, Atsushi
Shinohara1
1

Graduate School of Science, Osaka University, 2 Radioisotope Research Center, Osaka University,
Faculty of Comprehensive Human Sciences, Shokei Gakuin University, 4 College of Science, Ibaraki University,
5
Atmosphere and Ocean Research Institute, the University of Tokyo, 6Radio Isotope Center, the University of Tokyo
3

Abstract - Radioactivities of Sr-90 in air-dust filters collected in
Hitachi, Kawasaki and Toyonaka were determined using solidstate extraction method and low background beta-ray counting
system. In Hitachi, though the Sr-90 activity concentration was
decreased with time, the activity rates of Sr-90/Cs-137 kept about
10-3 order. This fact suggests that Sr-90 transportation behavior
in the atmosphere is similar to that of Cs-137 during the time ofsample collection.
Key word – Sr-90, solid-phase extraction, air dustI.

INTRODUCTION

On 12th March, 2011, a large amount of radioactive
nuclides have been released into the environment by the
nuclear accident at the Fukushima Daiichi Nuclear Power
Station. Measurement about radioactive nuclides will give
us much information about the accident circumstance.
There are many measurement results of I-131, Cs-134, Cs137 in natural samples. However, for other nuclides, suchas the pure beta emitter nuclide Sr-90 has not beenmeasurement sufficiently. Strontium-90 is considered oneof the harmful radioactive nuclides. Therefore,
measurement of Sr-90 in air dust is important forcalculating exposure. We developed a new simple andquick strontium isolation technique using solid phaseextraction and determined Sr-90 activities in air dust.

III.

RESULTSWe measured Sr-90 in air dust samples of Hitachi,
Kawasaki and Toyonaka City. We analyzed some air dust
samples for Sr-90 detection that had high Cs-137 activity,and strontium isolation with solid phase extraction was
performed. The measurement result of Hitachi is shown in
Table.1 and Fig.1. Without Pb separation, we can easily
observe the Cherenkov light form Bi-210, that is daughter
nuclide of Pb-210. However, there is a ND(not detectable)
result and it indicates that the measurement sample wassufficiently Pb-210. In Hitachi, the Sr-90 activity
concentration in air was decreased with time. All of theratios of Sr-90/Cs-137 were about 10-3. It is possible thatafter April, Sr-90 has been the same behavior of Cs-137.
Strontium-90 was also determined in samples of Kawasaki
and Osaka. In the presentation, we will discuss about theresults of Sr-90 in air dust and compare with the results byother group about Sr-90 in soil and fallout.
Table.1 Sr-90 detection results of Hitachi

II. EXPERIMENTAL
In this study, we used the 3M EmporeTM Strontium Rad
Disk to extract strontium ion. This filter can collect mg
order of Sr2+ ion efficiently. However, it is known that thisfiler also catches Pb2+[1]. Natural radioactive nuclide Pb210 seriously will be interferences for Sr identification inbeta ray counting. In this study, cation exchange withEDTA solution was adopted for Sr purification after solid
phase extraction. We made test experiments withradioactive Sr tracer and obtained high chemical yield as
90 %. The time for chemical operation of this method was
3-4 hours. The activity of Sr-90 was determined by thegrowth curve in sequential measurements of Cherenkov
light from Y-90 by the low background liquid scintillation
counter. Using Sr-90 standard solution, we determined that
Cherenkov light detection efficiency for Y-90 68.7% anddetection limit of Sr-90 is 0.004 Bq in this system.

Fig.1 The time dependence change of Sr-90 and Cs-137 in Hitachi[1]L.L.Smith and K.A.Orlandini. Radiochimica Acta 73,165-170(1996)－ 15 －

FKO-08

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Dosimetric Implications of the Fukushima Release for Pacific albacore in the
Northern California Current
Delvan R. Neville1, A. Jason Phillips1, Kathryn A. Higley1
1

Oregon State University, Corvallis, OR; nevilled@onid.orst.edu

Abstract – Using activity concentrations in Pacific albacore atboth pre-Fukushima and post-Fukushima levels, the averageannual whole body internal dose for these nekton is estimated.
MCNP & voxelized phantoms applied for determination ofabsorbed fraction. Analyzed tissues include both edible tissue,
viscera and other non-edible tissues.
Keywords – Cs-137, Cs-134, Pacific albacore, radioecology,
FukushimaI.

INTRODUCTION

An unfortunate result of the already devastating
earthquake and tsunami on March 11, 2011 was a release ofradionuclides from the Fukushima Daichi power generating
station. It will be several years before this release into theNorth Pacific Gyre will be carried, at diluted and decayed
activity concentrations, to the West Coast of North
America[1]. During the interim, migratory species may bepassing through the extent of this liquid plume, and feeding
throughout that range. This work intends to address thedosimetric implications for migratory Pacific albacore,
Thunnus alalunga.

elsewhere in the animal, to allow utilizing this existing
body of work for animal dosimetric estimations
B. Whole Body Dosimetry
Absorbed fractions were calculated for activity indifferent body compartments using MCNP and a voxelized
model developed from CT & MRI of a pelagic fish.
Activity concentrations for Cs-134 and Cs-137 measured in
Pacific albacore were then used to calculate annual internal
dose to the animal for both those that exhibited trace
concentrations of Fukushima effluents and those thatremained at pre-Fukushima concentrations. The internaland external dose from naturally occurring K-40 is also
provided for comparison. Additionally, dose estimatesusing the prior "edible-only" paradigm are presented.
[1]

A. State of existing body of knowledge
Historically, reported activity concentrations in the
United States have almost exclusively sampled the edible
tissues. In the case of albacore, this excludes not just skin,bone and viscera, but the fatty red muscle tissue along the
belly. These were conducted at national labs, with theprimary goal of ensuring Cold War-era radionuclides
releases were not affecting food quality.
However, muscle tissue is one of the most radioresistant tissues in the body. One goal of this work is toaddress the dosimetric impact to biota by determining
concentrations for the whole body, rather than simply inedible tissue.
There is a large body of work reporting concentration
ratios for nekton in the Pacific, which is the ratio of theactivity concentration in the tissue over the activity
concentration in the water, by mass. These concentration
ratios vary wildly, as they depend on the assumption thatthe animal sampled is in equilibrium with activity in thesurrounding environment, including the complicated food
web transfer through other species. Nonetheless, they arestill widely used for determinations of the expectedconcentrations after a release until a more thoroughdetermination may be made. Another goal of this work is
to relate edible muscle concentrations to concentrations－ 16 －

Behrens, E., Schwarzkopf, F.U., Lubbecke, J.F. & Boning, C.W.
2012. Model simulations on the long-term dispersal of 137Cs
released into the Pacific Ocean off Fukushima. Environmental
Research Letters 7:1-10.

API-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

ANNRI at J-PARC

1

Hideo Harada1(on behalf of ANNRI project)

Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

The Accurate Neutron-Nucleus Reaction measurement
Instrument (ANNRI) has been installed at the beam line no.
4 of the Material and Life science experimental Facility(MLF) in the Japan Proton Accelerator Research Complex(J-PARC). It was constructed in order to supply accurate
neutron capture cross sections of minor actinides andfission products required for developing innovative nuclear
systems [1].

astrophysics, nuclear data, and trace-element analysis using
pulsed neutrons” has also been started since April 2012.
The ANNRI is a unique instrument for high-resolution
neutron-capture �-ray spectroscopy by utilizing the world’s
strongest pulsed-neutron beam as shown in Fig. 3 and thehigh-efficiency Ge and NaI spectrometers. The ANNRI is
expected to be usefully utilized not only for nuclear datameasurements for the study of innovative nuclear systems,
but also for the study of nuclear astrophysics [9-10] and forthe analyses of trace elements [11-12].

Fig. 1 A bird’s-eye view of the layout of J-PARC/MLF
Fig. 3 Comparison of neutron flux of J-PARC/MLF/ANNRI with CERN/n_TOF andLANL/LANCE/DANCE
Current status and recent topics of the ANNRI will be
reviewed in this symposium.

References[1]Fig. 2 Photo of ANNRI (outside) and Ge spectrometer
The ANNRI project team has developed the neutron
beam line optimized for neutron time-of-flight experiments[2, 3], the advanced Ge [4] and NaI [5] spectrometers for
detecting prompt � rays, and the measurement method ofneutron capture cross sections. The team has started themeasurements of neutron capture cross sections of minor
actinides and fission products since 2009, and successfully
obtained the neutron capture cross sections of 244, 246Cm and237
Np [6-8].
At the time of the Great East Japan Earthquake on March
11, 2011, the ANNRI suffered serious damages. However,
the team members of BL04 immediately recovered fromthe situation. The recovered ANNRI has been used again
for the user program since Feb. 2012. The project researchusing the ANNRI entitled as “Research on nuclear

OECD/NEA WPEC Subgroup 26 Report, “Uncertainty and Target
Accuracy Assessment for Innovative Systems Using Recent
Covariance Data Evaluations”, 2008.
[2] K. Kino, et al., Nucl. Instru. Method. A 626-627, 58 (2011).
[3] Y. Kiyanagi, J. Korean Phys. Soc. 59, 779 (2011).
[4] H. Harada, et al., J. Korean Phys. Soc. 59, 1547 (2011).
[5] T. Ohsaki et al., Nucl. Instru. Method. A 425, 302 (1999).
[6] S. Goko, et al., J. Nucl. Sci. Technol. 47, 1097 (2010).
[7] A. Kimura, et al., J. Nucl. Sci. Technol. 49, [7], 708 (2012).
[8] K. Hirose et al., J. Nucl. Sci. Technol. 50, [2], 188-200 (2013).
[9] T. Hayakawa et al., Astrophysical Journal, 707, 859 (2009).
[10] F. Kappeler et al., Reviews of Modern Physics, 83, 157 (2011).
[11] M. Islam, et al., Analytical Chemistry, 83, 7486 (2011).
[12] Y. Toh et al., Applied Radiation and Isotopes 70, 984 (2012).

－ 17 －

API-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Nanomaterial and nanotechnology in nuclear energy chemistry
Yu-Liang Zhao1,2, Wei-Qun Shi1, Li-YongYuan1, Zhi-Fang Chai1
1

Nuclear Energy Chemistry Group, CAS Key Laboratory of Nuclear Analytical Techniques, and
CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety,
Institute of High Energy Physics, Chinese Academy of Sciences (CAS), Beijing 100049, China
2
National Center for Nanosciences and Technology, Beijing 100190, China

Keywords: Nanomaterial, Nanotechnology,
Nuclear energy chemistryWith the increasing human demands for energy,
applications of newly emerging technology for safer andcheaper energy become new challenges and new front inenergy sciences. Major nuclear countries in the world haveinitiated forward-looking researches toward futureadvanced nuclear energy systems, in which nanomaterials
and nanotechnologies play important roles. Nanomaterials
and nanotechnology show some exciting application
potentials in future nuclear energy systems. In the talk, wewill discuss the recent research progress in nanomaterials
and nanotechnologies associated with advanced nuclear
fuel fabrication, spent nuclear fuel reprocessing, nuclear
waste disposal and nuclear environmental remediation, etc.
We will focus mostly on chemical aspects of above
processes. The talk will highlight research activities in ourLaboratory and China, and future challenges andopportunities of nanomaterials and nanotechnologies innuclear energy chemistry.
For example, graphene nanomaterials has been
demonstrated to effectively loaded ions, molecules, andatomic clusters onto their basal plane through weakinteractions such as van der Waal’s forces, electrostatic�������������� ���� �-�� ���������� ���� ��� ����������� �������
noncovalent interactions, decorated graphene can be highly
stable in both acidic and basic media. Carbon
nanomaterials have great potentials in areas whose issues
are difficultly solved by conventional methods or bulk
materials. We may use nanoparticles-loading graphene
layered materials (like a 3D network material) as fillers of
separation columns for nuclear fuel cycling and radioactive
wastes treatments. The enhanced performances make thegraphene material be able to selectively adsorb heavy
metals (e.g., lanthanides or actinide) with a super loadageand an in-situ rebirth capacity, which may bring
revolutionary progress into the nuclear fuel cycling
industries.
To integrate the advance of nanomaterials and theneed of nuclear energy production is a challenge in nuclear
energy chemistry. For example, a variety of tetradentate
ligands,
6,6`-bis(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2`bipyridines (BTBPs), have been experimentally proved as
effective ligands for selective extraction of Am(III) over
Eu(III). Recently, in exploring the origin of their selectivity,
we found that in 1:1 (metal:ligand) type complexes
substitution of electron-donating groups to the BTBP
molecule can enhance its coordination ability and thus theenergetic stability of the formed Am(III) and Eu(III)complexes in the gas phase. Eu(III) can coordinate to the
BTBPs with higher stability in energy than Am(III), no

matter whether there are nitrate ions in the inner-spherecomplexes. The presence of nitrate ions leads to formationof the probable Am(III) and Eu(III) complexes,
M(NO3)3(H2O)n (M = Am, Eu), in nitric acid solutions. It
has been found that the changes of Gibbs free energy play
an important role for Am(III)/Eu(III) separation. In fact, theweaker complexing ability of Am(III) with nitrate ions andwater molecules makes the decomposition ofAm(NO3)3(H2O)4 more favorable in energy, which may
thus increase the possibility of formation ofAm(BTBPs)(NO3)3. These findings may shed light on thedesign of novel extractants for Am(III)/Eu(III) separation.
However, the single atom lay of the graphene
nanomaterials can first use as novel substrate and then as
novel designs of a complex-based the extractant-platform
for Am(III)/Eu(III) separation, and for selective separationsof other Ln and Ac ions, or selective separations of ionsamong Ac elements.

Figure 1, The superior performance of graphene-based materials.
Basal plane functionalization could lead to graphene-based
integrated function nanomaterials. Regiofunctionalization ofgraphene towards multifunctional and all-purpose devices. In theexample, different functional groups for Am(III)/Eu(III)separation, or for separations of other Ln and Ac ions, or selective
separations of ions among Ac elements, can be bonded in turn to
the graphene substrate (Copyright @ RSC)3.

References
1. W. Q Shi, L. Y Yuan, Z. J Li, J. H Lan, Y. L Zhao, Z. F
2.
3.
4.
5.

－ 18 －

Chai. Radiochim Acta. 2012, 100: 727.
L. Y Yuan, Y. L Liu, W. Q Shi, Z. Li, J. H Lan, Y. X Feng,
Y. L Zhao, Z. F Chai, J. Mater. Chem. 2012, 22: 17019.
L. Yan, Y. B Zheng, F. Zhao, S. J Li, X. F Gao, B. Q Xu, P.
Weiss, Y. L. Zhao, Chem. Soc. Rev., 2012, 41: 97-114.
J.H Lan, W.Q Shi, L.Y Yuan, Y.L Zhao, J Li, Z.F Chai,
Inorg. Chem., 2012, DOI: org/10.1021/ic200078j.
Y. L Zhao, C. L Bai, et al, Progress of Nanosciences in
China, Front. Phys. DOI 10.1007/s11467-013-0324-x, 1-32,
2013.

APO-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Development of Real-Time Radioisotope Imaging System to Study Plant Nutrition
Tomoko M. Nakanishi1, Natsuko I. Kobayashi1, Atsushi Hirose1, Takayuki Saito1, Ryohei Sugita1,
Hisashi Suzuki2, Ren Iwata3, Keitaro Tanoi1
1

Graduate School of Agricultural and Life Sciences, The University of Tokyo
National Institute of Radiological Sciences3
Cyclotron and Radioisotope Center, Tohoku University
2

Abstract – We have been developing two types of real-time radioisotope imaging systems, one for macroscopic
imaging targeting the whole plant itself and the otherfor microscopic imaging under modified fulorescent
microscope to get both fluorescent and radioisotope
images (Hirose et al. 2012; Kanno et al. 2012;
Kobayashi et al. 2012). Now we can visualize the realtime movement of C-14, Na-22, Mg-28, P-32, S-35, K42, Ca-45, Rb-86 or Cs-137, from root kept in dark to
up-ground part where light was irradiated. There are awide range of application of this imaging , such as tomeasure the uptake manner in root, speed or
distribution or translocation manner, as well as
distribution, translocation or deposition of the nutrient
element in upground part. Here we present some
representative real-time images in plants.

Fig.1b micoscopic real-time RI imaging system
microscopic images. As an example, Mg-28, P-32 andK-42 uptake manners were shown as successive images.

Keywords – real-time radioisotope imaging system, plant nutrition,
C-14, Na-22, Mg-28, P-32, S-35, K-42, Ca-45, Rb-86 or Cs-137

Plants Prepared for Imaging
Rice (Oryza sativa. L. cv. Nipponbare) seedlings
and Arabidopsis thaliana seedlings were grown forabout 12 days and 40days, respectively, in culture
solution. Then the plant was placed in front of the fiber
optic plate where CsI scintilator was deposited. Thenthe radioisotope (RI) was supplied to the water culture
solution and the RI image from roots ro up-ground partwas monitored by highly sensitive CCD camera (Fig.1).

Fig.1a macoscopic real-time RI imaging system

Conclusion
The real-time imaging system we developed showed
the uptake manner of the wide range of the nutrient
elements. There are two great advantages of RI imaging,allows imaging under light and enables numericaltreatment of the image, since the image is based onradiation count. The imaging system for C-14 labeled
carbon dioxide gas is now developing to study real-time
photosynthesis.
References

The real-time images
The real-time images of absorption manner using
varuious radioisotopes allows to calculate uptake
amount and transfer rate both in macroscopic andKanno, S.et al. Philosophical Transactions of The Royal
Society B 367: 1501 (2012)
Kobayashi, I.N. et al. Radioisotopes 61:121 (2012)
Hirose, A. et al. J. Radioanal. Nucl. Chem.,in press.

－ 19 －APO-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

MCNP study on the development of industrial SPECT in terms of a radiation
measurement design and void influence in multiphase media
Sung-Hee Jung1, Jang-Guen Park1, Jong-Bum Kim1, Jin-Ho Moon1, Chan-Hyeong Kim2

1
2

Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon, 305-353, Korea
Dept. of Nuclear Engineering, Hanyang Univ., 17 Haengdang-dong, Seongdong-gu, Seoul, 133-791, Korea

Abstract – There have been extensive studies on the developmentof SPECT (Single Photon Emission Computer Tomography) for
industrial applications. Owing to its intrinsic limitation originatedfrom the dimensions and density of objects in industrial processunits, it has been a challenging issue to get a spatial resolution
good enough to draw informative data from it. This study
demonstrates the feasibility of a radiation measurement array
proposed for a greater region of interest resulting in better spatial
image resolution. Considering that the industrial process units
are designed to mix up different materials in different phases, theinfluence of a void ratio into the image quality of the industrial
SPECT was investigated with the Monte Carlo code for a
Liquid/Vapor phase system.
Keywords –Industrial SPECT, Radioisotope tracer, Multiphaseflow investigation, Gamma radiation collimation, MCNPXI.

INTRODUCTION

Industrial image diagnosis technology based on the
medical SPECT principle has been studied at the Korea
Atomic Energy Research Institute [1]. The technology
visualizes the distribution of process media as a function oftime at a certain cross-section of the object underinvestigation [2]. The system was redesigned in a diverging
collimator configuration substituting the conventional
parallel configuration.

Fig. 1. Radiation detection geometry for MCNP simulation withconventional (left) and proposed (right) collimator arrays of industrial
SPECT.

II. METHODS AND RESULTS
A. Redesign of radiation collimator configuration
The configurations in Fig. 1 show the conventional andnewly proposed radiation measurement arrays for an
MCNPX simulation. Besides the diverging orientation ofcollimation, the proposed array is identical to theconventional one. The cylindrical vessel is 40 cm indiameter and contains water. Radiation probes are NaI(Tl)with 1.3 cm in diameter and 2.5 cm in length. The
radioisotope is 68Ga with 511 keV of gamma radiation andthe energy window for measurement was set to 10% of it,
460-562 keV. The radioisotope was positioned at fivedifferent points, 0, 4, 8, 12, and 16 cm from the center toevaluate the precision of the reconstructed images atvarious locations.

Fig. 2. Reconstructed images of the radioisotope with the geometry ofdiverging configuration.

B. Influence of void fraction to image quality
Homogeneous void formation at the same layer with the
6 detectors of industrial SPECT was modeled with MCNP
code.
Table 1. NRMSE for quantitative comparison of image quality
Source68
Ga(511 keV)
137
Cs(662 keV)Counting
Method
Gross
Peak
Gross
Peak

5%
1.93
1.69
1.88
1.42

Void volume fraction
10%
20%
2.33
3.67
2.02
2.60
2.19
3.59
1.99
2.52

III. CONCLUSION
The study showed that the diverging collimatordemonstrates a better image quality because the collimators
cover a wider angle being able to reconstruct the location ofradioisotope more precisely compared to a parallelgeometry.
Void formation in the vessel hardly affects the image
quality in industrial SPECT. There are two reasons forthese results: (1) the homogeneous void distribution in thevessel uniformly influences the signals of every detector,and (2) there are few gamma interactions in the void
because the density of the void is as low as 0.001205 g/cm3.
ACKNOWLEDGEMENT
This work was carried out under the Nuclear R&D
Program of the Korean Government.
REFERENCES[1][2]－ 20 －

J. G. Park, et. al., Development of an Industrial SPECT to Study
Dynamic Behavior of Plant Process Flow, Trans. Korean Nucl. Soc.,
Autumn Meeting, Pyeongchang, Korea, Oct. 30, 2008
S. Legoupil, G. Pascal, D. Chambellan, and D. Bloyet, Tomographfor Industrial Flow Visualization Using Radioactive Tracers, IEEE
Transactions on Nuclear Science, Vo.43, No.2, pp.751, 1996.

APO-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Tracking the Deportment of Uranium Chain Daughters during Alkaline Leachingof an Australian Monazite
1

Mellodee Anvia1,2 and Susan A. Brown1

ANSTO Minerals, Locked Bag 2001, Kirrawee DC, NSW 2232, Australia
2
School of Chemistry, The University of Sydney, NSW 2006, Australia

Monazite contains between 50–68% rare earths and is thesecond most abundant source of the rare earth elements
after bastnasite [1, 2]. Monazite may contain up to 20%
thorium and 0.3% uranium and so is an example of anaturally occurring radioactive material (NORM). The
deportment of radionuclides from NORM is of particularconcern during rare earth extraction [3]. Standard methods
for measuring activity concentrations in order to track
radionuclide deportment using techniques such as gamma,alpha and beta spectrometry have in general proved to be
unsuccessful. In this work, we have developed an analyticalmethod to track the deportment of 238U and 235U daughters
during the alkaline leaching of an Australian monazite
concentrate. During the alkaline leaching stage it was foundthat uranium isotopes (238U and 235U) and 210Pb reported toboth the trisodium phosphate liquor (leach liquor) and therare earth hydroxide residue; while 230Th, 226Ra, 210Po(238U) and 231Pa and 227Ac (235U) reported to the rare earthhydroxide. Following hydrochloric acid leaching of the rareearth hydroxide, the major contaminants found in the leach
liquor included 210Pb, 226Ra and 210Po. These contaminantradionuclides were later removed from the hydrochloric
acid leach liquor by a ‘deactivation’ and ‘lead elimination’
step, which is commonly used in industry. The results
indicated that removal for most radionuclides was greaterthan 90%.
[1] Gupta, C. K.; Krishnamurthy, N. Extractive Metallurgy of Rare
Earths; CRC Press Florida, 2005.
[2] Bashir, V. S. Mater. Sci. Forum. 1988, 30, 33.
[3] International Atomic Energy Agency. Radiation Protection and
NORM Residue Management in the Production of Rare Earths fromThorium Containing Minerals, Safety Reports Series No.68, IAEA Vienna,2011.

－ 21 －

NCO-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Nuclear chemistry and radiochemistry studies at IMP
Z. Qin1*, F.-L. Fan1, Y. Wang1, F.-Y. Fan1, X.-L. Wu1, J. Bai1, X.-J. Yin1, L.-L. Tian1,
W. Tian1 , Z. Li1, C.-M. Tan1,
1

Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000, China

most commonly used PET radiopharmaceutical is 2[18F] fluoro-2-deoxy-D-glucose ([18F]-FDG). 10 MeV
proton mini-medical cyclotron are under construction
at IMP, [18F]-FDG system will be developed byourselves. The water target system was ready to testwith proton beam.

This paper will review the relative research of
nuclear chemistry of IMP.
(1) Synthesis and chemical properties of thesuperheavy elements
The study of the chemistry of transactinide
elements (Z �� ����� ��� �� ������ ��� ������ ��������� ���
current nuclear chemistry research. In IMP, two newtransactinide isotopes of 259Db and 265Bh have been
produced successfully via the reactions of 241Am(22Ne, 4n)259Db and 243Am (26Mg, 4n)265Bh,
respectively[1,2]. In order to study the gas phasechemical behaviour of transactinide elements, an online isothermal chromatography apparatus has been
established at IMP [3]. The isothermal gas
chromatographic behaviour of the group 5 elements
Nb, Ta and Db was investigated in a brominating
atmosphere using the OLGA technique [4]. The
nuclide 258Db was synthesized successfully by the
nuclear reaction 243Am (20Ne, 5n)258Db registering
258
Db – 254��� �-decay chains. It was found that Dbforms a very volatile compound, most likely thepentabromide, being more volatile than similar
compounds formed under identical conditions with
Nb and Ta, respectively. This observation is in
disagreement
withprevious
experimental
investigations of the same compound [5] but inagreement with theoretical prediction [6].
At the same time, metal carbonyl complexes wereused for studying the gas-phase chemical behavior of
Mo and W isotopes with an on-line low temperature
isothermal gas chromatography apparatus. The result
showed that short-lived isotopes of Mo and W canform carbonyl complexes which are very volatile andinteract most likely in physisorption processes. The
first Sg(CO)6 experiment have been completed at
RIKEN under a large scale international collaboration
between GSI/Maunz, RIKEN, JAEA, LBNL and IMP.

The liquid-liquid extraction behavior of short-lived
molybdenum and tungsten isotopes from HCl and
HNO3 as well as HF/HNO3 acid media was alsostudied using the �-benzoinoxime/chloroform system[7].

(3) Extraction of uranium from the salt-lake
Many materials were developed and as theabsorbent to remove uranium from salt lake.
Adsorption of uranium from aqueous solution onto theyeast cells (Rhodotorula glutinis), magneticallymodified yeast cells, magnetic Fe3O4@SiO2
composite particles and magnesium silicate hollow
spheres was investigated in a batch system [8,9]. The
result showed that these absorbents exhibit muchhigher sorption capability for uranium.
At the present, the fabric containing amidoximegroup as the absorbent for uranium has beensynthesized by graft acryloonitrile (AN) onto
polypropylene (PP) and amidoximation after electrobeam (EB) irradiation. The detail experiment is still
underway.
(4) Transmutation chemistry
In order to transmutation of long-lived fission
products and minor-actinides in ADS, the production ofminor-actinide containing sphere-pac fuel is underdevelopment in collaboration with the international anddomestic scientists.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

(2) Synthesis of radiopharmaceutical
Positron emission tomography (PET) has become apowerful and widely used imaging technology. The－ 22 －

Gan, Z. G. Qin, Z. Fan, H. M. et al., European Physical Journal A10,
21, 2001.
Gan, Z. G. Guo, J. S. Wu, X. L. et al., Euro. Phys. J. A20,385, 2004
Lin, M. S., Qin, Z., Lei, F. A., et al. Radiochimica Acta 98, 321-326
2010.
Qin, Z., Lin, M. S., Fan, F.L., et al., Radiochimica Acta. 100:285289, 2012.
Gäggeler, H. W., Jost, D. T., Kovacs, J., et al. Radiochim. Acta 57,
93, 1992.
Pershina, V., Sepp, W.-D., Fricke, B., et al. J. Chem.Phys. 97, (2):1116, 1992.
Fan, F. L. Lei, F. A. Zhang, L. N. et al. Radiochimica Acta.
97:297-302. 2009.
Bai, J., Wu X. L., Fan, F. L. et al., Enzyme and Microbial
Technology, 51:382, 2012
Fan, F. L., Qin Z., Bai J., et al. Journal of Environmental
Radioactivity, 106: 40-46, 2012

NCO-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Preparation of Low Valent Technetium Metal-metal Bonded Species via
Solvothermal Reduction of Pertechnetate Salts
1

W.M. Kerlin1, F. Poineau1, P.M. Forster1, A.P. Sattelberger2, K.R. Czerwinski1

Department of Chemistry, Radiochemistry Program, University of Nevada Las Vegas, Las Vegas, NV 89154, USA
2
Energy Engineering and Systems Analysis Directorate, Argonne National Laboratory, Argonne, IL 60439, USA

Abstract – A new one-step solvothermal synthesis route for
reduction of pertechnetate salts to low valent technetium metalmetal bonded dimers will be presented. The reaction of potassium
pertechnetate with glacial acetic acid plus either halo acids or halo
salts under in-situ hydrogen production by sodium borohydride atvarious temperatures yields multiple products consisting oftetraacetate Tc-Tc (II,III) and Tc-Tc (III,III) paddle wheel dimers.
Solid products isolated and analyzed via Single Crystal X-ray
Diffraction (SC-XRD) in these reactions consist of polymeric chainsTc2+5 core: Tc2��-O2CCH3)4(O2CCH3), Tc2��-O2CCH3)4Cl, Tc2��O2CCH3)4Br, Tc2��-O2CCH3)4I, molecular Tc2+5 core: Tc2(�O2CCH3)3Cl2(H2O)2·H2O, K[Tc2��-O2CCH3)4Br2], and molecular
Tc2+6 core: Tc2��-O2CCH3)4Cl2, Tc2��-O2CCH3)4Br2. Of thecompounds listed, four are newly discovered using the one-step
technique and two more additions to crystal database. Additional
spectroscopic (X-ray Absorbance Fine Structure, UV-Vis, and FTIR) characterization of the new compounds will be shown and used
to propose a mechanism. Analysis of the mother liquor of eachreaction by UV-Vis and formation of crystals over time due tooxidation of solutions affords a possible insight into mechanism of
the Tc2+5 to Tc2+6 core formation. The oxidation states of Tc-Tc
dimers formed is also dependent on temperature and pH of thestarting solutions and will be explained in extensive detail. These
one step reactions of reducing Tc(VII) to low valent technetium
provides high yield intermediates for potential waste forms, use innuclear fuel cycle separations, and radiopharmaceuticals.
Keywords – technetium carboxylates; metal-metal bonds; metalhalogen bond; hydro/solvo-thermal reactions; polymers

I.

II. EXPERIMENTAL
A. Synthesis of Tc2+5 and Tc2+6 cores
Addition of 6.0 mL of glacial acetic acid into a small glassvial containing 0.25 mmol potassium pertechnetate, and 4
molar equivalent of desired halogen salt (such as sodium
iodide) or haloacid (such as hydrobromic acid) is placed intoa 23 mL Teflon lined Parr 4749 autoclave vessel containing
320 mg of sodium borohydride and 200 uL of DI water. The
autoclave system is sealed and placed in a oven at 210 °C for
72 hrs, Equations 1-3. Figure 1, shows single-crystals of thepolymeric chain Tc2��-O2CCH3)4I and molecular view ofTc2��-O2CCH3)4Br2 .
2 KTcO4 + 4 CH3COOH + NaI + ex. NaBH4 ���Tc2(�-O2CCH3)4I(1)

2 KTcO4 + 4 CH3COOH + 2 HBr + ex. NaBH4 �
Tc2��-O2CCH3)4Br2 (2)2 KTcO4 + 5 CH3COOH + ex. NaBH4 ����2��-O2CCH3)4(O2CCH3) (3)Bond lengths of Tc2+5 cores are shorter than the Tc2+6
cores and the effects of the bonding halogens will be
discussed. These compounds are being considered potential
waste forms sue to insolubility in all organic solvents andacidic solutions.

INTRODUCTION

Transition metals of groups six through nine exhibit
unique direct multiple metal-metal bonding cores. The
isotope 99��� ��- = 293 keV) is a group seven radioactive
element that is of concern in radioactive waste due to thelong-lived half-life (2.13 x105 years). Exploring andunderstanding the role of metal-metal bonding in Tc canprovide routes for the development of novel and stable waste
forms. The fundamental chemistry of low valent Tc is notwell explored compared to the surrounding elements Mo, Re,
and Ru. Currently over 200 compounds containing the Re2+n(n = 4, 5, 6) cores are known, whereas less than 30
compounds with Tc2+n (n = 4, 5, 6) core exist.1 One example
of a Tc2+6 core is Tc2(O2CCH3)4Cl2 and has been shown to bea stable starting compound for synthesis of technetium binary
halides.2,3 The reduction of pertechnate, a waste product ofspent nuclear reprocessing, to lower valent intermediates
provides potential waste forms and insight into
radiopharmaceuticals cores.

Figure 1. Ortep views of the (a) Tc2��-O2CCH3)4I, (b) Tc2��-O2CCH3)4Br2
Acknowledgement: Funding for this research was provided by a SISGR
Grant from the U.S. Department of Energy, Office of Science, Office of Basic
Energy Sciences, under Contract No. 47824B.

REFERENCES
[1]
[2]
[3]

－ 23 －

Cotton, A., C. Murillo, R. Walton.; Multiple Bonds Between Metal
Atoms, Springer, Inc.: New York, 2005, Chapter 7, p. 251-269.
Zaitseva, L. I., et al., Russ. J. Inorg. Chem. 1980, 25, 1449
Poineau, F.; et al., J. Am.Chem. Soc., 2010, 132, 15864

NCO-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The Statues of Chemical Characterization of a Spent Nuclear Fuel
Yeong-Keong Ha, Soon-Dal Park, Yang-Soon Park, Jung-Suk Kim, Kyuseok Song

Korea Atomic Energy Research Institute, 989-111 Daedeokdaero, Yuseong, Daejeon, 305-353, Korea
Abstract –The high burnup nuclear fuel requires an experimental
data to support the fuel integrity, a safety analysis, and ashielding design. At high burnups, the composition of a nuclear
fuel changes in a non-homogeneous manner throughout the radius.
We present the R&D activities being performed in KAERI for
spent fuels discharged from PWR in Korea; focused on the local
chemical properties such as ‘local burnup', 'structural changes'
and 'the distribution of retained fission gas'.

0.25

Isotope ratio (Am, Cm/U235)

Am243/U235
Cm244/U235

Keywords – spent fuel, burnup, actinide, isotopic distribution,
lattice parameter, fission gas

0.20

0.15

0.10

0.05

0.00
4000

3000

2000

1000

0

Distance (um)I.

INTRODUCTION

To provide basic data about the local chemical
properties of a spent fuel, ‘radial distribution of isotopes’,‘lattice changes along the radius’ and ‘the quantitative
analysis of retained fission gas' were performed.
For the analysis of isotopic distribution and latticechanges, a shielded LA-ICP-MS and a micro-XRD wereused, respectively. The generation yield, release fraction
and retained fraction of fission gas of a fuel are importantfactors for determination of maximum burnup ofcommercial nuclear fuel. Thus, the gas analysis was
performed along the axis and radius of a fuel rod.
Fig. 1. The local chemical properties of a spent nuclear fuel; (top)actinides distribution, (bottom) changes in lattice parameters

II. EXPERIMENTAL
For the determination of average burnup of a PWR
nuclear fuel, IDMS using 148Nd-isotope as a burnup
monitor was used. A shielded LA-ICP-MS system wasused for the analysis of isotopic distribution of the spent
fuel. A shielded micro-XRD system was used for the
analysis of structural changes of a fuel pellet. The inert gas
fusion method was used for the analysis of retained fission
gas. A hydrogen analyzer equipped with electrode furnace
was employed for complete fusion of a fuel to extract theretained gas, and a QMS was used as a gas analyzer.
III. RESULTS AND DISCUSSION

B. Quantitative Analysis of Retained Fission Gas
A small fragment of spent fuel was fused with tin andnickel at a fussion current of 850A for 120 sec. The
recovery of Kr and Xe was ca. 96~108 % during 2 mincollection for reference materials in Al foil. The axial andradial distribution of RFG was investigated. The amount ofretained Xe and Kr increased along the radius, and it
decreased along the axis. The measured values were in therange of 75-84% of fission gas generation expected by code
calculation. When combined with the released gas, themeasured value was approached 95% of calculated one.

A. Isotopic Distribution and Structural Changes

IV. CONCLUSION

By LA-ICP-MS system, radial distribution of actinides
with respect to 235U was measured successfully. The 236U to235
U ratio was almost constant, while the isotopic ratio of
Pu and minor actinides were increased significantly at thepellet periphery. For a comparison, ORIGEN2 code wasused to calculate the isotope ratios. The measured values
agreed comparatively well with that of the calculated one.
The lattice parameters of the irradiated fuel revealed thelarger values than that of non-irradiated UO2 due to theradiation damage during the reactor operation and coolingafter discharge.

The measured data can contribute to provide dataneeded for understanding an irradiation behavior of a highburnup fuel, and can contribute to study the advanced fuelsuch as ultra high burn-up fuel under developing.
ACKNOWLEDGEMENTS
This work was supported by the National Research
Foundation of Korea (NRF) grant funded by the Korea
government (MSIP).

－ 24 －

NCO-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of 93Zr from intermediate level radioactive effluent

I. Laszak1, J.P. Degros2, C. Gautier2, P. Fichet2, F. Goutelard2, J.N. Saas3, A. Vian3, J.F. Valéry4
1

CEA Saclay, DEN/DANS/DPC/SEARS/LANIE, Nuclear, Isotopic Elementary Analytical Development Laboratory,
Building 391, PC33, 91191 GIF SUR YVETTE CEDEX, FRANCE2
CEA Saclay, DEN/DANS/DPC/SEARS/LASE, Operator Support Analyses Laboratory,
Building 459, PC171, 91191 GIF SUR YVETTE CEDEX, FRANCE
3
AREVA NC La Hague, Central Control Laboratory,
50444 BEAUMONT-HAGUE CEDEX, FRANCE
4AREVA NC, Recycling Business Unit,
AREVA tower, 92084 PARIS La Défense CEDEXThe French Atomic Energy Commission (CEA) was asked by
AREVA to develop a methodology in order to perform 93Zr
measurements on an intermediate level radioactive effluent. The
difficulty encountered related to the solution containing highcontents of fission products which is incompatible with the sample
acceptance criteria of the CEA laboratory in charge of thisdevelopment (Operator Support Analyses Laboratory - LASE).
Indeed, the total radioactivity was about 400 GBq/L for the beta
emitters and 4 GBq/L for the alpha emitters when the expectedconcentration of 93Zr was roughly 2 MBq/L, thus implying adrastic decontamination step before acceptance and measurement.
This study is a joint work between the LASE and the LCC (Central
Control Laboratory, AREVA NC La Hague) and required toestablish a proper scientific and experimental coordination
between these two laboratories.
The first experimental steps were performed at the LCC. Because
zirconium was essentially contained in the solid phase within thesample solution, it was decided to separate the precipitate using
centrifugation prior to mineralization. Once the Zr was perfectly
and entirely solubilized, a simple 500 fold dilution was needed forthe samples to be accepted at the LASE for further analysis. The
main goal was then to perform additional decontamination on thesamples and to eliminate the various interfering species, mostly
93m
Nb and 93Mo, as the 93Zr would be measured by ICP-MS
because of the very low detection limit offered (0.05ng/g) andbecause it also allowed us to follow the 93Zr decontamination
completion. The main separating steps involve a co-precipitationof zirconium with Ba3[AlF6]2(s) followed by several solvent
extraction steps. These are alternating stages of zirconium and of
niobium / molybdenum extraction in the organic phase, using
either N-benzoyl-N-phenylhydroxylamine or cupferron in CHCl3
while tuning accordingly the aqueous phase in order to retrieve amaximum amount of zirconium (forming highly stable complexes).
Ultimately, the aqueous phase contained all of the zirconium asan oxalate complex and ICP-MS measurement was performed todetermine the 93Zr concentration. The separation yield was thendetermined by measuring the total concentration of zirconium
using ICP-AES. Care was taken throughout the whole procedure
to circumvent any zirconium cross-contamination. The 93Zr
concentration was found to be of 15Bq/µg (Zr, total) with aseparation yield above 90%. A 2g/L total concentration of
zirconium was determined, leading to a 30 MBq/L 93Zr
concentration in the effluent, a result one order higher than the
one expected.
Keywords – 93Zr; zirconium; radiochemistry;
intermediate level radioactive effluent; AREVA; CEA.

ICP-MS;－ 25 －

NCO-05

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Selective Separation of Cesium from Simulated High Level Liquid Waste
using a Silica-based (Calix[4] + Dodecanol)/SiO2-P Adsorbent
Yuanlai Xu1, Seong-Yun Kim1*, Tatsuya Ito2, Haruki Tokuda1, Tsutomu Tada1,
Keitaro Hitomi1, Keizo Ishii2
1
Cyclotron and Radioisotope Center, Tohoku University, Aramaki-Aza-Aoba 6-3, Sendai, 980-8578 Japan
2
Graduate School of Engineering, Graduate School of Engineering, Tohoku University,
Aramaki-Aza-Aoba 6-6-01-2, Sendai, 980-8579 Japan�Corresponding author: Tel.: +81-175-72-4227; fax: +81-175-72-4611.
E-mail address: kim@cyric.tohoku.ac.jp (S.-Y. Kim)

Keywords – Cesium; Separation; (Calix[4] + Dodecanol)/SiO2-P
Adsorbent; High level liquid waste (HLLW); Macroporous silicabased supramolecular absorbent.

In order to separate Cs(I) from high level liquid waste(HLLW), a macroporous silica-based supramolecular
recognition absorbent, (Calix[4] + Dodecanol)/SiO2-P, wasprepared by impregnating and fixing the 1,3-[(2,4Diethylheptylethoxy)oxy]-2,4-crown-6-calix[4]arene(Calix[4]arene-R14) extractant and its molecule modifier 1dodecanol into a macroporous SiO2 silica based polymer
support (SiO2-P). Adsorption and separation behavior ofCs(I) or other typical fission produces (FPs) onto adsorbent
were investigated by batch and column methods,
respectively. It was found that (Calix[4] +Dodecanol)/SiO2-P adsorbent showed strong adsorption
affinity to Cs(I). A relatively large Kd value of Cs(I) above
90 cm3/g was obtained in the presence of 4 M HNO3
solution and reach equilibrium state within 1hr at 298 K.
From calculated thermodynamic parameters, thisadsorption process for Cs(I) could occur spontaneously at
the given temperature and was confirmed to be an
exothermic reaction. Meanwhile, low value of TOC (totalorganic carbon) in separated liquid phase from batch
experiment reflected that (Calix[4] + Dodecanol)/SiO2-P
adsorbent had excellent chemistry stability againstconcentrated HNO3 solution. In addition, tested Cs(I) were
eluted out with distilled water chromatographically andseparated from simulated HLLW successfully using(Calix[4] + Dodecanol)/SiO2-P packed column. All results
showed that (Calix[4] + Dodecanol)/SiO2-P adsorbent had
excellent adsorption affinity and high selectivity for Cs(I)from HLLW.

－ 26 －

NFO-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Age Determination of a single Pu and Pu/U mixed oxide particle
Yutaka MIYAMOTO, Fumitaka ESAKA, Daisuke SUZUKI, Masaaki MAGARA
Research Group for Analytical Chemistry, Nuclear Science and Engineering Directorate
Japan Atomic Energy Agency (JAEA), Tokai, Ibaraki 319-1195, JAPAN

Abstract – Age-dating of a single Pu oxide particle and a Pu/U

mixed oxide (MOX) particle ~1 µm in diameter was demonstrated.
The particles were prepared from the U and Pu standard referencematerials for this demonstration. They were separately dissolved,
and Am, U, and Pu were chemically separated from the solution via
anion-exchange chromatography. The isotope ratios of Am and Pu
in the eluted fractions were measured using a high-resolution
inductively coupled plasma mass spectrometer (HR-ICP-MS). The
precision and accuracy of the Pu age were improved through theaddition of 243Am or 243Am-242Pu mixed spikes to the sample
solutions and by the trace chemical separation of Pu and Am. The
determined age in this work was in good agreement with the
expected age with high accuracy and precision. These results
indicate that a combination of measurement using a mass
spectrometer and chemical separation of the spiked samples
provides an effective tool for the analysis of environmental samples
collected during nuclear safeguard inspections.
Keywords – Age dating, MOX, Plutonium, Trace analysis, Ionexchange separation, Safeguards

I.

INTRODUCTION

Isotopic and quantitative analyses of U and Pu in
environmental swipe samples collected during routineInternational Atomic Energy Agency (IAEA) safeguard
inspections are important for detecting undeclared nuclear
activities. Age determination of nuclear materials collected asenvironmental samples from nuclear facilities is also usefulfor detecting undeclared activities, as the age provides
information regarding the origins and history of the nuclear
material. Plutonium of less than nanograms (ng) purified
within a few years may be contained in the environmental
samples collected during IAEA safeguard inspections. We
present a method for determining the purification age of asingle Pu oxide and a Pu/U mixed oxide (MOX) particle.
These oxide particles ~1 µm in diameter were prepared from
U and Pu standard reference materials for this work, andaccuracy and precision of the analytical results were
evaluated.

dissolved in a mixture of HF and HNO3. Finally, an 8 M
HNO3 solution was prepared. The sample solution was spiked
with an 243Am or 243Am-242Pu mixed solution purified byanion-exchange chromatography. One-third of the sample
solution was used for measurement of the Am/Pu atomic ratio
via ICP-MS. The remaining portion was passed through asingle anion-exchange column to chemically separate Pu, U,
and Am. The isotope ratios in the collected each fraction
were measured with a HR-ICP-MS (Element-1) equippedwith an Apex-Q desolvating inlet system. All treatments,
except for the particle preparation from the standard solution,
were carried out in clean rooms (ISO Class 5 and 6) at the“CLEAR” clean laboratory at JAEA.
III. RESULT AND DISCUSSIONSThe Pu purification age was determined using the
Am/241Pu ratio and the general age-dating equation. The
addition of 243Am and 242Pu spikes to the samples gave aprecise and accurate Pu age. The determined ages of both the
Pu oxide and MOX particles were in good agreement with the
expected age (3.9 years). The accuracy in the determined age
in the Pu oxide particle was 7.1–105 days and the uncertainty
was 0.16–0.5 years. Addition of purified spikes, including243
Am and 242Pu, to the samples led to more precise andaccurate age determination, even for a young Pu particle
purified only a few years ago[2].
241

ACKNOWLEGEMENT
The authors would like to acknowledge Mr. N. Kohno forthe particle production. The authors are also thankful to Mr.
H. Fukuyama, Mr. T. Onodera, and Ms. R. Usui for the
sample preparation and Mr. Y. Takahashi for the ICP-MS
measurements. This work was supported by the Nuclear
Regulation Authority, Japan.
REFERENCES[1][2]

II. EXPERIMENTAL
Some Pu oxide particles and five types of MOX particles
which consist of different Pu/U atomic ratio were preparedfrom the standard reference materials, NBS-SRM 947
purified 3.9 years ago and NBL-CRM U010. Small portion of
the mixture of these solutions was calcined, and the obtainedoxides were ground[1]. The particles 0.5–�� ��� ��� ���������
were selected under SEM observation. Each particle was－ 27 －

F. Esaka et al., Talanta, 83, 569 (2010).
Y. Miyamoto et al., Radiochim. Acta, in press (2013).

NFO-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Radiochemical measurement of 10-15 MeV proton induced fission yields for U-238
Narek Gharibyan1, Kenton J. Moody1, Thomas A. Brown2, John D. Despotopulos1, Julie M. Gostic3,
Roger A. Henderson1, Evgeny Tereshatov1, Scott J. Tumey2 and Dawn A. Shaughnessy1
1Chemical Sciences Division, Lawrence Livermore National Laboratory
Atmospheric, Earth, and Energy Division, Lawrence Livermore National Laboratory
3
Air Force Technical Applications Center, Patrick Air Force Base, Florida

2

Keywords – Fission yields, protons, fission product separation, U238I.

INTRODUCTION

The improvements in fidelity of nuclear forensic exercise
samples require the development of analytical referencematerials with the end goal of establishing a realistic exercise
sample. This is designed to test the national laboratory
analysis and data evaluation communities through a truly
coupled, end-to-end “unknown sample” exercise. The
fabrication of such a sample requires an accurate knowledgeof cross sections and fission yields for numerous reactions
that can be explored to obtain fission products and/or shortlived actinide isotopes. Due to the limited amount of nuclear
data and the large uncertainties associated with the reported
values of proton-induced fission for U-238, experiments were
performed to measure the fission mass yields and the crosssection. Radiochemical separations were established forfission products of interest in order to improve the fission
yields in comparison to those obtained from the initially
irradiated samples.

separation of wing and valley fission products. Various
chemical separation methods were developed based on thesorption behavior of the fission products on ion exchange
resins. Chemical fractions containing the fission products ofinterest were counted individually and the total fission yields
were back calculated for each sample.
III. RESULTS
The measured fission yields are based on the results
generated by the GAMANAL program [1] evaluation of the
raw gamma spectra. Fission yields for short lived fission
products, as low as t1/2=14 minutes, were acquired. An
example of a fission mass yield obtained from theseexperiments is provided in Figure 1. The measured values of
the cross sections and fission yields are relatively close to
those reported in literature [2-4].

Relative Yield

Abstract – The production of realistic nuclear forensics debris
requires an accurate knowledge of cross sections and fission yields
for large number of systems. Proton induced fission of U-238 was
examined for incident energies in the range of 10-15 MeV. Fission
yields were first measured directly from the irradiated materials.
The valley and wing fission products were then isolated in various
chemical fractions in order to increase the counting statistics
leading to improvements in the fission yields. In addition to the total
fission cross section and the fission mass yields for U-238, proton
based reaction cross sections on U-238 and U-235 were alsomeasured.

60

80

100

120

140

160

180

Mass

II. EXPERIMENTAL

Figure 1. Fission mass yield from 11.9 MeV protons on U-238.

A stacking foil technique was employed in the irradiationof nat. U foil with 10-15 MeV protons with Y as the beam
intensity monitor. A series of irradiations were performed
using the tandem Van De Graff accelerator located at theCenter for Accelerated Mass Spectrometry at Lawrence
Livermore National Laboratory (LLNL). Irradiated samples
were transferred to the Nuclear Counting Facility on site at
LLNL for the initial counting. After sufficient data wereobtained, the uranium foils were dissolved and separated into
three fractions: one as a standard and one each for the

Acknowledgements – This work was performed under the auspicesof the U.S. Department of Energy by Lawrence Livermore National
Laboratory under contract DE-AC52-07NA27344.
[1]
[2]
[3]
[4]

－ 28 －

Gunnink, R., Niday, J.B., UCRL-51061, Vol. I (1972)
Yokoyama, A., et al., Z. Phys. A 356, 55-60 (1996)
Baba, H., et al., Z. Phys. A 356, 61-70 (1996)
Karttunen, E., et al., Nucl. Sci. Eng. 109, 350-359 (1991)

NFO-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effect of Interferences on Actinide and Strontium Separations in Unusual Matrices
Ralf Sudowe1, Evelyn M. Bond2, Ashlee R. Dailey1, Derek R. Mclain1, Audrey R. Roman1
1

2

University of Nevada Las Vegas, Las Vegas, Nevada 89154, USA
Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA

Abstract – Insufficient information is currently available about theeffects that the interferences present in complex matrices can haveon radiochemical separations utilizing extraction chromatography.
This poses a particular challenge for sample analysis in theaftermath of a nuclear incident involving an Improvised Nuclear
Device or a Radiological Dispersion Device. This research aims at
obtaining this information by examining the composition of common
urban materials and by investigating the influence that theirconstituents have on radioanalytical separations. To address thisissue the compositions of several different sample matrices ofinterest has been investigated. Subsequently the uptake of Sr, Pu,
Am and Cm on different commercially available resins was studied
in the presence of varying concentrations of potentially interfering
elements such as Al, K, Ca, K, Cr, Fe, Ni, Zr and Nd.
Keywords – Extraction chromatography, Actinide, Strontium,
SeparationsI.

INTRODUCTION

Most current radioanalytical methods have been developed
for the analysis of air, water, soil and bioassay samples.
While these protocols build the foundation of operational
environmental monitoring, they are not necessarily suitable
for the analysis of samples that will be encountered in theaftermath of a nuclear incident involving an improvised
nuclear device or a dirty bomb. Of particular interest for
emergency response and nuclear forensics are therefore
methods that can be applied to the analysis of steel, concrete,
Extraction
melt glass, asphalt and bone samples.
chromatographic resins have been used for radiochemical
separations for many years now, and a large body of data has
been published on the retention capabilities of many of theseresins for a large variety of elements that can be found inenvironmental samples. Little can be found, however, on theeffect that the matrix constituents found in debris samples canhave on analyte uptake. Even though it is known that theelements of interested are retained on the respective resins toa high degree, the samples analyzed will have a much more
complex composition than previously encountered. Theirbehavior might therefore potentially deviate from normal
sorption characteristics.
In particular the competition
between the potential interference and the analyte of interest
has to be studied in a systematic manner. The goal of thisstudy is to obtain information about the major and minor
constituents that are present in several sample matrices ofinterest for emergency response and to investigate theinfluence that they can have on the radiochemical
determination of several actinide elements and radiostrontium.

II. EXPERIMENTAL
The composition of several different matrices of interest
was determined by either obtaining information fromreference materials or by performing elemental analysis on
suitable samples. Batch studies were then used to determine
the uptake of the analyte of interest on a particular resin in thepresence of varying concentrations of different alkali, earth
alkali and transition metals, as well as lanthanides. The
uptake of Sr on SR resin [1] was investigated in addition to
the uptake of Pu, Am and Cm on DGA and UTEVA resin [2,3]. Single analyte solutions were contacted with small
amounts of resin in the presence of varying concentrations of
the potential interference. Aliquots were taken and theamount of analyte remaining in solution was determinedusing either LSC measurement or gamma spectroscopy.
Simultaneously the concentration of the interfering element
after contact with the resin was measured by ICP-AES.
III. RESULTS
The compositions of several different sample matrices ofinterest, such as bone ash, steel, concrete, asphalt and melt
glass has been investigated. The uptake of Sr on Sr resin wasstudied in the presence of varying concentrations of Mg, Al,
P, K, Ca, Cr, Fe, Ni, Cu and Zr. The adsorption of Pu, Am
and Cm on DGA and UTEVA resin was studied in thepresence of varying concentrations of Fe, Zr, Mo, Sr, Tc, Cs
and Nd. The presence of several of the interferences studied
led to a significant decrease in uptake of the element ofinterest on the resin. Others appeared to have no influence.
In some cases the presence of the interference lead to anincreased adsorption of the analyte on the resin, hinting at asynergistic effect that needs to be studied in greater detail.
REFERENCES
[1]
[2]
[3]

－ 29 －

E.P. Horwitz et al, A novel strontium-selective extraction
chromatographic resin, Solvent Extraction Ion Exchange 10, 313(1992)
E.P. Horwitz et al, Novel extraction of chromatographic resins basedon tetraalkyldiglycolamides: Characterization and potential
applications, Solvent Extraction Ion Exchange 23, 319 (2005)
E.P. Horwitz et al, Separation and preconcentration of uranium from
acidic media by extraction chromatography, Analytica Chimica Acta,
266, 25 (1992)

Oral Presentations
Tuesday, 24 September 2013
Hall & Meeting Room, Kanazawa Bunka HallTime
09:00-09:10
09:10-09:20
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09:40-09:50
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19:00-19:20
19:20-19:40
19:40-20:00
20:00-

9:00

PL-03

9:30

PL-04

Tuesday, 24 SeptemberHall
Meeting RoomPlenary
A. Tuerler
Plenary
S. Nagao

10:00

Coffee Break

10:20

ENI-01

10:50

ENO-01

11:10

ENO-02

11:30

ENO-03

11:50

ENO-04

12:10
13:20

ENO-05

13:40

ENO-06

14:00

ENO-07

14:20

ENO-08

14:40

ENO-09

15:00

ENO-10

15:20

NCI-01

Invited

H. Foerstendorf
General
NCI-02
Z.J. Guo
GeneralH. Tuovinen
NCI-03GeneralM.- C. Wu
General
NCO-06
T. Ohnuki
Lunch Time
General
NCO-07
S. Sachs
General
NCO-08Y. Iwahana
General
NCO-09J. Krmela
GeneralNCO-10K. Masumoto
GeneralNCO-11
H.W. Gaeggeler
GeneralNCO-12
A. Sakaguchi

InvitedS. Dmitriev
InvitedCh.E. Duellmann
Invited
H. Haba
GeneralV. Pershina
GeneralD. Rudolph
GeneralA. Yakushev
GeneralJ. EvenGeneralH. Nitsche
GeneralR. Eichler
General
T.K. Sato

Coffee Break

15:40

ENI-02

16:10

ENO-11

16:30

ENO-12

16:50

ENO-13

17:10

FKI-05

17:40

FKO-0918:00

FKO-10Invited
J.V. Krtaz
GeneralJ.H. Park
GeneralJ. Zheng
GeneralI. Milanovic
InvitedK. Minato
GeneralY. OuraGeneralK. Hirose

NEI-01

Invited

NEI-02

Z.F. Chai
InvitedNEO-01

A. Goswami
GeneralNEO-02NEO-03NEO-04NEO-05

18:50
Poster Session
20:00－ 31 －

E. Loefstroem-Engdahl

GeneralY. Tomobuchi
GeneralF. Poineau
GeneralA. Braatz
GeneralR. ChenPL-03APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Advances in the Production and Chemistry of the Heaviest Elements
1

Andreas Türler1,2

Laboratory of Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, Villigen-PSI, Switzerland
2
Laboratory of Radiochemistry and Environmental Chemistry, University of Bern, Bern, Switzerland

Abstract – Now that the discovery of all elements in the 7th period
has been announced, has the far end of the Periodic Table of the
Elements been reached? What is the heaviest element in the
Periodic System? Are there still undiscovered ones which mighteven be found in nature? Is there an 8th period and how many
elements will it contain? Will we need to introduce the g-orbitals
and will the current principles governing the groups and periodsof the Periodic Table still be valid for the heaviest elements?
These intricate questions are the topic of current research infundamental nuclear chemistry.

even under optimum conditions a production cross sectionof 1 pb translates into the synthesis of only 1 atom of asuperheavy nuclide every 36 h on average. Second, of themore than 50 new nuclides produced in these experiments a
number of them have t1/2 > 1 s and, thus, live long enoughfor chemical investigations. This result is in strong contrast
to the previously known, more neutron deficient isotopes ofMt, Ds, Rg, and Cn in the range of few milliseconds.

Keywords – APSORC’13 Keywords

B. Chemical Investigations of Heavy Elements

I.

INTRODUCTION

For increasingly heavy nuclei the electrostatic repulsionsof protons cannot be sufficiently compensated by theattractive nuclear force through an increasing number of
mediating neutrons. Therefore, the heaviest stable known
nucleus is already reached with 208Pb. All isotopes ofheavier elements, including some elements such as Bi, Th,
and U that still can be found in nature as remnants of thelast nucleosynthesis process, are radioactive and decay��������������� ��� ����������� �-particle and �¯-particle
emissions back to the last stable element Pb.
A. Synthesis of Heavy Elements
All elements heavier than Pu (Z=94) are man-made.
Transactinide elements (Z�104) are synthesized currently
only in complete heavy ion fusion reactions at high power
accelerators on a “one atom at a time” level. Spectacular
progress was obtained by using the very tightly bound,
doubly magic nucleus 48Ca and actinide target nuclei.
Oganessian et al. were able to synthesize single atoms ofelements 113 through 118 (with 294118 currently being theheaviest observed nucleus) and observe their radioactive
decay [1]. So far, only elements 114 and 116 have beenauthenticated by IUPAC and the element names flerovium,
Fl, and livermorium, Lv, suggested by the team of
discoverers, have recently been made official by IUPAC.
The addition of 6 new elements in the past decade wasremarkable in several ways. First, the maximum production
cross sections of elements Rf through Cn (Z=104-112)
could be described rather well by an exponential decay law,where the cross sections dropped by roughly a factor of 10
when increasing the atomic number by 2 units. In thesynthesis of 277Cn production cross sections of less than 1
pb (10-36 cm2) were determined. However, by using 48Ca
projectiles, this trend was broken and rather constantmaximum production cross sections of several picobarns
were measured for synthesis of elements Cn through Lv(Z=112-116) and even for elements 117 and 118 values
near or slightly below 1 pb were observed. Nevertheless,

The place an element occupies in the Periodic Table is
not only defined by its atomic number, i.e. the number ofprotons in the nucleus, but also by its electronic
configuration, which defines its chemical properties.
Strictly speaking, a new element is assigned its proper
place only after its chemical properties have been
sufficiently investigated. In some cases it has been possible
to experimentally investigate chemical properties oftransactinide elements and even synthesize simple
compounds. Due to the predicted strong influence ofrelativistic effects, the experimental investigation ofsuperheavy elements is especially fascinating.
The difficulties involved in the production and rapid
chemical isolation of few single atoms of a transactinide
element from numerous other reaction products and thesubsequent detection of the nuclear decay require thedevelopment of unique separation methods. Chemical
studies of transactinide elements and simple transactinide
compounds have been accomplished in the liquid as well as
in the gaseous phase. For the heavy transactinides, whichvery likely are volatile in their elemental state, gas phasechemistry is the method of choice [2]. Lately, the required
decontamination factors from interfering nuclear reaction
products grew so large that chemical experiments were
coupled to kinematic preseparators that already remove asubstantial fraction of the primary beam and of transfer
reaction products.
In this contribution the advances made in the synthesis
and chemical investigations of transactinide elements arereviewed [3]. Latest results on attempts to synthesize
elements beyond Z=118 and experiments to chemicallyinvestigate Fl will be highlighted as well as the first
synthesis of volatile transactinide carbonyl complexes.
[1]
[2]
[3]

－ 32 －

Yu. Ts. Oganessian, Radiochim. Acta 99, 429 (2011).
R. Eichler et al., Angew. Chem. Int. Ed. 47, 3262 (2008).
A. Türler, V.G. Pershina, Chem. Rev. 113, 1237 (2013).

APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013PL-04

�����������������������������������������������������������������������������
�������������������������
Seiya Nagao

Low Level Radioactivity Laboratory, Institute of Nature and Environmental Technology, Kanazawa University
This study applies a combined use of carbon isotope composition(�14C and �13C) to suspended solids in river waters and surface
sediments from the river mouth, continental shelf off the coast ofJapan. This study is intended to investigate the fate of terrestrial
particulate organic matter that is released from the river to thecoastal marine environment at three river-coastal systems. Our
results indicate that the combined �14C and �13C measurements ofthe particulate organic matter can provide unique information on
the sources and age of sediments and their transport behavior.

Figure 1 shows the �14C values of organic matter in theriverine suspended solids plotted as a function of �13C
values. The paired � 14C vs. �13C distributions vary withsampling site and divided into two groups. Riverine POC in
wetland has lower in �13C and higher in � 14C rather thanthose of rivers in forest and fluvial plain. This indicateshigher contribution of younger organic matter at thewetland river systems.

Keywords Ð�13C, �14C, suspended solids, transport

100

14

� C (ä)

-100

-200

-300
-30

-28

-26

-24

-22

13

� C (ä)Figure 1 Relationship between �14C and �13C of organic matter in thesuspended solids for the Bekanbeushi (�), Ishikari (�), Kuzuryu (�)and Hino Rivers (�).

Figure 2 shows �14C and �13C values of organic matterin riverine suspended solids and surface marine sediments
at the Kumaki-Nanao Bay system. The � 14C decreased
from the headwater to the middle sites at the Kumaki River,
but increased to the coastal sediments. These results
indicate that the middle and lower watershed area has main
sources of particulate organic matter exported to the costal
marine environments.
100

Headwater

0
-100

Upper

Nanao Bay

-200

14

We selected a river in wetland, Bekanbeushi River, andrivers in forest and paddy field such as the Ishikari,
Kuzuryu and Hino Rivers. The river-coastal systems were
set up at the Bekanbeuchi River-Lake Akkeshi, the TokachiRiver and the Kumaki River-off the coast of the rivers inJapan.
14
C measurements were performed by accelerator mass
spectrometry at the Japan Atomic Energy Agency and theInstitute for Environmental Studies in Japan. The � 14C isdefined as the deviation in parts per thousand from themodern standard. �13C values were determined for subsamples of the CO2 gas generated during graphite
production, using an isotope ratio mass spectrometer.

0� C (ä)Global riverine discharge of organic matter to the ocean
represents a substantial source of dissolved terrestrial
matter and organic carbon particulates. Continental margins
are recognized as the dominant reservoir for organic carbon
burial in the marine environment. An accurate inventory for
terrestrial and marine organic carbon in continental margin
sediments is important for quantitative understanding of
biogeochemical cycles.
A variety of geochemical approaches have been
employed to define the mixing ratio of marine andterrestrial organic matter, including �13C and lignin
biomarker analyses. Radiocarbon abundances have become
an additional indicator of terrestrial versus marine sources
because nuclear weapons testing in the 1950s and 1960s
injected large quantities of 14C into the atmosphere. The
�14C values of organic matter in river suspended particles
range from �980 to +75ä, but plankton and particulateorganic carbon in marine environments have enriched 14C
values ranging from � 45 to +110ä. Therefore, thesimultaneous use of � 14C and �13C values adds a second
dimension to isotopic studies of carbon cycling in surface
aquatic environments.
This study investigates the fate of terrestrial particulateorganic matter that is released from the river to the coastal
marine environment at three research fields in Japan.

Middle

-300
-400
-500
-30

Kumaki River

-28

-26

-24

-22

-20

-18

13

� C (ä)Figure 2 �14C and �13C of organic matter in the Kumaki River suspended
solids (�) and the Nanao Bay sediments (�).

－ 33 －

ENI-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Surface speciation of dissolved radionuclides on mineral phases – A vibrational and
X-ray absorption spectroscopic study
1

2

H. Foerstendorf1, K. Gückel1, N. Jordan1, A. Rossberg1,2, V. Brendler1

Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Dresden, Germany
Rossendorf Beamline at the European Synchrotron Radiation Facility (ESRF), Grenoble, France

Abstract – Binary and ternary surface complexes of U(VI) and
Np(V) on gibbsite were spectroscopically identified. Se(VI) forms
two different types of outer-sphere complexes depending on the solid
metal oxide.

surface species with a bidendately coordinated carbonate ligand (Fig. 1D).

OH2
HO
OH
O U O

Keywords – Surface complexes, minerals, spectroscopy

INTRODUCTIONO

A detailed description of the molecular interactions of radionuclides with minerals is required for the prediction of
their dissemination in the environment. In the past decade,vibrational spectroscopy has been developed to a powerfultool for the study of surface complexes of heavy metal ionson solid phases. In particular, a combined approach of vibrational and X-ray absorption spectroscopy potentially provides
comprehensive molecular information. In this study, a surveyof very recent results obtained from sorption reactions of radionuclides, namely U(VI), Np(V) and Se(VI) on metal oxides is given.
RESULTS
A. Surface processes of U(VI) and Np(V) on gibbsite
Gibbsite is widely used as a model system foralumosilicate minerals and clays. In addition, it is a ubiquitous weathering product of these minerals and the mostcommon crystalline aluminum hydroxide.
The results of the U(VI) sorption experiments indicate theformation of a monomeric binary inner-sphere surface complex irrespective of the prevailing atmospheric condition andsurface loading (Fig. 1A). In addition, it was found that
U(VI) surface precipitation occurs at a micromolar concentration level in an inert gas atmosphere. This is circumvented bylowering the initial U(VI) concentration or in the presence of
atmospheric CO2 due to the formation of ternary uranyl
carbonato surface complexes. The ternary complex was identified as a dimeric inner-sphere uranyl surface species containing a bidentately coordinated carbonate ligand by EXAFS
spectroscopy (Fig. 1B)[1].
Inner-sphere complexation was also derived from spectroscopic results of the Np(V)/gibbsite sorption system. Whilst
the neptunyl(V) ion forms a mononuclear surface species under inert gas condition (Fig. 1C), a ternary surface complex in
the presence of atmospherically derived CO2. This ternary
species is most likely a mononuclear Al–O–NpO2–O2CO-

OH2
O
O
O U
C O
OH2
H2 O
OH2
O O

O

HO

O

O U OO H
O
O

O

Np

O

O
O

C
O

O
O
Np
O
OH
O
O 2

Al

Al

Al

Al

A

B

C

D

Fig. 1: Proposed surface complexes of U(VI) and Np(V) on gibbsite.

B. Surface speciation of Se(VI)The sorption of selenate ions on different metal oxide
phases exhibits a new type of outer-sphere complexes. As it
was already postulated for transition metal cations to form
classical and extended outer-sphere complexes [2], this is obviously also true for oxoanions, such as SeO42�. With respect
to the high sensitivity of vibrational spectroscopy to symmetry properties of molecules, the spectra of the sorptioncom�������������������������������������������������������Fe2O3) [4] clearly indicate the formation of different types ofouter-sphere complexes (Fig. 2). These findings are corroborated by macroscopic analytical techniques.

Fig. 2: IR spectra of SeO42� species and the derived surface species.

REFERENCES
[1]
[2]
[3]
[4]

－ 34 －

Gückel, K. et al. (2012) Chem. Geol. 326-327, 27-35.
Lee, S. S. et al. (2010) Langmuir 26, 16647-16651.
Jordan, N. et al. (2011) Geochim. Cosmochim. Acta 75, 1519-1530.
Jordan, N. et al. (2013) Geochim. Cosmochim. Acta 103, 63-75.

ENO-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Adsorption of Eu(III) and Am(III) on granite: Effects of temperature, fulvic acid andbackground electrolyte
Z.J. GUO, Z.Y. CHEN, Q. JIN, W.S. WU

School of Nuclear Science and Technology, Lanzhou University, Lanzhou, 730000, China
E-mail: guozhj@lzu.edu.cn
Abstract –The adsorption of Eu(III) and Am(III) on crushed Beishangranite (BS03, 600m) was investigated as a function of temperature,
background electrolyte and the presence of fulvic acid at different
concentrations. It was found that temperature did not affectapparently the distribution coefficient (Kd) of Eu(III) in the range of
25-80 oC. At pH < 5.0, the Kd value decreased in CaCl2 solution ascompared to that in NaCl solution at the same ionic strength,
suggesting cation exchange reactions occurred in low pH range.
Whereas in high pH range, the Kd values in CaCl2 and NaClsolutions at the same ionic strength are identical, which indicate
inner-sphere surface complexes formed. FA significantly decreased
Kd of Eu(III) especially at pH > 4 and the extent of the decreasedepended on FA concentration and varied with aqueous pH as well.
Aging of freshly crushed granite in synthetic underground water at
150 oC for two weeks did not affect apparently Eu(III) Kd values. A
surface complexation model (SCM) using Generalized Composite(GC) approach was constructed based on experimental data of
Eu(III) in NaCl solutions and verified by experimental data of
Eu(III) in CaCl2 solutions as well as in synthetic underground water.
The SCM was used to predict Am(III) adsorption on the granite andthe calculated results were in accordance with the experimental
data of Am(III)III. RESULTS AND DISCUSSION
In Generalized Composite (GC) approach [2], a rock is
integrally considered and surface reactions on which areassumed to occur on a type of “general sites”, although thechemical environmental of surface sites on different minerals
and even those on different crystal planes of the same mineral
are actually different. In addition, the GC approach ignores
electrostatic effect. As a result, a GC model for a radionuclide
sorption on a rock is actually the simplest model with theleast adjustable parameters.

Keywords –Eu(III), Am(III), adsorption, granite, temperature effect,
fulvic acid, surface complexation modelI.

INTRODUCTION

Beishan granite (Beishan, Gansu province) has been
considered as a preliminary selection of host rock forgeological disposal of high-level radioactive waste in China,[1]. Considering temperature variation, potential change inelectrolytes of underground water, and the presence of humic
substances in the near field of a repository, it is necessary toevaluate adsorption of radionuclides on the granite at variableconditions.
II. MATERIAL AND METHODS
152+154

Eu(III) and 241Am(III) radiotracers were obtained
from Chinese Atomic Energy Institute. All other chemicals
used were of analytical grade. Beishan granite was sampledfrom the borehole BS03 at a depth of 600 m. To simplify theadsorption system, carbonates in Beishan granite wasremoved and the exchangeable cations were transformed into
Na-form or Ca-form. Batch sorption was carried out with
polyethylene tubes in nitrogen atmosphere glove box.

Figure. Eu(III) sorption in CaCl2 and “real” systems, (a) Sorption edge ofEu(III) on Ca-granite, Co = 6.74×10�8 M, m/V = 1 g/L and CCaCl2 = 0.033 M;(b) Sorption isotherm of Eu(III) on Ca-granite, CCaCl2 = 0.033M, m/V = 1g/L
and pH = 4.00±0.10; (c) Sorption isotherm of Eu(III) on Ca-granite, CCaCl2 =0.033 M, m/V = 1g/L and pH = 6.50±0.10; (d) Sorption edge of Eu(III) on
Na-granite with simulated underground water Co = 6.74×10�8 M, m/V = 1
g/L and CNaCl = 0.1 M.
[1]Guidelines for the R&D for geological disposal of high-level
radioactive waste. Beijing: China Atomic Energy Authority (CAEA),
Ministry of Environmental Protection, Ministry of Science andTechnology, 2006 (in Chinese)[2] Davis J A, Meece D E, Kohler M, Curtis G P. Approaches to surface
complexation modeling of Uranium(VI) adsorption on aquifer
sediments. Geochimica et Cosmochimica Acta, 2004, 68: 3621-3641.
[3] Guo Z, Chen Z, Wu W, Liu C, Chen T, Tian W, Li C, The adsorptionof Eu(III) on Beishan granite, SCIENTIA SINICA Chimica, 2011, 41:907-913.

－ 35 －APSORC’13 – 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

ENO-02Behaviour of radionuclides and secondary mineral formation in the
Talvivaara mining process
Hanna Tuovinen(1), Esa Pohjolainen(2), Daniela Vesterbacka(1), Caroline Kirk(3),David Read(3), Dina Solatie(4), Jukka Lehto(1)(1)

Laboratory of Radiochemistry, Department of Chemistry, University of Helsinki,
P.O. Box 55, FI-00014 University of Helsinki, Finland(2)
Geological Survey of Finland, Betonimiehenkuja 4, FI-02151 Espoo, Finland(3)
Department of Chemistry, Loughborough University, Loughborough, Leicestershire, LE11 3TU, UK(4)
Regional Laboratory of Northern Finland, Finnish Radiation and Nuclear Safety Authority, Lähteentie 2, FI96400 Rovaniemi, Finland
The Talvivaara nickel deposits are located in Sotkamo, Eastern Finland. The deposits comprise one of thelargest known nickel sulphide resources in Europe. Talvivaara is an operational, open cast mine where
Talvivaara Mining Company uses bioheap leaching to extract the metals (Ni, Zn, Cu, Co) from the black schist
ore. In 2010 the company announced the commencement of uranium production as an addition to its normal
mining operations. In heap leaching, uranium dissolves in the pregnant leach solution (PLS) along with mainbase metals and will be extracted using the solvent extraction (SX) process. The uranium produced will be in theform of yellowcake with an estimated annual production of approximately 350 tons. Currently, the uranium isdiverted into a gypsum pond and part of it also ends up in the nickel concentrate as an impurity.
Bioheap leaching is a naturally occurring exothermic process catalysed by indigenous bacteria. The key
parameters are particle size (< 8 mm), pH of the pregnant leach solution (2 – 2.5), temperature (20-90 oC) andthe oxidation and aeration rates. The ore is first extracted using conventional large scale open pit drill and blast
methods, then crushed and screened in four stages. It is agglomerated in a rotating drum, where recirculated PLS
is added to the ore in order to consolidate the finer particles. It is then stacked eight meters high on the primaryheap pad for primary leaching. The heap is irrigated from above and the leachate collected from the base of theheaps. The pregnant leach solution is collected in the PLS ponds where a 10% side flow is taken for metals
recovery; the remaining 90% per cent is recycled back to irrigation to increase the metal grade. The metals are
precipitated from the PLS using hydrogen sulphide and the resulting intermediate products transported forfurther processing in refineries. After approximately 2 years bioleaching on the primary pad, the leached ore isreclaimed, conveyed and restacked onto secondary heap pads. At this stage, the main part of copper and cobalt
is recovered. After secondary leaching, the barren ore will remain permanently in the secondary heaps.
The leaching process oxidizes U(IV) to U(VI) in the form of the uranyl ion (UO22+) at low pH. Radioactive
progeny from the 238U series are also mobilized and fractionate depending on chemical properties and theambient conditions. The aim of this study is to generate new data leading to a better understanding of the
behaviour of radionuclides, especially 226Ra, 210Pb and 210Po, at each stage of the Talvivaara mining process. In
addition the formation of secondary minerals during the leaching process is poorly understood.
Samples were collected from the primary heaps, secondary heaps, the PLS-ponds and gypsum pond in 2011,2012 and 2013. After pre-treatment, gamma spectrometry was used for direct determination of uranium andthorium progeny. Samples were then analysed by X-ray diffraction (XRD) to determine the main minerals
present. The uranium-bearing minerals were determined by electron probe micro-analysis (EPMA). Uranium,
thorium and heavy metals were determined by ICP-MS. For alpha spectrometry, uranium and thorium wereseparated using anion exchange chromatography, 210Po with silver plate precipitation and 210Pb was precipitatedfrom the remaining solution. Leaching experiments were performed in order to determine 226Ra, 210Pb and 210Po– bearing mineral phases.
Preliminary results provide information on the formation of secondary phases and the relative abundance of theinitial ore minerals. Uranium in the gypsum pond is found at least in association with goethite (FeO(OH)). The
high content of sulphate restricts solubility of radium; 226Ra concentrating in precipitated sulphate minerals. For
lead, the formation of anglesite (PbSO4) is probable and polonium is also likely to be bound to secondary
minerals in the heaps. The results of this work will play an important role in estimating radiation doses andpotential health implications to the local population resulting from past and anticipated disposal. A summary of
the main results obtained to date is given in the presentation.

－ 36 －

ENO-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Evaluation of HTO and selenium diffusion behavior in compacted bentonite withdifferent lengths
Chuan-Pin Lee 1, Ming-Chee Wu 1,*,Ching-Yuan Liu 2, Chun-Hua Pan 1, Tsuey-Lin Tsai 3, Hwa-Jou
Wei 3, Lee-Chung Men 3
1* Department of Earth Sciences, National Cheng Kung University, Tainan, Taiwan, 70101
Department of Chemical and Materials Engineering, National Central University, Taoyuan, Taiwan, 32001,
3
Chemistry Divisions, Institute of Nuclear Energy Research, Taoyuan, Taiwan, 32546

2

Abstract – n this study, diffusion behavior of selenium(Se)with a concentration of 0.1mM in bentonite (MX80) wasinvestigated using through-diffusion methods with various
lengths (0.25, 0.5, 0.75, 1.0, 2.0, 2.5 cm), respectively.
Before performing the through-diffusion experiments of Se,
a non-reactive tracer (HTO) was applied and achieved tocharacterize the physical process in compacted MX80
columns with different lengths. It shows that the diffusion
process of Se in synthetic seawater (SW) and groundwater(GW) reached equilibrium after 250 and 300 days,
respectively. Moreover, both retardation factor (Rfcal) anddistribution coefficients (Kdcal ) of Se obtained fromaccumulative concentration’s method in through-diffusion
test showed an obvious discrepancy in an increasing
length/diameter (L/D) ratio. In fact, it presented anagreement of RfH/Se and KdH/Se in an increasing L/D ratio incomparison between HTO and Se. It appears that the RfH/Se
and KdH/Se obtained from the through-diffusion experiments
are higher than those derived from the batch experiments.
Therefore, it demonstrates that reliable Rf and Kd of Se bythrough-diffusion experiments could be achieved at a nonreactive radiotracer(HTO) prior to tests and would be
more confident for long-term performance assessment.
Keywords – Diffusion, Selenium, distribution coefficients,

apparent diffusion coefficient－ 37 －

ENO-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Sorption Behavior of Dy(III) and Np(V) on microbial consortia
Toshihiko Ohnuki1, Naofumi Kozai1, Fuminori Sakamoto
1

Japan Atomic Energy Agency, Tokai, Ibaraki, 319-1195 Japan

Abstract – To elucidate sorption of trivalent and pentavalentactinides by the consortia of microorganisms sampled atHoronobe, Hokkaido, Japan. In the sorption experiments ofNd(III), Dy(III) (analogue of trivalent actinides), and
Np(V) were contacted with the consortia in the solution at
pH between 3 and 7 in resting condition. The coordination
environment of the sorbed Dy by the consortia wasanalyzed by EXAFS. For the sorption of Nd and Dy on the
consortia, the Kd increased with increasing pH, and wasnearly the same as that by single species of S. putrefaciens.
For the sorption of Np on the consortia, the K d was higher
than that for a single species of S. putrefaciens, indicatingthat the sorption behavior of Np on the consortia isdifferent from that by a single species of S. putrefaciens.
These results indicate that the consortia poses higher
affinity to Np than a single species of S. putrefaciens.
Keywords – Neptunium, trivalent actinides, sorption, consortia of
microorganisms

I.

INTRODUCTION

The presence of actinides (ANs) in radioactive wastes isa major environmental concern due to their long radioactive
half-lives, and its chemical toxicity. The high capacity of
microbial surfaces to bind ANs may affect the migration of
ANs in the environment. Unfortunately, we have only
limited knowledge of the role of microorganisms in the
migration of ANs in the environment.
Many researches have been carried out to study
adsorption of ANs on the cell surface o microorganisms.
Usually in the adsorption experiment single species of
microorganism was used, even though microorganisms
habit in consortia in environment. The adsorption ofdivalent cations of Cd, Cu, Ca, Pb, Sr, and Zn by the
consortia was nearly the same as that by a single species.
However, sorption behavior of ANs by consortia has notbeen elucidated.
In the present study, sorption behavior of trivalentlanthanides of Nd(III) and Dy(III) (alternative use forAm(III) and Cm(III), and of Np(V), by consortia of
microorganisms using batch type sorption experiments..
II. EXPERIMENTAL
Sample locations were at 140 m in depth in the site of
JAEA Horonobe Deep Geological Research Center,
Horonobe, Hokkaido, Japan. Samples were collected 3
different points on February, 2011. The samples were
inoculated in the Fe-reducing bacteria growth medium
containing NaHCO3 1g: NH4Cl 0.6g: KH2PO4 0.24g: KCl
0.04 g: Na-acetate 1 g: Na-citrate 0.4 g: Fe(OH)3 0.4g in 1
L distilled water under anaerobic condition. The pre-grownconsortia were cultured in the medium containing beef

extract or shewanella medium under aerobic condition.
Culture in the consortia were analyzed by 16S rRNA
analysis.
For the sorption experiments of Nd(III), Dy(III), and
Np(V) by the consortia were conducted in resting condition.
The solution sampled at 4 and 24 hrs after the exposure
were centrifuged for 10 min at 4000 rpm. The supernatant
was filtered through a membrane filter of 0.2 m tomeasure concentrations of the dissolved elements. The
concentration of Nd and Dy was 0.1 mM, and Np was 0.01
mM. The sorption experiments were performed in aerobic
condition.
The concentrations of Nd and Dy were measured by
ICP-AES, and that of Np by liquid scintillation analyzer.
The coordination environments of the sorbed Dy(III) by
consortia were determined by XAFS analysis using KEK
PF.
III. RESULTS AND DISCUSSION
The consortia contained many kind sof bacteria
involving Pseudomona and Shewanella family by random
clone analysis.
For the sorption of Nd and Dy on the consortia,
distribution coefficients (Kd) were between 104-105 ml/g at
pH between 3-7. The Kd for Nd and Dy increased withincreasing pH. Higher Kd in Dy than Nd was determined.
The Kd of Nd and Dy for the single species of Shewanella
putrefaciens, was approximately 104 ml/g at pH around 4,
and increased with increasing pH. XAFS analysis showedthat the FT spectrum of Dy sorbed on the consortia
resembled to that of Dy sorbed on a single species of
Shewanella putrefaciens, but not to DyPO4, indicatng thatthe coordination environment of Dy was nearly the same asthat on P. putrefaciens. These results indicate that thesorption behavior of Nd and Dy on the consortia is nearly
the same as that by a single species of S. putrefaciens.
For the sorption of Np on the consortia, the Kd wasapproximately 104 ml/g at pH 4. The Kd remained constantwith increasing pH of the solution. The Kd for a single
species of S. putrefaciens was about 102 ml/g at pH
between 4 and 6.5. The Kd increased with increasing pH.
These results indicate that the sorption behavior of Np on
the consortia is different from that by a single species of S.
putrefaciens. Since higher Kd is measured in the consortia
than a single species of S. putrefaciens, the consortia poses
higher affinity to Np than a single species of S. putrefaciens.
This research project has been conducted as the regulatory
supporting research funded by the Nuclear Regulation
Authority (NRA), Japan.

－ 38 －.

ENO-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Interaction of Eu(III) with Mammalian Cells as a Function of Eu(III) Concentration
and Nutrient Composition
Susanne Sachs, Anne Heller, Gert Bernhard

Helmholtz-Zentrum Dresden-Rossendorf e.V., Institute of Resource Ecology, P.O. Box 510 119, 01314 Dresden, Germany

Eu(III), interaction, mammalian cells, toxicity, speciationI.

INTRODUCTION

In case of the release of long-lived radionuclides, e.g., actinides, into the environment, knowledge about their behavior
in biosystems is necessary to assess and prevent health risks
for humans. This includes knowledge about bioavailability
and toxicity of actinides for/onto cells, which are governed toa large extent by their speciation [1]. In order to enable a better understanding of these processes, we study interaction
processes of trivalent actinides/lanthanides with mammaliancells on a cellular level combining biochemical and spectroscopic methods. In the present work we studied the cellular
tolerance of FaDu cells (human squamous cell carcinoma cellline) toward Eu(III), as an analog for trivalent actinides, andits uptake into the cells as a function of the metal concentration and the nutrient composition. In parallel, the Eu(III) speciation in the culture media was studied by time-resolved laser-induced fluorescence spectroscopy (TRLFS) to correlate
Eu(III) toxicity and uptake with its chemical speciation.

toxicity is higher in the absence of FBS than in its presence.
This discrepancy is attributed to the different Eu(III) species
in the media and points to an unequal bioavailability ofEu(III). In the presence of FBS, Eu(III) is stabilized in solution by complexation with FBS constituents, most probably
serum proteins, which was verified by ultrafiltration. In contrast, in the absence of FBS, the Eu(III) solubility is very low.
ICP-MS analysis of Eu(III) precipitates as well as TRLFS
point to the occurrence of ternary or higher Eu(III) complexes
with phosphate as the dominant ligand. The additional presence of citrate does not significantly affect the Eu(III) toxicity onto the cells in the presence of FBS. However, in its absence, an excess of citrate decreases the Eu(III) toxicity mostprobably due to a change of the chemical speciation.
Independent from the initial Eu(III) speciation, the Eu(III)uptake by the cells is low. It is predominantly located on thecell surface.
Under the studied experimental conditions, the toleranceof FaDu cells versus Eu(III) appears to be not significantly
influenced by the presence of 152Eu, i.e., there seems to be no
additional radiotoxic effect.

Cell viability / (% of control)

The Eu(III) toxicity onto FaDu cells is influenced by its chemical
speciation that is determined by the composition of the culture medium. However, independent from its speciation, Eu(III) seems to bebound to the cell surface and does not significantly enter the cells.

II. EXPERIMENTAL
FaDu cells were grown in Dulbecco’s modified eagle medium supplemented with fetal bovine serum (FBS), nonessential amino acids, HEPES buffer, penicillin/streptomycin,
sodium pyruvate (37°C, 5% CO2, 95% humidity) andsubcultivated as described in [2]. The Eu(III) toxicity onto
FaDu cells ([Eu]: 5-2000 µM) and its uptake into the cells([Eu]: 10, 1000 µM) was studied in the presence and absenceof FBS as described in [2,3]. In addition, the impact of citrate
was studied. To differentiate between chemotoxic and radiotoxic effects of Eu(III), first experiments were performed in
the presence of FBS ([Eu]: 10, 1000 µM) applying 152Eu as
radioactive tracer. The Eu(III) speciation was studied by
TRLFS as described in [4].
III. RESULTS

50

Presence of FBS
Absence of FBS
0

10

100

[Eu]tot / (µM)

1000

Fig. 1: Cell viability after 24 h of incubation with Eu(III).

ACKNOWLEDGMENTS
We thank J. Seibt, S. Heller, A. Ritter, C. Eckardt, and S.
Weiß for experimental and technical support as well as J.
Pawelke and E. Leßmann for the first batch of FaDu cells,
FBS and training in cell cultivation techniques.
[1][2]

As an example, the viability of FaDu cells after 24 h of incubation with 5-2000 µM Eu(III) in the presence and absenceof FBS (no citrate present) is shown in Fig. 1. The Eu(III)

100

[3]
[4]

－ 39 －

Ansoborlo, E. et al., Biochimie 88 (2006), 1605.
Sachs, S., Bernhard, G., Annual Report 2011, HZDR-013. HelmholtzZentrum Dresden-Rossendorf, Dresden (2012), p. 12.
Sachs, S., Heller, A., Annual Report 2012, HZDR-030. HelmholtzZentrum Dresden-Rossendorf, Dresden (2013), p. 26.
Heller, A. et al., Annual Report 2011, HZDR-013. Helmholtz-Zentrum
Dresden-Rossendorf, Dresden (2012), p. 13.

ENO-06 

 


         

      
         
  
   
                    
          







  


 

  
  

  



  


  

 





 

  

  
   



  



  

 

 
  

  

  
 


 


  



  

  
  

 

  




－ 40 －

ENO-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The Issue of Separation of Uranium from Drinking Water in the Czech Republic
1

Jan Krmela1������������������������� �������������������, The Czech Republic, jan.krmela@ujv.cz

Abstract
Natural ground water used for the preparation of drinking watercontains a number of cations, anions, elements and other substances
depending on the bedrock composition (Ca, Mg, Fe, Mn, heavy
metals, radioactive elements, arsenic, chromium, carbonates,
sulfates, phosphates, silicates, fulvic and humic acids etc.).
Information about composition of drinking water is important tocomply with all the requirements on sanitary of drinking water.
The elements that affect the quality of drinking water mainly fromgroundwater, also includes radioactive elements contained in
bedrock sections where water is extracted. These are the elementswith long half-lives, mainly alpha emitters (U, Ra, Rn, Th, andelements of the decay series).
Uranium and its decay products are found in all environmental
compartments. Radionuclides come to the environment bothnaturally - weathering and leaching of the rocks, and as aconsequence of human activities in connection with the use of raw
materials.
Uranium occurs naturally in four oxidation states. The mostmobility has hexa-valent state (uranyl ion). Uranyl is highly soluble
form of uranium in water. Mobility of uranium in soil and water isaffected by many factors.
Complex processes in soil and rock lead to redox reactions forming
both insoluble compounds (lower valence forms of uranium) andsoluble form of U (VI) (forming by reoxidation), which is again
leachable into groundwater. The content of uranium in groundwater
depends on the geological composition of the ground, and can reachup to hundreds of �g/L.
At present the issue associated with removing uranium fromdrinking water is solved in the Czech Republic. New limit for theconcentration of natural uranium (234U, 235U and 238U) was
recommended ��������������������L as the highest limit based on theWorld Health Organization (WHO). Advice of the Chief Health
Officer of the Czech Republic came into force on 1st January 2010,
which decreased the limit for uranium in drinking water from������������������������������������������� by WHO. However,the WHO ������������������������������������L in 2011 based on a���� ��������� ������ ������� ����� ������L uranium in drinking water
has not negative effect on the human organism (chemical toxicity)[1]. Limit in the Czech Republic remained at the same level �����/L.
Change the limit leaded to solving the issue on the waterworks in
the Czech Republic, which had not any experiences withradioactivity. Some waterworks installed a new device from
Germany (ion exchanges), but did not solve what they do withsaturated ion exchanges. Ion exchanges as the most suitablematerial for removing of uranium from drinking water is not reused(without regeneration), but it is used in the uranium industry, whereis putted to start of processing of uranium ore. Ion exchanges are
replaced with a new one in the waterworks and saturated ion
exchanges are discarded in the uranium industry.
Regeneration of ion exchanges could be cheaper, because ion
exchanges could be reused and processing of ion exchangers could
be cheaper, because it is possible to put the regenerant before theprocess of precipitation of “yellow cake” in the processing of
uranium ore.
This project TA02010044 was supported by TA CR.
Key words - Uranium, Drinking water, Ion exchanger[1]－ 41 －

WHO: Uranium in Drinking-water, Background document fordevelopment of WHO guidelines for Drinking-water Duality,
WHO/SDE/WSH/03.04/118/Rev/1, 2011.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

ENO-08Air-born contamination caused in a high-energy proton accelerator room
1

K. Mausmoto1, A. Toyoda1, H. Matsumura1, T. Kunifuda2

High Energy Accelerator Research Organization, Tsukuba, 305-0801, Japan
2
Tokyo Nuclear Service, Tsukuba, 300-2646, Japan

Abstract – Surface contamination caused during the operation of
12-GeV proton synchrotron, KEK have been studied by gammaray spectrometry and imaging plate technique. The surface ofaccelerator component was wiped with the filter paper. PSL valueof imaging plate contacted on the filter paper decreased
according to the half-life of 2 weeks. Therefore, it was assumed
that 32P might be produced from Ar by the high-energy protons
and neutrons and deposited on the accelerator components.
Keywords – Air-born activity, High-energy accelerator,
Imaging plate

I.

32

P,

INTRODUCTION

It is well known that various radioisotopes are inducedin the stratosphere by cosmic rays. During the operation ofa high-energy proton accelerator, air components are also
activated by primary protons and secondary neutrons andsimilar radioisotopes are produced. It is interesting to know
the behavior of radioisotopes in an accelerator room. The
radioisotopes are deposited on the surface of accelerator
components and cause surface contamination problem. In
this work, these radioisotopes were wiped with a filter
paper. The radioactivity was measured by the gamma-ray
spectrometry and the imaging plate technique.
II. EXPERIMENTAL
This work was performed at the 12-GeV proton
synchrotron, KEK. After stopping, smeared samples wereobtained from on beam pipes, magnets, wall and floor in
the accelerator room. In order to measure the activity ofbeta and gamma nuclides, a GM-counter, a liquid
scintillation counter, a Ge-detector and an imaging plate
were used.
III. RSULTS AND DISCUSSIONS(1) A liquid scintillation counter
Tritium was only observed. Carbon-14 could notdetected by the background effect.
(2) GM-counter and Imaging plate
Figure 1 shows the decay curves of seven filter papers
sampled from the beam line. It was found that the half-lifeof major activity was 2 weeks. Therefore, it was assumed
that 32P was produced and deposited. As the similar result
was obtained by a GM-counter, Imaging plate was also
detected beta activity. A polyethylene film pasted on thewall and surface was wiped with a filter after beam
stopping. In this case, 32P was also observed as a major
activity.

(3) Ge-detector
Many radioisotopes such as 7Be, 54Mn, were observed.
7
Be was produced by the spallation reactions of oxygen andnitrogen in air and deposited on the surface of beam line.
The gamma activity obtained by the Ge-detector was notcorrelated with the result of imaging plate technique.
Therefore, beta activity is important for surface
contamination.
IV. CONCLUSION
An imaging plate technique is very useful to measure theradioactive decay of many samples simultaneously on thesame condition.
Induced radioisotopes in air were deposited on the beamline. Because, the radioisotopes attached to aerosol anddeposited on the surface of beam line. A major acitivity was
32
P, which might be produced by the spallation reaction of
Ar in air.
In case of high-energy and high-intensity accelerators,
radioactive aerosol formation will become important
problem of radiation control. And this phenomenon wasinteresting subject to achieve the cosmic ray reaction in thestratosphere on the ground level.

－ 42 －

ENO-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Application of 210Pb in Glaciology
H.W. Gäggeler, L. Tobler, M. Schwikowski

Paul Scherrer Institut, Labor für Radio- und Umweltchemie, 5232 Villigen, Switzerland .
Keywords – 210Pb dating, climate research, environmental
pollution, non-dating application of 210Pb
I.

ABSTRACT

Glaciers are increasingly used as proxies for climate change.
Advances and retreats of these ice bodies are prime
information on climate variability. Moreover, glaciers havefound widespread application as archive of current and past
atmospheric information. To fully benefit from suchinformation, the glaciers have first to be dated. 210Pb is one of
the most frequently used radionuclide that enables dating for
one to two centuries BP (before present). 210Pb is ubiquitous
in atmosphere, since it is a decay product of natural radon(222Rn). Attached to aerosol particles 210Pb is then scavenged
by precipitation and deposited on the Earth surface.
210
Pb has proven to be much more versatile as information
species besides dating. This contribution summarizes someexamples that includes (besides dating, see e.g. figure 1);
Determination of annual snow accumulation rates at remotesites using the 210Po/210Pb disequilibria.
Thinning of glaciers as a function of depth caused by theincreasing mass of overlying fresh snow and ice.
Folding of low lying ice layers due to topographic conditions
that lead to non regular age-depth relationships.
Variability of seasonal deposition at high altitudes due toconvective processes in summer.
Study of heavy metal percolation in temperate glaciers

Presented examples originate from glaciers studied at our
institute. Ice core drillings were performed in the European
Alps, the South American Andes, the Russian and Mongolian
Altai, the Mt. Cook area in New Zealand and in Svalbard(Norway).
References

Determination of sublimation rates at glacier sites in arid
areas such as the Andes.
210

Fig. 1: 210Pb activity concentrations along an ice core fromthe Belukha saddle in the Altai mountains (Siberia, Russia)
together with three additional time horizons from the nuclear
weapons testing (1963: measured via tritium), and the wellknown volcanic eruptions from Katmai (1912) and Tambora(1816) identified via increased excess sulphateconcentrations. The right axis depicts the age deduced fromthe 210Pb measurement (deduced from [1])Pb activity concentrations as indicator of air masses, withlow values for precipitation from marine air and high values
for continental air, respectively.

[1] Olivier, S.., C. Blaser, S. Brütsch, N. Frolova, H.W. Gäggeler, K.A.
Henderson, A.S. Palmer, T. Papina, M. Schwikowski, Temporal variationsof mineral dust, biogenic tracers and anthropogenic species during the past
two centuries from Belukha ice core, Siberian Altai, J. Geophys. Res.
Atmospheres, 111, DO5309, doi:10.1029/2005/Doo5830 (2006)－ 43 －

ENO-10APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Depth distributions of uranium-236 and cesium-137 in the Japan Sea;
toward the potential use as a new oceanic circulation tracer
Aya Sakaguchi1, Akinobu Kadokura1, Peter Steier2, Yoshio Takahashi1,
Kiyoshi Shizuma3, Tomoeki Nakakuki1, Masayoshi Yamamoto4
1

Graduate School of Science, Hiroshima Univ.
2
VERA-Laboratory, Univ. of Vienna
3
Graduate School of Engineering, Hiroshima Univ.
4
Low Level Radioactivity Laboratory, Kanazawa Univ.

We present a feasibility study for using 236U as an oceanic
circulation tracer based on depth profiles of 236U and 137Cs in theJapan/East Sea. The concentration of the predominantly
anthropogenic 236U, measured with Accelerator Mass Spectrometry(AMS), decreased from the order of 107 atom/kg in surface water to
106 atom/kg close to the sea floor (3000 m). The profile has asmooth trend with depth and concentration values are generally
proportional to that of 137Cs for the same water sample. The
cumulative inventory of dissolved 236U in the water column was
estimated to be 1012-1013 atom/m2, which is similar to the globalfallout level (17.8x1012 atom/m2) in Japan. Additional analyses ofsuspended solids (SS) and bottom sediments yielded negligible
amounts of 236U. Our results suggest that 236U behaves as aconservative nuclide in seawater, with potential advantages overother tracers of oceanic circulation.

Keywords – the Japan Sea, GEOTRACES, U-236, Cs-137,
globalfallout

II. MATERIAL AND METHOD
Bottom sediments (4 sites) and seawater samples (7 sites)
were collected from the Japan Sea in the research cruise with
R/V Hakuhomaru, 2010 . The sediment core was cut into 1
cm segments from the surface to 5 cm in depth within a few
hours after the sampling. About 20 L of seawater samples
were collected from some depths in each site, andimmediately after the sampling, the water was filtered with
0.45 �m pore-size membrane-filters. After the appropriate
pre-treatment for each sample, uranium isotope and 137Cs
were measured with AMS and Ge-detector, respectively. The
detail of these methods were published in Sakaguchi et al.,(2012)[2].
III. RESULTS AND DISCUSSION
236

I.
137

U was successfully detected for all seawater samples, andU/238U atom ratios in seawater were in the range of (0.191.75)×10-9. The dissolved 236U concentration showed a
subsurface maximum and decreased steeply with depth. The
minimum value was found at a depth of 2500 m and bottom(about 3000 m in depth) in the northern and the southernareas, respectively. These profiles are markedly different
from that of natural 238U which is nearly constant over thedepth, suggesting that 236U has not yet reached steady state.
For the SS sample, 236U could not be detected in significant
levels. The total 236U inventory of the water column was
estimated at 1012-1013 atom/m2. This value is nearly the sameas the global fallout level (17.8×1012 atom/m2)[1][2]. 236U
was also found in the bottom sediments, and the inventory
was about 1/40 compared with that in water column. All
above characters are comparable with 137Cs which isanthropogenic conservative nuclide in ocean. Actually, thediffusion coefficients for both nuclides show the nearly samevalue. The detail discussion of this study has been shown in
Sakaguchi et al., (2012)
236

INTRODUCTION

Cs (T1/2=30.2 y) has been spread all over the world as a
fission product of atmospheric nuclear weapons tests in the
1960s. This nuclide has been used as a powerful tool for
oceanography due to the well-defined origin and conservative
behaviour in water. However, the number of atoms has
decayed already to one thirds compared with its initial levels,and it will become more difficult to measure. In this situation,
we focus on 236U (T1/2=2.342×107 y) as a candidate for a newisotopic tracer for oceanography. The detection of 236U in theenvironment has become possible only recently, by thedevelopment of measuring techniques with high sensitivity
based on AMS. Our group showed that global fallout frombomb tests contains 236U, which might be produced as nuclear
reactions of 235U(n,�) and/or 238U(n,3n)[1]. So 236U has been
therefore globally distributed in the surface environment.
Thus, 236U has a similar potential as a tracer forenvironmental dynamics as 137Cs, especially for
oceanography.
In this study, a comprehensive attempt was made to measure
the concentration of 236U in marine samples such as water,
suspended solid and bottom sediments to clarify theenvironmental behaviour of this isotope. Furthermore, thediscussion of the circulation of deep and bottom water in"Miniature Ocean", the Japan Sea, has been attempted.

[1]
[2]
[3]

－ 44 －

A. Sakaguchi, K. Kawai, P. Steier et al. Science of the Total
Environment. 407, 4238-4242, 2009.
A. Sakaguchi, K. Kawai, P. Steier, et al., Science of the Total
Environment, 408, 5392-5398, 2010.
A. Sakaguchi, A. Kadokura, P. Steier,et al, Earth and Planetary Science
Letters, 333-334, 165-170, 2012.

ENI-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Ultratrace Analysis of Long-lived Radionuclides by Resonance Ionization
Mass Spectrometry (RIMS)
J.V. Kratz

Institute for Nuclear Chemistry, Johannes Gutenberg-University, Mainz, Germany
Keywords – Ultratrace analytical method, resonant laser ionization,
isotopic composition, plutonium analyses, actinide ionization potentials,
optical spectroscopy with 255Fm, IONTOF-SIMS coupled with RIMS

Abstract For long-lived radionuclides such as actinides,
conventional radioanalyses by ���������������������������
unsatisfactory limits of detection (LOD). Resonanceionization mass spectrometry, on the contrary, achieves
limits of detection of 106 atoms and is free from isobaric
interferences [1,2]. The multiple step resonant excitation of
evaporated atoms with laser light and the mass selective
detection is presented for isotopes of plutonium as an
example. We use a frequency-doubled Nd:YAG laser witha repetition rate of 10 kHz to pump three titanium-sapphirelasers delivering wave lengths of 420.76 nm, 847.28 nm,
and 767.53 nm to resonantly excite plutonium into a
Rydberg state from where ionization is achieved byapplying an electric field [3]. For isotopic composition
measurements, the wavelengths of lasers 1 and 2 must be
readjusted for each isotope while laser 3 can be maintainedat the same wavelength. The accuracy of isotopic ratios
determined this way is demonstrated with a certified NIST
standard. Applications are presented for fallout plutonium,
reactor plutonium, samples from the Chernobyl area,
wapons plutonium from the Mururoa island, seawater
plutonium from the Northern Sea, and from the Irish Sea.
Migration of plutonium through a granite fracture in theGrimsel underground laboratory has also been investigated[4].
By detecting ionization thresholds as a function of theapplied electric field, accurate ionization potentials IP ofAc, Th, U, Np, Pu, Am, Cm, Bk, Cf, and Es have been
determined by extrapolation to zero field strength [5, 6, 7].
In a first attempt to determine also the IP of Fm, a sample
of 20.1-h 255Fm produced at the HFIR at Oak Ridge has
been investigated. By resonance excitation with a dye laser
and ionization with an excimer laser in a buffer gas cell,
two excited states of Fm (5f12 7s 7p) have been identified
and mass spectra of 255Fm+ and the daughter 251Cf+ havebeen measured by a quadrupole mass spectrometer coupled
to a channeltron detector [8]. By measuring the drift timesof these ions and of 238UO+, ion mobilities in the electricfield could be determined. These are potentially useful todetermine ionic radii of the heavy actinides and superheavy
elements.
By using a commercial IONTOF-SIMS apparatus, analysesof hot micro particles with high lateral resolution in the
sub-micron range have been exploited [9]. For thedetermination of the location of these hot particles (x,ycoordinate on the target holder) their content of fissile
material via fission track analysis [10] has been used.

In order to avoid isobaric interferences, the sputtered ions
(SIMS) were suppressed by a pulsed counter voltage
applied to the target holder, and the abundantly sputteredneutral particles were resonantly excited and ionized by
RIMS. The resulting ions were directed by an alternating
acceleration voltage into the TOF mass spectrometer.
[1] N. Erdmann, G. Herrmann, G. Huber, S. Köhler, J.V.
Kratz, A. Mansel, M. Nunnemann, G. Passler, N.
Trautmann, A. Turchin, A. Waldek
Fresenius J. Anal. Chem. 359, 378 (1997)[2] M. Nunnemann, N. Erdmann, H.-U. Hasse, G. Huber,
J.V. Kratz, P. Kunz, A. Mansel, G. Passler, O. Stetzer, N.
Trautmann, A. Waldek
J. Alloys and Compounds 271-273, 45 (1998)[3] C. Grüning, G. Huber, P. Klopp, J.V. Kratz, P. Kunz, G.
Passler, N. Trautmann, A. Waldek, K. Wendt
Int. J. Mass Spectrometry 235, 171 (2004)[4] S. Bürger, R.A. Buda, H. Geckeis, G. Huber, J.V. Kratz,
P. Kunz, Ch. Lierse von Gostomski, G. Passler, A.
Remmert, N. Trautmann
in: Radioactivity in the environment – Volume 8, series
editor: M.S. Baxter, Elsevier 2006, 581[5] S. Köhler, R. Deißenberger, K. Eberhardt, N. Erdmann,
G. Herrmann, G. Huber, J.V. Kratz, M. Nunnemann, G.
Passler, P.M. Rao, J. Riegel, N. Trautmann, K. Wendt
Spectrochimica Acta, Part B 52, 717 (1997)[6] J.R. Peterson, N. Erdmann, M. Nunnemann, K.
Eberhardt, G. Huber, J.V. Kratz, G. Passler, O. Stetzer, P.
Thörle, N. Trautmann, A. Waldek
J. Alloys and Compounds 271-273, 876 (1998)[7] N. Erdmann, M. Nunnemann, K. Eberhardt, G.
Herrmann, G. Huber, S. Köhler, J.V. Kratz, G. Passler, J.R.
Peterson, N. Trautmann, A. Waldek
J. Alloys and Compounds 271-273, 837 (1998)
8] H. Backe, A. Dretzke, K. Eberhardt, S. Fritzsche, C.
Grüning, G. Gwinner, R. G. Haire, G. Huber, J.V. Kratz, G.
Kube, P. Kunz, J. Lassen, W. Lauth, G. Passler, R. Repnow,
D. Schwalm, P. Schwamb, M. Sewtz, P. Thörle, N.
Trautmann, A. Waldek
J. Nucl. Sci. Tech., Suppl. 3, 86 (2002)[9] N. Erdmann, J. V. Kratz, N. Trautmann, G. Passler
Anal. Bioanal., Chem. 395, 1911 (2009)[10] O. Stetzer, M. Betti, J. van Geel, N. Erdmann, J.V.
Kratz, R. Schenkel, N. Trautmann
Nucl. Instr. and Meth. in Physics Research A525, 582(2004)－ 45 －

ENO-11APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The Bulk Analysis with TIMS Measurements Performed in KAERI for Nuclear
Safeguards
Jong-Ho Park, Sunyoung Lee, Young-Geun Ha, Seon A Lee, Kahee Jeong, Kyuseok Song
Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, Daejeon 305-353, Korea.

Abstract

KAERI has been developing the techniques for bulk
analysis of environmental samples to support the internationalsociety for nuclear safeguards purpose. The analytical procedure,
which consists of screening, ashing, acid digestion, chemical
separation, and isotopic measurements by TIMS, was established.
The analytical results of simulated environmental samples preparedfrom certified reference materials fell into the criteria that the IAEA
requires for the NWAL qualification.

rhenium filament with minimized residue. A thermal
ionization mass spectrometer (TRITON, Thermo Fisher
Scientific) was utilized for isotopic measurement.
A simulated samples were prepared with cotton swipe
containing known amounts of uranium (CRM 112-A) andplutonium (REIMEP 16D) reference materials. The routine
procedure was applied for the bulk analysis of the simulated
samples.

Environmental Sample, Safeguards, Isotopic Analysis, TIMS

B. ResultI.

INTRODUCTION

Highly accurate and precise analysis of nuclear materials
in environmental samples plays essential roles in monitoring
undeclared nuclear activities.1 The IAEA has been
maintaining a Network of Analytical Laboratories (NWAL)
for nuclear safeguards. Since 2009, Korea Atomic Energy
Research Institute (KAERI) has been developing thetechniques for bulk analysis of environmental samples tosupport the international society as one of the members of
NWAL. The analytical techniques that KAERI is utilizing
with TIMS measurements for bulk analysis are briefly
introduced in this paper.

The analytical results of simulated environmental samples
prepared from certified reference materials are shown in
Table 1. The accuracy and the precision of the result fell into
the criteria that the IAEA requires for the NWAL
qualification. The measured n(235U)/n(238U) of the samples
agreed with the certified value within less than 1% of
accuracy.
Table 1. The result of bulk analysis of simulated environmental samples

Cert.
#1

n(235U)/n(238U)
7.2543e-3n(240Pu)/n(239Pu)
1.110e-1

5.32[±0.52]e-5

7.27[±0.18]e-3

1.150[±0.005]e-1#2

6.71[±0.97]e-5
7.28[±0.11]e-3
1.140[±0.002]e-1
Numbers in parentheses indicate expanded uncertainties U = k·u c

A. Sample Analysis Procedure
Decomposition and acid digestion of environmental
samples were carried out to prepare sample solutions in nitricacid, called as the mother solution. The solutions were
weighed precisely, and then divided into three fordetermination of U isotope ratios and Pu quantity, fordetermination of U quantity and Pu isotope ratio, and forarchive, respectively. Appropriate spike isotopic referencematerials were added to the corresponding mother solution
portion. IRMM 040a (233U) and IRMM 085 (242Pu) were used
for quantification of uranium and plutonium, respectively.
The Pu isotopes were eluted into the conical PFA vial
through the UTEVA columns with 2M HNO3/0.02M ascorbicn(234U)/n(238U)
5.2841e-5[1]Acid/0.02M NH2OH�HCl after loading the sample solution
adjusted with 8M HNO3/0.3% H2O2 on the UTEVA columns.
The uranium isotopes were eluted through the columns with
0.007M ammonium oxalate solution. The purified Pu and U
solutions were evaporated to dryness with concentrated nitricacid, HF and HClO4 until any residue was not found in the
PFA vial. Each sample was loaded on a pre-degassed－ 46 －

D. L. Donohue, J. Alloy Compd. 1998, 271-273, 11.

ENO-12APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of plutonium isotopes at ultratrace level in seawater samples bysector-field ICP-MS combined with chromatographic separation
Wenting Bu1,2, Jian Zheng*2, Qiuju Guo*1, Tatsuo Aono2, Keiko Tagami2, Shigeo Uchida212School of Physics, Peking University, China
National Institute of Radiological Sciences, Japan

Plutonium isotopes are released into the environment as a consequence of human nuclear activities
including nuclear weapon testing, nuclear fuel reprocessing and nuclear accident. As the world’s ocean
covers ca. 70 % of the earth surface, it received majority of Pu isotopes released into the environment byatmospheric nuclear weapons tests. For example, it has been estimated that the total global fallout
239+240
Pu released into the environment was about 10.87 PBq, and 6.6 PBq entered the world’s ocean[1].
Besides, a significant amount of Pu isotopes were injected directly to the world’s ocean by close-in fallout
from the nuclear explosions conducted at the Pacific Proving Ground by US and the French Polynesia byFrance.
Due to their radiotoxicity and long half-lives, Pu isotopes are regarded as highly hazardous pollutantsin the marine environment and are of great research interest. Accurate and precise determination of
plutonium isotopes in marine samples is important for radioecological assessment. In addition, Pu
isotopes have also been used for tracing of oceanographic processes, such as water mass circulation,transport and scavenging of particulate matter, etc.
The concentration of Pu in seawater is extremely low (239+240Pu, 1.2-7.4 mBq/m3 in the surface seawaterof the NW Pacific Ocean).[2] By the traditional alpha spectrometry method, usually large volume (~ 200 L)
of seawater sample is needed for the analysis of Pu, and the 240Pu/239Pu atom ratio, which is an important
fingerprint for Pu source identification and for tracing of oceanographic processes, cannot be obtained.[3]Due to the low detection limit and the relatively simple sample preparing procedures, ICP-MS has beentreated as a promising method for the analysis of Pu in environmental samples in recent years. However,when using ICP-MS, the detection of 239Pu and 240Pu can be affected by spectral interferences caused by
238
UH+ and 238UH2+ formations, especially for the environmental samples with high U concentrations. The
concentration of U in seawater in the Pacific Ocean is about several ��/L and the atom ratio of 238U/239Pu
can be up to 1011.[4] Thus, complex procedures for the preconcentration of Pu and separation of Pu from U
were employed for the determination of Pu in seawater prior to the analysis by ICP-MS, which somehow
may lead to a low Pu recovery.
In this work, we presented a simple method for the analysis of Pu concentration and its isotopic
composition in seawater samples by sector field ICP-MS combined with chromatographic separation
technique. High precision and accuracy were achieved by using this method. The detailed analyticalprocedures and the merits of this method will be discussed at the conference.
Acknowledgments
This work was supported by the Ministry of Education, Culture, Sports, Sciences and Technology (MEXT)(24110004), Japan, and partly supported by the Agency for Natural Resources and Energy, the Ministryof Economy, Trade and Industry (METI), Japan.
References[1] Aarkrog, A., Deep-Sea Res. II, 50, 2597-2606, 2003.
[2] Povinec, P. P., Livingston, H. D., Shima, S. et al., Deep-Sea Res. II, 50, 2607-2637, 2003.
[3] Yamada, M. and Zheng, J., Appl. Radiat. Isot., 66, 103-107, 2008.
[4] Chen, J. H., Edwards, R. L., Wasserburg G. J., Earth Planet. Sci. Lett., 80, 241-251, 1986.

－ 47 －

ENO-13APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Semi-automated Procedure for the Determination of 89,90Sr in Environmental
Samples by Cherenkov Counting���������������, Željko Grahek

Division for marine and ������������������������������������������������, Zagreb, Croatia
Abstract - Development of new chromatographic resins in the lasttwo decades Sr resin, AnaLig-01 and SuperLig 620 has significantly
simplified separation of strontium from various types of samples.
These resins, that have principles based on molecular recognition,
are highly selective for strontium binding. In combination withappropriate detection methods they enable automatic determinationof radioactive strontium. Sequential injection analysis andequilibration based sensor column analysis were developed for thedetermination of long lived 90Sr (28.8 y) in liquid radioactive waste
and water samples.1-3 However, 89Sr that has short half-life (50.5 d),can also be present in samples, especially in those exposed to fresh
fallout from nuclear reactor. Classical analysis of 89Sr requires
isolation of 90Y, usually after attaining of secular equilibrium of90
Sr-90Y and the whole procedure takes at least 16 days. However,by using Cherenkov counting technique, determination time may besignificantly reduced. Unlike 90Sr that emits low energy electrons,
its daughter 90Y as well as 89Sr, generates Cherenkov photons inaqueous media. Consequently, by successive counting within 64
hours, 89Sr and 90Sr via 90Y can be determined. Therefore, the main
aim of this research is development of semi-automated procedure forthe determination of 89,90Sr. It includes solid phase extraction (SPE)of strontium from liquid samples and Cherenkov counting of its
isotopes. The procedure is based on sample - column equilibrationand off-line detection of bound 89,90Sr on the column. Sample ispumped through column at constant flow rate until the breakthroughor saturation point is achieved. The 89,90Sr is determined by counting
on column in PE vial. It will be shown how strontium can beselectively bound on the Sr resin, AnaLig-01 and SuperLig 620
resins and separated from interfering radionuclides. Also, influenceof column geometry, amount of resin and media in PE vial aroundthe column on quantity determination, detection efficiency andachievable lower detection limits will be discussed. The method istested in proficiency testing samples and natural water samples.

Figure 1. Detection efficiency of 89Sr and 90Y bound on AnaLig-01 resin
depending on surrounding media (TriCarb 3180)

REFERENCES
[1]

[2]

[3]

Keywords – semi-automated procedure, solid phase extraction,
Cherenkov counting, 89,90Sr determination－ 48 －

O. B. Egorov, M. J. O’Hara, J. W. Grate, Equilibration-Based
Preconcentrating Minicolumn Sensors for Trace Level Monitoring ofRadionuclides and Metal Ions in Water without Consumable
Reagents. Anal. Chem. 2006 78(15) 5480-5490.
J. W Grate, O. B. Egorov, M. J. O'Hara, T. A. Devol, Radionuclide
Sensors for Environmental Monitoring: From Flow Injection SolidPhase Absorptiometry to Equilibration-Based Preconcentrating
Minicolumn Sensors with Radiometric Detection. Chem. Rev. 2008
108(2) 543-562.
M. J. O'Hara, S.R. Burge, J. W. Grate, Automated radioanalyticalsystem for the determination of Sr-90 in environmental water samples
by Y-90 Cherenkov radiation counting. Anal. Chem. 2009 81(3) 12281237.

FKI-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Research and Development towards
Decommissioning of Fukushima Daiichi Nuclear Power Plants
Kazuo Minato

Nuclear Science Research Institute, Tokai Research and Development Center,
Japan Atomic Energy Agency
Tokai-mura, Ibaraki-ken 319-1195, Japan
Abstract – Towards the decommissioning of Fukushima Daiichi
Nuclear Power Plants, science-based research and development
is important and useful, as well as technology and engineeringdevelopment. Research and development activities based onradiation chemistry, radiochemistry, thermodynamics, etc., havecontributed to safe and efficient decommissioning of the plants.
Keywords – Fukushima Daiichi, Decommissioning, Radiation
Chemistry, Radiochemistry, Thermodynamics

I.

INTRODUCTION

Two and a half years have passed since the accident at
Fukushima Daiichi Nuclear Power Station Units 1-4,
Tokyo Electric Power Company, Inc. (TEPCO). The
research and development towards decommissioning of theplants, concerning the removal of fuels from spent fuelpools, removal of fuel debris, processing and disposal ofradioactive waste, and remote control equipment anddevices, have been being made as national projects, which
are based on the Mid-and-Long-Term Roadmap towards
the Decommissioning of TEPCO's Fukushima Daiichi
Nuclear Power Station Units 1-4 [1]. Besides TEPCO, plantmakers, research institutes, etc., jointly participate in the
projects. Among them the Japan Atomic Energy Agency isplaying an important part in science-based research anddevelopment to support the decommissioning of the plants.
II. RADIOLYSIS OF SEAWATER
One of the distinguishing features of the accident is thatseawater was injected to the damaged reactor cores andspent fuel pools in the early stage of actions. The
accumulated radioactive water, including seawater, in thereactor and turbine buildings has been being processed fordecontamination and desalination. This process generates
spent zeolites highly contaminated with radioactive cesium.
For safe storage of the spent zeolites, hydrogen generation
should be clarified.
Gamma-ray irradiation experiments revealed that theyield of hydrogen from seawater was larger than that frompure water and comparable to the primary yield, indicatingthat oxidation of hydrogen by radical products of waterradiolysis is not effective in seawater due to the presence of
Cl- and Br- ions. Furthermore, hydrogen generation wasincreased by addition of the zeolite to seawater. This meansthat the radiation energy deposited on zeolite is involved inhydrogen formation [2].
Based on the experimental data, hydrogen generation in
the vessels was evaluated, and the procedures to represshydrogen generation in the spent zeolite were suggested.

III. RADIOCHEMICAL ANALYSIS OF WASTE
The radioactive materials were released into theenvironment by the accident. A huge amount of the waste
contaminated with the radioactive materials was generated.
To classify the waste and to establish ways of processing
and disposal of the waste, inventory of radioactive
materials in the waste should be clarified.
The analysis of rubbles, trees, and accumulated water
sampled in the site of the nuclear power station revealed
that the main radionuclide was 137Cs (and 134Cs) with verysmall amounts of fission products, actinides, and activation
products, which is quite different from those of theradioactive waste generated from ordinary nuclear power
stations and reprocessing plants. The development of
separation method of a target nuclide before radiochemical
analysis was inevitable, and the analytical scheme andmethods have been developed for the nuclides, such as 3H,
14
C, 36Cl, 79Se, 90Sr, 99Tc, 129I, 60Co, 94Nb, 137Cs, 152Eu,
154
Eu, 238Pu, 239Pu, 240Pu, 241Am, and 244Cm.
IV. THERMODYNAMIC ANALYSIS OF FUELS
A large amount of seawater was injected into the reactor
pressure vessels in the accident. Several elements contained
in seawater possibly reacted with degraded fuel debris andmolten corium. These reactions may have affectedvolatilization of fission products, property of fuel debris,and formation of corrosive gases.
Thermodynamic evaluation indicated that volatility ofCs, Sr, and Te was potentially increased due to the change
in stable chemical species, and that corrosive gases, such as
HCl and H2S, were possibly generated, depending on
temperature and oxygen potential [3].
Experiments on the high temperature reaction between
sea salt deposit and (U,Zr)O2 simulated fuel debris (simdebris) were also made. A dense layer of calcium andsodium uranate formed on the surface of a sim-debris under
airflow. When the oxygen partial pressure was low,
calcium was dissolved into the cubic sim-debris phase toform solid solution (Ca,U,Zr)O2+x [4].
REFERENCES
[1]
[2]
[3]
[4]

－ 49 －

http://www.meti.go.jp/english/earthquake/nuclear/decommissioning/index.html
Y. Kumagai, R. Nagaishi, et al., At. Energy Soc. Jpn., 10, 235-239(2011).
M. Kurata, N. Shirasu and T. Ogawa, Trans. At. Energy Soc. Jpn., inpress.
M. Takano and T. Nish, J. Nucl. Mater., 443, 32-39 (2013).

FKO-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of atmospheric radiocesium on filter tapes used at automated SPM
monitoring stations for estimation of transport pathways of radionuclides from
Fukushima Daiichi Nuclear Power Plant
Yasuji Oura1, Mitsuru Ebihara1, Haruo Tsuruta2, Teruyuki Nakajima2, Toshimasa Ohara3
Mitsunori Ishimoto4, Yosuke Katsumura4
1

Department of Chemistry, Tokyo Metropolitan University
Atmosphere and Ocean Research Institute, The University of Tokyo
3
Center for Regional Environmental Research, National Institute for Environmental Studies
4
Nuclear Professional School, The University of Tokyo
2

I.

INTRODUCTION

Enormous amount of artificial radionuclides were emitted
into the atmosphere by a nuclear accident at Fukushima
Daiichi nuclear power plant (FDNPP) in March 2011. The
radionuclide in the atmosphere was transported withatmospheric stream into eastern Japan area widely. Sincesome institutes in Kanto region monitored atmosphericradioactivity periodically, it was partially evident that whenradioactive plumes passed through Kanto region. However,data on atmospheric radioactivity during an initial period in
Tohoku region in where FDNPP presents is nothing, thus
passing routes of radioactive plumes in Tohoku region andhow radioactivity went though is not clear.
A lot of automated air pollution monitoring stations areplaced by local governments around in Japan. Suspended
particulate matters (SPM) are also monitored hourly in thestation. SPM collected during the accicdent at the stations in
Tohoku and Kanto region must play an important role tosolve when and how much atmospheric radionuclides passed
through in Tohoku and Kanto regions. So we determined134
Cs and 137Cs contents in SPM collected on filer tapes at
SPM monitoring stations. The determined contents are also
expected to help a development of air pollution transportmodel calculation.
II. EXPERIMENTAL

Fukushima, 8 stations in Ibaraki, 4 stations in Saitama, and 6
stations in Chiba prefectures were subjected to gamma
spectroscopy. SPM was collected on roll paper tapecontinuously and SPM on a paper tape was visible as a black
circle (we call it spot in this article). �Spots of SPM
collected from 15 to 16 March and from 20 to 23 March in2011 were cut one-by-one. Each spot was sandwiched
between medical papers, and it was fixed on a thin plastic
sheet by an adhesive tape. Gamma rays from samples were
measured for 1 to 3 hours with a Ge detector.
III. RESULTS AND DISCUSSION
We observed the different arrival time of radioactive
plume on 15 and 20-21 March among stations. For example,
137
Cs concentrations at 3 stations in Fukushima city and 4
stations in Ibaraki prefecture are shown in Figs. 1 and 2,
respectively. It was found that high 137Cs concentration (> 10
Bq/m3) continued for about 12 hours in Fukushima city. This
peak was not observed by radiation dose monitoringaround that time. In Ibaraki prefecture, a high 137Csconcentration (> 200 Bq/m3) appeared at 8 am, 21 March at 2
stations in Tsuchiura but not observed in both Shimozuma
and Tsukuba. This difference is expected to be helpful forsolving passways of radioactive plume in Ibaraki. Analysis ofradioactive Cs on filter tapes collected by automated SPM
monitoring stations even at 1 - 2 years after FDNPP accident
is concluded to give very valuable information.

Filter tapes used at 3 stations in Miyagi, 19 stations in

Fig.1 Atmospheric 137Cs concentration at 3 stations in Fukushima city.

－ 50 －

Fig.2 Atmospheric 137Cs concentration at 4 stations
in Ibaraki prefecture.

FKO-10APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Two-Years Trend of Monthly 137Cs Deposition Observed within 300 km of the
Fukushima Dai-ichi Nuclear Plant
1

Katsumi Hirose 1,2

Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioicho,
Chiyodaku, Tokyo 102-8554, Japan2
Geosphere Research Institute, Saitama University, 255 Shimo-okubo, Sakura-ku, Saitama, 338-8570, Japan

Abstract – Monthly depositions, which directly reflect
atmospheric processes including emission from the Fukushima
Daiichi nuclear power plant (FDNPP), are an important tool tore-construct accident sequence. In order to elucidate deposition
behavior of the FDNPP-derived radionuclides after the major
emission in March 2011, two-years trends of the monthly 137Cs
deposition at monitoring stations within 300 km of the FDNPP
were examined. The monthly 137Cs deposition showed marked
peaks in winter 2012 and winter 2013 at the Futaba site about 5
km of the FDNPP, whereas 2013 winter the peak at the sites insouth Kanto and Tohoku regions was not pronounced. We discuss
two-years trend of the monthly 137Cs deposition taking into
account its spatial variation and effect of precipitation amount.
Keywords – Fukushima Dai-ichi nuclear power plant, monthly
deposition, 137Cs, temporal variation, emission historyI.

INTRODUCTION

The 2011 Great East Japan Earthquake and resulting
tsunami caused severe accident in the Fukushima Dai-ichi
nuclear power plant (FDNPP). As a result, large amounts ofradionuclides have been released in the environment. In
order to trace long-term trend of FDNPP-derived
radionuclides emitted into atmosphere, it is important to docontinuous monitoring of radionuclides in surface air anddeposition. Especially monthly deposition of the FDNPPderived radionuclides is one of the powerful tools to
elucidate long-term environmental effects of the FDNPP
accident. The results of monthly 137Cs deposition [1,2]revealed that the effects of the FDNPP accident at least
continued until the early 2012. In this paper, we describe
two-years trend of the monthly 137Cs deposition observed in
the Kanto and Tohoku regions and discuss processes
controlling temporal variation of the monthly 137Cs
deposition.
II. SAMPLING AND METHOD
Monthly deposition samples (rainwater and falling dust)
were collected by rainwater samplers with surface areas of
0.5 m2, respectively, which are usually installed on the roofof main monitoring building in each monitoring site.
Monthly deposition sampling in 45 monitoring sites
covering Japanese Island has been stationary performed tomonitor basic levels of radioactivity deposition. Monthly
rainwater and falling dust samples was collected inappropriate bottles on the first day morning of every month.
Water sample was transferred into an evaporation dish anddried on a hot plate. The resultant residues were weighted
after drying in an oven at 110�C and then transferred to aplastic container. Dried residue sample in a plastic

container was subjected by gamma spectrometry. Gamma
spectrometry was performed in each measurementlaboratory of local government. Major radionuclides inmonthly deposition samples were radiocesium (134Cs and137
Cs). In this analysis, we focused 137Cs deposition because
at initial stage, the 134Cs/137Cs activity ratio was constant(Hirose, 2012). All of monthly deposition data has beenrecorded in NRA homepage.
III. RESULT AND DISCUSSION
Two-years trend of the monthly 137Cs deposition at themonitoring stations within 300 km of the FDNPP was
examined. The FDNPP-derived 137Cs has been stillmeasured in January 2013 at most of the monitoring
stations within 300 km of the FDNPP. A typical time
sequence of the monthly 137Cs deposition is as follows: 1.
Pronounced high 137Cs deposition (3.34 MBq m-2) occurredin March 2011 at the Futaba monitoring station, where islocated about 5 km of the FDNPP. 2. The monthly 137Cs
deposition at Futaba rapidly decreased in April 2011 as aresult of cease of major radioactivity emission from the
FDNPP. 3. A minimum monthly 137Cs deposition (1.55
kBq m-2) appeared in October 2011 and then gradually
increased to a maximum (19.5 kBq m-2) in February 2012.
4. A cause of higher 137Cs deposition in winter, 2012 waspresumed to be resuspension of 137Cs-enriched particles [2].
5. After a peak in February 2012, the monthly 137Cs
deposition deceased and reached a minimum in August
2012. However, the monthly 137Cs deposition increased in
winter, 2013 (January 2013: 18.9 kBq m-2).
The temporal variations of the monthly 137Cs depositionat the monitoring stations within 300 km of the FDNPP
spatially differed from each other. In order to have better
understanding of temporal variations of the monthly 137Cs
deposition and its spatial difference, we calculate 137Csconcentrations in rainwater from the 137Cs deposition andprecipitation amount to eliminate effect of precipitation
amount. The temporal variation of the 137Cs concentrationin rainwater at Hitachinaka is similar to that at Futaba. Thisfinding suggests that the temporal change of the 137Csconcentration in rainwater at Hitachinaka waspredominantly affected by that at Futaba, in other words,
source intensity at the FDNPP.
REFERENCES[1][2]－ 51 －

Hirose, K., J. Environ. Radioact., 111, 13-17, 2012.
Hirose, K., Appl. Radiat. Isot. doi.org/10.1016/j.apradiso.2013.03.
076

NCI-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Synthesis and study of properties of superheavy elements
status, problems, and prospects
S. Dmitriev

The Flerov Laboratory of Nuclear Reactions, JINR, Dubna,
dmitriev@jinr.ru
The study of nuclear physical and chemical properties ofrecently discovered superheavy elements (SHE, Z = 112–118) as well as synthesis of new elements (Z>118) remain
one of the most crucial tasks in modern science. Over the
past decade, the unique results [1] have been obtained thatare of utmost importance both in nuclear physics andastrophysics (experimental evidence of existence of islandsof increased stability of SHE) as well as in chemistry(influence of relativistic effects on the chemical propertiesof the elements 112–114). As per the IUPAC decision, thetwo new elements are now officially called Fl - Flerovium(element 114) and Lv - Livermorium (element 116).
The discovery of elements 117 [2] and 118 closed the 7th
period of Mendeleev’s Periodic Table of the Elements.
Possibilities to study synthesis of heavier elements inreactions with the double-magic 48�������������������������
because production of actinides with Z>98 (Es, Fm, etc.) in
necessary quantity (several mg) is impossible in neutroncapture reactions within the framework of existing today
reactor technologies. One needs to use ions heavier than48
�����������������50Ti, 58Fe, and 64Ni; however, production
cross sections with these ions are expected to be at least
one order of magnitude less. Implementation of the largescale program on the study of earlier synthesized SHE
requires, in turn, significant experiment efficiency
improvement.
Further development implies the construction of a first-everSHE factory at JINR FLNR, which shall include thefollowing:- a new accelerator complex with the average-mass ion
beam intensity 10-20 times higher than that of today;- physical and chemical new-generation experimental setups (highly effective gas-filled recoil separator, gas catcher,selective laser ionization, etc.).
The work was carried out with the financial support
from the Russian Foundation of Basic Research (projectcode # 13-03-12058-ofi-m-2013).
[1][2]

Yu. Ts. Oganessian, S. N. Dmitriev, Russian Chem.Review, 78,
1077, 2009.
Yu. Ts. Oganessian et al., Phys. Rev. Lett., 104, 142502, 2010.

－ 52 －

NCI-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The Search for New Chemical Elements and the Possibilities to Synthesize
Transactinide "Chemistry" Isotopes
1

Christoph E. Düllmann1,2,3

Johannes Gutenberg-Universität Mainz, 55128 Mainz, Germany
GSI Helmholtzzentrum für Schwerionenforschung, 64291 Darmstadt, Germany
3Helmholtz Institute Mainz, 55099 Mainz, Germany

2

On overview on nuclear reactions leading to isotopes of thetransactinide (Z�104) elements with sufficiently long half-lives forchemical study will be presented.
Transactinides, Superheavy elements, Nuclear fusion reactions

Elements up to Z=112 as well as 114 and 116 are
officially recognized as discovered and have been
named [1]. The current literature contains reports about
the synthesis of all elements up to Z=118 [2], meaningthat more than 10% of all elements are members of thetransactinide series with Z=104-118. Searchexperiments for the new elements with Z=119 and
Z=120 have been performed, e.g., at the GSI Darmstadt.
Elements up to Hs (Z=108) as well as Cn (Z=112) andFl (Z=114) have been chemically investigated [3], using
isotopes with half-lives of at least about one second,which is the current limit for chemical studies. The
figure shows the cutout of the current chart of nuclei ofthe more than 100 transactinide isotopes. These can besynthesized in nuclear fusion reactions. Traditionally,
these are grouped into different classes depending on
the excitation energy of the compound nucleus ifformed at a beam energy corresponding to the height of
the Coulomb barrier.

the more than 100 transactinide isotopes, synthesized innuclear fusion reactions. Selecting the optimum nuclear
reaction to synthesize a certain isotope is a sensible
topic, which requires proper attention in any experimentwith the heaviest elements, regardless of the specificaspect under study. The figure shows that isotopes
suitable for chemistry studies with current technology
exist for all elements up to Fl (Z=114).
I will first present the search for new elements using therecoil separator TASCA [4] at GSI and then discuss the
optimum reactions leading to the relatively long-lived
isotopes of the transactinides as they are frequently usedin chemical studies of these elements, including
elements which were not studied chemically to date.
[1]
[2]
[3]
[4]

R. D. Loss and J. Corish, Pure Appl. Chem. 84, 1669 (2012).
Y. Oganessian, Radiochim. Acta 99, 429 (2011).
A. Türler and V. Pershina, Chem. Rev. 113, 1237 (2013).
A. Semchenkov et al., Nucl. Instrum. Meth. B 266, 4153 (2008)

Chart of nuclei of transactinide elements. Half-lives are given, and decay modes color coded. Isotopes often used in chemical studies are shown in a red border.
Long-lived isotopes of elements that were not studied chemically so far are shown in a blue border. Dashed lines show nuclear shell closures.

－ 53 －

NCI-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Production and Decay Studies of Transactinide Nuclides with GARIS at RIKEN
Hiromitsu Haba

Nishina Center for Accelerator-Based Science, RIKEN, Wako, Saitama 351-0198, Japan
Abstract – The isotopes of 261Rf, 262Db, and 265Sg were produced
248
248
in
the
Cm(18O,5n)261Rf,
Cm(19F,5n)262Db,
and
248
22
265
Cm( Ne,5n) Sg reactions, respectively, using a gas-jet
transport system coupled to the gas-filled recoil ion separator,
GARIS at RIKEN. Production and decay properties of those
nuclides were investigated in detail with a rotating wheel
apparatus for � and spontaneous fission spectrometry under low
background conditions.
Keywords – Superheavy elements; RIKEN gas-filled recoil ion
separator, GARIS; 261Rf; 262Db; 265Sg

Chemical characterization of superheavy elements(SHEs, atomic numbers Z � 104) is an extremelyinteresting and challenging research subject in modern
nuclear and radiochemistry [1,2]. We have been developing
a gas-jet transport system coupled to the RIKEN gas-filled
recoil ion separator GARIS as a novel technique for the
next-generation SHE chemistry [3–5]. With this method,
breakthroughs in SHE chemistry are expected: (i) the
background radioactivities originating from unwanted byproducts are strongly suppressed, (ii) the intense primary
heavy-ion beam is absent in a gas-jet chamber and hencehigh gas-jet yield is achieved, and (iii) the beam-free
conditions also make it possible to investigate newchemical reactions. In this work, we investigatedproduction and decay properties of isotopes of 261Rf (Z =104), 262Db (Z = 105), and 265Sg (Z = 106) available forchemical studies using the GARIS gas-jet system.
A schematic of the experimental setup is shown in Fig. 1.
Oxygen-18, 19F, and 22Ne beams were extracted from the
RIKEN Linear Accelerator, RILAC. The isotopes of261
Rfa,b, 262Db, and 265Sga,b were produced in the reactions
248
248
Cm(18O,5n)261Rf,
Cm(19F,5n)262Db,
and
of
248
22
265
Cm( Ne,5n) Sg, respectively. The evaporation
residues of interest were separated in flight from the beamand the majority of the nuclear transfer products by GARIS
and were guided to a gas-jet chamber at the focal plane of
GARIS. The evaporation residues were thermalized in He
gas, attached to KCl aerosol particles, and were transported
through a Teflon capillary to a chemistry laboratory. Alphaand spontaneous fission (SF) decays of 261Rfa,b, 262Db, and265
Sga,b were then investigated with the rotating wheel
apparatus MANON (Measurement system for Alphaparticle and spontaneous fissioN events ON line) under low
background conditions.
The 1.9-s isomeric state (261Rfb) in 261Rf was directly
populated in the 248Cm(18O,5n)261Rfb reaction for the firsttime [6]. The identification of 261Rfb was based on six �-�correlations linking � decays of 261Rfb and its daughter
257
No. The �-particle energy of 261Rfb was measured to beE� = 8.52 ± 0.05 MeV. The half-life was determined to be
T1/2 = 1.9 ± 0.4 s based on both 8.52-MeV � and SF decays.
The SF branch is bSF = 0.73 ± 0.06. The cross section forthe 248Cm(18O,5n)261Rfb reaction is �(261Rfb) = 11 ± 2 nb at

95.1 MeV, which gives a cross section ratio of
�(261Rfa)/�(261Rfb) = 1.1 ± 0.2. In the 265Sg experiment [7],eighteen and twenty four events were assigned to 265Sga and265
Sgb, respectively, based on �-�(-�) and �-SF correlations.
The half-life and �-particle energy of 265Sga were measured
to be T1/2 = 8.5+2.6–1.6 s and E� = 8.84 ± 0.05 MeV,
respectively, and those of 265Sgb were T1/2 = 14.4+3.7–2.5 s
and E� = 8.69 ± 0.05 MeV. As a daughter product of
265
Sga,b, the decay properties of 261Rfb were derived: T1/2 =2.6+0.7–0.5 s, E� = 8.51 ± 0.06 MeV, and bSF = 0.82 ± 0.09.
These results confirm and refine the complicated decay
pattern suggested for the decay chain 265Sga,b � 261Rfa,b �
257
No � in [8]. The production cross sections for 265Sga
and 265Sgb were determined to be �(265Sga) = 180+80–60 pb
and �(265Sgb) = 200+60–50 pb at 117.8 MeV. Recently, decay
properties of 262Db and its �-decay daughter 258Lr were
investigated [9]: E� = 8.46 ± 0.04 MeV (� intensity I� = 70
± 6%) and 8.68 ± 0.04 MeV (I� = 30 ± 6%), T1/2 = 34+4–3 s,and bSF = 55 ± 4% for 262Db; T1/2 = 3.5+0.5–0.4 s and bSF(and/or bEC) = 2.6 ± 1.8% for 258Lr. Based on those decay
properties, the cross section for the 248Cm(19F,5n)262Db
reaction in [10,11] was revised to �(262Db) = 2.2 ± 0.7 nb at
103 MeV. In the conference, perspectives of SHE nuclear
chemistry opened by GARIS will be also presented.
(a) GARIS(b) Gas-jet transport system

Differential pumping section
Beam from
RILAC

Evaporation Residues
Focal plane(ERs)
Gas inlet

Mylar window~100 kPa

Beam dump

ERs
Rotating
targetElastic scattering
beam monitor

~0.1
kPa
D1

Irradiation room

Q1

Q2

0

1

Chemistry laboratory

D2

He/KCl2m0(c) MANON
7 pairs of Si PIN photodiodes
Rotating wheel

100 mmTeflon capillary(10 m)
Mylar

ExhaustFig.1. (a) RIKEN gas-filled recoil ion separator, GARIS. (b) Gas-jet
transport system coupled to the focal plane of GARIS. (c) The rotating
wheel apparatus MANON for �/SF-spectrometry.
M. Schädel, Angew. Chem. Int. Ed. 45, 368 (2006).
A. Türler and V. Pershina, Chem. Rev. 113, 1237 (2013).
H. Haba et al., J. Nucl. Radiochem. Sci. 8, 55 (2007).
H. Haba et al., J. Nucl. Radiochem. Sci. 9, 27 (2008).
H. Haba et al., Chem. Lett. 38, 426 (2009).
H. Haba et al., Phys. Rev. C 83, 034602 (2011).
H. Haba et al., Phys. Rev. C 85, 024611 (2012).
Ch. E. Düllmann and A. Türler, Phys. Rev. C 77, 064320 (2008).
H. Haba et al., EuCheMS International Conference on Nuclear andRadiochemistry (NRC8), Sept. 18, 2012, Como, Iraly.
[10] Y. Nagame et al., J. Nucl. Radiochem. Sci. 3, 85 (2002).
[11] K. Tsukada et al., Radiochim. Acta 97, 83 (2009).
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

－ 54 －

NCO-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Theoretical Predictions of the Electronic Structure and Properties of the Heaviest
Elements
Valeria Pershina11Helmholtzzentrum für Schwerionenforschung, Planckstr. 1, D-64291 Darmstadt, Germany

Abstract - Recent theoretical works on predictions of chemical
properties and experimental behaviour of the heaviest elements arepresented and critically compared
Keywords – Superheavy elements/Electronic structure/Relativistic
calculationsI.

INTRODUCTION

One of the main aims of studies in the area of the chemistryof the heaviest elements is to place a newly produced elementin the proper position of the Periodic Table [1]. It is achievedby comparing behaviour of the new element with that of its
lighter homologs in the chemical group. Having this in mind,
a large number of interesting and important chemical
experiments on the heaviest elements were performed in the
recent years [2]. Theoretical investigations in this area havealso been very fruitful and resulted in some remarkableachievements [2, 3]. In the presentation, recent advances in
the relativistic electronic structure calculations for theheaviest elements and predictions of their experimental
behaviour are overviewed. An emphasis is put on thereliability of the theoretical approaches and models withrespect to the experimental outcome.
II. THEORETICAL METHODS AND RESULTS
For the heaviest elements, electronic structure
calculations should be made with the use of methods thattreat relativistic and electron correlation effects at the highest
possible level of theory. In the recent years, the relativistic
quantum theory and computational algorithms received
tremendous developments [4]. As a result, very accurate
calculations of the electronic structure and properties ofsuperheavy atoms and molecules became possible. On theirbasis, reliable predictions of experimental behaviour of theseelements in the sophisticated and expensive experiments withsingle species have been made [5].
For atoms, Dirac-Coulomb-Breit (DCB) calculations withelectron correlation at the highest level of theory, i.e., acoupled-cluster (CC) method, were performed for elements
till Z=122 [6]. Accurate predictions of such properties likeelectronic
configurations,
ionization
potentials,
polarizabilities, that are important for the placement of theelements and for the chemical experiments, have been made.
In the molecular theory, fully relativistic (4-component)
and 2-component wave-function (ab initio Dirac-Fock) [7]and Density-Functional-Theory (DFT) [8] methods have beendeveloped to such an extent that very accurate predictions ofbinding molecular energies, optimized geometry, electronic
density distributions, etc. are now available. On their basis,
predictions of experimental behaviour for gas-phase andaqueous chemistry chromatography experiments have been
made [2, 3, 5]. For the gas-phase experiments, direct
calculations of adsorption energy of atoms and molecules on
metal or other surfaces using relativistic DFT methods are
now possible via a cluster approach [9].
In the presentation, we will overview results of atomic
calculations till Z=122 that are important for placing theseelements in the Periodic Table. They are also used forpredictions of adsorption of atoms of these elements onneutral surfaces to guarantee their transportation from anaccelerator to the chemistry set up.
For the gas-phase chemistry experiments, predictions ofvolatility of group-4 through 8 compounds are presented andcompared. General trends and a common character of thechemical behaviour are outlined. Predictions of volatility ofelements in the atomic state, like of element 112, Cn, element
113, and element 114, Fl, as adsorption on neutral and metal
surfaces are also described and compared [9]. Interestingcases of volatility of even heavier elements, like 115, or 119
and 120 are considered.
Influence of relativistic effects on properties andexperimental behaviour of the heaviest elements is elucidated.
Future perspectives for the chemical studies on theheaviest elements from the theoretical point of view are
outlined.
Acknowledgment: The author is thankful to her free-willcollaborators J. Anton, T. Jacob, A. Borschevsky, E. Eliav and U.
Kaldor. She also thanks her colleagues, experimentalists, forvaluable discussions of experimental results.

REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

－ 55 －The Chemistry of Superheavy Elements, M: Schädel ed., Kluwer,
Dorderecht, 2003.
A. Türler and V. Pershina, Chem. Rev. 113, 1237 (2013).
V. Pershina, Radiochim. Acta 99, 459 (2011).
Relativistic Electronic Structure Theory, P. Schwerdtfeger ed., Parts I
and 2, Elsevier, Dordrecht, 2002 and 2004.
V. Pershina, In: Relativistic Methods for Chemists, Y. Ishikawa, M.
Barysz, eds., Springer, Dordrecht (2010), pp. 452-520.
U. Kador, E. Eliav, In: Ref. [4], Part 2, pp. 279-350.
K. G. Dyall and K. Faegri, Relativistic Quantum Chemistry, Oxford
University Press, 2007.
J. Anton, B. Fricke, E. Engel, Phys. Rev. A 69, 012505 (2004).
V. Pershina, J. Anton and T. Jacob, J. Chem. Phys. 131, 084713 (2009).

NCO-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Spectroscopy of Element 115 Decay Chains
D. Rudolph1, U. Forsberg1, P. Golubev1, L.G. Sarmiento1, A. Yakushev2, L.-L. Andersson3,
Ch.E. Düllmann2,3,4, J.M. Gates5, K.E. Gregorich5, F.P. Heßberger2,3, R.-D. Herzberg6, J. Khuyagbaatar2,3,
J.V. Kratz4, K. Rykaczewski7, M. Schädel2,8, S. Åberg1, D. Ackermann2, M. Block2, H. Brand2,
B.G. Carlsson1, D. Cox6, X. Derkx3,4, A. Di Nitto4, K. Eberhardt4, J. Even3, C. Fahlander1, J. Gerl2,
C.J. Gross7, E. Jäger2, B. Kindler2, J. Krier2, I. Kojouharov2, N. Kurz2, B. Lommel2, A. Mistry6,
C. Mokry4, H. Nitsche5, J.P. Omtvedt9, P. Papadakis6, I. Ragnarsson1, J. Runke2, H. Schaffner2,
B. Schausten2, P. Thörle-Pospiech4, T. Torres2, A. Türler10, A. Ward6, D. Ward1, N. Wiehl3,4
1

Lund University, S-22100 Lund, Sweden
GSI Helmholtzzentrum für Schwerionenforschung GmbH, D-64291 Darmstadt, Germany
3Helmholtz Institute Mainz, D-55099 Mainz, Germany
4
Johannes Gutenberg-Universität Mainz, D-55099 Mainz, Germany
5
Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
6
University of Liverpool, Liverpool L69 7ZE, United Kingdom
7
Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
8
Advanced Research Center, Japan Atomic Energy Agency, Tokai, Japan
9
University of Oslo, NO-0315 Oslo, Norway
10
Paul Scherrer Institute and University of Bern, CH-5232 Villingen, Switzerland

2

During the past decade, a number of correlated �-decay
chains, which all terminate by spontaneous fission, have been
observed in several independent experiments using 48Cainduced fusion-evaporation reactions on actinide targets [1].
These are interpreted to originate from the production ofneutron-rich isotopes with proton numbers Z = 113 to 118.
However, neither their mass, A, nor their atomic number, Z,
have been measured directly.
In November 2012, a three-week experiment was conductedat the GSI Helmholtzzentrum für SchwerionenforschungGmbH in Darmstadt, Germany, using high-resolution �-,electron, X-ray and �-ray coincidence spectroscopy to observe
�-X-ray events to identify uniquely atomic numbers of
isotopes in Z = 115 decay chains. The reaction 48Ca+243Am
was used, with fusion-evaporation products being focused
into the TASISpec set-up [2-4], which was coupled to thegas-filled separator TASCA [5,6].
A beam integral of roughly 7·1018 48Ca particles led to theobservation of about 25 correlated �-decay chains withcharacteristics similar to those previously published [7,8].
Results from the ongoing data analysis will be presented.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

Yuri Oganessian, J. Phys. G 34, R165 (2007).
L.-L. Andersson et al., Nucl. Instrum. Meth. A 622, 164 (2010).
L.G. Sarmiento, L.-L. Andersson and D. Rudolph, Nucl. Instrum.
Meth. A 667, 26 (2012).
U. Forsberg et al., Acta Phys. Pol. B 43, 305 (2012).
A. Semchenkov et al., Nucl. Instrum. Meth. B 266, 4153 (2008).
J.M. Gates et al., Phys. Rev. C 83, 054618 (2011).
Yu. Ts. Oganessian et al., Phys. Rev. C. 69, 021601 (2004).
Yu. Ts. Oganessian et al., Phys. Rev. Lett. 108, 022502 (2012).

－ 56 －

NCO-08
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Chemistry at a one-atom-per-week level
A. Yakushev
GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt, Germany

Long-lived isotopes of superheavy elements (SHE) withatomic number Z  108 can be produced via fusion reactions
between heavy actinide targets and neutron-rich projectiles at
a rate of single atoms per day or per week only. Investigating
the neutron-rich SHE nuclei using rapid chemical separationand subsequent on-line detection provides an independentchemical characterization and an alternative separation
technique to electromagnetic recoil separators. The highly
efficient separation of Hs in the form of HsO4 is animpressive example for such studies of the nuclear reaction
mechanism and nuclear structure [1,2]. Approaching theheaviest elements, copernicium (Cn), element 113 andflerovium (Fl), which are accessible for chemistry
experiments, the coupling of chemistry setups to a recoil
separator promises extremely high sensitivity due to strong
suppression of background from unwanted species.
FL: NOBLE GAS OR VOLATILE METAL?

RESULTS
Two decay chains, one from 288Fl and one 289Fl weredetected. Both decays from Fl isotopes occurred in the firstdetector array at room temperature. The positions of decay
chain members are shown in Fig. 1 together with distributionsof Pb, Hg, and Rn and the Monte−Carlo simulated deposition
peak for 285Cn (dashed line). The observed behavior of Fl in
the chromatography column is indicative of Fl being lessreactive than the nearest homolog Pb. The evaluated lower
limit of the adsorption enthalpy −Hads(Fl) > 48 kJ/mol
reveals the formation of a metal-metal bond with Au, which
is at least as strong as that of Cn, and thus demonstrates themetallic character of Fl.

Electron shells of SHE are influenced by strong relativistic
effects caused by the high value of Z. Early atomic
calculations for Fl predicted this to have quasi-closed electron
shell configuration 6d107s27p1/22, and to be noble gas-like due
to very strong relativistic effects [3]. Recent fully relativistic
calculations studying Fl in different environments suggest
this to be less reactive compared to its lighter homologues in
the group, but still exhibiting metallic character [4]. The
dilemma, is Fl a noble gas or a noble metal, calls forexperiments. Comparative studies of the interaction of Fl, Cn,
Pb, Hg and Rn in the elemental state with metal surfaces are a
powerful tool for distinguishing between metallic and noblegas-like chemical behaviour. This was shown in experimentswith Cn [5]. For Fl, the formation of a weak physisorption
bond upon adsorption on gold was inferred from firstexperiments [6].

0
-50
-100
-150

a)
COMPACT I

COMPACT II

b)

Pb

c)

Hg

Rel. Yield / % per Detector

20
0
20
0
10

d)

Rn

5
0
10

Fl

e)

Cn

Fl
Cn

Fl

0

10

2

Cn
Ds

20

30

40

50

60

0

Counts / Det.

INTRODUCTIONCOMPACT [1,2]. Two detector arrays connected in series
were used, both covered with a thin gold layer. The firstdetector array was connected directly to the exit of TASCA
and kept at room temperature. A negative temperature
gradient from +20 to −162 °C was applied along the second
detector array placed downstream of the first one. The use of
two detectors in series allowed the detection of species in awide volatility range – from the non-volatile Pb to the noble
gas Rn.

Temp / °C

Keywords – superheavy elements, element 114, flerovium, gas
chromatography, adsorption

Detector Number

GAS-SOLID CHROMATOGRAPHY OF FL AT TASCA

Fig.1: The observed gas-chromatography behavior of Fl and Cn in
COMPACT compared to those of Pb, Hg and Rn.

The present gas chromatography study on Fl upon theadsorption on gold was performed at a gas-filled separator
TASCA [7]. Flerovium isotopes were produced in the nuclear
reaction 244Pu(48Ca;3,4n)288,289Fl. Thez were separated in
TASCA and stopped in a gas-filled chamber and flushed by a
He/Ar gas mixture within 0.8 s to a detection setup

[1]
[2]
[3]
[4]
[5]
[6]
[7]

－ 57 －

J. Dvorak et al. Phys. Rev. Letters 97, 242501 (2006).
J. Dvorak et al. Phys. Rev. Letters 100, 132503 (2008).
K.S. Pitzer. J. Chem. Phys. 63, 1032 (1975).
V. Pershina et al. J. Chem. Phys. 131, 084713 (2009).
R. Eichler et al. Angew. Chem, Int. Ed. 47, 3262-3266 (2008).
R. Eichler et al. Radiochim. Acta 98, 133-139 (2010).
A. Semchenkov et al. NIM B 266, 4153-4161 (2008).

NCO-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Sg(CO)6 – The First Organometallic Transactinde Complex opening a Window to a
New Compound ClassJ. Even 1, A. Yakushev2, Ch.E. Düllmann1,2,3, H. Haba4, M. Asai5, T.Sato5, H. Brand2, A. Di Nitto3,
R. Eichler6,7, F. Fangli8, W. Hartmann2, M. Huang4, E. Jäger2, D. Kaji4, J. Kanaya4, Y. Kaneya5,
J. Khuyagbaatar1, B. Kindler2, J.V. Kratz3; J.Krier2,Y. Kudou4, N. Kurz2, B. Lommel2, S. Miyashita5,
K. Morimoto4, K. Morita4, Y. Nagame5, H. Nitsche9,10, K. Ooe11, M. Schädel5, J. Steiner2, T. Sumita4,
K. Tanaka4, A. Toyoshima5, K. Tsukada5, A. Türler 6,7, I. Usoltsev 6,7, Y. Wakabayashi4, Y. Wang8,
N. Wiehl1,3, S. Yamaki4,12, Q. Zhi8
1

Helmholtz-Institut Mainz, Johannes Gutenberg-Universität, 55099 Mainz, Germany;
GSI – Helmholtzzentrum für Schwerionenforschung, Planckstr. 1, 64291 Darmstadt, Germany;
3
Johannes Gutenberg-Universität Mainz, 55099 Mainz, Germany;
4
Nishina Center for Accelerator-Based Science, RIKEN, Wako, Saitama 351-0198, Japan;
5Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan;
6
University of Berne, Freiestrasse 3, CH-3012 Berne, Switzerland;
7
Paul Scherrer Institute, CH-5232 Villigen, Switzerland;
8
Institute of Modern Physics Lanzhou; Chinese Academy of Sciences, 509 Nanchang Road, CN-730000 Lanzhou, China;
9
University of California, Berkeley, CA 94720-1460; U.S.A.;
10
Lawrence Berkeley National Laboratory, Berkeley, CA 94720-8169 U.S.A.,
11
Niigata University, Niigata, Niigata 950-2181, Japan,
12
Saitama University, Saitama 338-8570, Japan.
2

Abstract – We report on the synthesis and chemical investigation of
the first organometallic compound of a transactinide element,
namely seaborgium hexacarbonyl.
Keywords – Seaborgium, Carbonyl Complex, Adsorption, Hot
chemistryIn the last decades, simple inorganic compounds of thetransactinde elements (TAN) were studied in gas phasechemical reactions [1]. Accessing, e.g., metal complexes
with organic ligands or organometallic compounds was
impossible due to technical restrictions, like the destructive
plasma present behind the target created by the intense heavy
ion beam. Thanks to the novel approach of physicalpreseparation in a recoil separator to reject the beam [2],these limitations could be overcome [3]. In previous
experiments, we demonstrated the formation of volatile delement carbonyl complexes with recoiling ions thermalized
in a carbon monoxide containing atmosphere [4]. Short-lived
isotopes of the lighter homologs of seaborgium –molybdenum and tungsten showed this to be an appropriate
method to study group 6 elements under conditions relevant
for a transactinide chemistry experiment.
Seaborgium hexacarbonyl has been predicted to be stable[5]. The π-back bonding, characteristic for the metal-carbon
bond in carbonyl complexes, is expected to be stronger thanin the complexes of the lighter homologues due to therelativistic expansion of the d-orbitals. Furthermore, Sg(CO)6
is predicted to be as volatile as tungsten hexacarbonyl andtherefore suitable for, e.g., thermochromatography studies [6].
Based on previous studies with molybdenum and tungsten, an
experiment aiming at the study of seaborgium hexacarbonyl

was conducted at the gas-filled recoil ion separator GARIS at
RIKEN. In our experiment, 265a,bSg (t1/2=8.5 s, 14.4 s) [7] wassynthesized in the reaction 248Cm(22Ne,5n). Seaborgium wasseparated within GARIS from the primary beam and was
guided to the recoil transfer chamber (RTC) mounted in the
focal plane of GARIS [8]. The 265Sg was thermalized within
the RTC in a helium carbon-monoxide mixture under ambientconditions. This way it formed volatile carbonyl complexes
and was transported in the gas stream to the radiochemistrylaboratory. There, its adsorption on silicon dioxide wasstudied with the thermochromatography detector COMPACT.
The combination of preseparation with GARIS and detection
in COMPACT allowed the study of seaborgium underbackground-free conditions.
Our results indicate the observation of Sg(CO) 6 and allow
to compare its behavior to that of W(CO)6 and to theoreticalpredictions. At the moment, the data analysis is ongoing.
Experimental details and results will be presented at theconference.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

A. Türler and V. Pershina, Chem. Rev. 2013, 113, 1237−1312.
Ch E. Düllmann et al., Nucl. Instr. Meth. A 2005, 551, 528–539.
Ch.E. Düllmann et al., Radiochim. Acta 2009, 97, 403-418.
J. Even, et al., Inorg.Chem. 2012, 51, 6431-6422.
C.S. Nash, B. E. Bursten, J. Am. Chem. Soc. 1999,121, 10830-10831.
V. Pershina and J. Anton, submitted to J. Chem Phys. 2013.
H. Haba et al., Phys. Rev. C 2012, 85, 024611.
H. Haba et al, Chem. Lett. 2009, 38, 426-427.

This experiment was performed at RI Beam Factory operated by
RIKEN Nishina Center and CNS, University of Tokyo. We thank the ion
source and RILAC operators Financial support from the German BMBF
under contract 06MZ7164 and from JAEA Tokai, Advanced Science
Research Center's Reimei research program is gratefully acknowledged..

－ 58 －

NCO-10APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Superheavy Element Z and A Measurements at the Berkeley Gas-Filled Separator
H. Nitsche 1, 2, G. K. Pang 2, J. M. Gates 2, K. E. Gregorich 2 N. E. Esker 1, O. R, Gothe 1
12

University of California, Berkeley, Department of Chemistry, Berkeley, CA 94720-1460, USA
Lawrence Berkeley National Laboratory, Nuclear Science Division, Berkeley, CA 94720-8169, USA

Since the dawn of the new Millenium, six new superheavy
elements (SHE) (113, 114, 115, 116, 117, and 118) have been
produced in reactions of 48Ca beams with actinide targets. So
far, these experiments have led to the discovery of 52 newisotopes [1,2]. Several independent confirmation experiments
led to the recent naming of flerovium, Fl, and livermorium,
Lv, for elements 114 and 116, respectively [3-6��� � ���� �decay chains of these SHE terminate by spontaneous fission,
before reaching the part of the Chart of the Nuclides where Z
and A are well-established. The SHE Z and A assignments������������������������������������������-particle decayenergies with model calculations [7], supplemented withcross-bombardment information. Thus, neither Z nor A have����� ��������� ���������� � ������� ������ ��������� �-decayenergies to adjust mass models, these Z and A assignments
must be proven to be correct. Otherwise a situation could
arise where data from incorrect assignments are used tomodify mass models which, in turn, reinforce the incorrect
assignments. Identifying Z by detecting �� - K x-ray
coincidences [9], known as x-ray fingerprinting, is an alreadyestablished process. The first results of x-ray finger printing
experiments conducted for element 115 produced in the243
Am(48Ca,3n)288115 reaction using the Berkeley Gas-Filled
Separator (BGS) at the 88-inch cyclotron at Lawrence
Berkeley National Laboratory will also be presented.
However, to simultaneously identify both Z and A with the
BGS, we are making several upgrades to its detection setup,
design and construct a new mass analyzer, as well a gas
catcher and a radiofrequency quadrupole ion trap (RFQ) to
match the output of the BGS to the acceptance of the mass
analyzer. The first SHE to be studied using these new
upgrades at the BGS will be 289Fl [9] produced in the fusion
evaporation reaction of 244Pu(48Ca,3n). Z-identification isconducted in the same manner as described above andcoupling of the x-ray fingerprinting setup with a mass
analyzer, then provides a simultaneous determination of A
and Z.
[1]
[2]
[3]
[4]
[5]

[6]
[7]
[8]
[9]

Acknowledgement:This work is supported by U.S. Department of Energy, Office of Science,
Nuclear Physics, Low Energy Physics Program, and was performed atLawrence Berkeley National Laboratory under Contract No. DE-AC0205CH11231.

Y.T. Oganessian, J. Phys. G 34, R165 (2007).
Y.T. Oganessian, Radiochim. Acta 99, 429 (2011)
L. Stavsetra, K. E. Gregorich, J. Dvorak, P. A. Ellison, I. Dragojevic´,
M. A. Garcia, and H. Nitsche, Phys. Ref. Let. 103, 132502 (2009).
Ch. E. Düllmann et al., Phys. Ref. Let. 104, 252701 (2010).
P. A. Ellison, K. E. Gregorich, J. S. Berryman, D. L. Bleuel, R. M.
Clark I. Dragojevic´, J. Dvorak, P. FallonC. Fineman-Sotomayor, J. M.
Gates, O. R. Gothe, I.Y. Lee, W. D. Loveland, J. P. McLaughlin, S.
Paschalis, M. Petri, J. Qian, L. Stavsetra, M. Wiedeking, and H.
Nitsche, Phys. Ref. Let. 105, 182701 (2010).
J. M. Gates et al., Phys. Rev. C 83, 054618 (2011).
A. Sobiczewski et al., Prog. Part. Nucl. Phys. 58, 292 (2007).
C.E. Bemis et al., Phys. Rev. Lett. 31, 647 (1973).
Y.T. Oganessian et al., Phys. Rev. C 69, 054607 (2004).

－ 59 －

NCO-11APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Intermetallic Actinide compounds for SHE Production TargetsadcaR. Eichlera,b, I. Usoltseva,b, J.P. Omtvedt, O. V. Petrushkin, D. Piguet, A. V. Sabel’nikovc, A.
a,bcc
Türler , G. K. Vostokin , A. V. Yeremin

Laboratory for Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, CH-5232 Villigen, Switzerlandb
Department of Chemistry & Biochemistry, University of Berne, Freiestrasse 3, CH-3012 Berne, SwitzerlandcFlerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, 141980 Dubna, RussiadUniversity of Oslo, 0316 Oslo, Norway

Recent experiments with superheavy elements require highintensive heavy ion beams and highly sophisticated target
technologies able to stand the harsh irradiation conditions.
Especially, stationary target technologies based on painting
and molecular plating of actinide oxides onto thin Ti foils
reveal severe target degradation by the intensive beams.
These effects lead to a considerable drop in the production
rates and transport yields of SHE to chemical setups.
Seeking for better target material possibilities we focusedour research onto metallic targets. These metallic targets
are expected to be superior to the widely used nowadays
solely electroplated targets due to higher thermal
conductivity, electrical conductivity, chemical stability, andmechanical stability. We proposed a simple method whichallows producing Pd-based intermetallic targets for highintensity irradiations [1]. Based on the molecular plating
technique [2] followed by coupled reduction [3] thismethod was successfully applied to different lanthanide andactinide isotopes [1]. First irradiation experiments withintermetallic targets were carried out at the Oslo Cyclotron
Laboratory, University of Oslo, Norway. Here, a 3.5 µm
238
U/Pd target was irradiated at the MC-35 Scanditronix
cyclotron using a 0.5 �A proton beam with cyclotron
energy of 30 MeV. This experiment showed the possibilityof safe handling of such targets in accelerator environments.
Two 243Am/Pd intermetallic targets have been prepared andirradiated at the U-400 cyclotron at the Flerov Laboratory
for Nuclear Reactions for several days. Both 243Am targets
were characterized by alpha-particle spectroscopy and lightmicroscopy before and after irradiation with high intensity
beams of 48Ca. For direct comparison, the performance of a‘classical’ electroplated 243AmO2/Ti target was investigated.
Figure 1 shows optical micrographs revealing the clear
superiority of intermetallic targets. Challenges andpossibilities connected to the use of intermetallic
compounds as high power irradiation targets will bepresented.

A:

B:
Figure 1: Micrographs of irradiated targets. A) titanium
based target after irradiation with 48Ca particles at
intensities of up to 7�1012 48Ca per second for about 120
hours; B) palladium based target after irradiation with 48Caparticles at almost two times higher intensities compared tothe titanium based target of up to 1.2�1013 48Ca per second
for about 60 hours. The Pd foil and the actinide distribution
remain nearly unchanged.
Acknowledgments: We thank the crews form the ion sourceand U-400 cyclotron of FLNR Dubna for providing intense
beams of 48Ca. This research was supported by Swiss
National Science Foundation grant 200020_126639.
References[1]I. Usoltsev, et al., Preparation of Pd-based intermetallic targets for highintensity irradiations, Nucl. Instr. and Meth. Phys. Res.A691, 5–9 2012.
[2]W. Parker, et al., Nucl. Instr. and Meth. 26, 61 (1964).
[3]S. Möbius, L. Hellwig, C. Keller, J. Less-Common Met. 121, 43 (1986).

－ 60 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

NCO-12The First Successful Observation of Mass-separated Lawrencium (Lr, Z = 103)
Ions with ISOL Technique
T. K. Sato1, M. Asai1, N. Sato2, Y. Kaneya1,3, K. Tsukada1, A. Toyoshima1, S. Miyashita1,
Y. Nagame1, M. Schädel1, A. Osa3, S. Ichikawa1,4, K. Ooe5, T. Stora6, J. V. Kratz7
1

Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
3
Graduate School of Science and Engineering, Ibaraki University, 2-1-1, Bunkyo, Mito, Ibaraki 310-8512, Japan3
Department of Research Reactor and Tandem Accelerator, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
4
Nishina Center for Accelerator-Based Science, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
5
Institute of Science and Technology, Niigata University, Niigata 950-2181, Japan
6
ISOLDE, CERN, CH-1211 Geneva 23, Switzerland
7
Institut für Kernchemie, Universität Mainz, D-55099 Mainz, Germany
2

Abstract – In order to determine the first ionization potential of
the heaviest actinide lawrencium (Lr, Z=103), we have developed
a surface ionization ion-source as part of the JAEA-ISOL (Isotope
Separator On-Line) setup, which is coupled to a He/CdI2 gas-jet
transport system. We will report on the first successful ionizationand mass separation of 27-s 256Lr produced in the 249Cf+11B
reaction.
Keywords – Lawrencium (Lr), Heavy actinide, Ionization
potential, ISOL, Surface ionization, Ion source

I.

INTRODUCTION

The ground-state electronic configuration of lawrencium(Lr, Z = 103) that is the heaviest actinide element ispredicted to be [Rn]5f147s27p1/2, which is different from thatof the lanthanide homolog lutetium (Lu) [Xe]4f146s25d. The
reason for this change in the ground state configuration isthat the 7p orbital of Lr is stabilized below the 6d orbital bystrong relativistic effects [1]. The weakly-bound outermost
electron results in a significantly lower first ionization
potential of Lr as compared to its neighboring heavy
actinides [2]. The ionization potential of Lr, however, has
not been determined experimentally owing to its low
production rate and short half-life. In order to determine theionization potential of Lr, we have developed a surface
ionization type ion-source for the JAEA-ISOL coupled to agas-jet transport system [3]. As a step to determination of
the ionization potential of Lr, we conducted to ionize ashort-lived Lr isotope by using the ion-source in several
ionization conditions.
II. EXPERIMENTAL
The isotope 256Lr (T1/2 = 27 s) was produced in thereaction of 249,250,251Cf(11B, xn)256Lr [4]. A 249,250,251Cf target(249Cf: 63%, 250Cf: 12%, and 251Cf : 25%) with 185 ± 25
�g/cm2 on a 1.85 mg/cm2 thick Be backing foil was
irradiated with a 67.9-MeV (63 MeV in the middle of thetarget) 11B4+ beam from the JAEA tandem accelerator. For
comparison the lutetium isotopes 168mLu and 168gLu, withhalf-lives of 6.7 min and 5.5 min, respectively, weresynthesized in the 162Dy(11B, 5n) reaction. The nuclear

reaction products recoiling from the targets weretransported to the ion-source by a He/CdI2 gas-jet transportsystem. The products were ionized in the ion-source,
accelerated with 30 kV, and then mass-separated with amass-separator in ISOL. The amount of ions collected at
the end of the ISOL after mass-separation was determinedby �- or �-ray measurements. To calculate ionization
efficiencies, nuclear reaction products transported from atarget recoil chamber were collected directly and measured
prior to the ionization experiments. To compare theionization efficiencies on different surface material of theion-source, a rhenium (Re) surface and a tantalum (Ta)surface were employed in this study.
III. RESULTS AND DISCUSSION
We successfully ionized and mass-separated 256Lr for
the first time by using the developed ion-source andapplying the ISOL technique. The Ionization efficiencies of
Lr and Lu on the Re surface were obtained to be 42 + 20-1
9 % and 19.9 ± 7.0 %, respectively. In the case of the Ta
surface, the efficiency of Lr was 19 + 9-8 % while that of Lu
was 4.0 ± 1.4 %. The ionization efficiency of each elementon the Re surface was larger than that on the Ta surface
because the work function of Re is higher than that of Ta.
Under both conditions, the ionization efficiencies of Lr
are larger than those of Lu. The results indicate that theionization potential of Lr must be lower than that of Lu.
This is consistent with the theoretical prediction from acoupled cluster (CC) calculation that takes into accountrelativistic effects [3].
In the presentation, we will report on the firstexperimental determination of the first ionization potentialof Lr based on our latest results.
[1]
[2]
[3]
[4]

－ 61 －

Zou, Y. and Fischer, C. F. Phys. Rev. Lett. 88 (2002) 183001.
Borschevsky, A. et al. Eur. Phys. J. D45 (2007) 115.
Sato, T. K. et al. Rev. Sci. Instrum. 84 (2013) 023304.
Sato, N. et al. JAEA Rev. 2010-056 (2010) 52.

NEI-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Nuclear Energy Chemistry in China: Present Status and Future Perspectives
Zhi-Fang Chai

Nuclear Energy Chemistry Group, Key Laboratory of Nuclear Analytical Techniques
Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
E-mail: chaizf@ihep.ac.cn
Nuclear energy chemistry is one of the most challenging
subjects in modern science, and its development is tightly
related to the advanced nuclear fuel cycle and persistentdevelopment of nuclear energy. Nuclear energy chemistryin China is now experiencing a renaissance, which is being
strongly motivated by China’s huge energy demand. In thistalk, the recent progresses in nuclear energy chemistry of
China are selectively highlighted, with emphasis on thefront-end chemistry, actinide solid-state chemistry
associated with nuclear fuel fabrication, actinide solution
chemistry and nuclear fuel reprocessing as well as
chemistry in nuclear waste disposal and management.
Some positive measures about how to promote the nuclear
energy chemistry in China are discussed, and future
perspectives are briefly outlined as well.
Acknowledgement – This work was supported by Natural Science
Foundation of China (Grants 91026007, 91226201 and 11275219) andthe "Strategic Priority Research Program" of the Chinese Academy of
Sciences (Grants.XDA030104).
[1]

WQ Shi, YL Zhao, ZF Chai. Radiochim Acta. 2012, 100: 529.

－ 62 －

NEI-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Evaluation of new extractants relevant to the back-end of nuclear fuel cycle
A. Goswami
Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai – 400 085, INDIA
E-mail: agoswami@barc.gov.in

Abstract:. Conventionally, PUREX and THOREX processes have been proposed for the reprocessing of U and Th based spent fuels
employing tri-n-butyl phosphate (TBP) as extractant. However, some major limitations of TBP have been identified and need to beaddressed. Evaluation of alternative extractants is, therefore, desirable which can overcome at least some of these problems. Extensive
studies have been carried out on the evaluation of N,N-dialkyl amides as extractants in the back-end of the nuclear fuel cycle foraddressing the issues related to the reprocessing of U and Th based spent fuels. Similarly, efforts have been made on the evaluation of
new solvents for the partitioning of minor actinides (MA) from high-level waste (HLW) solutions. This talk presents an overview ofstudies carried out at Radiochemistry Division on (a) spent fuel reprocessing of U/Th based spent fuels employing N,N-dialkyl amides
as extractants, and (b) partitioning of minor actinides using novel solvents .
Keywords – Reprocessing; Actinide partitioning; Tributyl phosphate; Dialkyl amides; Diglycolamides

chemical properties (including extraction/stripping) of these
extractants for hydrometallurgical applications. A flow sheet
has been proposed using DHOA as extractant. Merits of flowsheets proposed for the separation and recovery of minor
actinides from HLW have also been discussed. Detailed batchas well as mixer settler studies have shown that tridentate
diglycolamide based ligands such as TODGA and TEHDGA
have excellent properties for the partitioning of actinides from
HLW solution.
103
102
101

DAm

The challenging task of recovery and purification of 239Pu from
irradiated U and of 233U from irradiated Th are accomplishedpresently by the well known PUREX and THOREX processes,
respectively [1]. These processes employ tri-n-butyl-phosphate(TBP) in n-dodecane as solvent. However, a few drawbacks
associated with the use of TBP have been identified: (i)deleterious nature of its degradation products (ii) relatively
lower distribution coefficient of Pu(IV) as compared to that ofU(VI) (iii) significant solubility of TBP towards aqueous phase,and (iv) non-incinerable nature of the spent solvent yielding
large volumes of secondary radioactive waste. These
shortcomings may pose a serious challenge particularly during
the reprocessing of short-cooled (MOX) thermal reactor,
Advanced Heavy Water Reactor (AHWR, being developed inIndia based on Th) as well as fast reactor spent fuels with larger
Pu content and significantly higher burn up [2]. In this context,
large number of eco-friendly N,N-dialkyl amides were evaluatedas alternative extractants at Radiochemistry Division, BARC,
Mumbai, India. Amongst these amides, N,N-dihexyloctanamide(DHOA) and N,N-di(2-ethylhexyl)isobutyramide (D2EHIBA)
received considerable attention as potential alternatives
extractants for the reprocessing of U and Th based spent
nuclear fuels, respectively [3]. Batch extraction, mixer settler/
centrifugal contactor runs were carried out with these reagents
under Pu rich feed (relevant to fast reactor) and AHWR feed
conditions, respectively. These data were compared with thoseobtained with TBP as extractant under identical experimental
conditions and a flow sheet for AHWR spent fuel reprocessing
has been proposed [4].
Actinide partitioning is the proposed strategy for
effective mitigation of the long term hazards associated withhigh-level waste (HLW). Octyl-(phenyl)–N,N-diisobutyl
carbamoyl methyl phosphine oxide (CMPO) has been studied
extensively during eighties for actinide partitioning from wastes
of different origin. However, the last two decades, substituted
malonamide extractants such as N,N’-dimethyl-N,N’-dibutyl
tetradecyl malonamide (DMDBTDMA) and N,N’-dimethylN,N’-dioctyl hexylethoxy malonamide (DMDOHEMA) haveemerged as viable green alternatives to phosphine oxides.
Recently, diglycolamide based extractants such as N,N,N�,N�tetraoctyl diglycolamide (TODGA) and N,N,N�,N�-tetra-2ethylhexyl diglycolamide (TEHDGA) have received
considerable attention due to overwhelmingly favorable
extraction and stripping efficiencies of minor actinides fromdifferent types of transuranium (TRU) wastes (Fig.1) [5,6]. We
have carried out comparative evaluation of the key physical and

100
10-1

TRPO
CMPO
DMDBTDMATODGATEHDGA

10-2
10-3
0

1

2

3

4

[HNO3], M

5

6

Fig.1: Variation of DAm with HNO3 concentration; Extractants: 30%
TRPO, 0.2M CMPO+1.2M TBP, 1M DMDBTDMA, 0.1M TODGA +0.5M DHOA and 0.2M TEHDGA + 30% iso-decanol; Diluent: ndodecane; Temperature: 25°C

Acknowledgement: Author thanks Dr. P.K. Mohapatra and
Dr. P.N. Pathak for their help in preparing this paper.
References
1.

2.
3.
4.
5.
6.

－ 63 －“Reactor Hand Book”, S.M. Stoller and R.B. Richards (Eds.), v. 2,“Fuel reprocessing”, Interscience Publishers & Inc., New York,1961.
R.K. Sinha, A. Kakodkar, A. Nucl. Engg. Design, 2006, 236, 683.
V.K. Manchanda, P.N. Pathak, Sep. & Purif. Technol., 35(2004) 85.
N. Kumari, D.R. Prabhu, A.S. Kanekar, P.N. Pathak. Ind. Engg.
Chem. Res., 51 (44) (2012) 14535.
S.A. Ansari, P.N. Pathak, Prasanta K. Mohapatra, Vijay K.
Manchanda. Chemical Reviews, 112(3) (2012) 1751.
Seraj A. Ansari, Priyanath Pathak, Prashant K. Mohapatra andVijay K. Manchanda. Sep.& Purif. Reviews, 40 (2011) 43.

NEO-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Hexanoic acid as alternative diluent in a GANEX process based on TBP and
CyMe4-BTBPElin Löfström-Engdahl1, Emma Aneheim1, Christian Ekberg1, Hanna Elfversson1 and Gunnar
Skarnemark1
Nuclear chemistry , Industrial Materials Recycling2, Department of chemical and Biological Engineering,
Chalmers University of Technology, SE 412 96 Gothenburg, Sweden
1

Abstract – Used nuclear fuel is radiotoxic for mankind andits environment for a long time. However, if it can betransmuted the radiotoxicity can be reduced.
Simultaneously the long term heat load is decreased,making a final storage more volume efficient. Before thetransmutation the actinides within the used fuel need to be
separated from the fission, corrosion and activation
products. This separation can be achieved by using thetechnique liquid-liquid extraction.
One extraction process that can be used for such a
separation is the GroupActiNideEXtraction (GANEX)
process. In a GANEX process all the actinides are to be
separated from the rest of the fuel as one group. This
extraction leaves all the fission, corrosion and activation
products in the aqueous stream. One GANEX process thatcan successfully accomplish the An(III)/Ln(III) separation
utilizes the diluent cyclohexanone in combination with theextractant tributylphosphate (TBP) (30 % vol) and asecond ligand, CyMe4-BTBP (10 mM). However, there aresome issues when using cyclohexanone as diluent, forexample; it has a low flash point and it degrades in contact
with the acidic aqueous phase. In this work an alternative

diluent has therefore been tried in order to rule out if it canreplace cyclohexanone. The diluent used was hexanoic acid.
In the system containing 12 mM CyMe4-BTBP and 30 %vol TBP in hexanoic acid and the aqueous phase being 4 M
HNO3 the distribution ratio for plutonium is high (DPu = 76
± 17), while the one for uranium is lower (DU = 2.2 ± 0.25).
The distribution ratios for americium and curium are
unfortunately much lower than that of plutonium (DAm= 1.1± 0.27, DCm=1.6 ± 1.81). The concentration CyMe4-BTBP
ligand, the extractant of curium and americium, could
unfortunately not be increased, because of limited solubility
in hexanoic acid. The distribution ratios for fission,
corrosion and activation products were low for mostly
metals; however, silver, cadmium, palladium andmolybdenum all have distributions ratios above 1 istherefore troublesome. Europium is used as arepresentative lanthanide, which are similar to the trivalentactinides and therefore hard to separate. The distribution
ratio for europium is low in this system (D Eu = 0.12 ±0.016). However, to conclude, the low americium andcurium extractions indicate that hexanoic acid cannot
replace cyclohexanone in a GANEX process.

－ 64 －

NEO-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effect of alcohols on separation behavior of rare earth elements using
benzimidazole-type anion-exchange resin in nitric acid solutions
1

Tomobuchi Yusuke1, Yu Tachibana1, Masao Nomura2 and Tatsuya Suzuki1
Department of Nuclear System Safety Engineering, Graduate School of Engineering, Nagaoka University of Technology,
2
Laboratory for Nuclear Reactors, Tokyo Institute of Technology

Abstract - Chromatographic separation experiments of trivalentrare earth elements were performed using benzimidazole typeanion-exchange resin in nitric/alcohol mixed solvent systems atroom temperature. As a result, it was found those trivalent rareearth elements are able to be separated mutually in a 20 % HNO3
and 80 % MeOH mixed solvent. Based on these results, we
systematically examined using various alcohols to make clear therole of alcohols in anion-exchange reactions at various
temperatures.

Keywords - rare earth elements, alcohols, benzimidazole-typeanion-exchange resin, mutual separation
I. INTRODUCTION
As a final disposal method for the high level liquid
waste(abbreviated as HLLW) generated by spent-nuclear-fuelreprocessing plants, the geologic disposal concept of thevitrified HLLW has been proposed and investigated globally.
Especially, from the viewpoint of minimizing the long-term
radiological risk and facilitating the management of HLLW, a
separation of the long-lived minor actinides(MA = Am andCm) from HLLW is strongly desired.1) Moreover, a mutual
separation of Am and Cm is also required after the separationof MA from HLLW because the relatively high decay heat ofCm makes it difficult to fabricate nuclear fuels reproduced
from spent nuclear fuels.2) On the other hand, it has been wellknown that the difficulty of a mutual separation between
trivalent Am and Cm is due to similar chemical properties.2)
In fact, although a few reports by Hale et al. using
diethylenetriaminepentaacetic acid and Suzuki et al. withtertiary pyridine have been reported, little systematic
information is available on the mutual separation mechanisms
between Am and Cm.2,3) Therefore, as a part of thefundamental researches to innovate conventional separation
technologies, we have studied on the chromatographic
separation of trivalent rare earth elements(abbreviated as
REE (REE = La, Ce, Pr, Nd, Sm, Eu, and Gd)) which havethe same valence level in solutions and the similar ion radii ascompared with those of MA, using benzimidazole type anionexchange resin (abbreviated as AR-01) embedded in highporous silica beads in nitric acid/alcohol mixed solvent
systems.
II. EXPERIMENTAL
All REE were used without further purification. The purityof all REE was more than 98.0%. All chemicals for sample
preparations were of special pure grade. AR-01 resin

consisted of styrene-divinylbenzene copolymers with 4-(1methylbenzoimidazole-2-yl)phenyl and 4-(1,3-dimethylbenzoimidazole-2-yl)phenyl, was supplied from Asahi Kasei
Corporation. Each concentration of REE species in thesolutions were determined by ICP-MS(7700x, Agilent).
III. RESULTS
Chromatographic separation experiments of trivalent REE
were performed using AR-01 resin in a nitric acid solvent
system and a nitric/alcohol mixed solvent system at room
temperature. As a result, it was found that mutual separationsof REE cannot be achieved completely in HNO3
solutions(data no shown), but REE are able to be separated
mutually in a 20 % HNO3 and 80 % MeOH mixed
solvent(see Figure 1). In addition, retention times obtained
from these chromatograms of the REE increase withincreasing the ion radii in order of Gd, Eu, Sm, Nd, Pr, Ce,and La, i.e., it could be estimated that the separation
mechanisms proceed through anion-exchange reactions
between 4-(1,3-dimethyl-benzoimidazole-2-yl)phenyl groupsof AR-01 and [Ln(NO3)n]3-n (n �� �� . Based on these results,
we concluded that the examined separation technique isapplied to mutual separation of Am and Cm.

ACKNOWLEGEMENT
This work was partially supported by the Grant-in-Aid for
Scientific Research (B) (KAKENHI No. 23360423).
REFERENCES
[1]

[2]
[3]

－ 65 －

Kolarik, Z., Journal of Nuclear Fuel Cycle and Environment, 5, 21-35(1998)
Suzuki, T., Otake, K., Sato, M., Ikeda, A., Aida, M., Fujii, Y., Hara, M.,
Mitsugashira, T.,Ozawa, M., Journal of Radioanalytical and Nuclear
Chemistry, 272, 257-262 (2007)
Hale, W.H., Lowe, J.T., Inorganic and Nuclear Chemistry Letters, 5,363-368 (1969)

NEO-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Speciation and Reactivity of Heptavalent Technetium in Concentrated Acids.
Frederic Poineau1, Philippe Weck2, Benjamin P. Burton-Pye3, Alesya Maruk4, Gayane Kirakosyan4,
Ibthihel Denden5, Daniel. B Rego1, Erik V. Johnstone1, William Kerlin1, Eunja Kim1, Mairlynn Ferrier1,
Alfred P. Sattelberger7, Wayne Lukens6, Massoud Fattahi5, Lynn C. Francesconi3, Konstantin E. German4,
and Kenneth R. Czerwinski1.
1

Department of Chemistry, University of Nevada Las Vegas, Las Vegas, NV, USA.
2
Sandia National Laboratories, Albuquerque, NM 87185, USA.
3
Department of Chemistry, Hunter college of the City University of New York, NY, USA
4
A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, RussianFederation
5 Laboratory Subatech, Ecoles des Mines de Nantes, Nantes, France
6
Energy Engineering and Systems Analysis Directorate, Argonne National Laboratory, Lemont, IL, USA.
7
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, 94720, USA

Keywords – Technetium, Speciation, EXAFS spectroscopy.

Discovered 75 years ago, technetium is the lightest
radioelement. Thirty four isotopes are known; the mostcommon isotopes being 99Tc (t1/2 = 2.1 x 105 y) and 99mTc (t1/2= 6 h). The isotope 99Tc is a fission product of the nuclear
industry, while the isotope 99mTc is used in nuclear medicine
as an imaging agent. Current researches focus on thedevelopment of 99mTc radiopharmaceuticals, and on thedevelopment of separation process and waste form storage for99
Tc. Technetium exhibits nine oxidation states (-1 to +7).
Under oxidizing conditions, the aqueous chemistry of Tc(+7)
is dominated by the pertechnetate anion, TcO4-. In high acidconcentration, TcO4- can be protonated and pertechnetic acid,HTcO4, is formed. The structure and reactivity of HTcO4 ispoorly studied. Studying the chemistry of Tc(+7) inconcentrated acids is relevant to the fundamental and appliedchemistry of technetium; it will allow to better understand the
behavior of Tc(+7) in separation processes whereconcentrated acids are used. In this work, the speciation andreactivity of Tc(+7) in concentrated HNO3, H2SO4 and HClO4
is investigated. The resulting complexes are characterized by
NMR, UV-visible and EXAFS spectroscopy and DFT
calculations. Results show the formation of TcO3(H2O)2(OH)in concentrated H2SO4 and HClO4 while TcO4- inconcentrated HNO3. The complex TcO3(H2O)2(OH) reacts in
13 M H2SO4 with MeOH to produce TcO(HSO4)3(OH)-. In
HNO3 > 7 M , the pertechnetate anion reacts with hydrogen
peroxide to produce TcO(O2)2(H2O)OH. The results
demonstrate the complex and little explored chemistry of Tc
in concentrated acids.

－ 66 －

NEO-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Fluorescence Studies of Complex Stoichiometry of Metal ions in Extraction
Systems Combining Dibutyl Phosphoric Acid and Tri-n-butyl Phosphate
Alexander Braatz and Mikael Nilsson

University of California, Irvine
Department of Chemical Engineering & Materials Science
916 Engineering Tower
Irvine, CA 92697-2575
abraatz@uci.edu
Advanced nuclear fuel cycles are dependent on successful
chemical separation of the various elements present in theused fuel. Numerous extraction systems have beendeveloped for the recovery and separation of the various
metal ions present in the used fuel. Extraction oflanthanides and actinides by tri-n-butyl phosphate (TBP)
and dibutyl phosphoric acid (HDBP) is of importance forone of these processes, the PUREX process.
The
combination of these two extraction reagents have beenshown to synergistically enhance metal ion extraction anddisplay characteristics of microemulsion aggregates ofreverse micelle type. To improve our understanding of thecomplexes formed in this system we further studied theextraction of lanthanides and actinides, in our casedysprosium, Dy, and uranium, U, with TBP and HDBP in
conjunction with 2D fluorescence spectrometry. Aqueous
samples containing Dy3+ and UO22+ in nitric acid were
contacted with organic phases containing varying ratios of
TBP and HDBP in n-dodecane and the distribution was
followed by neutron activation analysis. 2D Fluorescence
spectra were examined for all lanthanides and uranium.
Typically, europium is used as a benchmark for lanthanides
in fluorescence studies but we show here that several otherlanthanides exhibit excellent spectroscopic characteristics
using this technique. The effects of acid on the fluorescence
spectra will be investigated. Possible explanations ofphenomena and comparison to existing Eu studies found inliterature will also be presented.

－ 67 －

NEO-05

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Column study on electrochemical separation of cesium ions from wastewater using
copper hexacyanoferrate film
Rongzhi Chen 1), Hisashi Tanaka 1), Miyuki Asai 1), Chikako Fukushima 1), Tohru Kawamoto 1), Manabu Ishizaki 2),
Masato Kurihara 1,2), Makoto Arisaka 3), Takuya Nankawa 3) and Masayuki Watanabe 3)
1)
Nanosystem Research Institute, AIST, Tsukuba central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan2)
Department of Material and Biological Chemistry, Faculty of Science, Yamagata University, 1-4-12 Kojirakawamachi, Yamagata 990-8560, Japan
3)
Japan Atomic Energy Agency, 2-4 Shirane Shirakata, Tokai-mura, Naka-gun, Ibaraki 319-1195, Japan
Abstract – We coated the copper hexacyanoferrate (CuHCF) on
the gold electrodes, and then performed the Cs removal byelectrochemical separation (ES). The prepared CuHCF
nanoparticles can be simply and uniformly coated on electrodes
by wet process like conventional printing methods, so any sizes orpatterns are feasible at low cost, which indicated the potential asa promising sorption electrode of large size in the columns forsequential removal and recycle of Cs from wastewater.

Metalhexacyanoferrate
complex,
Keywords:
Electrochemical separation, Cesium, Radioactive waste,
Nanoparticle ink, Prussian blue complex.
Introduction

Transition metal hexacyanoferrates (HCFs) are
preferred to be competitive ion exchangers over othermaterials due to their selectivity and high capacity. Amongthem, copper (II) hexacyanoferrate (III) (CuHCF) is often
selected as the agent in practical analysis. This compound
has been much used as precipitants for alkali metal cations,especially cesium, to remove them from aqueousradioactive wastes [1].
However, small sized CuHCF particles can easily
contaminate water, which restricts its direct use for column
operations. Herein, we developed and coated the waterdispersible CuHCF nanoparticles on the electrodesubstance, and then performed Cs removal. This study
evaluates the electrochemical Cs sorbability of CuHCF NPs
film and estimates the potential as a promising sorption
electrode of large size in the columns for sequential
removal and recycle of Cs from wastewater.

Fig. CV of a Cu-HCF film under different temperatures (from 298
to 338 K), and effect of temperature on Cs sorption using CuHCF
film

In order to using our film for practical analysis in thefield-scale applications, column study is needed. We
synthesized water-dispersed nanoparticle CuHCF ink andthen coated its nanoparticles on SUS316L sheet electrodes.
The Cs adsorption and desorption were alternately repeatedfor 5 cycles (30 min/cycle), initial Cs conc. is 9.858 ppm.
The well balance of Cs desorption and adsorption,
indicated the CuHCF film has a long life in the columns forsequential removal and recycle of Cs from wastewater.

Experimental & Results

The Cs adsorption was performed in a three-electrodecell in which an Hg/Hg2Cl2/KCl (saturated solution) as
reference electrode, a platinum electrode (as counterelectrode), and the CuHCF film coated adsorbent electrodewere used as the working electrodes. The redox reaction for
Cs separation process is proposed as follows [1]:Cu3[Fe III (CN)6]2) + 2e� + 2Cs+ � Cs2Cu3[Fe II (CN)6]2
To examine the effect of temperature, electrochemical
characterization of CuHCF film and its Cs adsorptions wereconducted at 298, 313, and 323 K, respectively. Cs removal
decreased with the increase in temperature for CuHCF film
(Fig. 3b). Namely, the Cs adsorption process was
exothermic in nature.

Fig. Cs alternate adsorption and desorption performance using
CuHCF film

Effective regeneration and large surface coating willallow it to be used in the column for sequential removal
processes.
[1] RZ. Chen, et al., Electrochimica Acta, 2013, 87
119－ 68 －

Oral Presentations
Wednesday, 25 September 2013
Hall & Meeting Room, Kanazawa Bunka HallTime
09:00-09:10
09:10-09:20
09:20-09:30
09:30-09:40
09:40-09:50
09:50-10:00
10:00-10:10
10:10-10:20
10:20-10:30
10:30-10:40
10:40-10:50
10:50-11:00
11:00-11:10
11:10-11:20
11:20-11:30
11:30-11:40
11:40-11:50
11:50-12:00
12:00-12:10
12:10-13:20
13:20-13:30
13:30-13:40
13:40-13:50
13:50-14:00
14:00-14:10
14:10-14:20
14:20-14:30
14:30-14:40
14:40-14:50
14:50-15:00
15:00-15:10
15:10-15:20
15:20-15:30
15:30-15:40
15:40-15:50
15:50-16:00
16:00-16:10
16:10-16:20
16:20-16:30
16:30-16:40
16:40-16:50
16:50-17:00
17:00-17:10
17:10-17:20
17:20-17:30
17:30-17:40
17:40-17:50
17:50-18:00
18:00-18:10
18:10-18:20
18:20-18:30
18:30-18:40
18:40-18:50
18:50-19:00
19:00-19:20
19:20-19:40
19:40-20:00
20:00-

9:00

PL-05

Wednesday, 25 SeptemberHall
Meeting RoomPlenary

9:30

PL-06

M. A. Denecke
Plenary
J. Hatazawa

10:00

Coffee Break

10:20

RPI-01

Invited

ACI-01

Invited

10:50

RPI-02

D. S. Wilbur
Invited

ACI-02

J. Li
Invited

11:20

RPO-01

11:40

RPO-02

12:00

S. Lahiri
General
ACO-01
E. Aneheim
General
ACO-02
Y. Hatsukawa
Group Photo (Hall)
Lunch Time

Y. Kitatsuji
GeneralA. Kirishima
GeneralH. Hayashi

13:20
13:40 JNRS General Assembly(For Member of JNRS))
14:00
14:20
14:40

JNRS Meeting

15:00
15:20

Coffee Break

15:40

RPO-03

16:00

FKO-11

16:20

FKO-12

16:40

FKO-13

17:00

FKO-14

17:20

General

ACO-03GeneralE. Rasmussen
GeneralK. Minami
GeneralT. Kawamoto
GeneralD. Parajuli

ACO-04

L. Safavi-Tehrani

NCO-13
NCO-14
NCO-15

Coffee Break
17:50

JNRS Award Presentation(Open Session)
T. Kimura

18:30
18:50
Poster Session
20:00－ 69 －

GeneralT.H. Park
GeneralN. Aoyagi
General
A. Toyoshima
GeneralP. Steinegger
GeneralR. TripathiPL-05APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Actinide speciation using synchrotron-based methods
1

M. A. Denecke1

Dalton Nuclear Institute, University of Manchester, Manchester, M13 9PL, UK

Abstract – Synchrotron-based techniques are increasingly
used to characterize materials and elucidate determinant
processes relevant to the nuclear fuel cycle. Most recent
advances are driven by the need to characterize materials
with high spatial resolution, for example localizedcomponentsofheterogeneous
systemsorinterstitial/interfacial junctions. In this presentation,
examples of synchrotron-based investigations covering awide range of wavelengths (infra-red to hard X-ray) andspatial resolution (nanometer range to bulk) will be
introduced. The examples are chosen to illustrate various
themes of research and development over the entire rangeof the nuclear fuel cycle, from power plant lifetime extension
scenarios to nuclear waste disposal and future fuel/target
development.
Keywords –Actinide speciation, X-ray techniques, synchrotron
radiation－ 70 －

PL-06APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Radionuclides in Diagnostic Nuclear Medicine
Jun Hatazawa

Department of Nuclear Medicine and Tracer Kinetics, Osaka University Graduate School of Medicine
WPI-Immunology Frontier Research Center, Osaka University
Abstract – Diagnostic Nuclear Medicine (NM) is an essential
procedure in modern medical practice. Recent survey reported
that more than 2 million NM examinations are conducted every
year in Japan. Around 75% of diagnostic NM employs single
photon emission tomography (SPECT) with 99mTc, 123I, 133Xe, or
201
Tl-labeled compound, and 25% positron emission tomography(PET) with 18F-fluorodeoxy glucose, 15O-labeled H2O, CO, O2, or
11
C-labeled compounds. Modern medicine is based on theintervention of molecular pathology of the diseases. Therefore,
NM is expanding in number and in quality in daily medical
practice including early diagnosis of Alzheimer’s diseases, cancer,
and cardiovascular diseases, strategy decision of treatment,
evaluation of regeneration medicine. Furthermore, the NM is
being utilized to facilitate new drug development. Combining
molecular diagnosis with radionuclide therapy (Theranostics) is
another future direction of clinical NM.
Keywords – Nuclear Medicine, Molecular Imaging, Theranostics

Nuclear Medicine is now employed as a major
tool of sensitively detecting molecular changes ofthe diseases before symptom onset. In
Alzheimer’s disease, amyloid deposition in brain
tissue can be detected more than 10 years earlier
than the onset. Abnormality in cerebral perfusion
predicts a probability of ischemic stroke onset.
PET examination can detect small cancer involume before invasion and remote metastasis.
Therapy response can be detected mostsensitively among imaging modalities. The
number of NM examination is therefore
increasing dramatically recent years.
The application of NM is extending tofacilitate new drug development (PET microdosing test). Because of high specific activity ofradionuclide-labeled
compound,pharmacokinetics of candidate compounds can be
examined in humans. Combining moleculardiagnosis of NM with radio-nuclide therapy(Theranostics) is another direction of NM. Nano
particles with designed chemistry, size, surface
charge, and target-specific binding ligands can
extend “Nuclear Medicine Theranostics” byspecifically carrying therapeutic radioisotopes
and drugs to diseased tissues.
There are several problems to expand clinical
NM. The shortage of 99Mo supply is most critical.

99

Mo is now being produced by old nuclear
reactors of specific countries. 99Mo-99mTc
generator completely depends on the import of99
Mo. We are now trying to produce 99Mo withaccelerator by 100Mo(n,2n)99Mo reaction. After
improving irradiation of solid target, separationand purification of 99Mo in solid target, we
obtained 99mTc for bone scintigraphy of rats.
Following steps of this project are mass
production, clinical trial, approval by regulatory
authority, and commercial delivery.
For the NM theranostics, we need radionuclides with specific characteristics. It should
emit gamma ray with appropriate energy(100~200keV) for imaging and beta particles fortherapy. Nowadays, 89Sr and 90Yo are utilized totreat bone metastasis of cancers and malignant
lymphoma, respectively. Since these tracers are
pure beta particle emitting radionuclides, anevaluation of radio-nuclides accumulation is notpossible by NM imaging. 131I (gamma ray of
364keV, beta particle of 606keV) is utilized forthe treatment of hyperthyroidism, pheochromocytoma, and thyroid cancer. Imaging is possibleby adapting heavy collimation of high energy
gamma ray.
Functional nano particles are now applied to
NM. Non-radioactive nano particles have beensafely used in clinical trials of anti-cancer drugs(Nature 496:S58-60, 2012). The difficulty ofradionuclides labeled nano particles is that thelabeling process should be rapid because ofphysical decay of radionuclides. Long enoughphysical decay (13 hour of 64Cu, 13 hour of 123I,
and 100 hour of 124I) is required for this purpose.
Finally, the process from experimental study toclinical trial (translational medical center) has
been installed in Osaka University Hospital under
the support of Ministry of Health, Labor, andWelfare, Japan, which will be introduced in thispresentation.

－ 71 －

RPI-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Addressing Challenges in Preparation of 211At-Labeled Biomolecules for Use in
Targeted Alpha Therapy
D. Scott Wilbur1, Donald K. Hamlin1, Ming-Kuan Chyan1, Ethan R. Balkin1, John M. Pagel2,3,
Oliver W. Press2,3, and Brenda M. Sandmaier2,31

Radiation Oncology and 2Medicine, University of Washington, Seattle, WA, USA
3Fred Hutchinson Cancer Research Center, Seattle, WA, USA

Abstract – There are significant challenges in the development of
211
At-labeled biomolecules for application to targeted alphatherapy. Challenges that we have addressed include developmentof: (1) labeling methods to obtain high in vivo 211At-label stability,(2) approaches to consistently obtain high recovery yields ofNa[211At]At from irradiated bismuth targets, (3) methods tooptimize biomolecule labeling yields, (4) reagents for use of 211At
in pretargeting approach to cancer therapy, and (5) 211At-labeled
antibodies in conditioning for hematopoietic cell transplantation.
Keywords – Astatine-211, antibodies, pretargeting, biotin

I.

INTRODUCTION

There are only ten �-emitting radionuclides identified ashaving properties suitable for targeted alpha therapy [1]. Of
that small group of radionuclides, astatine-211 (211At) is
particularly attractive due to its reasonable half-life (t1/2 =7.21 h), lack of �-emitting daughter radionuclides, andrelative ease of preparation from an inexpensive target
material (bismuth metal). However, application of 211At tothe development of targeted alpha therapy has beendifficult due to the low number of cyclotrons with
(operating) alpha beams used in its production [2], and ahost of problems involving the labeling chemistry and invivo stability of 211At-labeled biomolecules [3]. We haveinvestigated 211At-labeled biomolecules for over two
decades and have had to address many challenging
problems associated with 211At during that time.
II. RESULTS AND DISCUSSION
One of the most impactful challenges to development ofAt-labeled biomolecules has been their low in vivo
stability. Early studies demonstrated that the 211At label
was stabilized on non-activated aryl compounds. However,
the in vivo stability is only retained in slowly metabolizedbiomolecules, such as intact monoclonal antibodies (MAbs).
Thus, in vivo stability has been a problem with MAb
fragments, peptides or smaller biomolecules, where thearyl-At bond can be rapidly cleaved in vivo. We haveinvestigated chelation of 211At, oxidation of 211At on arylgroups, and changing the bonding atom to boron forstabilization of the 211At bonding. In the latter approach, anumber of boron cage molecules have been evaluated as
pendant groups for attachment of 211At to biomolecules.
Of the different types of boron cage molecules studied,the closo-decaborate(2-) cage [B10 cage] has proven toprovide high in vivo stability. In addition to high stability,that pendant group has made labeling of proteins much
more efficient and easy to conduct. This is due to the fact
211

that the high electrophilic reactivity of the closodecaborate(2-) moiety permits conjugation with proteinsprior to astatination. This is in contrast to using a 2-steplabeling procedure required with aryl-astatine reagents.
Another significant challenge became apparent when thesize of the bismuth target was increased in preparation fortranslating 211At-labeled MAbs into clinical studies. Ourstandard method for isolation of 211At was “dry distillation”.
However, the larger bismuth target and requisite larger
quartz glassware resulted in low and inconsistentdistillation yields of 211At. Therefore, we switched to a“wet chemistry” isolation approach. That approach hasprovided very consistent and high recovery yields. Anotheradvantage of the wet chemistry approach is that it may
permit automation of the isolation process.
Developing 211At-labeled reagents for use in pretargeting
approaches to cancer therapy has been another challenge.
For example, it initially appeared that preparation of an211
At-labeled biotin reagent might be relatively straightforward. However, many of the biotin derivatives prepared
localized to kidneys or liver, or did not work in thepretargeting protocol. In some studies, biotin derivatives
that did not localize in tumor bound with MAb-streptavidin
conjugates. We knew the lack of binding with tumor could
be due to formation of biotin-sulfone. We investigatedformation of biotin-sulfone with chloramine-T (ChT)
oxidant, but believed that our labeling conditions did notform the sulfone as the labeled product bound to an avidin
column. Presently, we are investigating labeling biotin
derivatives with other oxidants or no oxidant.
The oxidant ChT has also been found to cause problems
with 211At-labeled MAb-B10 conjugates. Studies todecrease the amount of ChT in the radiolabeling reactions
with MAb-B10 conjugates have shown that no oxidant isrequired in the 211At reactions. We now know that underacidic or neutral conditions, At is electropositive enough toundergo electrophilic reactions with closo-decaborate(2-)
cages. In reactions without oxidant we obtain labelingyields equivalent to those with oxidant.
A further challenge is developing methods to keep 211Atlabeled small biomolecules from localizing in kidneys. We
have conducted a number of studies in that area as well. An
overview of some of our research to circumvent challenges
encountered when using 211At in development of Targeted
Alpha Therapy agents will be presented.
REFERENCES
[1]
[2]
[3]

－ 72 －

D. S. Wilbur, Current Radiopharm. 4, 214 (2011).
M. R. Zalutsky, M. Pruszynski, Current Radiopharm. 4, 177 (2011)
D. S. Wilbur, Current Radiopharm. 1, 144 (2008).

RPI-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Generation of nuclear data for the production of 97Ru from 12C+89Y reaction
Moumita Maiti1, Susanta Lahiri2

1

Department of Physics, Indian Institute of Technology Roorkee, Roorkee-247667, India
2
Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata-700064, India

Keywords – 97Ru, cross section measurement, yield, stacked foil
technique, 89Y target, 12C projectileI.

INTRODUCTION

Due to the suitable nuclear properties, 97Ru has been
proposed for a number of applications. Besides highchemical reactivity of ruthenium helps to produce
various 97Ru-labelled complexes concerned to theapplication. Investigation on the production cross sectionof 97Ru is important as it helps to optimize the production
and to maintain the purity of the product.
Several attempts to produce 97Ru through p, 3He and �particle induced reactions on suitable targets have beenreported. In a recent attempt we produced no-carrier-added(NCA) 97Ru through 93Nb(7Li,3n)97Ru reaction anddeveloped radiochemical separations[1]. This article reports
the experimental measurement of production cross section
and yield of 97Ru from 12C+89Y reaction.

nat
Y(12C,4n)97Rh(EC)97Ru&
producedthroughnat
1297m
Y( C,4n) Rh(EC: 94.4%, IT: 5.6%) 97Ru reactions.
Measured cross sections of 97Ru at different projectile
energies are therefore cumulative of all reaction channels.
All possible errors are considered in the error analysis andthe data presented up to the 95% confidence level. Figure 1
shows the maximum cross section of 97Ru is ~780 mb at~67 MeV bombarding energy and the trend of themeasured data nicely follows the theoretical estimation of
PACE4, which essentially calculates the fusion-evaporation
cross section following the Hauser-Feshbach model.
Moreover, measured cross sections of 97Ru are comparable
to the sum of cross sections of 97Ru+97Rh. Figure 2 shows
the measured yield of 97Ru at various bombarding energies.
The maximum yield of 110 kBq/µA.h was obtained at ~67
MeV energy. However, a thick target yield of >0.5
MBq/�A.h can easily be achieved if the thickness of the Y
foil and proper projectile window is chosen.

Cross section [mb]Abstract – This article reports the measurement of cross section
and yield of 97Ru in 12C induced reaction on natural yttrium target
in the 40-75 MeV incident energy range. Cumulative crosssection/yield of 97Ru was measured by stacked foil technique��������� ��� ���� ����� �-ray spectrometry. Measured data follows
the trend of theoretical estimation.

II. EXPERIMENTAL
Production cross sections and yield of 97Ru produced in
C+89Y reactions were measured by the stacked foil
technique followed by off-����� �-ray spectroscopy. Thinself supporting Y foils (99.9% purity) of thickness 1.9-2
mg/cm2 were prepared by proper rolling. A target stack wasassembled with 3 such Y foils; each Y foil was backed byan aluminum catcher foil of thickness 1.5 mg/cm2, and wasirradiated with 12C6+ ions. A total of four such target stacks
were irradiated independently varying the incident energy
with an overlap between them. The experiment was carriedout at the BARC-TIFR pelletron accelerator facility,
Mumbai, India. The integrated charge was recorded in each
irradiation by an electron-suppressed Faraday cup stationed
at the back of the target assembly. The cross sections of97
Ru produced at various incident energies were calculatedusing the standard activation equation whose detail
description is available elsewhere [2].
12

900
800
700
600
500
400
300
200
100
0

Rh-97
Ru-97
Rh-97+Ru-97
Ru-97 [mb]45 50 55 60 65 70 75 80 85 90

Energy [MeV]
Figure 1. Comparison of cross sections of 97Ru (symbol) with thetheoretical excitation functions (lines) of 97Ru, 97Rh and sum of(97Rh+97Ru) as obtained from PACE4

III. RESULTS AND DISCUSSION
Production 97Ru was contributed by the direct reaction (i)Y(12C,p3n)97Ru and (ii) indirect reaction, through the
decay of short-lived 97Rh(30.7min),97mRh(46.2min)

Figure 2. Measured yield of 97Ru at different projectile energies

nat

[1]
[2]

－ 73 －

M. Maiti, S. Lahiri, Radiochim. Acta 99, 359 (2011)
M. Maiti, S. Lahiri, Phys. Rev. C 81, 024603 (2010)

RPO-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Towards an automatic procedure for the production of astatinated antibodies
1

Emma Aneheim1, Sture Lindegren1, Holger Jensen2

Targeted Alpha Therapy group, Department of Radiation Physics, Sahlgrenska Academy at Gothenburg University, SE41345
Gothenburg, Sweden
2
Cyclotron and PET Unit, KF-3982, Rigshospitalet, Copenhagen, Denmark

In recent time targeted radiotherapy of cancer tumors have been
given a larger interest. For microscopic tumors, alpha therapy is
especially interesting due to the high LET of the alpha particles.
One promising nuclide for targeted alpha therapy is 211At. 211At
decays with 100% alpha-emission along two different branches anddoes not emit any major quantities of gamma, allowing for safe
handling of large activities. At Sahlgrenska Academy in Sweden,
research regarding alpha therapy using astatine and monoclonal
antibodies has been ongoing for over fifteen years. The research has
been taken from bench to bedside including a number of preclinicalstudies and a phase I clinical trial on nine patients with recurrent
ovarian cancer. However, to be able to move forward towards phase
II/III studies the current synthesis of radiolabeled antibodies would
benefit from being automated. The automation will be performed
using a custom made radiopharmaceutical module from Scintomics
Gmbh. This procedure, however, requires both modifications of thesynthesis, as well as an adaptation of the astatine distillation
process. The work presented here concerns such an automation of
the production of astatinated antibodies.
Keywords – Astatine-211, antibodies, radiopharmaceutical module－ 74 －

RPO-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013������������������������������������������������
Yuichi Hatsukawa1, Kazuyuki Hashimoto1, Kazuaki Tsukada1, Tetsuya Sato1, Masato Asai1, Atsushi
Toyoshima1, Yasuki Nagai1, Toru Tanimori2, Shinya Sonoda2, Shigeto Kabuki3,
Hideo Saji4, Hiroyuki Kimura4
1

Japan Atomic Energy Agency
Department of Physics, Kyoto University
3
School of Medicine, Tokai University
4
Faculty of Pharmaceutical Sciences, Kyoto University2��������� – ����� ���� ������������ ��� ���� �������� ������� ������
�������������������������������������������������������������������
������������������������������������� ��������������� �����������
�������������������������������������������������������������
��������� ��� ���� ��������������� ��������� ������ ��� �����������
����������������������������������������������������
���������–����������������������������������������������
������������������������������������I.

INTRODUCTION

Technetium-99m is used in radioactive medical
diagonostic tests, for example as a radioactive tracer that
medical equipment can detect in the human body. It is well
suited to the role because it emits readily detectable 141
keV gamma rays, and its half-life is 6.01 hours (meaningthat about 94% of it decays to technetium-99 in 24 hours).
There are at least 31 commonly used radiopharmaceuticals
based on technetium-99m for imaging and functional
studies of the brain, myocardium, thyroid, lungs, liver,gallbladder, kidneys, skeleton, blood, and tumors. Recent
years, with the develop-ment of the Compton camera which
can realize high position resolution, technetium isotopes
emitting high energy gamma-rays are required. In thisstudy, technetium-95m which emits some gamma rays
around 800 keV was produced by the 95Mo(p,n)95mTc
reaction.

accelerator. Averaged beam currents were 1.2 A. After a
few weeks cooling time, about 300-500 kBq of 95mTc wereextracted from the irradiated MoO3 target after a chemical
separation shown in Fig.1
Using purified 95mTc, a labeled compound, 95mTc-MDP(methylene diphosphate) was synthesized. In order toexamine quality of the labeled compounds obtained in thisstudy, thin-layer chromatography (TLC) method was
carried out. A spot of solution of the labeled compound wasplaced at the edge of the TLC plate, and the plate stood upright in a solvent. Two kind of solvents, Methyl ethyl
ketone (MEK) and physiological saline were used. Afterabout 10 -30 min dipping time, TLC plates were dried andtaken autoradiography images using imaging plates for 12hours. The result of labeling experiment was shown in Fig.
2. According to this result, labeled compound, 95mTc-MDP
was synthesized well.
Then, Compton camera imaging was taken by theElectron-tracking Compton gamma-ray camera which wasdeveloped by prof. T. Tanimori’s group of Kyoto university
for medical usage.[2-3] The results obtained from theseexperiments will be discussed in the APSORC meeting.

Fig.2 Autoradiography images form 95mTc-MDP. MEK
and physiological saline was used as solvents.
����������
[1] M.Izumo, et al., Appl. Radiat. Isot. 42 297-310 (1991)[2] T. Tanimori et al., New Astron. Rev. 48 (2004) 236.
[3] S.Kabuki et al., NIM,A623(2010) 606

Fig.1 Chemical purification procedure of Tc-95m from
MoO3 target.
II. EXPERIMENTAL and RESULTS
A 300-700 miligrams of natMoO3 targets were irradiatedwith 15 MeV proton beam for 7 hours at the JAEA Tandem－ 75 －APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

ACI-01����������������������������� �������������������������������������
�������������������������������������������
Jing Su and Jun Li*
Department of Chemistry, Tsinghua University, Beijing 100084, China*E-Mail: junli@tsinghua.edu.cn
Abstract Ð Investigations of the actinide spectroscopy andchemistry have been an active field of research recently. Actinide
complexes are challenging for theoretical studies because of theirsignificant relativistic effects and strong electron correlation
effects. �������������� ������������� ������ ��� �� ���������
������������� ���������� ��� ���������� ��������� ������������ ������
���� ����������� ����������� ��� ������� ������� ���� �������� ������� ������������ ��������� � ��� ����� ����� ��� ����� �������� ���� ������� ��������
����� �� ������� ��� ������ relativistic quantum mechanical andp������������� ������������� studies on actinyl complexes anduranium halides. Computational details on how to accurately
describe excited states with spin-orbit coupling (SOC) will begiven. We will focus on the electronic structures of UO2X3- andUO2X42- (X = F, Cl, Br, I) complexes. Theoretical simulation of
their experimental photoelectron spectra will also be discussed.

������ �� Observed and calculated adiabatic (ADE) and verticalÐa(VDE) detachment energies for UO2X3 (X = F, Cl, Br, I).
�Exp
DFT/PBECCSD(T)
�
SR
SO
SR
SO
Ð
UO2F3
ADE
6.25 (5)5.44 5.31
6.48
6.35
VDE
6.53 (5)5.62 5.52
6.81
6.71
Ð
UO2Cl3ADE
6.64 (5)5.47 5.41
6.82
6.76
VDE
6.72 (5)5.52 5.47
6.88
6.83
Ð
UO2Br3ADE
6.27 (5)5.24 5.18
6.45
6.39
VDE
6.37 (5)5.24 5.18
6.45
6.39
Ð
UO2I3
ADE
5.60 (5)4.84 4.71
5.86
5.73
VDE
5.72 (5)4.85 4.72
5.86
5.73
�
�
All the energies are in eV.
The numbers in parentheses�
represent the experimental uncertainties in the last digit. These
SO results are estimated using the SR CCSD(T) energies with the������ SO-corrections from the DFT/PBE calculations.

Keywords Ð Actinyl, Relativistic Effects, Spin-Orbit Coupling,
Photoelectron Spectrum, Ab initio Wavefunction Theory

I.

INTRODUCTION

Uranyl halides play important roles in the extraction of
uranium into the aqueous phase and in serving as usefulstarting materials for the syntheses of a wide variety ofuranium compounds. In this work, we report a joint
photoelectron spectroscopy (PES) and relativistic quantum
chemistry study on the bonding and stability of a series ofgaseous tricoordinate uranyl halide complexes: UO2X3Ð (X= F, Cl, Br, I). Low temperature PES spectra were obtained
at 20 K for the first time by Wang and coworkers at Brown
University and these uranyl trihalides were observed to behighly stable electronically with extremely high electron
binding energies. Theoretical results from ab initio
wavefucntion theory (WFT) calculations agree well withexperiments (Table 1). Extensive bonding analyses for
UO2X3Ð and the doubly-charged tetracoordinate complexes(UO2X42Ð) show that the U�X bonds are dominated byionic interactions with weak covalency. Further theoretical
calculations show that the gaseous UO2X42Ð complexes arethermodynamically unstable against dissociation to UO2X3Ð
+ XÐ with decreasing dynamic stability from X = F to I.
The competition between the U�X bonding and the
Coulomb repulsions determines the kinetic stability of
UO2X42Ð (Figure 1).1-4

��������. Linear transit (LT) energy curves illustrating the dissociation of
UO2X42Ð � UO2X3Ð + XÐ (X = F, Cl, Br, I). The energies are obtained
from the DFT/PBE calculations.

REFERENCES
[1]

[2]

[3]

[4]

[5]

－ 76 －

J. Su, P. D. Dau, Y.-H. Qiu, H.-T. Liu, C.-F. Xu, D.-L. Huang, L.-S.
Wang, J. Li, ÒProbing the Electronic Structure and Chemical
Bonding in Tricoordinate Uranyl Complexes UO2X3Ð (X = F, Cl, Br,
I).Ó ������������ 52, 6617-6626 (����).
P. D. Dau, J. Su, H.-T. Liu, J.-B. Liu, D.-L. Huang, J. Li , L.-S.
Wang, "Observation and investigation of UO2F42- and its solvation
complexes with water and acetone nitrile", ���������. 3, 1137�1146(����).
F. Wei, G. Wu, W. H. E. Schwarz, J. Li, ÒExcited States andAbsorption Spectra of UF6: A RASPT2 Theoretical Study with SpinOrbit CouplingÓ, ��������������������� 7, 3223-3231 (����).
J. Su, Y.-L. Wang, F. Wei, W. H. E. Schwarz, J. Li, ÒTheoretical
Study of the Luminescent States and Electronic Spectra of UO2Cl2 in
an Argon MatrixÓ, ��������������������� 7, 3293-3303 (����).
J. Su, K. Zhang, W. H. E. Schwarz, J. Li, ÒUranyl-glycine-watercomplexes in solution: comprehensive computational modeling of
coordination geometries, stabilization energies, and luminescence
properties.Ó ������������ 50, 2082-2093 (����).

ACI-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Flow electrolysis of actinide ions utilizing electrocatalysis
Yoshihiro Kitatsuji

Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

Abstract – Flow electrolysis enables the exhaustive redox reaction
rapidly even the electrochemically irreversible reaction such as
reduction of actinide (V) ions. The flow electrolysis cell withplatinized glassy carbon fiber working electrode which acts aselectrocatalyst is effective to decrease overpotentials of reductionof NpO2+ and PuO2+. A rapid and precise method for the
preparation of U, Np and Pu ions of a desired oxidation state wasproposed by taking advantage of the electrocatalytic reaction.

The platinization of GC working electrode (abbreviated as
Pt/GC-WE, hereafter) was carried out by electrodepositionof platinum black onto GC fiber from an aqueous H2PtCl6
solution.
Flow electrolysis was performed by passing a solution
containing an actinide ion through narrow paths among GC
fibers in the column electrode at a constant flow rate.

Keywords – platinized electrode, actinide ion, flow electrolysis,
selective redox reaction

I.

III. RESULTS AND DISCUSSIONINTRODUCTION

Actinide ions (An) such as U, Np and Pu exist stably astrivalent to hexavalent ions in acidic and neutral solutions.
Control of the oxidation state of these ions to a desired one
and determine them are inevitable for the efficient chemical
separation or the precise analyses of them, because
chemical reactions such as liquid-liquid distribution andcomplex formation with ligands depend strongly on theoxidation state of the ions.
Electrode reactions of An4+/An3+ and AnO22+/AnO2+
couples are electrochemically reversible, and they havebeen well studied. On the other hand, those of An4+ andAnO2+ ions couples, which accompanying formation or
cleavage of An-O bond, are generally electrochemicallyirreversible and required a large overpotential. For thisreason, selective control of oxidation state of actinide ionsby electrolysis is difficult.
Flow electrolysis can attain the exhaustive redox
reduction even irreversible one, because electrolytes areelectrolyzed repeatedly during the stay of the sample
solution in the flow cell. It was reported that reduction of
AnO2+ and oxidation of U4+ can be carried out rapidly when
flow electrolysis was applied1.
Catalytic reaction can decrease the overpotential as aresult of facilitation of the charge transfer between the ion
and the electrode. The author has studied redox
mechanisms of actinide ions, and clarified thatelectrocatalytic reaction at Pt electrode can decrease
overpotential of reduction of NpO2+ ion2. Based on thesestudies, platinized carbon fiber electrode as a working
electrode of the flow electrolysis is expected to be a rapid
and precise electrolytic method for controlling oxidation
state of actinide ions.

Relations between current and potential for reductions of
UO22+, NpO2+ and PuO22+ in 1 M HClO4 were investigated.
Two-electron reduction of NpO2+ to Np3+ is occurred at 0.14 V when the ordinary GC-WE were employed. This
reduction is explained by the catalytic reaction where
Np4+/Np3+ couple acts as an electron transfer mediator for
NpO2+ reduction. So the potential observed for the NpO2+
reduction is close to that of Np4+ reduction. On the other
hand, overpotential of NpO2+ reduction is mitigated by
Pt/GC-WE electrode, and two-step reduction, i. e. the oneelectron reduction of NpO2+ to Np4+ followed by that of
Np4+ to Np3+, proceeded at the Pt/GC-WE. The
overpotential of reduction of PuO2+ is also decreased at
Pt/GC-WE, but reduction of UO22+ to U4+ in 1 M HClO4
was less affected by the electrode materials.
Based on the results of the flow electrolysis with Pt/GCWE, the selective adjustment of the oxidation states ofactinide ions can utilize. For example, when a solution
containing Np ions of various oxidation states iselectrolyzed at the potential in the ranges more positive
than +1.1 V, from +0.2 to 0 V, and more negative than
�0.26 V, the oxidation state of Np is adjusted to NpO22+,
Np4+ and Np3+, respectively; when a solution containing U,
Np and Pu ions is electrolyzed at the potential in the range
between +0.20 and +0.15 V, U, Np and Pu ions of different
oxidation states (i.e., UO22+, Np4+ and Pu3+) can beprepared3.
REFERENCES
[1]
[2]
[3]

II. EXPERIMENTAL
Flow electrolysis was performed by using the column
electrode system with glassy carbon (GC) fiber working
electrode. The GC fiber was packed tightly in a porous
glass cylinder of 8 mm inner diameter and 50 mm long.

－ 77 －

H. Aoyagi, Y. Kitatsuji, Z. Yoshida, S. Kihara, Anal. Chim. Acta,
538(2005)283.
Y. Kitatsuji, T. Kimura, S. Kihara, J. Electroanal. Chem.,
641(2010)83.
Y. Kitatsuji, T. Kimura, S. Kihara, Electrochim. Acta, 74(2012)215.

ACO-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of the thermodynamic quantities of U(VI) complexation with“aliphatic” and “aromatic” di-carboxylic acids by calorimetry
Akira Kirishima and Nobuaki Sato

Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,
2-1-1, Katahira, Aoba-ku, Sendai,980-8577, JapanThe thermodynamic quantities (�G, �H, �S) of complex formation of U(VI) with four “aliphatic” di-carboxylic
acids, i.e., glutalic acid (GA)[1], oxydiacetic acid (ODA), thiodiacetic acid (TDA), iminodiacetic acid (IDA), andfour “aromatic” di-carboxylic acids, i.e., isopthalic acid (IPA), 2,5-frandicarboxylic acid (FDA), 2,5thiophenedicarboxylic acid (TDCA) and dipicolinic acid (DPA) were determined by the potentiometric titration andmicro-calorimetric titration. So far, extensive data on stability constant have been obtained and summarized indatabases for a variety of combinations of actinide ions and ligands, which plays important role as the basic
parameters for the prediction of migration behavior of these elements in the geosphere, and for the development of
new separation process. However, enthalpy and entropy data of actinide elements are scarce in comparison withstability constants. These data are demanded not only for the understanding of the reaction mechanism but also forthe estimation of stability constants at elevated temperatures outside the range of 20 � 30 oC by the extrapolationfrom those at a room temperature with using thermodynamic models. Following our previous study reporting
thermodynamic data (�G, �H, �S) of complexation of 8 di-carboxylates with U(VI) [1], this paper presents thethermodynamic quantities of U(VI) complexation with four “aliphatic” di-acetic acids and four “aromatic” di-acetic
acids. Those ligands have a different center atom between two carboxylic groups, i.e., carbon for GA and IPA,
oxygen for ODA and FDA, sulfur for TDA and TDCA, and nitrogen for IDA and DPA, which may coordinate witha metal cation. The obtained thermodynamic quantities are compared with each other for the discussion of theeffect of structural difference i.e., aliphatic- and aromatic structure and types of central atom in the ligands on thecomplex formation thermodynamics.
From the obtained thermodynamic quantities, it is indicated that these reactions are mainly driven by the entropychange while the enthalpy change is not promoting the progress of the reaction. The �G, �H and �S of 1:1 IDA
complex show remarkable difference from those of GA complex, while those of ODA and TDA complex are
almost equal to those of GA complex. The -�G of 1:1 IDA complex with U(VI) was 30 kJ/mol larger than that of
GA complex, which is attributed to the chelate effect of the ligand. Our calorimetric measurement has revealed that
this “chelate effect” should be ascribed to the “entropy effect” since T�S of IDA complex was 50 kJ/mol larger thanthat of GA complex.
[1] A. Kirishima, Y. Onishi, N. Sato and O. Tochiyama, Radiochim. Acta 96 (2008) 581–589.

－ 78 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

ACO-02

Electrochemical Behavior of Americium in NaCl-2CsCl Melt
1

Hirokazu Hayashi1, Mitsuo Akabori1, Kazuo Minato1,2

Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency,
2-4 Shirakata-shirane, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195, Japan
2
Present address: Tokai Research and Development Center, Japan Atomic Energy Agency,
2-4 Shirakata-shirane, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195, Japan
Abstract –The behavior of Am in NaCl-2CsCl melt wasinvestigated by voltammetry, and potentiometry with an yttriastabilized zirconia membrance electrode. Redox reactions ofAm(III)/Am(II) and Am(II)/Am(0) were observed. Chemical
reaction of Am3+ ions with O2- ions in NaCl-2CsCl melt at 823K
has been considered to make Am2O3 precipitates.
Keywords – Am, molten salt, electrochemistryI.

molten NaCl-2CsCl containing oxide ion and silver ion([O2-]=0.01mol/kg, [Ag+]=0.37mol/kg) in which a silver
wire was dipped. The electromotive forth (EMF) of the cell
Ag|NaCl-2CsCl-AgCl-O2-|ZrO2-Y2O3|NaCl-CsCl-AmCl3O2-|Mulite|NaCl-2CsCl-AgCl|Ag was measured with anelectrometer (Keithley Model6514). Temperatures of themolten salt sample were measured with R typethermocouple set in an alumina tube.

INTRODUCTION

III. RESULTS AND DISCUSSION

For a basis of the future nuclear fuel cycle, it is very
important to understand and control the behavior of TRU(Np, Pu, Am, Cm) in the nuclear fuel cycle. Experimental
study of pyrochemical process of fuels containing TRU is
one of the important topics. But, few data are available inliterature on the behavior of TRU such as americium in
NaCl-2CsCl melt which is considered to be used as one of
the solvents for pyrochemical reprocessing. In the present
study, the behavior of Am in NaCl-2CsCl melt wasinvestigated by electrochemical methods.
II. EXPERIMENTAL
Anhydrous NaCl-2CsCl mixed salts (99.99%, Anderson
Physical Laboratory Engineered Materials (APL)),
cadmium chloride (99.9%, APL), and silver chloride(99.9%, APL) were used as purchased in this study. AmCl3
was prepared by the solid-solid reaction of americium
nitride and cadmium chloride [1]; 241AmO2 sample
prepared 35 years ago was used as a starting material. All
the materials were handled in a glove box or a hot cellmaintained with a purified argon gas atmosphere [2].
Typical impurities in the argon gas were H2O < 1 ppm andO2 < 1 ppm.
The sample in an alumina crucible was heated under an
Ar gas flow after setting a cover of the furnace having theelectrodes, and a stirrer made of Mo metal. Electrochemicalmeasurements with 3 electrodes were carried out for
AmCl3-(NaCl-2CsCl) system with X(AmCl3)=4.0×10-4
mainly at 823K using a PAR263A potensiostat/galvanostat
with a CorrWare electrochemical software (Scribner
Associates Inc.). The working electrode was a 1mm�tungsten wire. Assembled two tungsten wires (1mm��)
were used as the counter electrode. The reference electrode
was a silver wire (1mm�) dipped in the AgCl (X(AgCl)=
0.0487) - (NaCl-2CsCl) placed in a mulite tube.
Potentiometric titration of Am3+ ion with O2- ion using BaO(mixture of BaO and NaCl-2CsCl) was carried out at 823K.
The values for pO2- were monitored with a pO2- indicator
electrode made with yttria-stabilized zirconia filled with

A typical cyclic voltammogram shows 2 groups ofsignals close to the lower limit of the electrochemical
window. The lower limit signals around –2.3V correspondto electrodeposition of alkaline metal. The higher limit
signal around +1.0V corresponding to evolution of chlorine
gas was also observed. The signals can be assigned toredox reactions of Am(III)/Am(II) and Am(II)/Am(0)comparing with those in LiCl-KCl eutectic melt [3].
The EMF values were measured during the additions of
BaO from �= [O2-]/[Am3+]=0 to 2.22. ��is defined as theratio of added oxide ion over the initial Am(III) ion. The
titration curve shows only one equivalent point at � = 1.5.
This value corresponds to the formation of Am2O3
according to the reaction, 2Am3++3O2-=Am2O3(s). The
chemical form of the precipitation of plutonium in themolten salts has been reported as Pu2O3 [4, 5]. Our results
indicate the similarity of the precipitation behavior of Am
with that of Pu in molten salts.
ACKNOWLEDGMENTS
Part of the present study was carried out within thecollaborative research program of TRU behavior in
pyrochemical processes with Tohoku Electric Power
Company, Tokyo Electric Power Company and The Japan
Atomic Power Company.
REFERENCES
[1]
[2]
[3]
[4]
[5]

－ 79 －

H. Hayashi, M. Takano, M. Akabori, K. Minato, J. Alloys Compd.
456, 243-246 (2008).
K. Minato, M. Akabori, T. Tsuboi, S. Kurobane, H. Hayashi, M.
Takano, H. Otobe, M. Misumi, T. Sakamoto, I. Kato, T. Hida,
JAERI-Tech 2005-059 (2005) (in Japanese).
H. Hayashi, M. Akabori, K. Minato, Nucl. Technol., 162, 129-134(2008).
D. Lambertin, S. Ched’homme, G. Bourges, S. Sanchez, G. Picard, J.
Nucl. Mater., 341, 124-130 (2005).
C. Caravaca, A. Laplace, J. Vermeulen, J. Lacquement, J. Nucl.
Mater., 377, 340-347 (2008).

RPO-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Production of High Specific Activity Radiolanthanides for Medical Purposes using
the UC Irvine TRIGA Reactor
Leila Safavi-Tehrani1, George E. Miller2 and Mikael Nilsson1
University of California, Irvine
Department of Chemical Engineering & Materials Science2
Department of Chemistry
916 Engineering Tower, Irvine, CA 92697-2575
Lsafavit@uci.edu

1Radioactive lanthanides have become an
important imaging, diagnostic and therapeutic tool in the
medical field. For example, the neutron rich samarium
isotope of 153Sm has been proven to have desirable
characteristics for treatment of bone cancer. However, formedical purposes, the radioactive lanthanide isotope must
be produced at high specific activity, i.e. low concentrationof inactive carrier, so they are both beneficial for therapy
and the concentration of the metal ions does not exceed the
maximum sustainable by the human body. The objective ofour research is to produce radioactive lanthanides with highspecific activity in a small-scale research reactor using the
Szilard-Chalmers method. The Szilard-Chalmers process isa method that separates radioactive ions away from a bulkof nonradioactive ions by neutron capture. We propose an
innovative experiment setup to instantaneously separate theradioactive recoil product formed during irradiation fromthe bulk of non-radioactive ions. The instant separation
prevents the recoiled radioactive nucleus from reforming its
original bonds with the target matrix and chemicallyseparates it from the non-radioactive target matrix,
resulting in a carrier free radiolanthanide with increased
specific activity. We will present methods for preparationand synthesis of the material used for irradiations and theresults of enrichment factors and extraction yields inradioactive lanthanide solutions. We will also investigate
degradation by ionizing radiation that occurs during
neutron activation to determine the stability of the target
material during irradiations. The obtained results will becompared to previously published methods and theircorresponding results.

－ 80 －

FKO-11APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Mycoremediation: Fungus-based Soil Remediation of Radioisotope Contamination
1

Steven LaZar 1, Eric Rasmussen, MD, MDM, FACP 2, and Paul Stamets, D.Sc.3

Managing Director and Department of Energy (DOE) Program Manager, MGI, Seattle, Washington
Research Professor, Environmental Security and Global Medicine, San Diego State University, San Diego, California
3
Chief Scientist, Fungi Perfecti Research Laboratories, Kamilche Point, Washington, USA

2

Abstract – Fungal mycelia in soil can hyperaccumulate
radioisotopes at up to 25,000 Bq per kg of mushrooms [1].
Mycelium Group International (MGI) here introduces mycelial
radioactive decontamination techniques (mycoremediation) thatcan potentially restore safe soil levels on Fukushima farmland inless than ten years with high efficiency, without loss of topsoil,
and less expensively than current destructive methods.

Keywords – cesium, farmland, Fukushima, fungi, mycelium,
remediation, topsoil
1. Introduction
Mycoremediation uses selected fungi to reduce
contaminants in a step-function based on species and soil
characteristics, weather and season parameters, harvest
frequency, and contamination concentration.
The 2011 Fukushima nuclear disaster released more than
538,000 teraBecquerels (TBq) of radioactive Iodine-131,
Cesium-134, and Cesium-137. As a result of that cesium
deposition, the Japanese government has declared morethan 1,300 square kilometers of northern Japan to be unsafe
for human habitation and unsafe for food production.
Conventional remediation is currently removing valuable
farm topsoil at a rapid rate.
MGI has developed new capabilities for reducing
radioactive Cesium-137 contamination in soil to achievesafety goals set by the IAEA, while retaining valuable
topsoil and restoring safe farming decades earlier than
anticipated. MGI’s mycological research and industrial
process designs are currently undergoing independent
testing at two US Department of Energy Laboratories.
Our mycoremediation technique uses our unique strains ofcultivated fungi to remove Cesium-137 by either
biosorption or metabolism-dependent intracellular uptake.
Our fungi start as microscopic spores that form spreading

mycelial strands similar to a spider’s web in topsoil, withmeasurements in some species of 300 square meters permeter of plant root [2]. The mycelia in the soil thenconcentrate the Cesium-137 in their strands as they form
into mushrooms which are then harvested as radioactive
waste. Since, in some fungal biochemistry, cesium mimics
potassium - a necessary element in cellular metabolism local cesium uptake can be rapid. Also, since mycelium areonly a single cell thick and yet can comprise up to 45% ofsoil biomass in temperate zones [3], the calculated mycelial
surface area available for cesium absorption is enormous.
Some hyper-accumulating fungal species can form
mushrooms from mycelial mats every 60 days. Harvesting
radioactive mushrooms therefore results in the removal ofsignificant fractions of cesium contamination from topsoil
multiple times each year. Our current research is showingthat we can very likely use our mycoremediation
techniques on radioactive farmland around Fukushima tomeet IAEA safety standards in less than ten years while
preserving topsoil critical to the restarting of a productive
farm economy.
2. Mycoremediation Processes
MGI’s mycoremediation processes include in-situ
remediation, post-sort hot-pile remediation, and acid-leachresin column adsorption. The processes are safe, nearlysilent, rapidly implemented, have low infrastructure
requirements and can, in many cases, improve the soil tobetter than pre-contamination condition. The result is landagain available for crop production earlier than anticipated,with far less volume for radioactive waste disposal, and at a
cost that is substantially less than any other remediation
process.
[1]Epik and Yprack, 2003
[2]Jones, 1991
[3]Stamets, 2005

－ 81 －

FKO-12APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Automatic Cs-Uptake Device for Radioactive-Cs Evaluation in Environmental Water
Kimitaka Minami1, Takayuki Funabashi2, Ryuichi Kamimura2, Tetsuo Yasutaka1, Hisashi Tanaka1,
Akiko Kitajima1, Hiroshi Ogawa1, and Tohru Kawamoto1
1

National Institute of Advanced Industrial Science and Technology (AIST)
2
Tokyo Power Technology Ltd.

Abstract –We developed an automatic Cs-uptake device forconcentrating the dilute radioactive cesium (r-Cs) in environmental
water, especially paddy fields water. The device was set onto paddy
fields and the r-Cs in more than 400 L of water in 24 hours was
automatically concentrated in the small columns without external
power supply. With this device, 0.01 Bq/L of r-Cs concentration canbe evaluated by the r-Cs measurement of the columns.
Keywords – Prussian blue, radioactive cesium, environmental water,
monitoringI.

column was developed for the structure that was measured bysimple operation when it was measured by germanium
detector. The device was designed so that less than 5 cm sankin order to use in the paddy with the very shallow water depth.
The r-Cs concentrations in a pond and paddy in
Fukushima evaluated with the device were shown in Table 1.
By passing more than 400 L of water through the device,around 0.01 Bq/L of dissolved r-Cs in paddy water can beevaluated in the 1,800 seconds measurement by thegermanium semiconductor detector.

INTRODUCTION

By the Fukushima Daiichi Nuclear Power Plant accident
by the March 2011 Great East Japan Earthquake andsubsequent tsunami, radioactive materials were released into
the atmosphere and deposited over widespread agricultural,
forest, and urban areas.
Now, radioactive materials, especially radioactive cesium(r-Cs), gradually migrate into environmental water and affectfarm products even if these are low-level concentration. We
have developed a monitoring method to investigate the lowlevel r-Cs concentration in environmental water by eachexistence form. Yasutaka et al. (2013) developed a method toadsorb 90% of dissolved r-Cs in 20 L water within 10
minutes using Prussian Blue (PB) impregnated nonwoven
fabric. Tsuji et al. (2013) developed a cartridge filter which
can concentrate up to 30 g of suspended solid inenvironmental water and more than 98% of suspended solidr-Cs in 20 L water was concentrated within 10 minutes. In
this way, we can easily evaluate level of r-Cs in a short timeby using germanium detector.
In this study, we developed another device forconcentrating dilute r-Cs in environmental water, especiallypaddy fields water, as the average for a long time more than 1
day automatically without external power supply.

(a)

(b)

Fig 1. The automatic r-Cs uptake device (a) schematic view (b) appearance
Table 1. r-Cs Concentration in environmental water

II. SETUP AND RESULTS
The developed device was shown in Fig 1. It includes
pump, battery, cartridge filter, cesium adsorbed column with
PB nanoparticles, and flow meter. The pump and the battery
were chosen so that flow rate continually became 0.3 L/minfor 24 hours. Suspended solid in environmental water was
filtrated and concentrated by cartridge filter with large
filtration area and 1 m of pore-size. Dissolved Cs in thefiltrate was adsorbed and concentrated onto PB. This PB

[1]
[2]

－ 82 －

Yasutaka et al.(2013), Appl. Chem. (in Japanese), in press
Tuji et al. (2013), APSORC13

FKO-13APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Pilot plant for volume reduction of Cs-contaminated combustible materials
Kimitaka Minami1, Hiroshi Ogawa1, Hisashi Tanaka1, Akira Takahashi1, Tatsuya Uchida1, Akiko
Kitajima1, Durga Parajuli1, Tohru Kawamoto1, Masaki Yamaguchi2, Mitsuo Osada2, Nobuaki Otake2,
Syuichi Sato2, Ryuichi Kamimura2, and Yukiya Hakuta 1
1

Nanosystem Research Institute, AIST, Japan
2
Tokyo Power Technology Ltd., Japan

Abstract –We report the pilot plant test for volume reduction ofradioactive-Cs (r-Cs)-contaminated combustible materials for thevolume reduction of the contaminated waste, and to reduce the r-Cs
leaching from the waste. the combustible wood is incinerated by thebiomass boiler. The radioactive-Cs stored in ash is extracted into
the water, and finally is captured into the Prussian bluenanoparticle adsorbents.
Keywords – radioactive-Cs, Prussian blue, incineration, adsorbents

I.

INTRODUCTION

Around Fukushima area, there are so much combustible
materials contaminated by the radioactive Cs (r-Cs), e.g. thewood in forests, municipal waste, and waste from agriculture.
Japan government showed the policy that the municipal wastewith r-Cs contamination should be incinerated. In addition,
the biomass power system with the incineration of thecontaminated wood materials is also planned around
Fukushima area.
There are problems in the management of the incinerationof the combustible material. One is the large amount of thevolume of ash and the other is the r-Cs leaching from the ash.
In order to solve the problems, the extraction of leachable rCs from the ash as the pre-treatment before disposal isgathering attention. In order to confirm the method for thesafety management based on the incineration and the r-Cs
extraction from the ash, we carried out the plant-scale test.

Fig. 1. for volume reduction of Cs-contaminated combustible materials. (a)biomass boiler with gas-filters for Cs-reduction from exhaust, (b) Ashdecontamination unit.

II. METHOD AND RESUTSThe firewood was incinerated in a biomass boiler shown in
Fig. 1(a). To avoid the emission of the r-Cs in the exhaust,
the bag filter and HEPA filter is prepared. The r-Cs is trappedin ash mainly stored in the boiler and the bottom of the bag
filter. In the next step, the r-Cs is extracted from the ash into
the water in the ash-decontamination unit shown in
Fig.1(b)[1]. Finally the r-Cs is captured by the adsorbents
with Prussian blue nanoparticles shown in Fig.2.
When 465 kg of firewood was incinerated (r-Cs
concentration ∼ 0.3 kBq/kg), 1.35 kg of ash was obtained.
The highest r-Cs concentration of was ∼ 210 kBq/kg at thebag filter. The r-Cs in the exhaust in the incineration wasundetectable. The r-Cs extraction ratio from the ash into
water was 50-90%. The r-Cs in the water after thedecontamination of the adsorbent was also undetectable.

Fig. 2. Various Cs-adsorbents with Prussian blue nanoparticles[1]－ 83 －D Parajuli et al., Env. Sci. Tech., in press.

FKO-14APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Decontamination of Radioactive Cesium from Ash and Soil
Durga Parajuli1, Hisashi Tanaka1, Shigeharu Fukuda2, Ryuichi Kamimura2, Tohru Kawamoto1
1

Nanosystem Research Institute, AIST, 2Tokyo Power Ltd., Japan

Abstract – Methods for the removal of Cesium from contaminatedtsunami-debris, top-soil, and forest litter was studied. Incinerationof tree bark resulted over 95% volume reduction. Fly ashes fromwood, municipal garbage, and sewage sludge with enriched Cesium
were washed with water at varying temperatures. Cesium along withother alkali metals was easily washed from the garbage ash andwood ash. But, only acid treatment at higher temperature could
release Cesium from sewage sludge ash. Also, Cesium removal fromsoils with acid solutions was studied from 25 to 200 ºC. Though therelease was higher at higher temperatures, results varied with thesoil type.
Keywords – Radioactive Cesium, Extraction, Ash, Soil, Soil typeI.

INTRODUCTION

less than 8 kBq/kg, the disposal of enriched ash is
problematic. Therefore, Cs-extraction study was performed
taking ashes of tree-bark, household garbage, and municipal
sewage sludge. Over 70% Cs-133 along with other alkali
metals was easily washed with water from the garbage ash
and wood ash. Figure 1 shows the change in the residual massof the wood fly ash, Cs, and K in after washing with water in
1:10 ratio at different temperatures. The residual mass was
18-25% less, with higher drop at higher temperature. This
result shows 70-80% dissolution of Cs and more than 90% K.
These outcomes suggest the feasibility of compaction of theburnable waste by incineration followed by decontamination
by washing with water.

Now two years after the Fukushima Daiichi Nuclear
Power Plant disaster, the main problem is exposure to theradioactivity due to the long living radioisotopes of Cesium,134
Cs (approx. 1.8 x 1016 Bq) and 137Cs (approx. 1.5 x 1016
Bq).1-3 So, we are conducting elaborated study to address theissues of Cs contaminated tsunami-debris, paddy field soil,
forest litter and stream water so as to control the long term
entry of the radioactive Cs to the ecosystem.
II. EXPERIMENTAL
Wood incineration ash, municipal garbage incineration ash,and sewage sludge ash were studied for Cs extraction. Also,soil samples collected from different areas in Fukushima
prefecture were also tested for Cs removal. Ash samples were
washed with water in flow or batch by varying ash-water
ratio, temperature, etc. For comparison, dilute acid solutions
were also studied. Acid solutions were tested for the
extraction of Cs from clay containing substrates: sludge ash
and soil.
III. RESULTS AND DISCUSSION
Incineration of contaminated waste and extraction of Cs
Incineration is the most suitable option for volume
reduction and compaction of burnable wastes like tsunami
debris, forest litter, plants, and household garbage. For this,incineration experiment taking the radioactive cesium
contaminated tree bark was performed. When the volume was
reduced to 5% of the initial mass, its fly ash showed 137
kBq/kg Cs-activity. Because the current Japanese
Government’s guideline allows landfill of wastes showing

Figure 1. Change in residual mass of ash, Cs, and K with respect to the initial
mass in the wood ash before and after washing with water.

Extraction of Cs from Soil and Sludge ash
Unlike the significant Cs removal observed with wood ash
or garbage ash, the method was ineffective for the removal ofCs from soil and sewage sludge. So, a number of reagentswere tested, and mineral acid solutions at higher temperature
were found to be effective. However, the results varied
widely depending upon the soil type. At 95 ºC with 0.5 M
nitric acid solution, Cs removal from the brown forest soil
was around 50%, however only 20% release was observed for
Kuroboku-soil. Results to the date showed that Cs extraction
from soils other than Kuroboku type is effective with acid at
higher temperature.
References
[1]
[2]
[3]

－ 84 －

IAEA Radiological Assessment Report Series (2006)
Y. Masumoto, et al. Elements, 8, 207 (2012)
R. Stone, Science, 331, 1507 (2011).

ACO-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Rapid radioanalytical determination of U, Pu, and Am in radioactive wastes via
extraction chromatography, alpha spectrometry, and thermal ionization mass
spectrometry
Tae-Hong Park, Yong Sul Choi, Jong-Ho Park, Jong-Yun Kim, Sang-Eun Bae, Young-Hwan Cho,
Jei-Won Yeon, Kyuseok Song

Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute,989-111 Daedeok-daero, Yuseong-gu, Daejeon,305-353, Korea
Abstract
We optimize extraction chromatographic separation procedures toassay alpha particle emitting nuclides for disposal purpose ofradioactive wastes generated from power plants and pyroprocessing
laboratories. In particular, U isotopes are isolated on UTEVA resin,
whereas Pu and Am/Cm isotopes are subsequently separated on
TRU resin.
Keywords
Actinides, Extraction chromatography, Radioactive wastes

I.

INTRODUCTIONManagement of radioactive wastes requires sensitive andaccurate radioanalytical determination procedures that
include rapid and reliable chemical separation methods for abroad range of sample types, and radiometric evaluation tools[1]. Extraction chromatography has been successfully applied
to separate the radionuclides of interest for a wide variety ofenvironmental samples and thus many reliable procedures
have been also developed with commercially available resin[2]. Here, we optimize rapid and reliable radiochemical
determination of U, Pu, and Am/Cm isotopes via extraction
chromatography, coprecipitation, alpha spectrometry, andisotope dilution-thermal ionization mass spectrometry(IDMS-TIMS) by which we estimate the alpha-emitting
nuclide activities of low-level wastes generated from power
plants and pyroprocessing laboratories.
II. EXPERIMENTAL
A radiochemical determination procedure of Pu, andAm/Cm nuclides is illustrated in Scheme 1.

Scheme 1. Radiochemical determination of Pu and Am/Cm

III. RESULTS
The method in scheme 1 typically presented recovery
yields of nuclides > 90% when a cocktail of ~0.1 Bq of 242Pu,
and 243Am was separated on TRU resins. We also separated
out Pu, Am, and Cm isotopes from low-level waste samples,and determined the nuclide activities via alpha spectrometricmeasurements of CeF3 coprecipitating alpha-emitters and IDTIMS especially for 239Pu, 240Pu, and 241Pu.
IV. CONCULUSION
The methods developed in this report have shown good
separation of U, Pu, and Am/Cm nuclides from radioactive
wastes with high recovery yields. Because the isolated
nuclides are determined by alpha spectrometry and ID-TIMS
that can effectively quantify the nano- and picogram amountsof alpha emitters, the rapid and efficient chromatographic
separation procedures in this report need marginal amounts ofradioactive samples leading to reduction of chemical waste
and radiation exposure.
[1][2]－ 85 －M. H. Lee, E. C. Jung, W. H. Kim, K. Y. Jee, J. Alloys Compd. 444445 (2007) 544-549
S. L. Maxwell III, B. K. Culligan, G. W. Noyes, J. Radioanal. Nucl.
Chem. 286, (2010), 273-282

APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

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Abstract Ð Syntheses and optical properties of tetravalent or
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－ 86 －

NCO-13APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Chemical studies of Mo and W in preparation of a seabogrium (Sg) reduction
experiment using MDG, FEC, and SISAK
A. Toyoshima1, S. Miyashita1, M. Asai1, T. K. Sato1, Y. Kaneya1, K. Tsukada1, Y. Kitatsuji1,
Y. Nagame1, M. Schädel1, H. V. Lerum2, J. P. Omtvedt2, Y. Oshimi,3 K. Ooe3, Y. Kitayama4, A.
Yokoyama4, A. Wada5, Y. Oura5, H. Haba6, J. Kanaya6, M. Huang6, Y. Komori7, T. Yokokita7, Y.
Kasamatsu7, A. Shinohara7, V. Pershina8, J. V. Kratz91

Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan2
Department of Chemistry, University of Oslo, Oslo 0371, Norway
3
Institute of Science and Technology, Niigata University, Niigata 950-2181, Japan
4
College and Institute of Science and Engineering, Kanazawa University, Kanazawa 920-1192, Japan
5
Graduate School of Science and Engineering, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan
6
Nishina Center for Accelerator-Based Science, RIKEN, Wako, Saitama 351-0198, Japan
7
Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
8
GSI Helmholtzzentrum für Schwerionenforschung GmbH, D-64291 Darmstadt, Germany
9Institut für Kernchemie, Universität Mainz, 55128 Mainz, Germany

Abstract –We are developing a new chemistry assembly toperform continuous reduction experiments of seaborgium(element 106, Sg). In preparation for the Sg experiment, we havebegun studies on the dissolution, reduction, and extraction of Mo
and W isotopes. Our present status of the preparation with Mo
and W will be presented.
Keywords – Superheavy elements, Seaborgium (Sg),Electrochemistry, Solvent extraction, Flow electrolytic column,
SISAK, Membrane degasser

Seaborgium (Sg) is expected to be redox-active similarly toits lighter group-6 homologs, Mo and W. Theoretical
calculation show that Sg can be reduced from the moststable hexavalent state Sg(VI) to, e.g., the tetravalent one[1]. They also predict that the Sg(VI)/Sg(IV) couple will
have a more negative redox potential than those of thecorresponding W ions in acidic solution [1]. In such
reduction reactions, electrons occupy the vacant valence 6dorbital of the Sg(VI) ion. The redox potential of theSg(IV)/Sg(VI) couple, therefore, provides information on
the stability of the 6d orbital which is anticipated to be
influenced by increasingly strong relativistic effects.
Because of low production rates of 265a,bSg (a and bstand for two different states) in the 248Cm(22Ne, 5n)reaction and their short half-lives of 8.5 and 1.4 s [2], only
single atoms of Sg are present. This means that standard
electrochemical techniques are not applicable to its
reduction study. In our previous works, we have developed
a novel electrochemical method of electrolytic column
chromatography available for single ions [3]. Carbon fibers
modified with Nafion perfluorinated cation-exchange resin
were employed as a working electrode as well as a cationexchanger. This technique was successfully applied to theoxidation of nobelium (No) [4] and the reduction of
mendelevium (Md) [5]. It is, however, technically difficult
to apply this batch-wise chromatographic method to the
reduction study of Sg because of its very short half-lives.
We are, therefore, developing a new chemistry assembly
consisting of a membrane degasser (MDG), a flow
electrolytic column (FEC), the continuous liquid-liquid
extraction apparatus, and the liquid scintillation counting

system (SISAK) [6] to continuously perform thedissolution, reduction, separation, and detection of Sg,
respectively.
In preparation for our future experiment with Sg,
we have begun studies on the dissolution, reduction, andextraction of Mo and W isotopes. On-line experiments
using the newly developed MDG were carried out toexamine the dissolution efficiency of nuclear reaction
products transported by a gas-jet. The aqueous solution
dissolving the reaction products was successfully separated
from the carrier gas using the MDG after continuous
mixing of the carrier gas with the aqueous solution.
Electrolytic reduction of Mo and W was examined using a
FEC. Redox couples of Mo(VI)/Mo(V) and W(VI)/W(V) in
HCl have been so far characterized for macro amounts ofMo and W with cyclic voltammetry and UV/Vis.
absorption spectrometry. Batch extractions of hexavalent
93m
Mo and 181W were performed to search for suitableconditions in the separation between Sg(IV) and Sg(VI).
Variations of extraction ratios of Mo(VI) and W(VI)between toluene containing hinokitiol (HT) and HCl weresuccessfully observed as a function of HT and HClconcentrations. On-line extractions of short-lived 91mMo
and 176W were also carried out using SISAK and MDG.
Extraction ratios of these elements were increased withincreasing HT concentration, reflecting results of the batch
experiments. In the symposium, our present status of the
preparation with Mo and W will be presented.
[1]
[2]
[3]
[4]
[5]
[6]

－ 87 －

V. Pershina et al., J. Phys. Chem. A103, 8463 (1999).
H. Haba et al., Phys. Rev. C85, 024611 (2012).
A. Toyoshima et al., Radiochim. Acta 96, 323 (2008).
A. Toyoshima et al., J. Am. Chem. Soc. 126, 9180 (2009).
A. Toyoshima et al., to be submitted.
For example, J. P. Omtvedt et al., Eur. Phys. J. D45, 91 (2007).

NCO-14APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Diamond Detectors for Isothermal Vacuum Chromatography
P. Steinegger1,2, R. Dressler1, R. Eichler1,2, A. Türler1,21Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland
2
University of Bern, CH-3012 Bern, Switzerland

Keywords: Superheavy elements, isothermal vacuum chromatography, diamond detectors.

I.

INTRODUCTION

On-line thermochromatography is a well established gas
phase experiment for the chemical characterization of thesuperheavy elements. However, recent experiments with stateof the art detectors such as COLD [1] and COMPACT [2] arelimited in terms of the upper bound of the applied
temperature gradient. Therefore, the experimental
characterization of less volatile elements with stronger
adsorption interaction is not feasible. Already the rather
volatile mercury with -�HadsAu (Hg) = 98 kJ/mol [3] corresponding to a deposition temperature of about 430 K
using the experimental conditions of the COLD system reveals the constrained range of the currently used setups.
Pushing the starting temperature of the gradient above thecurrent limit, would open up a new range of elements
accessible by on-line thermochromatography, including
candidates like element 113.

in first experiments with carrier-free 211Pb, where the detector
was successfully tested in the immediate vicinity of theisothermal oven held at temperatures up to Tmax = 1193 K(see Fig. 1).
Acknowledgment: This project is supported by the Swiss
National Foundation project number 200020_144511 / 1.

3
1

4
2
5 mm
5

A. Diamond Detectors
The upper limit of the temperature gradient however,
evolves due to the maximum operation temperature of thecurrently applied Si PIN-diodes or Si PIPS-detectors
respectively at around 315 K. Above this threshold, thermal
excitation of the low band gap material (1.1 eV) prevents any
spectroscopic measurement.
In recent years the development of chemical vapor
deposition (CVD) single crystal diamonds made aconsiderable progress concerning the available size, quantity,
and most importantly the quality. Diamond, as a large band
gap material (5.5 eV), can be operated under IR and UV-Vis
irradiation as well as at elevated temperatures even higher
than 500 K without any spectroscopic degradation [4]. In
addition, diamond has the largest known thermal conductivity,
which is important for a reliable reconstruction of the surface
temperature at vacuum conditions.

Fig. 1: Isothermal vacuum chromatography with carrier-free 211Pb;
1 isothermal oven, 2 quartz column exit, 3 ceramic carrier, 4 wire bonds,
5 CVD diamond detector.

[1] R. Eichler et al., Radiochim. Acta 98(3) (2010) 133[2] �����������Ph.D. TU Munich (2007)[3] B. Eichler et al., Radiochim. Acta 33 (1983), 121[4] J. H. Kaneko et al., Nucl. Instr. and Meth. A 422 (1999),
211

B. Experimental Section
In the course of the development of an isothermal vacuum
chromatography setup for application in SHE chemistry
experiments, we tested the new detector material with respect
to the change of the spectroscopic behavior under heating and－ 88 －

NCO-15APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Angular distribution of projectile like fragments in 16O+89Y reaction
1

R. Tripathi1, S. Sodaye1, K. Mahata2, P. K. Pujari1

Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai, India
Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai, India

2

Keywords – Incomplete fusion, angular distribution

I.

INTRODUCTION

Reactions involving incomplete mass transfer, namely
direct and quasi-elastic transfer (QET), incomplete fusion(ICF) or massive transfer and deep inelastic collisions(DIC), have been an active area of investigation. Study ofthese reactions at beam energies below ~<10 MeV/nucleon
has been actively investigated in the recent past [1-5] asexisting theories and models [6-9] explain the observationsof such reactions at higher beam energies. Measurement ofangular distribution and cross sections data of PLFs (Z=37) in 19F+66Zn [3], 89Y [4], 159Tb [5] showed a systematic
decrease of PLF cross sections with their decreasing Z. A
comparison of PLF cross sections with those of respective
evaporation residues gave information about the relative
magnitude of cross section for total projectile break-up andbreak-up followed by the capture of one of the fragments[5]. As projectile structure plays an important role in thesereactions [10,11], angular distributions of projectile likefragments (Z=3-7) have been measured in 16O+89Y reaction
at Elab=62 and 84 MeV corresponding to Ec.m./Vb value of
1.18 and 1.58 respectively. Elastic scattering measurements
have been carried out at to determine the grazing angle andtotal reaction cross section.
II. EXPERIMENTAL DETAILS
Experiments were carried out at BARC-TIFR pelletron
accelerator facility, Mumbai. Self-supporting metallic
target of 89Y was bombarded with 16O beam and projectile
like fragments were measured in the forward hemi-sphereusing Si detector based E-�E telescopes. Telescope data
were normalized for the target thickness and beam current
using the data from a monitor detector kept at 200 withrespect to the beam direction to obtain absolute crosssections.
III. RESULTS AND DISCUSSION
Lab Angular distribution of PLFs at Elab=62 and 84 MeV,
obtained from a preliminary data analysis is shown in Fig.
1 (a) and (b) respectively. It can be seen from Fig. 1(a), thatthe angular distribution of PLFs become more and more
forward peaked with increasing mass transfer. This
indicates the increasing overlap of the projectile and target
nuclei with increasing mass transfer. This observation isconsistent with our
10earlier measurements in
19
F induced reactions
1[3-5]. However, thecomparable
cross
0.1
sections of C and N
PLFs indicate the role
0.01 E =62 MeVofalphacluster100Nstructure, leading to aClarge cross section for
B
10Beeven Z C PLF. Also, 12CLi
1
yield was significantly
larger than the other
0.1
E =84 MeV
isotopes indicating the
0.01
preferential break-up of
20 30 40 50 60 70 80 90 100
� (deg.)the 16O projectile into
12
Fig. 1. Angular distribution of
C+4He. At higher
PLFs in 16O+89Y reaction
beam energy, angular
distributions of all the
PLFs become forward peaked, suggesting the formation ofeven lighter PLFs in collision trajectories with deeper
interpenetration. A qualitative comparison of angular
distributions of PLFs at the two beam energies shows alarger decrease in the yields of lighter PLFs withdecreasing beam energy. This is consistent with the picturethat the formation of these PLFs involves substantial
overlap of the projectile and the target nuclei, which wasindicated by the sharp fall in the cross sections of lighter
PLFs with decreasing beam energy [3,4].
In the further analysis, angular distributions and kinetic
energy spectra of PLFs would be analyzed in more detail.
Integrated cross section data for PLFs would be comparedwith the incomplete fusion cross section data obtained from
evaporation residue measurements [12] as well as thoseobtained in 19F induced reactions.
d�/d� (mb/sr.)

Abstract – Angular distribution of projectile like fragments havebeen measured in 16O+89Y reaction at Elab=62 and 84 MeV. A
systematic change in the angular distribution of PLFs wasobserved with increasing mass transfer indicating the evolution ofreaction mechanism from quasi-elastic transfer to massive
transfer or incomplete fusion. Elastic scattering measurements
have been carried out to obtain grazing angle and total reaction
cross section.

lab

lab

lab

REFERENCES
Abhishek Yadav et al., Phys. Rev. C 85, 064617 (2012).
Rahbar Ali et al., J. Phys. G 37, 115101 (2010).
R. Tripathi et al., Phys. Rev. C 79, 064604 (2009).
R. Tripathiet al., J. of Physics. G. 35, 025101 (2008).
Amit Kumar et al., Eur. Phys. J A 49, (2013).
K. Siwek-Wilczynska et al.,Phys. Rev. Lett. 42, 1599 (1979).
T. Udagawa and T. Tamura, Phys. Rev. Lett. 45, 1311 (1980).
V. Zagrebaev and Yu. Penionzhkevich, Prog. Part. Nucl. Phys. 35,
575 (1995).
[9] B.G. Harvey, Nucl. Phys. A 444, 498 (1985).
[10] R. Tripathi et al., Eur. Phys. J. A 42, 25 (2009).
[11] Chr. V. Christov, Z. Phys. A 325, 221 (1986).
[12] B. S. Tomar et al., Z. Phys. A 343, 223 (1992).

[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

－ 89 －JNRS AwardAPSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Studies on Solution Chemistry of Actinides and Lanthanides
by Time-resolved Laser-induced Fluorescence Spectroscopy
Takaumi Kimura

Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency
Shirakata-shirane 2-4, Tokai-mura Naka-gun, Ibaraki, 319-1195, Japan
Abstract – Several topics on solution chemistry of actinides(An�and lanthanides(Ln) studied by time-resolved laser-induced
fluorescence spectroscopy(TRLFS) will be mentioned in thispresentation. Those are hydration studies of An(III) and Ln(III)and its applications, speciation study of U(VI), and luminescenceof U(IV) in aqueous solution.
Keywords – Hydration, Speciation, Actinides, Lanthanides, Timeresolved Laser-induced Fluorescence Spectroscopy(TRLFS)

As a highly sensitive and selective speciation method,time-resolved laser-induced fluorescence spectroscopy(TRLFS) is a powerful tool to study luminescentactinides(An) and lanthanides(Ln) in solution, in solid andat their interface. We have started hydration study ofCm(III)[1] and speciation study of U(VI)[2] by TRLFS in
the beginning of the nineteen-nineties.
A luminescence study of Cm(III) has shown a linear
correlation between the reciprocal of the excited-state
lifetime �obs and the number of water molecules NH2O in thefirst coordination sphere of complexes.
Frommeasurements of �obs of Cm3+ in D2O-H2O solutions and ofCm(III) doped lanthanum compounds, the following
correlation for �obs(ms) vs. NH2O was established: NH2O =0.65(1/��obs) - 0.88[1]. This relationship was applied to
study the residual hydration of Cm(III) complexes ofpolyaminopolycarboxylate ligands and to determine the
NH2O of Cm(III) in various aqueous solutions. All of the
NH2O values calculated from the lifetime were chemicallyreasonable[3]. For Am(III) and several Ln(III)(Ln=Nd, Sm,
Eu, Tb and Dy), the similar calibration relations were also
proposed and the validity was confirmed through the studyof a series of polyaminopolycarboxylate complexes[4-6].
The NH2O of Ln(III) in concentrated aqueous salt solutionsat room and liquid nitrogen temperatures was estimated on
the basis of the correlation obtained at each temperature[7].
To understand the solvation of An(III) and Ln(III) in nonaqueous solutions, their �obs in perprotonated andperdeuterated solvents, i.e., DMSO, DMF, MeOH andwater, were measured systematically and the quenching
behavior of the ions in the solvents and the preferential
solvation of them in water/non-aqueous solvent mixtures
were evaluated[8,9].
The determination of the NH2O by the measurement of�obs is a simple and effective method for the speciation
study of An(III) and Ln(III). This method makes it
possible to study chemical species at solid-water interface.
TRLFS accelerated the speciation study on sorption
behavior of Eu(III) and Cm(III) at mineral-water interface
in the presence or absence of humic substances[10] and on
the cell surfaces of microorganisms[11]. This also makes it
possible to compare directly the coordination environment

between An(III) and Ln(III) using same experimental
technique.
TRLFS improved the understanding ofseparation mechanisms of An(III) and Ln(III) using ion
exchange resin[12] and solvent extraction[13].
Chemical species of U(VI) in 0.1 M NaClO4 inequilibrium with 0.03 % CO2 partial pressure were
investigated by TRLFS[2]. The emission spectra of U(VI)solutions (pH = 3.8 to 7.0) in solid-liquid equilibrium withschoepite UO3�2H2O were interpreted by the summationof the emission spectra of the individual components,
UO22+(aq), (UO2)2(OH)22+(aq), (UO2)3(OH)5+(aq) andUO2CO3(aq). Numerical evaluation of the species gave asatisfactory agreement with the distribution of the species
calculated from the formation constants of U(VI).
Furthermore, the speciation study of U(VI) by TRLFS with
an optical cell system was extended to the hydrothermal
conditions[14]. The results shows that TRLFS is aneffective in-situ speciation method not only U(VI)hydrolysis but also for complexation at elevatedtemperatures(25-200 oC) and pressures(0.1-40 MPa).
U(IV) in aqueous solution has been considered to haveno luminescence except for phosphate complex. From ananalysis of transition energy level structure of U(IV), we
found there was a possibility of U4+ exhibiting
luminescence in aqueous solution and discovered theemission spectrum consisting of 12 bands in the range 280
to 560 nm[15]. Temperature dependence and isotope effectbetween H and D on the �obs suggest that water molecules
in a bulk solution participates considerably in quenchingprocess of the luminescence, which is quite different fromthe luminescence properties of An(III) and Ln(III).
REFERENCES
T. Kimura, G.R. Choppin, J. Alloy Compd., 213/214, 313-317(1994).
[2] Y. Kato, G. Meinrath, et al., Radiochim. Acta, 64, 107-111 (1994).
[3] T. Kimura, G.R. Choppin, et al., Radiochim. Acta, 72, 61-64 (1996).
[4] T. Kimura, Y. Kato, J. Alloy Compd., 225, 284-287 (1995).
[5] T. Kimura, Y. Kato, J. Alloy Compd., 271-273, 867-871 (1998).
[6] T. Kimura, Y. Kato, J. Alloy Compd., 275-277, 806-810 (1998).
[7] T. Kimura, Y. Kato, J. Alloy Compd., 278, 92-97 (1998).
[8] T. Kimura, R. Nagaishi, et al., Radiochim. Acta, 89, 125-130 (2001).
[9] T. Kimura, R. Nagaishi, et al., J. Alloy Compd., 323-324, 164-168(2001).
[10] Y. Takahashi, T. Kimura, et al., Geochim. Cosmochim. Acta, 66, 112 (2002).
[11] T. Ozaki, T. Kimura, et al., Radiochim. Acta, 94, 715-721 (2006).
[12] T. Kimura, Y. Kato, et al., J. Alloy Compd., 271-273, 719-722(1998).
[13] G. Tian, T. Kimura, et al., Radiochim. Acta, 92, 495-499 (2004).
[14] T. Kimura, R. Nagaishi, et al., J. Nucl. Sci. Technol., Suppl. 3, 233239 (2002).
[15] A. Kirishima, T. Kimura, et al., Radiochim. Acta, 92, 705-710(2004).
[1]－ 90 －

Oral Presentations
Thursday, 26 September 2013
Hall & Meeting Room, Kanazawa Bunka HallTime
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20:00-

9:00

PL-07

9:30

PL-08

S. B. Clark
Plenary
H. Ueno10:00

Coffee Break

10:20

NPI-01

10:50

NPO-01

11:10

NPO-02

11:30

NPO-03

11:50

NPO-04

12:10
13:00

Thursday, 26 SeptemberHall
Meeting RoomPlenary

EDI-01

InvitedW. SatoGeneral
EDI-02
K. Nomura
GeneralJ. Wang
EDI-03GeneralM. Kaneko
General
EDO-01
G. Yoshida
Lunch Time

J. JohnInvitedInvitedExcursion(Shirakawa-go)

17:00

19:00
Banquet－ 91 －

W.S. Wu
InvitedA. Yokoyama
GeneralS. B. Sarmani

PL-07APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Preparing the Next Generation of Radiochemists for Global Challenges
Sue B. Clark

Washington State University, Department of Chemistry, Pullman, WA 99164
Abstract – Nuclear and radiochemists are needed to support the
expansion of nuclear energy, nuclear medicine, andenvironmental management. In this presentation, the changing
needs for educating future generations of radiochemists aredescribed. Consideration of the global nature of these market
sectors is given, along with observations and recommendations
for changes in academic curricula and training opportunities.
Keywords– nuclear chemistry, education, curriculum development

I.

INTRODUCTION

Nuclear and radiochemistry is a sub-discipline withinchemistry, and is referred to simply as radiochemistry inthis presentation. These chemists study nuclear properties,
nuclear reactions, and the chemical manipulation ofradioactive substances for applications in physics,
chemistry, biology, medicine, earth and space sciences [1].
The global radiochemistry workforce includes individuals
employed in basic research and the allied fields of nuclear
energy, nuclear medicine, defense, and the interface of
these sectors with the environment. As nuclear energy andnuclear medicine grow world-wide, the need for a welleducated global workforce of critical thinkers is a challenge
for many countries. In this presentation, the preparation ofradiochemists for these future opportunities and challenges
is discussed.
II. RADIOCHEMISTS IN ENERGY
Nuclear power plants provided more than 12% of theworld's electricity production in 2011, generated by over
400 reactors in 30 countries worldwide, with a 70 new
nuclear plants under construction in 14 countries [2]. The
global nuclear power industry requires radiochemistry
expertise to support (1) the operation of existing nuclear
power plants and supporting facilities within a country’s
nuclear energy cycle, (2) the licensing and regulation ofthese facilities, and (3) research into future generations of
nuclear energy facilities and approaches.
Chemists who work in these areas require expertise inareas such as nuclear reactions, radiation detection,
radiation effects, separations, and chemical engineering, toname a few. As some countries move towards closing theirfuel cycles and implementation of fusion energy
technologies to transmute nuclear wastes while generatingenergy, developing unique expertise in the chemistry ofmaterials and their corrosion in extreme, high radiation
environments, and challenging chemical separations will be
required. Anticipating these needs and altering university
curricula to provide the necessary skills for those working
in fusion energy will be important for advancing such new
nuclear energy systems.

III. RADIOCHEMISTS IN MEDICINE
Nuclearmedicine
involvestheuseofradiopharmaceuticals for imaging to assess physiologicalprocesses, and to diagnose and treat diseases [3]. Future
generations of radiochemists are needed for careers inacademia, government laboratories, industry, and pharmacy.
Academic radiopharmaceutical chemists typically provide
the initial education and training, and the basic researchthat drives innovation in this technical area. Radiochemists
working in government laboratories build upon the basic
research foundation from academia to further develop
radiopharmaceutical compounds. Industrial radiochemists
synthesize radiopharmaceuticals, and conduct clinical trialsof potential new pharmaceuticals. Nuclear pharmacists are
the practitioners who prepare and sometimes administer the
drugs, in collaboration with physicians. As the use of
isotopes in the diagnosis and treatment of disease continues
to expand, a global workforce of radiochemists who arealso knowledgeable in biochemistry, molecular biology,
synthetic chemistry and medicine are needed worldwide.
IV. RADIOCHEMISTS IN ENVIRONMENTAL
MANAGEMENT
As with any industrial sector, nuclear energy and nuclear
medicine both generate waste streams that require
management for eventual disposal. Nuclear accidents andpast radioactive waste management practices in countries
that have used nuclear technologies for national defense
and/or energy production have resulted in environmental
legacies that require remediation. A new generation ofradiochemists who are prepared to resolve suchenvironmental legacies is needed. For example, as a resultof the Fukushima accident in Japan, a new professionalsociety of scientists was formed [4]. Developing strategies
that meet international regulatory requirements relies ondevelopment of a pipeline of radiochemists who are also
knowledgeable in disciplines such as environmental scienceand engineering, communications, sociology, and politicalscience.
V. REFERENCES
[1]
[2]
[3]
[4]

－ 92 －

National Research Council, “Assuring a future US-based nuclear andradiochemistry expertise”, 2012www.nei.org, accessed on30 May 2013www.snm.org, accessed on30 May 2013
Society for Remediation of Radioactive Contamination in theEnvironment;
http://www.uili.org/Cms/CmsArticlesReadOnly.aspx ?__item__=4077

PL-08APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Researches with stopped radioisotopes at the RIKEN RIBF facility
H. UenoRIKEN Nishina Center for Accelerator-Based Science, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanRIKEN has started the operation of the new facility for
the Radioactive-Isotope Beam Factory (RIBF) project [1]since 2006. In this project, intense primary beams aredelivered at the energy E/A = 350–440 MeV over the whole
range of the atomic number utilizing newly constructed
three cyclotrons, K = 700 fixed-frequency Ring Cyclotron(fRC), K = 980 Intermediate-Stage Ring Cyclotron (IRC),
and K = 2500 Superconducting Ring Cyclotron (SRC)
together with the existing K = 540 RIKEN Ring Cyclotron(RRC). Beams are delivered in the cyclotron cascadeacceleration scheme, in which AVF, RILAC, or RILAC2 isalso included as an injector depending on the energy andthe mass of a beam. The beam extracted from SRC is thentransported to superconducting in-flight RI separator
BigRIPS [2] in order produce radioactive-isotope beams(RIBs). BigRIPS is characterized by its large acceptanceand two-stage scheme. The former is realized by the large
aperture superconducting triplet Q-lens system, whichenables BigRIPS efficiently to collect in-flight 238U fission
products. The latter is effective in the isotope separationand particle identification event-by-event basis. After the
first beam was delivered on December 2006, the beam timefor 1701 days, including 298 days for BigRIPS-based
experiments, will be conducted until the end of September
2013. The beam current and the stability in beam delivery
have been improved significantly by the improved
performance of the 28-GHz ECR ion source and fRC, andthe installation of a He-gas charge-stripping system [3],where the maximum beam currents 415, 100, 38, and 15
pnA, have been recorded for typical primary beams of
BigRIPS-based experiments, 48Ca, 70Zn, 124Xe, and 238U,
respectively [4].
In order to fully capitalize the RIBF facility, several
experimental key devices have been installed downstreamof the BigRIPS separator. Many nuclear-physics
experiments are performed by means of the in-flightsecondary nuclear reaction of radioactive-isotope beams(RIBs). For this purpose, a multi-function spectrometer forparticle identifications (ZeroDegree [2]), a superconducting
large acceptance and multi-particle detection spectrograph(SAMURAI [5]), and a high-resolution spectrograph under
the scheme of the dispersion matching (SHARAQ [6]) wereconstructed following BigRIPS. In addition, theconstruction of the Rare-RI Ring [7], which is an
isochronous storage ring to measure the mass of rareradioactive isotopes, is underway. Aiming at the first e-RI
scattering experiments, the SCRIT [8] system is also underdevelopment.
Apart from the reaction-based approaches, nuclearstructure studies have also been conducted using stopped
RIBs, where measurements are performed on thetechniques of nuclear spectroscopy that take advantage of
intrinsic nuclear properties. In particular, at the BigRIPS

site, the EURICA (Euroball RIKEN Cluster Array) project[9] had been unfolded taking a high priority over the periodof year and half since April 2012. In this program, structureof far unstable nuclei, which can be currently accessible
only with the RIBF, have been investigated through the �-�spectroscopy with the �-ray detector array consisting of
twelve high purity germanium cluster detectors from theEuroball IV array [10]. Combining the recently developed
new method to produce spin-oriented RIBs [11], spinrelated observables of RIs such as nuclear moments andspin parities will be measured in the stopped-RI type
experiments. As for slowed-down and stopped RIBs, it
should be noted that the construction of the SLOWRI
system [12], which is a system to stop and extract the fast
fragmentation RI by means of He and Ar gas catchers
combined with the RF ion guide technique, has just started.
The system is expected to provide a unique opportunity toinvestigate nuclear structure of RIs through atomic-physics
techniques such as the laser spectroscopy.
Besides these BigRIPS-based experiments, which iscategorized as the high-energy mode in RIBF, beams arealso available in the low-energy mode whose acceleration
scheme is AVF or RILAC (�RRC), where the accelerators
in parentheses can be skipped in the cascade acceleration,
depending on the beam used. RIBs are also available at E/A~ 70 MeV in this mode with the former projectile-fragment
separator RIPS [13]. Researches with stopped RIBs areactively conducted in the low-energy mode, in which anadvanced usage of RIPS by changing the configuration of
the beam-transport line has been proposed [14].
In the talk, after the overview of the RIBF facility,
researches with stopped RIBs at BigRIPS and RIPS sites
will be presented.
Reference

Y. Yano, Nucl. Instrum. Methods Phys. Res. Sect. B261, 1009
(2007).
[2] T. Kubo, Nucl. Instrum. Methods Phys. Res. Sect. B204, 97 (2003).
[3] H. Okuno, N. Fukunishi, O. Kamigaito, Prog. Theor. Exp. Phys.
(2012) 03C002.
[4] Technical information on the available beams are found at
http://www.nishina.riken.jp/RIBF/[5] K. Yoneda et al., RIKEN Accel. Prog. Rep. 43, 178 (2010).
[6] T. Uesaka et al., Nucl. Instrum. Methods Phys. Res., Sect. B266,
4218 (2008).
[7] Y. Yamaguchi et al., Nucl. Instrum. Methods Phys. Res. Sect. B266,
4575 (2008).
[8] M. Wakasugi et al., Nucl. Instrum. Methods Phys. Res. Sect. A532,
216 (2004).
[9] S. Nishimura et al., RIKEN Accel. Prog. Rep. 45, x (2012).
[10] M. Wilhelm et al., Nucl. Instrum. Meth. A381, 462 (1996).
[11] T. Ichikawa et al., Nature Phys. 8, 918 (2012).
[12] M.Wada et al., Nucl. Instrum. Methods Phys. Res. Sect. A532, 40(2004).
[13] T. Kubo et al., Nucl. Instrum. Methods Phys. Res. Sect. B70, 309(1992).
[14] H. Ueno, Eur. Phys. J-Spec. Top. 162, 221 (2008).
[1]－ 93 －

NPI-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013������������������������� ������������� ���������������� �������������������
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������������������������������������������������������������������������������

Abstract – ������ ����������� ��������� ��� ���� ����� ��������� ��������� ������������� ��� ������ ��� ���� ������������������ ����������
�������� ������������ ������� ������ ���� ������ ������ ���������� ������� ��������������� ��� ���������� ��������� ������ ���� �������� � �����
���������������������������������������������������������������������
������ �������� ����� �� ������� ���������� ���������� ��� ���� �������
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Keywords – Zinc Oxide, Perturbed Angular Correlations, Indium,
Impurity, Local Structure������������������
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droplets of 111In HCl solution were added onto a disk of the
In-doped ZnO, and it was heated in air at 1373 K for 2 h for
diffusion of the probe[3]; ������ �������� �� ��������
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－ 94 －

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�������������� �������������������������������APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

NPO-01

Mössbauer Analysis of Iron Ore and Rapidly Reduced Iron Ore by MicroDischarge
Kiyoshi Nomura1, Paulo de Souza2, and Shoji Hirai3, Norimichi Kojima1

1) Graduate School of Art and Science, The University of Tokyo, Komaba 3-8-1, Meguro-ku, 153-8902, Japan
2) University of Tasmania, Australia, 3) Tokyo Toshi University, Japan
Abstract
Several samples of iron ore were analyzed by Mössbauer
spectrometry. Almost all iron ores are composed of hematite,goethite, and fine grains of oxides, of which the ratios aredifferent among production area. The amount of hematite,magnetite and geothite are consistent with those obtained byconventional chemical analysis. MD method is proven to beefficient in rapidly reducing iron ores.

I. INTRODUCTION
Iron ore contains several kinds of iron oxides such as Hematite(�-Fe2O3), and Magnetite (Fe3O4), and iron oxy-hydroxides such
as Goethite (�-FeOOH), and Lepidocrocite (�-FeOOH). A
chemical analysis is generally used for determining chemicalcomposition of iron ore [1]. On a number of different ores, we
compared qualitative and quantitative results obtained by
Mossbauer spectrometry with those by chemical analysis. Further,
we tried to perform the rapid reduction of iron ore by using microdischarge (MD) using carbon felt (CF) for shirt time [2].

two sextets come from the Fe2+ and Fe3+ species occupied inoctahedral (site B) and Fe3+ in tetrahedral (site A) sites of inversespinel, magnetite. Two doublets with small and large QS values
were observed. The former is due to Fe2+ species as wüstite (FeO).
The latter doublet with large QS is considered due to formation ofsiderite (FeCO3) although the QS value is larger than expected forthis mineral. The large QS may be a result of the dispersion inoxide matrix. Unquestionably the micro-discharge method
produces a noticeable fast reduction of all treated ores.
1) M. Yasutaka, S. Hirai, Japanese J. Iron and Steel, 97�2011�
70,2) H. Kurihara, T. Yajima, K. Nomura, J. of Powder Metallurgy
Association, 56 (2009) 116.

Fe ORE_C

1.00
0.96
0.92
0.88

II. EXPERIMENT

III. RESULT AND DISCUSSION
Results by Mössbauer spectra

Mössbauer spectra of Australian iron ores (C, E, and M) are
shown in Fig. 1. A outer sextet with a large magnetic field (Bhf
=51.5T, IS= 0.37mm/s, QS(2�)= -0.20 mm/s) is assigned to��Fe2O3, and the inner sextet with a small magnetic field (Bhf =37T, IS = 0.37mm/s, QS(2�) = 0.30mm/s) is to ��FeOOH. The
Mössbauer spectrum of sample E show the broaden sextet due to��Fe2O3 and paramagnetic peaks in addition to the more broaden
sextet peaks of ��FeOOH due to fine grains of iron ore or
isomorphic substitution of Fe3+ by Al3+. The amounts of ��Fe2O3
and ��FeOOH were consistent with the results by chemical
analysis.

Reduction treatment of iron ore by micro-discharge(MD) using carbon felt (CF)2)

A sample can be heated up to 1000oC by MD/CF for about 100
seconds. Mössbauer spectrum of sample M, treated in alumina
crucible by MD/CF with 500 W for 2 min, is shown in Fig. 2.
Two sextets and two doublets were additionally observed in the
Mössbauer spectrum. The Mössbauer parameters indicate that the－ 95 －

Relative Transmission

0.84
ORE-M

1.00
0.98
0.96
0.94
0.92

ORE-E

1.00
0.99
0.98
0.97
0.96

-10

-5

0

5

Velocity (mm/s)

10

Fig.1 MS spectra of Austrian iron ore.
1.00

Relative Transmission

Using five ore samples (A and B from Brazil, C, E and M from
Australia) and a reference Japanese standard sample (JSS805), thecontent ratios of Fe2O3, FeOOH, and Fe3O4 were determined by
Japanese Industrial Standard (JIS) method. The content ratios of
Fe2O3, FeOOH, and Fe3O4 obtained are as follows: sample A(91.7%, 2.8% 0.4%), sample B (85.4%, 10.2%, 0.2%), sample C(78.6%, 23.7%, 63.3%), sample E (23.7%, 63.7%, 0.2%), sample
M (63.3%, 29.3%, 1.1%)�).
Mössbauer spectra of the same samples were measured at room
temperature by using 57Co(Cr) source.

0.98
0.96
0.94
0.92

Ore-M after MD/CF
-10

-5

0

Velocity (mm/s)

510

Fig.2 MS spectrum of iron ore M treated by MD/CF.

NPO-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Three Ways to Fix Cs in Prussian Blues

1

Junhu WANG1, Alexandre I. RYKOV1,
and Kiyoshi NOMURA2

Mössbauer Effect Data Center, Dalian Institute of Chemical Physics, CAS, Dalian 116023, China
2
School of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku 113-8656, Japan

Prussian Blue (PB) and its analogues have a very highcapacity for incorporation, or sorption, of various alkali ions.
Among all the alkali elements in PB Cs is absorbed mostfirmly. The mobility of alkali ions in channels of thehexacyanometalate structure drops dramatically withincreasing the alkali ionic radius. We have explored threeroutes towards fixation of Cs in the solid phases of the PB
analogues. Our sorption experiments showed that theinsoluble hexacyanocobaltates are rather slow sorbents,
however, our newly synthesized soluble PB analogues arehaving much larger sorption capacity accessible at short times.
SolublePBA

Cs PBA

Solution
Mix

Insoluble
PBA

Fig.2. Mössbauer spectra of the insoluble pristine sorbent

Fig 1. Explored routes of Cs fixation in PB.
The sorption rate is the crucial functionality parameter ofa sorbent for sorption of the radioactive isotopes. This isbecause in a realistic radioactive contaminated environment
the PB sorbent attains too much activity well before thesaturation in Cs. Therefore, it is vital to compare the rates for
known ways of the synthesis of a target cyanometallate
CsFe[Co(CN)6] in Fig.1.
Measuring the Mössbauer spectra of the sorbents
allows to understand the changes in local surrounding of theFe2+ ions [1]. In Fig. 2, we show that the ionic charge of Fe2+
becomes distributed more isotropically with increasing Cs
content. The latter is controlled by the Rietveld analysis of xray diffraction patterns.

Fe3[Co(CN)�] ��xH�O and the products of its reaction after
soaking in solutions containing the Cs ion. The aliquotes of
35 mg of the sorbent were stirred in a beaker with 25 mL of
0.1 M solution of CsCl for 40 h at the temperatures of 20 °C,
35 oC, 50 oC and 65 oC. Inner doblet (lower EFG owing tosmaller charge anisotropy) is increasing with Cs content from
top to bottom.
This work was supported by the Chinese Academy of
Sciences Visiting Professorships for Senior International
Scientists. Grant No. 2011T1G15. Financial support obtained
from the Chinese Academy of Sciences for "100 Talents"
Project, the National Natural Science Foundation of China(No. 11079036) and the Natural Science Foundation of
Liaoning Province (No. 20092173) is also greatly
acknowledged.
[1] A.I. Rykov, J. Wang, T. Zhang and K. Nomura, Hyperfine Interact. DOI
10.1007/s10751-012-0705-5.

－ 96 －

NPO-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Theoretical study on Mössbauer parameters of iron assembled complexes
KANEKO Masashi1, DOTE Haruka1, NAKASHIMA Satoru2
1

2

Graduate School of Science, Hiroshima University
Natural Science Center for Basic Research and Development (N-BARD), Hiroshima University

Abstract – The calculation of 57Fe Mössbauer parameters (�Fe,��Q) using density functional theory to 20 benchmark complexes
was performed and showed a good correlation with experimentvalues. And the calculation to the mononuclear model of ironassembled complexes was also performed. The result of isomer
shift was in good agreement with experiment, while that ofquadrupole splitting did not show a good correlation withexperiment.

III.

RESULTS AND DISCUSSIONAs shown in Figs.1 and 2, calculated �Fe �����EQ werestrongly correlated with experiment values. The correlation
coefficients of �Fe �����EQ were 0.99 and 0.98 respectively.

Keywords – 57Fe Mössbauer spectroscopy, density functional
theory, iron assembled complex

I.

INTRODUCTION

Assembled complexes with transition metal ion as acenter metal can show various structures and properties.
And assembled iron(II) complexes bridged by bipyridinetype ligands (L) [Fe(NCX)2(L)2]n (X = S, Se, BH3; L = 1,2(bpa),
1,3-bis(4-pyridyl)propane
bis(4-pyridyl)ethane(bpp)) showed a stereospecific structure depending on theconformer of L[1][2]. Furthermore, in these system, thequadrupole splitting values obtained by 57Fe Mössbauer
spectroscopy experiment showed a drastic change
depending on anions, which were NCX-, in spite ofisomorphous structures[1][2].
Then we can easily perform the molecular orbital
calculation including transition metals using density
functional theory (DFT) thanks to the progress ofarithmetic capacity. And benchmark studies of Mössbauer
parameters (�Fe�� �EQ) on mononuclear complexes which
possess noncubic electric field gradient show a goodcorrelation between experiment and calculation value[3].
In the present study, we report the electronic states ofassembled systems using DFT to reveal the quadrupole
interaction by changing anions.
II. COMPUTATION DETAILSAll DFT calculations were performed using the ORCA
software package. The spin-unrestricted Kohn-Shammethod has been used for iron(II) high-spin octahedral
system. In the present study, we have used the simple
cluster model [Fe(NCX)2(pyridine)4] referenced by single
crystal X-ray analyses to 1D chain structures of bpa andbpp complexes. Single-point energies were calculated byusing a B3LYP functional. CP(PPP) for Fe and TZVP forother atoms were assigned to basis functions. Isomer shift
was calculated by fitting experiment �Fe with calculated �0,which is the electron density at Fe nucleus, using
benchmark study. 57Fe quadrupole splittings were
calculated using electric field gradient tensor (Vii) andasymmetry parameter (�) obtained by DFT calculation.

Fig.1 The correlation of �Fe between calculation and experiment.

��������������������������EQ between calculation and experiment.

And the result of mononuclear models referenced byiron assembled complexes was shown in Tbl.1. Calculated
�Fe values were in good agreement with experiment whilec���������� �EQ values did not correlate with experiment.
These results suggest the effect of assembly and thesereasons are under study.
Tbl.1 Mössbauer parameters of pyridine model referenced by[Fe(NCX)2(L)2] (unit in mm s-1).

[1]
[2]
[3]

－ 97 －

L

X

�Fe

exp

�Fecalc

��EQexp|

�EQcalc

bpa
bpa
bpa
bpp
bpp
bpp

S
Se
BH3
S
Se
BH3

1.18
1.18
1.19
1.20
1.19
1.19

1.03
1.03
1.03
1.03
1.02
1.00

2.17
0.74
1.51
2.19
1.24
1.71

3.12
3.32
3.94
2.96
3.07
3.27

T. Morita, et al., Bull. Chem. Soc. Jpn., 79, 738 (2006).
M. Atsuchi, et al., Inorg. Chim. Acta, 370, 82 (2011).
F. Neese, et al., Inorg. Chem., 44, 2245 (2005).

NPO-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Study on muon capture process for gaseous molecules containing C and O atoms
G. Yoshida1, K. Ninomiya1, M. Inagaki1, T.U. Ito2, W. Higemoto2, T. Nagatomo3, P. Strasser3,
N. Kawamura3, K. Shimomura3, Y. Miyake3, T. Miura4, M.K. Kubo5, and A. Shinohara1
1

Graduate School of Science, Osaka University
Advansed Science Research Center, Japan Atomic Energy Agency
3
Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK)4
Radiation Science Center, High Energy Accelerator Research Organization (KEK)5Colleage of Liberal Arts, International Christianity University
2

Abstract –Muonic atom is an atomic system which has a negative
muon substituted an electron. When a muon is stopped in a
substance, a muonic atom is formed. It is known that muonic atom
formation processes are influenced by the chemical environmentof muon capturing atom such as molecular structure (chemical
effect). However chemical effects still have not been wellinvestigated. In this study, we performed muon irradiation for CO,
CO2 and COS molecules, and measured muonic X-rays precisely
to investigate the chemical effect on muon capture processes.
Keywords – muon, muonic atom, exotic atom, muon capture

I.

INTRODUCTION

A negative muon is one of the elementary particles(lepton) that has charge and approximately two hundred
times heavier mass than that of an electron. When a muonis stopped in a substance, a muonic atom is formed. It is
know that muon capture processes are strongly influenced
by the structure of the muon capturing molecule; the muon
capture probability of each atom (muon capture ratios) andthe initial quantum state (n; principal quantum number andl; angular momentum quantum number) of the captured
muon are changed drastically. For example muon capture
probability ratio of boron atom to nitrogen atom for cubic
structure boron nitride is 20% smaller than that ofhexagonal structure [1]. This is called chemical effect.
To reveal the chemical effect on muonic atom formation
processes, we previously performed muon irradiations for
simple gaseous molecules containing nitrogen and oxygen
atoms (NO, N2O and NO2). In high density condition, suchas solid, liquid and high pressure gas samples, sample
density affects muonic cascade processes after muon
capture, hence we conducted all experiments at low
pressure condition below 1 atm. In this study, we focusedon gaseous simple molecules containing carbon and oxygen
atoms (CO, CO2 and COS).

III. RESULTS AND DISCUSSION
Muonic X-ray spectrum for CO2 sample obtained by thisexperiment is shown in Fig.1. In this study, we discussed
the experimental results about following two topics; muon
capture probabilities of C and O atoms, and muonic X-ray
structures (K�/K� and K�/K� X-ray ratio etc.).
The muon capture probabilities of C and O atoms were
determined from total intensity of muonic Lyman X-ray
series of each atom. The muon capture ratios comparedwith the previous reports in high pressure sample
conditions were in agreement [2,3].
The muonic X-ray structure reflects initial quantum stateof the captured muon. The initial quantum state of muon
was estimated using a simulation of muonic cascade
processes [4]. The experimental structure of muonic C Xrays for CO2 resembles that for COS, but that for CO
resembles neither. This implies that the initial quantum
state of muons captured by C atom differs between CO andother molecules. In fact, we found that muons captured by
C atoms in CO molecule tend to have large angularmomentum quantum number compared with that of CO2
and COS from the cascade calculation. In the presentation,
we will also discuss the initial quantum state of muons
captured by O atoms for CO, CO2 and COS samples.

II. EXPERIMENTAL
All muon irradiation experiments were performed atmuon science facility (MUSE) in J-PARC. Low pressure
sample gases (0.2 to 0.4 atm CO, CO2 and COS) were put
into a gas chamber and irradiated with low momentum
muon beam (18.8MeV/c). Muonic X-rays were measured
by germanium semi-conductor detectors.

Fig.1 Muonic X-ray spectra of CO2 sample. C(2-1) means the muonic Xray series at muon transition from principal quantum number two to one
on muonic carbon atom (K�X-ray).
[1]
[2]
[3]
[4]

－ 98 －

H.Schneuwly et al., Physical Review A 27, 950 (1983)
J.D.Knight et al., Physics Letters 79A 377 (1980)
M K.Kubo et al.,Radiochimica Acta 47 77 (1989)
V.R. Akylas et.al., Computer Physics Communications 15, 291(1978)APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

EDI-01

CINCH–II Project – Next Step in the Coordination of Education in Nuclear- andRadiochemistry in Europe
Jan John1�������������1��������������1, Teodora Retegan2, Christian Ekberg2, Gunnar Skarnemark2,
Jukka Lehto3, Teija Koivula3, Paul J. Scully4, Clemens Walther5, Jan-Willem Vahlbruch5, Nick Evans6,
David Read6, Eric Ansoborlo7, Bruce Hanson8, Lindis Skipperud9, Brit Salbu9, Jon Petter Omtvedt10
1

Czech Technical University in Prague, Czech Republic
Chalmers University of Technology, Gothenburg, Sweden
3
University of Helsinki, Finland
4
National Nuclear Laboratory Ltd., Warrington, United Kingdom
5
University of Hanover, Germany
6
Loughborough University, Great Britain
7
Commissariat à l’énergie atomique et aux énergies alternatives, France
8
Leeds University, United Kingdom
9
Norwegian University of Life Sciences, Aas, Norway
10
University of Oslo, Norway
2

Abstract

Any of the potential options for the nuclear power –both the renaissance, if any, or the phase out – will requiresignificant numbers of the respective specialists, amongst
others the nuclear and/or radiochemists. In parallel, asignificant demand exists for these specialists in
non-energy fields, such as environmental protection,
radiopharmacy, nuclear medicine, biology, authorities, etc.
Since the numbers of staff in teaching and the number ofuniverzities with facilities licensed for the work with open
sources of ionizing radiation has decreased on orsometimes even below the critical level, coordination andcollaboration are required to maintain the necessaryteaching and training capabilities.
The CINCH-II project, aiming at the Coordination of
education and training In Nuclear CHemistry in Europe,
will be a direct continuation of the CINCH-I project which,among others, identified the EuroMaster in Nuclear
Chemistry quality label recognized and guaranteed by theEuropean Chemistry Thematic Network Association as an
optimum common mutual recognition system in the field of
education in Nuclear Chemistry in Europe, surveyed thestatus of Nuclear Chemistry in industry / the needs of theend-users,
developedanefficient
systemofeducation/training compact modular courses, or developed
and tested two electronic tools as a basis of a future
efficient distance learning system.
In the first part of this paper, the achievements of the
CINCH-I project will be described. This description will
cover both the status review and the development activitiesof this Collaboration. In the status review field, the resultsof a detailed survey of the universities and curricula innuclear- and radiochemistry in Europe and Russia will bepresented. Another survey mapped the nuclear- andradiochemistry in industry – specifically the training andeducation needs of the end users. In the development
activities field, the main achievements of the CINCH
project will be presented. They are particularly the NukWik– an open platform for collaboration and sharing teachingmaterials in nuclear- and radiochemistry based on a wiki
engine. Further outputs are a set of compact joint modular

courses in different branches of modern nuclear- andradiochemistry, or an e learning platform (CINCH Moodle)
available for both education and training (applicable at the
Ph.D., life-long learning, and MSc. levels).
The expected outcomes of the follow-on CINCH-II
project will be described in detail. The CINCH-II project isbuilt around three pillars - Education, Vocational Education
and Training (VET), and Distance Learning - supported by
two cross-cutting activities – Vision, Sustainability andNuclear Awareness that includes also dissemination, andManagement. Its main objectives, expected to have thebroadest impact to the target groups, are further
development and implementation of the EuroMaster in
Nuclear Chemistry, completion of a pan-European offer ofmodular training courses for the customers from the end
users, development of a Training Passport in Nuclear
Chemistry and preparing the grounds for the European
Credit system for Vocational Education and Training(ECVET) application in nuclear chemistry, implementationof modern e-learning tools developed in CINCH-I andfurther development of new tools for the distance learning,laying the foundations of a Nuclear Chemistry Education
and Training Platform as a future sustainable Euratom
Fission Training Scheme (EFTS) in Nuclear Chemistry,development of a Sustainable Systems for Mobility within
the Nuclear Chemistry Network, or development ofmethods of raising awareness of the possible options fornuclear chemistry in potential students, academia andindustry. The CINCH-II project will mobilize the identified
existing fragmented capabilities to form the critical massrequired to implement the courses and meet the nuclear
chemistry postgraduate education and training needs,
including the high-level training of research workers, of theEuropean Union. Networking on the national level and withexisting European as well as international platforms will be
an important feature of the project.

－ 99 －

EDI-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Fostering of Personnel for Nuclear and Radiochemistry according to China’s NPP
Prospects after Fukushima Daiich Accident
Wangsuo WU1 Zhifang CHAI1,2

1Radiochemistry Laboratory, School of nuclear Science and Technology, Lanzhou University, Lanzhou 730000, China
2
Institute of High Energy Physics, Chinese Academy of Science, P.O. Box 918, Beijing 100049, China

PartI China’s NPPs Prospects after Fukushima Daiichi
Accident

Fig.1 NPPs Distribution in China
PartII Fostering of Personnel for Nuclear andRadiochemistry
Nuclear Talent Demand
Survey before 2020

Lanzhou University

discipline

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8

A strong impetus for radiochemistry is attributed to therapid development of nuclear energy in China. In average,
two nuclear power facilities per year will be installed evenafter Fukushima Daiich Accient. Nowadays there are 27
schools (or colleges) of nuclear science and technology (orengineering) in Chinese universities, of which 13 havenuclear and radiochemistry education and training with
about 300 undergraduate students per year. The number ofmaster and doctorate students in radiochemical field isabout 50-60 annually. Several universities and institutes
have research reactors, accelerators, neutron generators andother nuclear facilities used for radiochemical educationand training. An exciting fact is that some big scientificplatforms have been, are being or will be constructed, e.g.
the Chinese Advanced Research Reactor, Shanghai
Advanced Light Source, Chinese Spallation Neutron
Source, Thorium Melted Salt Reactor (TMSR), Accelerator
Driven Sub-critical System (ADS) and other big nuclear
facilities, which are providing or will provide radiochemists with advanced nuclear arsenal.
However, a quite number of problems in Chinese nuclear
and radiochemical educations still exist, among which thebiggest one is shortage of bright young radio-chemists in
China. In the meantime, experienced radiochemicalteachers are urgently needed. Some radiochemicallaboratories in Chinese universities are outdated and illequipped.
Some measures and strategies for pushing nuclear andradiochemistry research and education in China will be
proposed in this text as well.

－ 100 －

EDI-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Post-Fukushima Situation on Radiation Awareness Activities
and Nuclear and Radiochemistry Education in Japan
Akihiko Yokoyama,
Faculty of Chemistry, Institute of Science and Engineering, Kanazawa University,
Kakuma, Kanazawa, Ishikawa 920-1192, Japan
Abstract – The accident at Fukushima Daiichi Nuclear Power Plant
in 2011 altered the working environment for radiochemists in Japan,
who are supposed to be in charge of several problems such asradioactive contamination and nuclear wastes from reactors. Under
the circumstances, we are compelled to reexamine the education
relating to such matters. I discuss the effect of the accident on some
aspects of education of the field.
Keywords – Fukushima accident/ radioactive contamination/
radiation awareness/ education

Research work in any field is affected by the educational
prospects of the respective fields in both positive andnegative ways. I would like to describe the present situationand future prospects for nuclear and radiochemistry educationin Japan from my point of view, as a radiochemist,
radiochemistry being one small part of the total discussion.
After the accident at Fukushima Daiichi Nuclear Power
Plant in 2011, radiation-related topics such as radioactive
contamination and nuclear wastes from reactors came to be
the center of attention of people in this country. Furthermore,
people’s orientation concerning the nation’s energy policy
seems to be changing here. Under these circumstances I am
compelled to reexamine the radiation awareness activities
conducted for ordinary people (including children) as auniversity contribution to local communities. All these newsituations cannot help affecting the educational content inmany fields to some extent. I will discuss here the effect of
the accident on the education for my field.
Nuclear science is still important in many industries andresearch fields in relation to nuclear medicine, materialscience, and the nuclear power industry to name a few.[1]Momentum towards the development of human resources isincreasing in the nuclear power industry because ofinternational pressure for carbon-oxide reduction and theneed for development of nuclear waste treatment in Japan.[2]As a result, engineers, researchers and leaders of researchgroups have had to gain a broad perspective regarding energy
crisis and environmental problems.
On the other hand, the number of students in the nuclear
field, including radiochemistry, has decreased in recent years
in Japan. Tight budgets at universities interfere with themaintenance of nuclear facilities, which in turn has largely
discouraged students.[1,2]Besides those aspects, the Fukushima accident has added
several more complicated factors. We face several problems

such as decontamination of everything in the area around thenuclear power plant, not to mention the decommissioning of
the plant itself, all of which require radiochemical knowledge.
Primary education and secondary education had not paid
attention to radiation awareness for many years. Nowadays,
the situation is changing due to an education guidelinechange made by the government. It requires more
opportunities to lecture to young people and their teachers
and to discuss about radiation matters. The accidents havecreated more opportunities to talk to the general populationon these issues, too. I am, however, not sure of the futurecontents to teach in relation to the Fukushima issues
On the university and graduate school level, a new
methodology for human resources development for nuclear
science and technology had been proposed by several
universities in Japan and the Japan Atomic Energy Agency(JAEA). The network system has established a program byutilizing unique courses at universities and a real-time multidirectional network system as well as effective curriculums
with practical exercises by utilizing JAEA’s training andexperimental facilities.[3] The network aims to implement thesystem with an eye to improving it with expanded
experiences and increased the number of participant
universities as well as to update the curriculums learningfrom the Fukushima issues.
Despite many difficulties, we have to overcome thecurrent crisis to move towards a brighter dawn of the nuclear
sciences and I think we still have a good chance of realizing
the dream.
REFERENCES[1]The Japan Society of Nuclear and Radiochemical Sciences, Fifty Years’
History of Radiochemistry in Japan (CD), in Japanese (2007).
[2] References on Human Resources for Nuclear Science and Technology
in Japan: http://www.jaif.or.jp/ja/news/2007/jinzai-kenkyukai.html, inJapanese (2007), http://www.jaif.or.jp/ja/seisaku/jinzai-kyogikai_report0807.pdf, in Japanese (2008),
http://www.aec.go.jp/jicst/NC/iinkai/teirei/siryo2009/siryo15/siryo1.pdf,
in Japanese (2009).
[3] Y. Fujii, T. Nakanishi, T. Fukui, H. Kato, and H. Ojima, Japan Nuclear
Education Network (JNEN), A Multi-Directional Education Systemamong JAEA and Several Universities, Presentation by J. Sugimoto in
Conference on Nuclear Training and Education (2009)－ 101 －EDO-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Radiochemistry course in the undergraduate Nuclear Science Program at
Universiti Kebangsaan Malaysia
S. B. Sarmani, R. B. Yahaya, M. S. Yasir, A. Ab. Majid, K. S. Khoo,
I. A. Rahman, F. Mohamed

Nuclear Science Programme, Universiti Kebangsaan Malaysia, 43600 Bangi, Malaysia
Universiti Kebangsaan Malaysia (UKM), is the only
university in Asia offering an undergraduate degree
program in Nuclear Science since 1978. The program has
undergone several modifications due to changes in national
policy and priority. The last adjustment was made in 2011
to ensure that the program is aligned with the aims andstrategies of the National Nuclear Policy that guided therealization of Malaysia’s first Nuclear Power Plant by 2021.
The program covers nuclear sub-disciplines such as nuclear
physic, radiobiology, radiochemistry and radiation safety.
To graduate with a Bachelor of Science in Nuclear Science
students are required to pass a total of 122 credits
comprising of 20 credits of university courses and 102
credits of compulsory courses or core courses.
Radiochemistry course involves both lectures andlaboratory practicals. During the first year students aretaught about basic physical and chemical properties ofradioactive materials, radiation interaction and detection,
radiation safety. In the second year lecture topics coverbasic theory in radioanalytical chemistry, neutron
activation, XRF, XPS and PIXE, tracer techniques, isotope
dilution analysis, radioimmunoassay, nuclear dating andanalysis of radionuclides in the environment. In the thirdyear lectures are given on the chemistry of uranium,
thorium and other actinides, isotope production andchemical aspects of nuclear fuel cycle. In the final year
students may do a short project on applications ofradioanalytical techniques, measurements of radioactivity
in the environment or radiochemical separation. Recently,
more students are enrolled into the program because of the
National Nuclear Policy implementation and the program isin tandem with the thrusts and strategies of the policy.
However, it is very difficult in getting new text books onradiochemistry particularly and nuclear science andtechnology generally. In the absence of good text book
students are using on-line references published by reputable
universities and organisations world wide.

－ 102 －

Oral Presentations
Friday, 27 September 2013
Hall & Meeting Room, Kanazawa Bunka HallTime
09:00-09:10
09:10-09:20
09:20-09:30
09:30-09:40
09:40-09:50
09:50-10:00
10:00-10:10
10:10-10:20
10:20-10:30
10:30-10:40
10:40-10:50
10:50-11:00
11:00-11:10
11:10-11:20
11:20-11:30
11:30-11:40
11:40-11:50
11:50-12:00
12:00-12:10
12:10-13:20
13:20-13:30
13:30-13:40
13:40-13:50
13:50-14:00
14:00-14:10
14:10-14:20
14:20-14:30
14:30-14:40
14:40-14:50
14:50-15:00
15:00-15:10
15:10-15:20
15:20-15:30
15:30-15:40
15:40-15:50
15:50-16:00
16:00-16:10
16:10-16:20
16:20-16:30
16:30-16:40
16:40-16:50
16:50-17:00
17:00-17:10
17:10-17:20
17:20-17:30
17:30-17:40
17:40-17:50
17:50-18:00
18:00-18:10
18:10-18:20
18:20-18:30
18:30-18:40
18:40-18:50
18:50-19:00
19:00-19:20
19:20-19:40
19:40-20:00
20:00-

9:00

Friday, 27 September
Meeting Room
AAI-01
Invited

9:30

AAI-02

A. Chatt
InvitedT. Miura

10:00

Coffee Break

10:20 AAO-01

GeneralJ.H. Moon
GeneralY. TohGeneralK. Ninomiya
GeneralM. Fukushima
GeneralN. Shirai

10:40 AAO-02
11:00 AAO-03
11:20 AAO-04
11:40 AAO-05
12:00

Lunch Time

13:20

API-03

13:50

APO-04

14:10

APO-05

14:30

APO-06

14:50
15:10

InvitedY. Hamajima
GeneralC. Gautier
GeneralT.Yoshimura
GeneralJ.D. Despotopulos

Coffee BreakClosing Ceremony－ 103 －

AAI-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Simultaneous Analysis for As, Sb, and Se Species in Waterby Chemical Separation and Neutron Activation
W. Menendez Sanchez, Y. Shi, and A. Chatt
Trace Analysis Research Centre, Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3, Canada
Abstract – APSORC’13 Abstract
Keywords – solid-phase extraction, solvent extraction, HPLC, INAA,
speciation analysis, arsenic, antimony, seleniumI.

INTRODUCTION

Arsenic speciation analysis has become an increasing
health concern since the toxicity of the element depends upon
the chemical species. Inorganic arsenic species are more toxic
than their organic counterparts. Among the inorganic forms,
As(III), the major arsenic species present in fresh water
systems, is considered to be more toxic than As(V). It is wellknown that As(III) and As(V) undergo interconversion inaqueous solutions depending on pH, temperature, oxygen
content, microorganisms, etc. Co-contaminants such as
species of antimony and selenium in water can also affectarsenic speciation. There exists a need for simultaneous
analysis of all these species.
Simultaneous speciation neutron activation analysis(SSNAA) technique has been developed in our laboratory
over the last 20 years or so. This technique can now be used
for the simultaneous determination of not only various
species of a single element but also species of other elements
present in the same sample. Almost all speciation techniques
consist of two steps. The first step involves the separation of
species from a sample followed by the second step of
element-specific detection. Neutron activation analysis(NAA) methods in combination with high-performance liquid
chromatography (HPLC) were developed first for thedetermination of low levels of five arsenic species, namely
As(III),
As(V),
monomethylarsonicacid(MMA),
dimethylarsinic acid (DMA), and arsenobetaine (AsB) in
water samples. Organically bound arsenic (OBAs) and totalarsenic levels were measured. These methods were thenextended to include the determination of arsenic, antimony
and selenium species, namely As(III), As(V), AsB, OBAs,
MMA, DMA, Sb(III), Sb(V), and Se(IV), in natural water
samples by solvent extraction and solid-phase extraction(SPE).
II. EXPERIMENTAL
In the HPLC method [1], OBAs was first separated bysolid phase extraction using a C18 silica column. Next DMA
and AsB were separated in a cation exchange column
followed by injection into HPLC with 10 mM NH4H2PO4/(NH4)2HPO4 buffer as the mobile phase. The effluent

containing MMA, As(III), and As(V) species was theninjected into HPLC with 75 mM NH4H2P04/(NH4)2HP04
buffer at pH 5.5.
An independent solvent extraction method was developed
to separate soluble As(III) and As(V) compounds in waterusing APDC/MIBK [2].
In the SPE method [3], As(V), MMA, and DMA wereseparated and preconcentrated by an Alltech strongly anion
exchange (SAX), namely Extract-Clean SPE SAX, column
and strongly cation exchange (SCX), namely Extract-Clean
SPE SCX, column in tandem while As(III) remained in theeffluent. Once the columns were physically separated, acetate
buffer at pH 3.4 was used to elute MMA from the SAX
column. Then 5 mL of 1 M nitric acid was used to elute
As(V). The SCX column was also eluted with 5 mL of 1 M
nitric acid for DMA determination. This SPE method wasfurther extended to separate As(III), As(V), AsB, OBAs,
MMA, DMA, Sb(III), Sb(V), and Se(IV) in natural water
samples [4].
All samples were irradiated in the Dalhousie University
SLOWPOKE-2 Reactor facility at a neutron flux of either 5
or 2.5×1011 cm-2 s-1. Samples were counted using either aconventional or a Compton suppression gamma-ray
spectrometer. The 559.1-keV �-ray of 76As (t1/2 = 26.3 h) wasused for arsenic determination.
III.

RESULTS AND DISCUSSION

The detection limits (ng mL-1) of the HPLC-NAA method
were found to be 0.005 for OBAs, 0.02 for AsB, DMA,
MMA, As(III), and As(V) and 0.12 for total arsenic. The
detection limits of As(III) and As(V) in the solvent extraction
methods were 0.007 for fish/shellfish, 0.005 for As(III) and
0.006 mg kg-1 for As(V) in plants. The detection limits (ngmL-1) were 0.9, 1.7, 1.6, 3.8 and 16 for As(III), As(V), MMA,DMA and total arsenic, respectively.
[1]

References

[2]
[3]
[4]

－ 104 －

Y. Shi, R. Acharya, A. Chatt, J Radioanal Nucl Chem, 262(2004) 277286.
R. Zwicker, B.M. Zwicker, S. Laoharojanaphand, A. Chatt, JRadioanal Nucl Chem, 287(2011)211-216.
W. Menendez Sanchez, B. Zwicker, A. Chatt, J Radioanal Nucl Chem,
282(2009)133-138
W. Menendez Sanchez, Ph.D. Thesis, Dalhousie University, Halifax,
NS, Canada, 2009.

AAI-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Precise Determination of Bromine in PP Resin Pellet by Instrumental Neutron
Activation Analysis using Internal Standardization
Tsutomu Miura1, Ryo Okumura2, Yuto Iinuma2, Shun Sekimoto2, Koichi Takamiya2, Masaki Ohata1,
Akiharu Hioki1
1

National Metrology Institute of Japan, AIST
Kyoto University Research Reactor Institute2

Abstract – Instrumental neutron activation analysis with theinternal standardization was applied the precise determination ofbromine in PP resin. Gold was used as an internal standard. The
analytical results of Br were in excellent agreement with thevalues obtained by ID-ICPMS. The relative expanded uncertainty(k=2) was 1.9 %, and it was comparable to that of ID-ICP-MS.
Keywords – Neutron activation analysis, Bromine, certified
reference material, Uncertainty

I.

INTRODUCTION

National Metrology Institute of Japan is responsiblefor developing certified reference materials (CRMs) and forestablishing the traceability of SI (The International System
of Units) on chemical metrology in Japan. To establish SI
traceability, the primary method of measurements should
be applied to the characterization of the CRMs. Recently,
neutron activation analysis (NAA) using comparator
standard is recognized as a potential primary ratio method[1]. Despite the potential of NAA as primary ratio method,the evaluation of the measurement uncertainty is requiredin any analysis.
In general, there are three main
components of uncertainty in NAA, that is, sample
preparation uncertainty, neutron flux homogeneity, andgamma ray measurement uncertainty.
Usually, flux
monitor is used to correct the neutron flux in-homogeneity.
However, although the flux monitor can correct the neutron
flux variation using the count rate of the known amount of
the monitor nuclide, it does not reflect the neutron flux ofthe actual sample. The most practical method to eliminate
neutron flux in-homogeneity and to improve gamma ray
measurement uncertainty is an internal standard method [2].
In this paper, we presented that notable capability ofinternal standardization in NAA for determination of Br in
polypropylene (PP) resin pellet as a candidate CRM.

measurement system consisted of a Canberra GC40707500 Ge detector and a Laboratory Equipment
Corporation MCA600.
B. Results and discussions
It was found that the neutron flux varied according to
the sample position in the irradiation capsule. The relative
standard uncertainty of the in-homogeneity was estimatedto be about 5.1 % by 198Au sensitivity (cps/�g) at 411 keVof the internal standard (n=19). The uncertainty related to
the neutron flux homogeneity significantly contributes tothe overall uncertainty, if an internal standard is not applied.
The calibration curve linearity was also improved byinternal standardization. The calibration curves of 82Br
The relative
showed good and sufficient linearity.
uncertainty related to the calibration curve linearity was
improved to 0.97 % from 2.0 % for 82Br by using aninternal standardization. The analytical results of Br byproposed method were in excellent agreement with thevalues obtained by Isotope dilution-Inductively Coupled
Plasma Mass Spectrometry (ID-ICPMS). The relative
expanded uncertainty (k=2) was 1.9 %, and it wascomparable to that of ID-ICP-MS.

APSORC’13 HEADING (WITHOUT NUMBER)[1][2]

A. Instruments and methods
The PP resin pellet candidate CRM was produced
by a mixing machine. The calibration solution was
prepared from NMIJ primary Bromide standard solution.
The Au solution for the internal standard was preparedfrom a high purity metal. The calibration solutions
contained Br and Au. One hundred mg of the PP resin
pellet samples was used for Br analysis. The Au solution
was added to the samples before neutron irradiation. The
neutron irradiations were performed by KUR (Kyoto
University Research Reactor) PN-3(thermal neutron flux:
4.6 x 1012 cm-2s-1) for 10 min and TCPn (thermal neutron
flux: 8.0 x 1010 cm-2s-1) for 30 min. The � ray－ 105 －

Greenberg, R., Bode, P., De Nardi Fernandes, E., Spectrochim. Acta
B, 66 (2011) 193-241.
Miura, T, Chiba, K, Kuroiwa, T, Narukawa, T, Hioki, A, Matsue H.,
Talanta, 82 (2010) 1143-1148.

AAO-01APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Analysis of most popular and/or consumed fish species by neutron activation
analysis in six Asian countries
J. H. Moon1, B. F. Ni2, R. M. Theresia3, N. A. Abd. Salim4, B. Arporn5, C. D. Vu6
1

Korea Atomic Energy Research Institute, Daejeon, Korea
2
China Institute of Atomic Energy, Beijing, P.R. China
3
National Nuclear Energy Agency, Serpong, Indonesia
4
Malaysian Nuclear Agency, Bangi,Kajang, 43000 Selangor, Malaysia
5
Thailand Institute of Nuclear Technology, Bangkok, Thailand
6
Vietnam Atomic Energy Agency, Dalat, Vietnam

Abstract – Since 2000, collaborative studies for applying NAA
have been performed through the Forum for Nuclear Cooperationin Asia (FNCA) sponsored by the Japanese Government. Fishwere selected as a common target sample for a collaborative
study in 2011. Six Asian countries, China, Indonesia, Korea,
Malaysia, Thailand, and Vietnam, are greatly concerned about
the composition of arsenic, heavy metals, and essential traceelements and took part in this work. Fish samples were purchasedfrom commercial markets and prepared by following a protocolthat had been proposed for this study. Samples were analyzed bytheir own NAA systems. Each country has determined toxic and/or
essential elements. These data will be very helpful in themonitoring of the levels of food contamination and to evaluate thenutritional status for people living in Asia.
Keywords–Neutron Activation Analysis, FNCA, Fish Species,
Toxic Metals

I.

INTRODUCTION

Since 2000, collaborative studies applying a neutron
activation analysis (NAA) have been carried out as one of
FNCA (Forum for Nuclear Cooperation in Asia) projects
for the application of nuclear technology for socioeconomic development. Six Asian countries, China,
Indonesia, Korea, Malaysia, Thailand, and Vietnam agreed
to participate in the analysis of the most popular and/or
consumed fish species as a sub-theme of the NAA projectin 2011. The aims of this study were to determine theinorganic elemental contents in fish species of six Asian
countries by NAA and to evaluate the dietary intake levelsof nutritional and toxic elements for population of theparticipating countries.
II. EXPERIMENTAL

III. RESULTS
China determined 14 elements from 10 fish species andmost element concentration from the sea fish is higher thanfreshwater fish. Indonesia determined 17 elements from 6
types of fish samples, and As concentrations in sea fish ishigher than in freshwater fish and Hg is contained in all
types of fish. In Korea, 17 elements including As, Cr, andHg were analyzed from 7 fish species. Malaysia determined
Cr, Hg, Se, and Zn on eight species of marine fish, and thelevel of mercury in several fish showed a high value in
dietary intakes levels compared to the EPA guideline value.
Thailand analyzed As, Cd, Co, Cr, Fe, Hg, Rb, Sb, Sc, Se
and Zn in 10 fish species As in all fresh water fish species
does not exceed the standard recommended (2ug/g) but
exceeds it in all marine fish species, while Hg in two fresh
water fish species and three marine fish species exceed thestandard recommended (0.5ug/g). Vietnam analyzed 18
elements in 10 samples of 6 sea fish species and As from
Scad fish in the Vinh Hai district is higher than the WHO
tolerable value.
ACKNOWLEDGEMENT
This research has been carried out by the support of the
Ministry of Education, Culture, Science and Technology ofJapan.
REFERENCES[1][2]

Each participating country selected six to ten fish
species and purchased them from the commercial market
for this study. Analytical samples were prepared by cutting
the edible parts of the fish, cleaning, grounding, freezedrying, and homogenizing fish samples. The samples
prepared by each country were analyzed using their own
NAA facilities. Samples were activated by short and longirradiation to detect short-, median- and long-lived nuclides.
To detect the gamma-rays emitted from the irradiatedsamples, HPGe detectors coupled to multichannel analyzers
were used. The elemental content was determined byrelative method and/or k0-method.

－ 106 －

Ebihara M, Chung YS, Chueinta W, Ni BF, Otoshi T, Oura Y,
Santos FL, Sasajima F, Sutisna, Wood AKBH (2006) J. Radioanal.
Nucl. Chem. 269(2): 259-266
World Health Organization (2006) Trace elements in humannutrition and health. Geneva, WHO, Belgium

AAO-02APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Current status and future perspective on time-of-flight prompt gamma-ray analysis
combined with gamma-ray coincidence technique
Y. Toh1, M. Ebihara2, K. Hara1, A. Kimura1, H. Harada1, S. Nakamura1, M. Koizumi1, K. Furutaka, F.
Kitatani1
12Research Group for Applied Nuclear Physics, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo 192-0397,
Japan

Keywords – Prompt gamma-ray analysis (PGA); Time-of-flight(TOF); Coincidence method; Pulsed neutron; High-purity Ge
detectors

Prompt gamma-ray analysis (PGA) is a rapid, nondestructive and a nuclear analytical technique which canperform both qualitative and quantitative multi-element
analysis of elemental and isotopic compositions. The multiple
gamma-ray detection method, also known as the coincidence
method, is widely used in nuclear spectroscopy. By applying
the multiple gamma-ray detection method to PGA, called
MPGA (multiple prompt gamma-ray analysis), the signal-tonoise ratio (S/N) can be improved. The kinetic energy of aneutron can be measured with the time-of-flight (TOF)
technique at a pulsed neutron source by measuring the time ittakes a neutron to reach a sample. The neutron capture crosssections of most nuclides exhibit strong variations with theenergy of neutron. Therefore, the energy of the neutron
obtained by TOF method can be used for identification of
nuclides (elements). For further improvements of the S/N andsensitivity, we have developed a time-of-flight prompt
gamma-ray analysis combined with multiple gamma-ray
detection method (TOF-MPGA).
The Accurate Neutron-Nucleus Reaction Measurement
Instrument (ANNRI) has been designed and developed for
PGA, nuclear cross-section data and nuclear astrophysics(See Fig.1). ANNRI is located at the beamline No. 04 at theMaterial and Life Science Experimental Facility (MLF) of theJapan Proton Accelerator Research Complex (J-PARC). MLF
is high intensive pulsed neutron facility, which operates atapproximately 300 kW proton beam power, and will be
increased up to 1 MW in the near future. The germanium
detector-array, which consists of two cluster-Ge detectors,
eight coaxial-Ge detectors and BGO Compton suppression
detectors surrounding cluster-Ge and coaxial-Ge detectors,
was installed at the flight length of 21.5m in ANNRI. It is
designed to provide high gamma-ray energy resolution andhigh detection efficiency. The typical time resolution of Ge
detector is rather poor but this is not a disadvantage becauseof the proton beam pulse width of approximately 100ns(100ns double pulse, bunches separated by 600 ns). Frame
overlap occurs when fast neutrons from a given pulse cancatch-up with slower neutrons from a succeeding pulse.
Whenever there is frame overlap there is a problem because
the neutron energy cannot be unambiguously determined.
Disk choppers consisting of a neutron absorbing disk areplaced upstream of the Ge detectors. The disc choppers areused to prevent frame-overlap problems by limiting theneutrons which arrive at a sample. The rotation frequency ofthe choppers is the same as the source repetition rate (25Hz)
under normal operation.
We present some remarks regarding the current status ofexperiments in TOF-MPGA development and its future
perspective. The results of some standard sample
measurements are discussed. These are compared with theresults of the experiments of MPGA at Japan Research
Reactor-3, and the similarity and difference are also
discussed.

Figure 1 The Accurate Neutron-Nucleus Reaction Measurement Instrument (ANNRI)－ 107 －

AAO-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Simultaneous and Multielemental Analysis by Muonic X-rays for Inside JapaneseBronze and Gold Coins
K. Ninomiya1, M. K. Kubo2, T. Nagatomo3, G. Yoshida1, M. Inagaki1, A. Shinohara1, T. Suzuki2,
N. Kawamura3, P. Strasser3, K. Shimomura3, Y. Miyake3, Y. Kobayashi4, W. Higemoto5, S.
Sakamoto5,
T. Saito6
1

Graduate School of Science, Osaka University
Colleage of Liberal Arts, International Christianity University
3
Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK)4
Nishina Center for Accelerator-Based Science, RIKEN
5
J-PARC Center, Japan Atomic Energy Agency (JAEA)
6
National Museum of Japanese History
2

Abstract – A nondestructive, quantitative and multielemental
analysis method for bulk samples was developed, which was
based on the measurement of high-energy muonic X-rays emitted
from muonic atoms inside material after muon irradiation. We
demonstrated quantitative determination of the elemental
composition inside archaeological artifacts without sample
destruction.

quantitative analysis, we also carried out muon irradiation
for some standard alloys to obtain the relation between
their elemental compositions and the muonic X-ray
intensities.

Keywords – Elemental Analysis, Muonic Atom, Muonic X-ray

Muonic X-ray spectrum of the tempo-koban is shown in
Figure 1. Muonic X-rays originated muon capture in Au
and Ag atoms were identified. We easily determined that
tempo-koban was alloy made from Au and Ag, and thecompositions of the other elements were low. We also
found incident muon momentum dependence of muonic Au
X-ray intensity for the tempo-koban. This result showedthat elemental composition of tempo-koban changed as its
depth. The elemental composition inside the tempo-koban( > 5 �m in depth) was quantitatively determined (Au: 56%,
Ag: 44%). Our result well reproduced the previous analysis
result with destructive method [2]. The details will bereported in our presentation.

I.

INTRODUCTION

Quantitative elemental analysis is one of the mostimportant themes in the field of natural science. In
particular, non-destructive elemental analysis for insidematerial is very useful in the field of archeology. The
archeological sample surface is usually oxidized and coated.
The destructive analysis methods are never applied to thevery valuable sample. The elemental analysis methods
inside bulk material are strongly desired.
In this paper, we report the development of a nonquantitativeanddestructive,
position-sensitive,
simultaneous multielemental analysis method for bulk
samples by muonic X-ray measurements [1]. Muonic atomis the exotic atoms that has one negatively charged muon in
its atomic orbital. When a muon is stopped in material, amuonic atom is formed, and characteristic X-rays (muonic
X-rays) were emitted from the muonic atom. Because themass of a muon is 207 times larger than that of an electron,
the energies of muonic X-rays are very high. Therefore
muonic X-ray can penetrate a bulk sample layer and themuonic X-rays from inside sample are detectable. In
addition, this elemental analysis method has position
sensitivity; the depth of muonic atom formation in thesample is controllable by adjusting the incident muonenergy.
II. EXPERIMENTAL
We performed muon irradiation experiments at Muon
Science Establishment (MUSE) in J-PARC (Japan). We
measured muonic X-rays emitted from an old Japanesebronze coin (tempo-tsuho) and an old Japanese gold coin(tempo-koban) using high purity germanium detectors. For

III. RESULTS AND DISCUSSION

Figure 1: Muonic X-ray spectrum for old Japanese gold coin (tempokoban). Muonic Au and Ag X-rays were clearly detected and no X-ray
peaks originated from the other elements were identified.
[1][2]－ 108 －

K. Ninomiya et. al., Bull. Chem. Soc. Jpn., 85, 228 (2012)
M. Ueda et. al., IMES Discussion paper series, 96-E-26 (1996)

AAO-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Rapid Analysis for Selenium in Urine Samples using the 17.4-s Neutron Activation
Product 77mSe
Michiko Fukushima1, Amares Chatt2, Yoshitaka Nakamura3, Megumi Haga4,
Seiko Hoshi5, Takashi Sakata1
1Ishinomaki Senshu University, Ishinomaki, Miyagi, Japan;
2
Dalhousie University, Halifax, NS, Canada;
3
Meiji Co., Ltd., Odawara, Kanagawa, Japan;
4
formerly at Shokei Gakuin University, Natori, Miyagi, Japan;
5
Shokei Gakuin University, Natori, Miyagi, Japan
Abstract – APSORC’13 Abstract
Keywords – Selenium, urine samples, NAA, short half- life nuclide

I.

INTRODUCTION

Selenium is an essential trace element for humans.
Selenium deficiency causes dysfunction of various organs,including skeletal and cardiac muscles. The recommended
dietary allowance (RDA) levels for Se in Japan [1] are 10
and 15 µg d-1 for 1-2 and 3-5 years old children,
respectively. Although Se intake levels can be estimatedby directly analyzing foods and diets [2], some researchers
prefer to use bodily fluids or excretions as a betterreflection of body burden of Se. For example, Dael et al.
[3] used stable isotopes, namely 76Se as selenate and 74Se as
selenite as supplements given to infants, analyzed theirurine samples, and reported total Se intake of 60.8 ± 4.6 ��
per 72 h, apparent Se absorption of 45.6 ± 5.2 �� per 72 h,
and total urinary Se excretion 21.0 ± 4.2 �g per 72 h.
The techniques commonly used for the determination of
Se in biological fluids are atomic absorption spectrometry(AAS), inductively-coupled plasma (ICP) atomic emission
spectrometry (AES), and ICP mass spectrometry (ICP-MS).
All of these techniques are suitable but time-consuming.
The objective of the present project was to investigate a
rapid method for the quantitative determination of Se in
urine samples of children.
We have developed an
instrumental neutron activation analysis (INAA) method
for this purpose using the short-lived nuclide 77mSe (halflife = 17.4 s).

them with tap water followed by distilled water, and drying
them in an oven. About 0.7 g of pure sucrose was added toeach vial containing 1 mL urine and dried under IR lamp
overnight in a fumehood. The vials were then heat-sealed.
Comparator standards, for calculating Se concentrationsin urine samples using the relative NAA method, wereprepared by adding 1 mL of the Se standard solution����������� ����� ����� ��� ���� ��� ��� ��� ��� ����� ��� ��������
using the same procedure as the urine samples. Samples,comparator standards and various reference materials were
irradiated for 10 s in a neutron flux of 5×1011 cm-2s-1 at the
Ghana Research Reactor-1 (GHARR-1). After a 10-s
decay time the samples were counted for 30 s using a
conventional gamma-ray spectrometer. The Se levels wereassayed using the 161.9-keV gamma-ray of 77mSe. It isevident that the INAA part of the analysis can beaccomplished within 60 s which is quite rapid.
III.

To evaluate the accuracy of the INAA method
developed here the following standard reference material(SRM) and certified reference material (CRM) were used:
NIST SRM 2670a Toxic Elements in urine (Freeze Dried),
NIST SRM 1549 Non-Fat Milk Powder, NIST SRM 1577b
Bovine Liver, and NRC DOLT-3 Dogfish Liver. Our
values agreed within ± 10% of the certified values. Out of
the 75 urine samples analyzed by the INAA method
described above, only 4 samples were below the detection
limit of 10 ng mL-1. The average level of 71 samples was
79.2 ± 46.8 ng mL-1 with the highest value of 242 ng mL-1.

II. EXPERIMENTAL
24-h urine samples were collected from 75 healthy 3-5year-old children by their families in their own houses
living in two different cities of Miyagi Prefecture, Japan.
The average total volume of urine was 503 mL d-1. The
urine samples were kept in cold and dark place for twodays. After bringing the samples to the laboratory, they
were frozen until the analysis.
Prior to analysis the urine samples were defrosted and 1
mL of each sample was transferred to a precleaned
polyethylene irradiation vial using a calibrated Eppendorf
pipette. These vials were precleaned using the following
steps: soaking overnight in 2 mL of 4 M HNO3, washing

RESULTS AND DISCUSSION[1]

References

[2]
[3]

－ 109 －

Ministry of Health, Labour and Welfare of Japan. Dietary Reference
Intakes for Japanese, 2010.
Reiko Yamamoto, Rie Okita, Akane Hiruta, Tosiko Konno,
Research Reports of Shohkei Gakuin College 52 (2006) 205-218.
Peter Van Dael, Lena Davidsson, Rafael Munoz-Box, Laurent B.
Fay, Denis Barclay, British J. Nutrition 85 (2001) 157-163.

AAO-05

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Neutron activation analysis of iron meteorite
Naoki Shirai1, Yoshihiro Hidaka1, Shun Sekimoto2, Mitsuru Ebihara1, Hideyasu Kojima3,4
1

Tokyo Metropolitan University
Kyoto University Research Reactor Institute3
National Institute of Polar Research
4
Graduate University for Advanced Sciences

2

I.

INTRODUCTION

Iron meteorites are made of Fe-Ni metal phases with suchminor minerals as schreibersite, troilite, cohenite and other
Fe-Ni carbides [e.g., 1]. As most iron meteorites are
believed to be samples of the metallic core of asteroidal
parent bodies, petrological, mineralogical and chemical
studies of iron meteorites are fundamental for unravelingthe process of planetary differentiation.
Based on structure, iron meteorites were classified intohexahedrites, octahedrites and ataxites. Hexahedrites andataxites are nearly made of kamacite and taenite,
respectively. Octahedrites consist of kamacite and taenite
and they are further divided into six subgroups on the basisof the width of the kamacite from finest (<0.2 mm) tocoarsest (>3.3 mm). Almost all iron meteorites areclassified into octahedrites. Therefore, it is difficult todetermine representative elemental abundances of ironmeteorites due to their heterogeneity. Bulk elemental
abundances for iron meteorites have been obtained by using
neutron activation analysis (NAA) [e.g., 2]. Other
analytical methods such as inductively coupled plasma
mass spectrometry (ICP-MS) have not been very often
applied to iron meteorites [3, 4]. As subgroup IVB ironmeteorites are made of ataxites and these chemicalcompositions are highly homogeneous, Campbell andHumayun [3] applied laser ablation with ICP-MS (LA-ICPMS) to this subgroup. However, other subgroups have notbeen analyzed by using LA-ICP-MS for determination of
their bulk chemical compositions. D’Orazio and Folco [4]analyzed iron meteorites by using solution nebulization
ICP-MS. However, elements having smaller mass number
than 80 significantly suffered spectral interferences causedby molecular ions such as FeO+. There is a possibility ofvaporization of Ge as GeCl4 during the digestion of ironmeteorites. Kong et al. [5] developed the INAA procedurefor iron meteorites by using a TRIGA Mark II reactor at theInstitute for Atomic Energy, St. Paul’s University. In thisstudy, Kyoto University Research Reactor was used for
determination of elemental abundances of iron meteorites
and the analytical capability was evaluated in comparison
with the procedure of Kong et al. [5].

a neutron flux of 4.6 x 1012 cm-2s-1 at KURRI for
determination of Cu, Ge and Rh. The samples werereirradiated for 4 hrs at a neutron flux of 5.6 x 1012 cm-2s-1
at KURRI and were measured for gamma rays several
times with different cooling intervals. JB-1 and the Allendemeteorite were also analyzed for reference samples. In
addition, chemical standard samples were prepared for thedetermination of Cu, Ga, Ge, Mo, Ru, Rh, Pd, Sb, W, Re,
Os, Ir, Pt and Au. The analytical procedure used in thisstudy is basically similar to that described by Kong et al.
[5].
III. RESULTS AND DISCUSSIONSIn short irradiation of Canyon Diablo, 60mCo, 65Ni, 66Cu,
Ge and 104Rh could be detected. Among these elements,
Cu, Ge and Rh contents were calculated and shown in
Table 1, where literature values were also indicated forcomparison. Our values are in good agreement withliterature values [2,6].
The plots of Ni vs. Ga, Ge and Ir can separate ironmeteorites into about 12 subgroups. Usually, Ge has been
determined by using radiochemical NAA [2] and Ni data
have been obtained by INAA with long irradiation.
Considering that short-irradiation INAA is able todetermine both Ni and Ge. Therefore, our INAA procedure
is simple and effective in classification of iron meteorites.
75

Reference: [1] Goldstein J. I. et al. (2009) Chemie der Erde,69, 293-325. [2] Wasson J.T. and Kallemeyn G. W. (2002)
GCA, 66, 2445-2473. [3] Campbell A. J. and Humayun M.
(2005) GCA, 69, 4733-4744. [4] D’Orazio M. and Folco L.
(2003) Geostand. Newsl., 27 (3), 215-225. [5] Kong P. et al.
(1996) Anal. Chem., 68, 4130-4134. [6] Nichiporuk W. and
Brown H. (1965) J. Geophys. Res., 70 (2), 459-470.
Table 1. Cu, Ge and Rh abundances (in ppm) of Canyon
Diablo in comparison with literature.
This work
Literature
148, 150[2]Cu 136 ± 11
154 ± 10323, 330[2]Ge 329 ± 22314 ± 21
1.5[6]
Rh 1.33 ± 0.11 1.08 ± 0.10

II. EXPERIMENTAL
As the Canyon Diablo iron meteorite was used for control
sample in considering that it has been vigorously analyzed
and its elemental abundances were well established. A
piece of Canyon Diablo was cut into square plates
weighing 33 and 41 mg by using a ISOMET Low Speed
Saw. In INAA, samples were firstly irradiated for 10 sec at－ 110 －

API-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

What has been revealed in the Low-Level Radioactivity Measurement?
- Low Level Gamma-Ray Counting in Ogoya Underground Laboratory Yasunori Hamajima
Kanazawa Univ. LLRL.

Abstract – In Ogoya Underground Laboratory, low-level
radioactivity measurement is performed. We have 18 low
background Ge detectors and all detectors provide excellent
counting efficiency. We report recent results.
Keywords – low-level counting, underground laboratory, well-

type Ge detecto

I.

INTRODUCTION

In gamma ray measurements, it is important to reduce thebackground noise of detectors and activation of shielding
materials derived from secondary cosmic ray components(muons and neutrons). It is difficult to reduce thesecomponents by conventional shield at aboveground. The
intensity of secondary components decreases with the depthof overburden at the underground facility. Ogoya
Underground Laboratory (OUL) is in a 546 m tunnel of theformer Ogoya Copper Mine. It is located 270 m from thetunnel entrance, where the overburden is 270 mwe. The
background count rates of OUL detectors are about 1/100 of
the aboveground ones.

natural radio nuclides, fission products and activated nuclides
induced by environmental neutrons and fission neutrons.
In the recent results of extraterrestrial science, “Neutron
Activation Analysis of a Particle Returned from Asteroid
Itokawa” was in Science, 333, 1119-1121, (2011), and“Radar-Enabled Recovery of the Sutter’s Mill Meteorite, aCarbonaceous Chondrite Regolith Breccia” was reported in
Science 338, 1583-1587, (2012).
In those of Oceanography, “Surface pathway ofradioactive plume of TEPCO Fukushima NPP1 released
134Cs and 137Cs” was reported in Biogeosciences, 10, 30673078, (2013), and “Cross equator transport of 137Cs from
North Pacific Ocean to South Pacific Ocean (BEAGLE2003
cruises)” was in Progress in Oceanography, 89, 7-16, (2011).

Table 1. Specifications of Ge crystals and backgroundcounting rates.

I
J
K

planarplanarplanar18%(28cm2 x 2cm)
34%(38cm2 x 3cm)
34%(38cm2 x 3cm)

BG
(min
-1)
0.48
0.57
0.52

L

planar

18%28cm2 x 2cm)

0.57

II. DETECTORS AND SHIELDING IN OUL

M

planar22%(28cm2 x 2.8cm)

OUL has 11 well, 6 planar, and 1 coaxial Ge detectors, as
shown in Table 1. In order to measure a wide energy range
from 20 keV to about 3 MeV, the planar type detectors havelarge diameters and thicknesses and the well type detectors
have also large diameters. For most of detectors, ultra lowbackground aluminum was used for the end-cap. The cryostat
is the J-type and/or U-type and the preamplifier is locatedoutside of the lead shield. The lead shield is 15 to 25 cm thick,and its upper part is covered by 10 to 15 cm of iron. The
inner 3 to 5 cm of the lead shield is made of lead refined 200
years ago. The space near the detector head is filled with Hgshield encapsulated in a polyethylene bag and nitrogen gas
from the Dewar is blown to the top of the end cap.

N
C
D
A
B
G
H
W
X
Y
E

planarwell(10�x40mm)
well(21�x62mm)
well(21�x62.5mm)
well(21�x62.5mm)
well(21�x66.5mm)
well(21�x66.5m
well(21�x60mm)
well(21�x68mm)
well(21�x68mm)
well(21�x60mm)

22%(28cm2 x 3cm)
37%(61�x56mm,)
56% (72.0�x74.8mm)
56% (72.0�x75.0mm)
56% (72.0�x74.7mm,)
71.5%(74.0�x79mm)
71.7%(74.0�x80mm)
65% (75.1�x81mm)
73.4%(74.3�x80mm)
70.5%(74.3�x80mm)
68%(74.06�x80mm)

0.9
2.51
2
1.93
2.83
2.09
1.72
1.69
1.4
1.7

F

well(21�x55mm)

56%(75�x55mm)

2.1

U

coaxial

94% (78.9�x81mm)

1.12

Ge

III. RECENT RESULTS IN OUL
Some significant measurements have been made at OUL
such as the detection of low level cosmogenic nuclides,

Type(Al end cap)

Relative Eff, (size)

BG: integrated count rate (50 – 2000 keV)

－ 111 －APO-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Zr and U determination at trace level in simulated deep groundwater by Q ICP-MS
using TRU-based and TODGA-based extraction chromatography
1

C. Gautier1, M. Coppo1, C. Caussignac2, I. Laszak2, P. Fichet1, F. Goutelard1

Operator Support Analyses Laboratory, Atomic Energy Commission, CEA Saclay, DEN/DANS/DPC/SEARS/LASE,
Building 459, PC171, 91191 GIF SUR YVETTE CEDEX, FRANCE
2
Nuclear, Isotopic Elementary Analytical Development Laboratory, Atomic Energy Commission, CEA Saclay,
DEN/DANS/DPC/SEARS/LANIE, Building 391, PC33, 91191 GIF SUR YVETTE CEDEX, FRANCE

Abstract – APSORC’13 Abstract

In the past decades, metallic fuels, such as UZr metallic alloys, wereused as nuclear fuels. Direct disposal in deep geological repository
can be an option for the long-term management of spent nuclear
fuels. In the framework of such an issue, it is necessary to develop asource-term model for the release of radionuclides from the spent
nuclear fuels. The validation of the dedicated model requires theimplementation of leaching experiments in the conditions of a deep
geological repository. For the spent UZr fuels studied in France, theleaching and the release of two major radionuclides, 235U and 93Zr,
have to be investigated in the reference groundwater which isplanned to be a deep clayey Callovo-Oxfordian groundwatercontaining high concentrations of salts (alkali and alkaline earth
metals). Given the expected concentrations of 235U and 93Zr isotopes(< 10-6 mol L-1 or < 0.2 mg L-1) in leaching solutions, Q ICP-MS
can be considered as the most promising technique for theirsimultaneous measurements. However, due to the groundwatercomposition, sample dilution has to be applied before ICP-MS
analysis to avoid matrix effects. This option is incompatible with ourrequirements in terms of detection limits. Consequently, a fullanalytical procedure was implemented to determine Zr and U at
trace level in a simulated deep Callovo-Oxfordian groundwater by
Q ICP-MS.

20 fold factor for Zr and U measurements at trace level by Q ICPMS.
The leaching experiments are requested to be performed in hot cellsof the LECI laboratory (Laboratory for Studies on Irradiated Fuel)at CEA (French Alternative Energies and Atomic Energy
Commission) Saclay. Blank samples (containing 0.5M HNO3 +0.005M HF) were introduced during one week in the selected hot
cell where spent fuels are usually handled. The solutions wereanalyzed by Q ICP-MS to check whether the atmosphere of the hotcell induces problems of blank contamination for Zr and U
measurements at trace level. The measured concentrations werelower than the limits of quantification validated at 0.008 µg L-1 after
separation, which proved the feasibility of the scheduledexperiments.
The developed procedure was demonstrated to be very efficient forthis application but it could be also used for many other issues
concerning analysis of trace amount of radionuclides contained inhigh salt matrix.

Separation procedures based on extraction chromatography weredeveloped to eliminate the high salt contents and to concentrate Zr
and U simultaneously. Since U and Zr display different chemical
behaviors in solution, their speciation was first discussed.
Theoretical and experimental speciation studies showed theimportance of adjusting the medium to HNO3/HF (0.5M/0.005M) to
guarantee the stability over time of the analytes before removal ofthe matrix. Two preconcentration methods based on TRU® and
TODGA® resins were optimized for the simultaneous isolation of Zr
and U prior to Q ICP-MS measurements. Using TRU resin, alkali
and alkali earth metals contained in the deep groundwater were
removed with 2M HNO3 whereas Zr and U were recovered with a
HNO3/NH4HC2O4 (0.02M/0.05M) medium. For the separation
protocol based on TODGA resin, alkali and alkali earth metals were
eliminated with 3M and 11M HNO3 while Zr and U were
simultaneously stripped with a HNO3/HF (0.5M/0.2M) medium. The
procedure optimized on TODGA resin was the only one validatedwith the French AFNOR NF T90-210 standard by studying linearity,
limits of quantification (LOQ) and separation yields. The LOQ wasdetermined to be 0.008 µg L-1 for Zr and U after the separation.
Both analytes were recovered quantitatively. Compared to a direct
Q ICP-MS analysis after sample dilution, the developed
preconcentration method allowed improving the sensitivity up to a

－ 112 －APO-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Photoluminescence of Five- and Six-coordinate Tetracyanidonitridotechnetium(V)and –rhenium(V) Complexes
Takashi Yoshimura1, Hayato Ikeda2, Akitaka Ito3, Eri Sakuda3, Noboru Kitamura3, Tsutomu Takayama4
Tsutomu Sekine5, Atsushi Shinohara2
1

Radioisotope Research Center, Osaka University
Department of Chemistry, Graduate School of Science, Osaka University
3
Department of Chemical Sciences and Engineering, Graduate School of Chemical Sciences and Engineering, Hokkaido
University
4
Department of Chemistry, Daido University
5
Center for Advancement of Higher Education, Tohoku University
2

Abstract – Six-coordinate tetracyanidonitrido Re(V) and Tc(V)complexes with a volatile organic compound (VOC) and fivecoordinate complexes were synthesized and characterized.
Reversible luminescence switching between six- and five-coordinate
Re(V) complexes and between the relevant six-coordinate Re(V)complexes was achieved by exposing them to VOC vapor in the solidstate at room temperature. Luminescence changes were observed
from the five-coordinate Tc(V) complexes in a MeOH vapor
atmosphere in the solid state. In contrast, no vapochromic
luminescence was observed from the five-coordinate and sixcoordinate complexes in an acetone vapor atmosphere.
Keywords – Technetium, Rhenium, PhotoluminescenceI.

INTRODUCTION

Among the Group 7 metal ions, a very small number oftechnetium complexes have been reported to show
photoluminescence. In coordination compounds, molecularsensing can be done based on the color change of a complex
through changes in the coordination environments and/or
direct interaction of the metal ion with a molecule to besensed. In contrast, molecular sensing based on thevapochromic luminescence through a ligand substitution
reaction and the coordination number of a metal ion in thesolid state has been rarely reported. We report novel sixcoordinate nitrido Re(V) and Tc(V) complexes and their fivecoordinate square pyramidal complexes without an axial
ligand. The present study demonstrated for the first time thatthe nitrido Tc(V) complex showed luminescence in the solid
phase at room temperature. We demonstrate for the first timeinterconversion between the six-coordinate Re(V) complexes
through a solid state substitution reaction upon exposure to
VOC vapor, and between the five-/six-coordinate complexes
by a solid state ligand coordination/elimination reaction.[1]Re(V) and Tc(V) complexes were bistable between the fivecoordinate square pyramidal and six-coordinate octahedral
coordination environments. All of the five-coordinate squarepyramidal and six-coordinate octahedral complexes showedphotoluminescence in the solid state at room temperature.
The emission spectra and photophysical data of the fivecoordinate [ReN(CN)4]2- were significantly different fromthose of the relevant six-coordinate complexes.
Vapochromic luminescence between the bistable five- andsix-coordinate Re complexes with the VOCs (MeOH, EtOH,
acetone, or MeCN) and between the six-coordinate
complexes was investigated. We found unique reversible
coordination and elimination of a VOC at the axial site of the
Re complex in the solid state that gave rise to changes in theemissionmaximum
wavelength,
demonstrating
photoluminescence switching and sensing of VOC by thepresent Re(V) complexes at room temperature. Upon
exposure of MeOH vapor to the five-coordinate Tc complex,
the emission spectrum changed to that of the MeOH
coordinate complex. The coordinating MeOH molecule canbe removed by evacuation of the complex in vacuo. In
contrast, the emission band shapes of the five-coordinate Tc
complex remained unchanged even upon exposure of acetone
vapor. The emission spectrum of MeOH coordinate Tc
complex changed to that of the five-coordinate complex by
exposure to acetone vapor. This suggests that thecoordinating MeOH molecule in the Tc complex was
eliminated under acetone vapor atmosphere, but acetone was
not incorporated and did not coordinate at the axial site in the
Tc complex.
N

NC

M

NC

N

CN
CN

L1 vaporin vacuo

Six-coordinate Re(V) and Tc(V) complexes with a VOC,
(PPh4)2[MN(CN)4L] (M = Re, L = MeOH, EtOH, acetone, or
MeCN; M = Tc, L = MeOH), and five-coordinate(PPh4)2[MN(CN)4] (M = Re or Tc), were synthesized andtheir spectroscopic and photophysical properties were
investigated. Results demonstrate that the tetracyanidonitrido

Re

NC
L1

CN
CN

M = Tc, Re

N
NC

M

NC
L1

M = Tc, Re

II. RESULTS AND DISCUSSION

NC

N
CN

L2 vaporNC

CN

L1 vapor

NC

Re

CN
CN

L2

Scheme 1.
[1]－ 113 －

H. Ikeda, T. Yoshimura, A. Ito, E. Sakuda, N. Kitamura, T. Takayama,
T. Sekine, A. Shinohara, Inorg. Chem., 51, 12065-12074 (2012).

APO-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Studies of Flerovium and Element 115 Homologs with Macrocyclic Extractants
John D. Despotopulos1,2, Narek Gharibyan1, Roger A. Henderson1, William Kerlin2, Kenton J. Moody1,
Dawn A. Shaughnessy1, Evgeny Tereshatov1, Ralf Sudowe2
1
Lawrence Livermore National Laboratory,Chemical Sciences Division, Livermore, California 94551, USA
2
University of Nevada Las Vegas, Las Vegas, Nevada 89154, USA
Abstract – Recent studies of the chemical behavior of Copernicium(Cn, element 112) and Flerovium (Fl, element 114) together with thediscovery of isotopes of these elements with half-lives suitable forchemical studies have spurred a renewed interest in the developmentof rapid systems designed to study the chemical properties of
elements with Z ≥ 114 [1,2]. Due to the short half-lives of thetransactinide elements, fast and efficient separations are necessary
to evaluate their properties, such as ionic radii and chemical
speciation, by comparing to their lighter homologs. Separations
based on extraction chromatography resins using macrocyclic
extractants show promise for achieving the short separation times,
large extraction yields, and high separation factors required fortransactinide studies. In this study the potential of different
macrocyclic extractants for their future application to a Fl andelement 115 chemical system has been investigated.

Eichrom’s commercially available Pb resin is based on the dit-butylcyclohexano-18-crown-6 extractant sorbed to the resin
backbone in isodecanol. Consequently, this resin exhibitshigh selectivity for Pb2+ [4]. Thiacrown ethers, which replace
the oxygen atoms with sulfur, act as softer Lewis bases
compared to traditional crown ethers [5]. This uniqueproperty of thiacrowns should make them even better
extractants for softer metals such as Pb. Hexathia-18-crown-6(fig. 2) was synthesized and investigated.

Keywords – Transactinide, homolog, element 114/115, separationsI.

INTRODUCTION

Fig. 2: Hexathia-18-crown-6.

Studies of the chemical properties of superheavy
elements (SHE) pose interesting challenges due to their shorthalf-lives and low production rates. Chemical systems musthave extremely fast kinetics to be able to probe the chemical
properties of interest, such as chemical speciation, before theSHE decays to another element. To achieve chemistry onsuch time scales (~ seconds), the chemical system must also
have the potential to be easily automated. The transactinides(elements with Z > 103) are predicted to exhibit changes intheir chemical behavior compared to that of their lighter
homologs (elements in the same chemical group) or pseudohomologs (elements with the same oxidation state and similar
ionic radii) due to relativistic effects [3].
II. EXPERIMENTAL
A. Extractants and Resins
Crown ethers and their derivatives show high selectivity
for metal ions based on their size compared to the cavity ofthe ether. Di-t-butylcyclohexano-18-crown-6 (fig. 1) is
known to show high affinity for the Pb 2+ ion.

B. Extraction Studies
Batch experiments were performed for the direct
homologs of Fl (Pb and Sn) and element 115 (Bi and Sb)
using the Eichrom Pb resin. Promising results were obtained
from HCl/KI matrices as well as from simple mineral acidmatrices. Column studies were performed to asses these
extractions under dynamic conditions. Liquid-liquid
extractions were also performed using hexathia-18-crown-6
to determine its suitability and compare it to that of thestandard crown ether.
Acknowledgment: This work was performed under the auspices of
the U.S. Department of Energy by Lawrence Livermore National
Laboratory under Contract DE-AC52-07NA27344. This work was
funded by the Laboratory Directed Research and Development
Program at LLNL under project tracking code 11-ERD-011.

REFERENCES
[1]
[2]
[3]
[4]
[5]

Fig. 1: Di-t-butylcyclohexano-18-crown-6.

LLNL-ABS-631618－ 114 －

R. Eichler et al., Chemical characterization of element 112, Nature,
2007, 447, 72-75.
R. Eichler et al., Indication for a volatile element 114, Radiochim. Acta,
2010, 98, 133-139.
P. Pyykko, Relativistic effects in structural chemistry, Chemical
Reviews, 1988, 88, 563-594.
E. P. Horwitz, et al., A lead-selective extraction chromatographic resin
and its application to the isolation of lead from geological samples,
Analytical Chemica Acta, 1994, 292, 263-273.
E. Sekido, et al., Liquid-liquid extraction of some class b metal ionswith thiacrown ether 1,4,8,11-tetrathiacyclotetradecane, Analytical
Sciences, 1985, Vol. 1, 363-368.

Poster Session 1
Monday, 23 September 2013
18:50 ~ 20:00

Scientific Topics (Abbrev.)

1. Fukushima issues (FK)
2. Education in nuclear and radiochemistry (ED)
3. Nuclear forensics (NF)
4. Nuclear energy chemistry (NE)
5. Nuclear chemistry (NC)

6. Actinide chemistry (AC)
7. Environmental radiochemistry (EN)
8. Radiopharmaceutical chemistry and Nuclear medicine (RP)
9. Nuclear probes for materials science (NP)
10. Activation analysis (AA)
11. Application of nuclear and radiochemical techniques (AP)－ 115 －

23-FKP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013137

Cs Accumulation Enhanced by Potassium Starvation in Lotus japonicus

Jun Furukawa1, Hiroki Noda2, Ryohei Sugita3, Keitaro Tanoi3, Tomoko M. Nakanishi3, Shinobu Satoh1
1

Faculty of Life and Environmental Sciences, University of Tsukuba
Graduate School of Life and Environmental Sciences, University of Tsukuba
3
Graduate School of Agricultural and Life Sciences, The University of Tokyo

2

Abstract – Radionuclides released from Fukushima Dai-ich Nuclear
Power Plant spread to the environment. The transfer of 137Cs fromsoil to land plants is one of the most important steps for considering
the influx of 137Cs into ecosystem. To identify the responsible genes
for 137Cs uptake and translocation in plants, we focused on the K+
transport system in the model legume, Lotus japonicus. The
dynamics of 137Cs uptake and translocation was differed between
two accessions, B-129 and MG-20, and K starvation drasticallyenhanced 137Cs uptake in B-129. The expression levels of known K+transporters were also investigated under several K conditions.
Keywords – cesium-137, potassium, accumulation, Lotus japonicus

I.

137

Cs was detected with an image analyzer (BAS) and gamma
counter, respectively.
Real-time Radioisotope Imaging
RRIS (Real-time Radioisotope Imaging System) was used
for obtaining the images of 137Cs uptake and translocation indigitalL.japonicus.
RRIS
is
a
non-destructive
autoradiography system specialized for the use in living plantresearch [2]. The plants prepared as previous BAS
experiment were placed in RRIS and the 137Cs distribution
images were obtained for 24 h.
III. RESULTS AND DISCSSIONINTRODUCTION

After the Fukushima Dai-Ichi Nuclear Power Plant
accident, large amount of radioactive materials were released
into the environment and the major radionuclides leaking was
137
Cs. Cesium is known as an analog of potassium in the plant
nutrition and, therefore, one of the main route of 137Cs into
the ecosystem is an uptake process in land plant. Uptake andtranslocation of 137Cs is thought to be carried out by the K+
transport systems in plants [1]. However, because of thecomplexity of K+ transport system, the responsible
transporters, which transport 137Cs, were not well identified.
In this research, the identification of the K+ transport system,
which involved in the 137Cs uptake and transport, in Lotus
japonicus was attempted. L.japonicus has been proposed as amodel legume for molecular biology, and the results obtained
from L.japonicus are applicable to one of the major crops,
soybean.

As for the plants grown under normal K condition, 137Cs
in B-129 root was about twice the concentration of that in
MG-20. However, 137Cs concentration in shoot was notdiffered between two accessions. In the plants treated with -K
solution for 3 days, drastic enhancement of 137Cs uptake wasobserved in B-129 root. The increase of 137Cs translocationfrom root to shoot was observed both in B-129 and MG-20.
Because of the constant 137Cs concentration in MG-20 root,
the increase of 137Cs concentration in MG-20 shoot suggested
the high 137Cs translocation activity in MG-20 under K
starvation. Real-time 137Cs images clearly indicated the 137Cs
uptake site in root and the rapid uptake and translocation of137
Cs in B-129 (Figure 1).

II. MATERIAL AND METHODS
Plant Materials and Growth Conditions
Two L.japonicus accessions, Gifu B-129 (B-129) and
Miyakojima MG-20 (MG-20), were obtained from the
Biological Resource Center in Lotus and Glycine, Universityof Miyazaki, Japan. Seedlings were grown with continuously
aerated 1/10 strength Hoagland’s solution in a 2 L plastic
container under light- and temperature-controlled condition;light 16 h, darkness 8 h, 24oC. The solution was renewed
every 3 days. At the last 3 days before 137Cs uptake
experiment, the solutions with and without K were prepared.

Figure 1 Real-time imaging of 137Cs uptake and translocation in B-129 andMG-20 treated with -K solution for 3 days. Each panel indicates theradioactivity image obtained for every 2.4 h.

Potassium starvation promotes K uptake system, especiallyhigh affinity K+ transporter, in root [3]. Therefore, theexpression levels of known K+ transporters in L.japonicus
will be discussed.

137

Cs Uptake
Plants grown for one month were transferred to 50 mL of
1/10 strength Hoagland’s solution (without K) containing
137
CsCl and non-radioactive Cs (10 �M) for 12 h. After
harvesting shoots and roots, distribution and radioactivity of

IV. REFERENCES
[1]
[2]
[3]

－ 116 －White PJ and Broadley MR (2000) New Phytol., 147, 241-256.
Kanno S et al. (2012) Philos. Trans. R. Soc. B, 367, 1501-1508.
Wang TB et al. (1998) Plant Physiol., 118, 651-659.

23-FKP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Decontamination of the Contaminated Water on Severe Nuclear Accidents byTitanium Oxide Adsorption
Youko Takahatake1, Masahiro Nakamura1, Atsuhiro Shibata1, Kazunori Nomura1, Yoshikazu Koma1,
Yasuo Nakajima1
1

Japan Atomic Energy Agency

Abstract – In order to establish a decontamination process for contaminated water that generated in a severe nuclear power plant accident
such as the Fukushima accident, we proposed a new decontamination process. A new decontamination process is composed of codecontamination of radioactive transition metals and Cs with hexacyanoferrate(II) ion, and decontamination of radioactive metals including
Sr with titanium oxide adsorption. This study discussed the adsorptivity of a new titanium oxide and its applicability to the radioactive water
after co-decontamination of transition metals and Cs.
Keywords – Sr decontamination, titanium oxide adsorption, contaminated water of Fukushima accident

The massive amount of radioactive contaminated water
was generated in Fukushima Dai-ichi NPP. This water is
unique compared to contaminated water generated inprevious treated radioactive contaminated waters, concerning
the amount of minerals due to the utilization of seawater
during the emergency cooling of reactor cores. According to
the analysis of the water, it contains fission products (90Sr,
125
Sb and 134,137Cs), corrosion products and large amount of
non-radioactive metals. The special treatment system wasapplied to decontaminate it. If NPP accidents may be occur inthe future, the experience on this accident is utilized
effectively.
In order to minimize the amount of secondary waste fromthe water treatment system, we proposed a new
decontamination process (figure 1) for radioactive
contaminated water generated at NPP accidents. At first, thisprocess decontaminates transition metals and Cs
simultaneously by adding hexacyanoferrate(II) ion. This step
was already discussed [1]. The next step is decontaminationof Sr, Sb and remaining Co and Mn by titanium oxide
adsorption. This study discusses the adsorptivity of a newtitanium oxide and its applicability to the radioactive water
after co-decontamination of transition metals and Cs.
Titanium oxide adsorption is commonly used todecontaminate Sr and Co. One of adsorbents is “READ-Sr”,
which will be used for the treatment of low level liquid waste
at the Tokai Reprocessing Plant in Japan. An investigation of
its applicability to the decontamination of Sr from thecontaminated water containing seawater suggested thattitanium oxide adsorb other alkaline earth elements those areabundant in seawater[2]. Therefore, selectivity of Sr fromother alkaline earth elements is necessary.
We synthesized a new titanium oxide with titanium sulfate
and ammonium solution, and obtained distribution coefficient(Kd) of Sr, and separation factor (SF) between Sr and alkaline
earth elements by batch method. And then the titanium oxide
was added to the radioactive water after co-decontaminationof transition metals and Cs. This mixture was stirred for 45
minutes and filtrated with 0.1 µm membrane, and thendecontamination factor (DF) was calculated fromconcentration of each radioactive and non-radioactive
elements.
On experiment of radioactive water, Sr, Mn, Co and Sb
was successfully decontaminated, and their DFs were >16,
460, 260, 230, respectively. But Mg and Ca were adsorbed totitanium oxide; particularly Ca was adsorbed as much as Sr.
Selectivity of Sr to alkaline earth elements is important to
reduce secondary waste, so further improvement is necessary.

Figure 1. Schematic flow of a new decontamination process[1][2]

Decontamination of radioactive liquid waste with hexacyanoferrate(II),Takahatake et. al., Procedia Chemistry , 7: 610-615 (2012)
Strontium decontamination from the contaminated water by titaniumoxide adsorption, Takahatake et. al., Proceedings of International
Conference on Toward and Over the Fukushima Daiichi Accident(GLOBAL 2011), CD-ROM. (2011)

ACKNOWLEDGEMENTS
The authors would like to thank Masashi Kaneko, Kaname
Kubo and Jun Hashimoto of Fuji Sangyo KK for synthesizing
titanium oxide.

－ 117 －

23-FKP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Iodine-129 in the aquatic environment
adjacent to a spent nuclear fuel reprocessing plant, Rokkasho, Japan1

Shinji Ueda1, Hideki Kakiuchi1, Hidenao Hasegawa1
Naofumi Akata1, Hidehisa Kawamura2, Shun’ichi Hisamatsu1

Department of Radioecology, Institute for Environmental Sciences, 1-7 Rokkasho, Aomori 039-3212, Japan
2
Kyushu Environmental Evaluation Association, 1-10-1, Higashi, Fukuoka 813-0004, Japan

Abstract – The spent nuclear fuel reprocessing plant in Rokkasho,
Aomori Prefecture, Japan, has been undergoing final testing since
March 2006. Iodine-129 is one of radionuclides released into theatmosphere and the coastal water by the operation of the plant. We
measured the concentrations of 129I in various environmental
samples such as water, sediment, and aquatic biota collected in theaquatic environment adjacent to the reprocessing plant from 2005 to
2012. The concentration of 129I in the environmental samples
increased during testing of the chemical separation of dissolved fuel.
Since the end of that stage, the 129I concentration in lake water andaquatic biota samples has been rapidly decreasing, whereas theconcentration in sediment samples has remained steady.
Keywords – iodine-129, spent nuclear fuel reprocessing plant, water,
sediment, aquatic biota

I.

INTRODUCTION

Japan’s first commercial spent nuclear fuel reprocessing plant,
which is in Rokkasho, Aomori Prefecture (Fig. 1), isundergoing final testing. Since the cutting and chemical
separation using actual spent nuclear fuel started in March
2006, small amounts of radionuclides (85Kr, 3H, 129I, and 14C)
have been released into the atmosphere and the Pacific Ocean.
Iodine-129 released from the plant into the atmosphere andthe ocean enters Lake Obuchi, which is adjacent to the plant(Fig. 1), through various routes: from the ocean by tides,from river water, and from the atmosphere by deposition.
The aim of this study was to investigate the fluctuations of
129
I concentrations in water, sediment, and aquatic biota
samples collected in the aquatic environment, mainly in Lake
Obuchi, from 2005 to 2012.

II. MATERIALS AND METHODS
Water was sampled from five locations (Sts. 1–5), andsediment from two locations (Sts. 2, 3); samples fromaquatic biota (fish, seagrass, shellfish, shrimp, and plankton)
were collected from the lake in an area near the north shore(Fig. 1). The samples were analyzed for 129I with anaccelerator mass spectrometer (PRIME Lab, Purdue
University, USA).
III. RESULTS AND DISCUSSION
The concentrations of 129I in the water samples collected from
Lake Obuchi during 2006 to 2008 were approximately anorder of magnitude higher than the background level in 2005,
whereas the concentrations in the seawater samples collected
off the Rokkasho coast (St. 5) showed no increase over the
background level during the study period. The 129I
concentrations in aquatic biota samples during 2006 to 2008
were also approximately one order of magnitude higher thanthe background level. Most of the chemical separation of fuelmaterial was finished by 2008, and the rate of 129I releasefrom the plant markedly decreased thereafter. Corresponding
with the decrease in the release rate, the 129I concentrations in
the lake water and aquatic biota samples rapidly decreased
after 2008. In contrast, the 129I concentrations in the sediment
samples were stable even after the chemical separation was
finished.
The committed effective dose due to annual ingestion offoods with the maximum 129I concentration in the biota
sample in Lake Obuchi was calculated as 6.7 nSv y-1.
Outlet of waste water pipelinefrom the reprocessing plant(2.5 km off the coast)

Futamata River
50oN
N

Uranium enrichment plant

45o
Sea of Japan

40o

Pacific Ocean

St. 1
Low-level radioactive waste
disposal area disposal center

St. 2

35o

Obuchi fishing
port

St. 4
1m

St. 5

3m

30o

Rokkasho

Reprocessing plant

4m

Rokkasho Coast

St. 3

25o

Pacific Ocean
20o

0
120oE

1000km
125o

130o

135o

Aomori Prefecture
140o

145o

0

1 km

Lake Obuchi

150o

10

20

30

40

50 m

water depth

Fig. 1. Map of the sampling stations. Aquatic biota samples were collected in the hatched area.

This study was performed under a contract with the government of Aomori Prefecture, Japan.

－ 118 －

23-FKP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Specific activity and time dependence of radionuclides in soils affected by theaccident of the Fukushima Dai-ichi nuclear power plant (Part 2).
Tatsuya Shimasaki1, Yoshioki Shiraishi1, Osamu Kawahara1, Kumiko Goto1,
Masako Shimamoto1,Akihiro Kojima1 and Seiji Okada2
1

Institute of Source Development and Analysis, Kumamoto University
2
Center for AIDS Research, Kumamoto University

Abstract – The purpose of this study is to clear the specific activity
and the time dependence of the radionuclides in soils at Fukushima
prefecture and neighborhood area. We performed soil sampling forsix times at several points within 60km from FDNPP and at Tokyo
to October 30, 2012 from March 23, 2011. The concentration of 131I,
134
Cs, 136Cs, 137Cs and 129mTe were obtained, but only trace amountsof 95Nb, 110mAg and 140La were detected whitch were too low toprovide accurate concentrations. The concentration of radioactivity
on March 15, 2011 is 8234 kBq/m2 for 131I and 882 kBq/m2 for 137Cs
at Fukaya, Iitate village. Some radionuclides, such as 103Ru, and106
Ru and 140Ba, observed in the Chernobyl accident, were notmeasured in the soil samples. This is estimated that mainly noble
gasses and volantile radionuclides were released from FDNPP. For
the time dependence of 137Cs concentration in soil, it was decreased
approximately 30% in 19 months at Fukaya, Iitate village. However,at some sampling points, there was not a change at all.
Keywords – Fukushima Dai-ichi N, 137Cs, specific activity, timedependence, 134CsI.

INTRODUCTION

The Fukushima Dai-ichi Nuclear Power Plant (FDNPP)
lost all electricity due to a huge tsunami after the Richterscale magnitude 9 earthquake of March 11, 2011. The water
circulation system was severely damaged, and theradionuclides were released to the environment, specially fordays in the middle of March. The purpose of this study is toclear the specific activity and the time dependence of theradionuclides in soils at Fukushima prefecture andneighborhood area.

and 129mTe were obtained, but only trace amounts of 95Nb,
110m
Ag and 140La were detected whitch were too low toprovide accurate concentrations. Some radionuclides, such as
103
Ru, and 106Ru and 140Ba, observed in the Chernobyl
accident, were not measured in the soil samples. This isestimated that mainly noble gasses and volantile
radionuclides were released from FDNPP. The concentrationof radioactivity on March 15, 2011 is 8234±1654 kBq/m2
for 131I and 882 ± 182 kBq/m2 for 137Cs at Fukaya, Iitate
village. The highest difference was more than 100 times inFukusima. Only 137Cs from global fallout was observed in thesoil collected at kumamoto city. The ratio of the total
amounts of 137Cs in each section depth was shown in Fig.5.
Approximatery 95% of deposited 137Cs were found in theupper 3 cm of the soil. The ratio of the depth profiles did notchange at all sampling points during the measurement period.
Time dependence of radionuclides in soils
Fig.1 shows the temporal changes of 137Cs concentration
in soil at several sampling points during from March 23, 2011
to October 30, 2012. For the time dependence of 137Csconcentration in soil, it was decreased approximately 30% in
19 months at Iitate village, Fukaya district. It was decreased
approximately 20% in 15 months at Minamisouma city.
However, at some sampling points, there was not a change ofthe time dependence of 137Cs concentration at all. For theenvironment half life of the cesium-137 in the comparatively
land with a little vegetation, it was with the range for four
years from two years except a physical half life.

II. MATERIALS AND METHODS
We performed soil sampling for eight times at several
points within 60km from FDNPP and at Tokyo from March
23, 2011 to October 30, 2012. Soil samples, at 0-2, 0-3, 3-6
and 6-10 cm depths, were taken using a scraper with asampling area of 100cm2 (10cm×10cm). The second and thesubsequent sampling were carried out at 3 m intervals fromthe previous sampling points. The specific activity of samples
were measured by Ge detectors (SEIKO EG&G) and decay
corrected to March 15, 2011.
III. RESULTS AND DISCUSSION
Specific activity in soils
We were taken soil samples in Iitate village, Fukaya , on
March 23, 2011. The concentration of 131I, 134Cs, 136Cs, 137Cs－ 119 －

Fig. 1 The temporal changes of 137Cs concentration in soil at several
sampling points during from March 23, 2011 to October 30, 2012.

23-FKP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Differences between year 2011 and 2012 in Cs-137 concentration in brown rice grownin Fukushima Prefecture
Shigeto Fujimura1,2, Yuuki Sakuma1, Toshimi Yamauchi1, Kazutoshi Niitsuma1, Norio Sato3, Mutsuto
Sato1, Takashi Saito1, Kunio Yoshioka1
1

Fukushima Agricultural Technology Centre, 2 NARO Tohoku Agricultural Research Center
3
Inawashiro Town

Abstract – Brown rice was collected from ten paddy fields located infour sites in Fukushima Prefecture in year 2011 and 2012 to clear
the year difference in radiocesium concentration in brown rice.
Paddy fields with the same management including fertilization inboth years were selected. Cs-137 concentration in brown rice was in
the range of 2.8-290 Bq kg-1 in 2011 and 1.3-160 Bq kg-1 in 2012.
The concentration of Cs-137 was decreased by 40 % in the average
from year 2011 to year 2012.
Keywords – brown rice, Cs-137, paddy field, aging

I.

B. Measurement of Cs-137 concentration
The concentration of Cs-137 was determined using agermanium detector with a multichannel analyzer system.
The actual decay date was determined as October 1, 2011,using the half-life (i.e., decay constant) of the Cs-137. Brown
rice was dried for 48 h at 105 °C and dry weight wasdetermined.
III. RESULTS AND DISCUSSIONINTRODUCTIONRadionuclides was released into the environment as aconsequence of the accident at Fukushima Daiichi Nuclear
Power Plant (FNPP) that was triggered by the earthquake andsubsequent tsunami that occurred on 11 March 2011. Brown
rice (unpolished rice) produced during the 2011 growing
season was contaminated by radiocesium released from
FNPP. Concentration of radiocesium in agricultural products
is annually declined because radiocesium is fixed to sorption
site for cesium of soil. In addition, potassium and/or zeolite
was applied to farmland in Fukushima Prefecture to avoid thecontamination of radiocesium to brown rice in the year 2012.
In the results, concentrations of radiocesium in brown rice
were much lower in the year 2012 than in the year 2011. The
aim of this study is to clear the annually declined effect on
the concentration of brown rice to evaluate the effects ofpotassium and zeolite application on uptake of radiocesiumby crops.
II. MATERIALS AND METHODS

Concentration of Cs-137 in brown rice investigated in thisstudy was in the range of 2.8-290 Bq kg-1 in 2011 and 1.3160 Bq kg-1 in 2012 (Table 1). There were differences in theconcentration of Cs-137 between paddy fields in the samesite in both years. The differences between paddy fields in thesame sit would be due to the differences in exchangeable
potassium content and/or the sorption sites for cesium in soil.
The details will be published else where.
The concentration of Cs-137 in brown rice was 30-114 %in 2012 compared to those in 2011. It was increased in one often paddy fields. The concentration of Cs-137 in brown rice
was decreased by 40 % in the average from year 2011 to year
2012. It was suggested that uptake of radiocesium by rice
plant in the second year from the radiocesium contamination
is a half of that in the first year without decontamination nor
the application of potassium, zeolite and so on.
Table 1. Concentration of Cs-137 in brown rice.
Site

A. Brown rice sampled
Rice was grown in ten paddy fields in four sites (Aizu
Bange, Inawashiro Koriyma and Nihonmatsu) located in
Fukushima Prefecture during the year 2011 and 2012.
Management including fertilizer followed the conventional
practices in each site in both year except in Aizubange andInawashiro. In these two sites, potassium had not been
applied more than ten years in one paddy field and practical
fertilizer had been applied in another one. Brown rice was
sampled from the paddy fields in the year 2011 and 2012.

Concentration of Cs-137(Bq kg-1 dw)
2011
2012
Aizu Bange
1
22
10
2
3.3
2.0
Inawashiro
1
17
19
2
3.8
3.1
Koriyama
1
2.8
1.3
Nihonmatsu
1
200
160
2
290
160
3
130
50
4
61
26
5
74
22
Maximum
290
160
Minimum
2.8
1.3
Average29
16
Geometric average is shown for the concentration of Cs-137.

－ 120 －

No.

2012 / 2011
(%)
48
61
114
82
48
80
56
41
42
30
114
30
60

23-FKP-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Size-distribution of airborne radioactive particles from the Fukushima Accident
H. Muramatsu1, K. Kawasumi1, T. Kondo1, and K. Matsuo2

Department of Chemistry, Faculty of Education, Shinshu University, Nishinagano, Nagano-shi, Nagano 380-8544, Japan
2
Graduate School of Education, Shinshu University, Nishinagano, Nagano-shi, Nagano 380-8544, Japan

Abstract –The particle size distribution of radioactive aerosols has
been observed using the Andersen-type classifier combined with ahigh volume air sampler. Estimated AMADs of 131I-, 134Cs- and137
Cs-aerosols were ranging from 0.56 to 0.60 �m, which werelarger than that of 7Be-aerosols, about 0.2 �m.
Keywords – particle size distribution, radioactive aerosols, airborne
radionuclide, nuclear power plant accident

INTRODUCTION
The release of radioactive materials from the Fukushima I
nuclear power plant accident brought about seroius and wide
contaminations in the area of northeastern Japan. Released
radioacive materials from the reactors would migrate asradioactive aerosols, attaching to non-radioactive aerosols
suspended in the surface air and being affected by a transportof air masses which is somewhat complex and strongly
depends on the distribution of high and low atmosphericpressure regions around the Japanese Islands. In this report,
we describe the results of radioactivity measurements in theregion far from the site where the present nuclear accident
had occurred. Especially, are shown the results obtained in
the experiment done by using a high-volume cascade
impactor to estimate the size distribution of aerosols attachedby fission products.
EXPERIMENTAL
Air samplings were carried out at the sampling station on
the roof of the building (height above ground level 12 m)
located in our university campus (36º39´N, 138º12´E).
Suspended particles attached by fission products werecollected by using the Andersen-type classifier combinedwith the high volume air sampler (Model AH-600). The
sampler is a jet cascade impactor consisting of five multi-jet
stages (including a backup stage) and a filter, verticallystacked, designed for use at a flow rate of 566 L/min, and it
can collect the particles classified into five sizes from 1.1 �m
to 7.0 �m.
RESULTS AND DISCUSSION
The sampling was carried out at the sampling station from
April 7 to April 24, during 17 days, with the flow rate of 566
L/min and the total volume of 138400 m3. Aerosol particles
were classified and collected on four glass fiber filters, andon a back-up filter for aerosols smaller than 1.1 �m indiameter. About 60% of collected activities were found on
the back-up filter, which means that the majority ofradioactivity would attached to aerosols with the diameters
less than 1.1 �m. This tendency is much more remarkable forthe case of 7Be-aerosols, which is formed through attachingby the cosmogenic radionuclide of 7Be and whose size
distributions have been measured by using the same manner
mentioned below during a couple of years.
In order to estimate a size distribution and a mean particle
diameter, we used only three data, which the particle-size
range is neatly known, that is, corresponding to particle-size
ranges of 3.3-7.0, 2.0-3.3 and 1.1-2.0 �m. Under theassumption that the particle size distribution of radioactive
aerosols in surface air is in a lognormal and unimodal
distribution, the cumulative probability was plotted against
the particle diameter, as is shown in Fig.1. Activity Median
Aerodynamic Diameter (AMAD) was estimated by the value
when the cumulative probability is 50%. Estimated AMADsof 131I-, 134Cs- and 137Cs-aerosols were ranging from 0.56 to
0.60 �m, which were larger than that of 7Be-aerosols, around0.2 �m.
99.9999

Log Normal Probability Plots

99.99

Cumulative probability

1�������������

99
90��������������

50���������������
��������������

10
1
0.01
0.00010.01

0.1
1���������������������

10

Fig.1 Probability plot for the cumulative percent as a function of aerosol
particle diameter.

According to the physical characteristics reported by
Whitby for sulfur aerosols [1], the geometric mean radii of
0.57, 0.60, and 0.56 �m for 131I-, 134Cs- and 137Cs-aerosols,
respectively, seem to belong to the accumulation mode whosemean value is (0.48 ± 0.1) �m. Beyond the difference inorigin and chemistry between cosmogenic 7Be and fission
products of 131I, 134Cs and 137Cs, what controls mean radius ofradioactive aerosols is not clarified yet. It is surely consideredthat the difference in the formation and growth of both
radioactive aerosols would be important.
[1] Whitby, K. T., Atmos. Envir. 12, 135-159 (1978).

－ 121 －

23-FKP-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Long-term effects of radionuclides originating from the Fukushima nuclear power
plant accident in airborne particulate matters in Kawasaki
Ko Nakamachi1, Hirotaka Matsuno1, Teruyuki Honda1, Yoshikazu Kikawada2
1

Graduate School of Engineering, Tokyo City University
Faculty of Science and Technology, Sophia University

2

Abstract – This study is intended to elucidate the long-term effects ofatmospheric radioactive cesium in Kawasaki City, Kanagawa. As aresult, it became clear that the radioactive cesium activity
concentration in December 2012 had decreased to about 1/105ofthat observed immediately after the Fukushima Daiichi nuclear
power plant (FDNP) accident in March 2011 and sulfate aerosols
may act as a carrier and transport radioactive cesium.
Keywords – Fukushima Daiichi nuclear power plant accident,
radioactive cesium, carrier, airborne particulate matters, Kawasaki

I.

INTRODUCTION

The FDNP accident was caused by the Great East Japan
Earthquake, which occurred on March 11, 2011. The artificial
radionuclides 131I, 134Cs, and 137Cs were detected in the Kanto
region.
In this study, we focused on 131I, 134Cs, 137Cs, and otherradionuclides contained in airborne particulate matters(APM) sampled from filters in the Atomic Energy ResearchLaboratory of Tokyo City University located in the west of
Kawasaki City, Kanagawa, which is about 250 km southsouthwest from the FDNP.
The aim of this study was to determine the time series of theradioactive decay and the atmospheric dispersion of theartificial radionucl����� ��� �-ray spectrometry. Moreover,because we have been sampling the APM continuously frombefore the FDNP accident, we can compare the results before
and after the FDNP accident.

Fig. 1. The 134Cs and 137Cs activity concentration in
December 2012 had decreased to about 1/105 of the activity
concentration observed immediately after the FDNP accident.
Sulfate aerosols can act as carriers of radioactive cesium.
Because sulfates are formed from sulfur dioxide in theatmosphere, we indirectly examined the relationship between
radioactive cesium and sulfate by comparing the activity
concentration of radioactive cesium and the sulfur dioxidelevels recorded by the Kawasaki pollution monitoring center.
The fluctuations in the radioactive cesium concentration weresimilar to the fluctuation in the sulfur dioxide concentration.
This finding suggests that sulfate acts as a carrier andtransports radioactive cesium.

Fig.1 Time series of 134Cs and 137Cs activity concentration in Kawasaki

II. METHODS

IV. CONCLUSION

After sampling the APM from the filters, we compressed thefilter into an acrylic case to measure the �-rays. A high purity
germanium semiconductor detector was used for the analysis.
The measurements were carried out for 80,000 s. The Seiko
EG&G spectrum navigator environmental analysis program
was used for nuclide analysis.
III. RESULTS AND DISCUSSION
Immediately after the accident at the FDNP in March 2011,
Nb, 97Nb, 110mAg, 129Te, 129mTe, 131I, 134Cs, and 137Cs weredetected. The activity concentrations of 131I, 134Cs, and 137Cs
immediately after the accident were 1.66, 0.61, and 0.60
Bq/m3 respectively, and the 131I/137Cs activity concentration
ratio was 2.78. The time series of the radioactive cesium
activity concentration after the FDNP accident is shown in
95(1)

Immediately after the accident at the FDNP in March
2011, 95Nb, 97Nb, 110mAg, 129Te, 129mTe, 131I, 134Cs,
and 137Cs were detected.
(2) The activity concentrations of 131I, 134Cs, and 137Cs
immediately after the FDNP accident were 1.66, 0.61,
and 0.60 Bq/m3, respectively, and the 131I/137Cs
activity concentration ratio was 2.78.
(3) The 134Cs and 137Cs activity concentration in
December 2012 had decreased to about 1/105 of theactivity concentration observed immediately after the
FDNP accident (March 2011).
(4) The fluctuation in the radioactive cesium activity
concentration was similar to the fluctuations in thesulfur dioxide concentration; therefore, sulfate
aerosols may act as a carrier and transport radioactive
cesium.

－ 122 －

23-FKP-08
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Measurement of Iodine-129 concentration in water samples in relation with
Fukushima Daiichi Nuclear Power Plant accident
Hiroyuki Matsuzaki1, Hironori Tokuyama1, Yasuto Miyake1, Maki Honda2, Takeyasu Yamagata3,
Yasuyuki Muramatsu4
1

Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, Japan
2
Graduate School of Integrated Basic Sciences, Nihon University, Japan
3
College of Humanities and Sciences, Nihon University, Japan
4
Department of Chemistry, Gakushuin University, Japan

Abstract – Iodine-129 (129I) concentration in several water samples
were measured by means of Accelerator Mass Spectrometry anddiscussed in relation with Fukushima Daiichi Nuclear Power Plant(FDNPP) accident. 129I concentration of river waters collected Iitate
village and Minami-Soma city (North to North-west of FDNPP)
showed as high as 1.0·109 atoms/L and had not vary significantly
during period from March to October, 2012. The combination of
129 127
I/ I ratio and 127I concentration of these water samples can be
explained as mixture of fossil rain water (ground water) and therain radioactively contaminated by FDNPP accident.
Keywords – FDNPP accident, Iodine-129, Accelerator Mass
Spectrometry, tap water, environmental waterI.

INTRODUCTION

According to Fukushima Dai-ichi Nuclear Power Plant(FDNPP) accident, vast amount of radioactive nuclides
including radioactive iodine were spilled out into theenvironment. A rare isotope Iodine-129 (129I) was also widelydistributed in a very short time by the FDNPP accident. 129I
directly landing on the soil surface had been trapped in theupper layer of the soil and the depth profile should indicate
the migration and the interaction with the soil. If 129I was
trapped in the woods, it seems to take rather longer time forlanding on the ground. Either way, a certain portion of the 129I
should be moving downward and finally washed out by thegroundwater or river with a certain rate and transported into
the sea. The concentration of 129I in environmental water
samples taken from rivers and ponds are considered to reflect
the iodine transportation process by the fluvial system.

The University of Tokyo. An aliquot taken from the water
sample before adding carrier was analyzed for iodine
concentration by ICP-MS.
III. RESULTS AND DISCUSSION
129

I concentration of river waters collected Iitate village
and Minami-Soma city (North to North-west of FDNPP)
showed as high as 1.0·109 atoms/L and had not varysignificantly during period from March to October, 2012.
This concentration is quite high compared to the pre-accident
level (1-2·106 atoms/L), which was determined from theresult of measurement for tap water collected in 2006. The
combination of 129I/127I ratio and 127I concentration of thesewater samples can be explained as mixture of fossil rainwater (ground water) and the rain radioactively contaminatedby FDNPP accident (Fig. 1).

II. EXPERIMENTAL
River water samples and lake water samples werecollected from the South-west region (Abukuma area) andNorth to North-west region (Minami-Soma city and Iitate
village) during the period from April, 2011 to March, 2013.
500mL or 1 L of each water sample was served for analysis.
2mg of iodine carrier was added to water and mixed well in alittle reduced condition. Iodine was extracted by the solvent
extraction and the back extraction process and precipitated asa Silver Iodide (AgI). Collected AgI was mixed with
Niobium powder and pressed into a cathode of Accelerator
Mass Spectrometry (AMS). 129I/127I ratio was measured at
MALT (Micro Analysis Laboratory, Tandem accelerator),

Fig. 1. 129I/127I – 1/127I plots of several water samples. Lines
are the mixing lines between the end members.

Considering the accidental 129I deposition in Northwest of
FDNPP (~1.4·1014 atoms/m2) and annual precipitation rate(~1300 mm), it is figured out that no more than 1% of total
inventory is transported by the river system annually.

－ 123 －

23-FKP-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Observed radioactivities and activity ratios in aerosols from April 2011 at the
Geological Survey of Japan, Tsukuba, Japan
Yutaka KANAI1

1

Geological Survey of Japan, National Institute of Advanced Industrial Science and Technology

Abstract – The aerosol monitoring was started at the GSJ, Tsukuba,from the end of March 2011 for the assessment of environmental
impact and residents' dose rate. This paper reviewed the obtained
data and the geochemical behaviors of natural and artificial
radionuclides were studied. Many artificial nuclides derived fromthe FDNPP accident as well as natural 7Be and 210Pb were observedin this study and the most of them with short half-lives became
below the detection limit in June, 2011. Several high concentration
peaks of 134Cs and 137Cs were observed after June, and around 10-4
Bq/m3 concentration was estimated as temporal background level.
After middle April 2012, it became in half level. The observed
7
134
Cs/137Cs, 136Cs/137Cs and 132Te/13 Cs activity ratios showed
relatively good attenuation corresponding to their half-lives. For
131
I and 129mTe, the activity ratios showed a decreasing trend withfluctuations. 110mAg showed a bigger attenuation rate than its halflife and 95Nb showed increasing trend. The variation of activity ratiowith time observed at the GSJ was supposed to depend on particle
size, their chemical species, the source, discharge amount, mixing
and the transportation processes of nuclides.
Keywords – Radioactivity, Aerosol, the Geological Survey of Japan,
Tsukuba, Activity ratio, Natural and artificial nuclides

I.

INTRODUCTION

A big earthquake (M. 9.0) and the subsequent tsunami
on 11 March 2011 resulted in severe damages to the
Fukushima Daiichi Nuclear Power Plant (FDNPP). All thepower supply was lost and the luck of cooling system caused
the release of a large amount of radioactive nuclides such as
131
I and 137Cs into the environment.
We started the monitoring of radionuclides in aerosols at
the Geological Survey of Japan (GSJ) in Tsukuba from theend of March, about 20 days after the FDNPP accident, forthe purpose of assessing their environmental impacts and theradiation dose for safety of the habitant. In this paper wesummarize and focus on the geochemical behavior of
artificial radionuclides as well as natural radionuclides using
their activity ratios.
II. OBSERVED RADIOACTIVITIES IN AEROSOLS
Tsukuba is located about 170 km south-southwestward
from the FDNPP. The radionuclide concentrations observedat the GSJ would be greatly dependent on those emitted fromthe FDNPP and the climate conditions, because the released
radioactive nuclides would move as a plume. 95Nb,
99
Mo/99mTc, 110mAg, 129mTe/129Te, 131I, 132Te/132I, 134Cs, 136Cs,
137
Cs, 140Ba/140La, 141Ce and 144Ce were main artificial
nuclides observed in this study and the most of them withshort half-lives became below the detection limit in June,
2011. Several high concentration peaks of 134Cs and 137Cs
were observed after June, and around 10-4 Bq/m3
concentration was estimated as temporal background level,
which is about 2 orders of magnitude higher level than that
before the accident. After middle April 2012, it became in a
half level.
III. ACTIVITY RATIOS BETWEEN NUCLIDESSupposing the nuclear reactions almost stopped at thetime of accident, activity ratio of nuclide versus 137Cs should
decrease nearly with the half-life of nuclide because that of137
Cs is by far larger. Variations of the activity ratio of 134Cs,
136
Cs, 131I, 129mTe, 132Te, 110mAg and 95Nb versus 137Cs were
examined.
The observed macroscopic 134Cs/137Cs, 136Cs/137Cs and132
Te/137Cs activity ratios showed relatively good attenuation
corresponding to their half-lives, although these nuclides
might be released from the different three reactors that might
have different activity ratios owing to the different burn-up.
As 134Cs, 136Cs and 137Cs are isotopes of the same element,
the change and large fluctuation of activity ratio duringtransport would not occur. The small fluctuation after several
months from the accident might suggest complex release andmixing of the source reactors at different situations. The
131 137
I/ Cs activity ratio in aerosol showed a decreasing trendwith a little fluctuation, and also the tendency of a little
higher concentration after 60 d. The change of composition(gas/particle), the release rate and temperature at the reactors,
transport processes and their mixing would contribute to theactivity ratios. Although 129mTe and 132Te show thedecreasing trend, the former showed rather large fluctuation
with a high value. There may be complicated processes
concerning the older and younger air masses whose132
Te/129mTe activity ratios differ from each other because ofhalf-lives. On the other hand, 110mAg showed a bigger
attenuation than that supposed from its half-life, probably
owing to its chemistry and the discharge rate. Although 95Nb
was emitted in the atmosphere together with other radioactive
nuclides in the accident, 95Nb/137Cs activity ratio showed
increasing trend with time.
It was shown that the activity ratios of artificial nuclides
observed at the GSJ might depend on their chemical species,
particle size, diversity of the source, change of discharge andthe transportation processes of nuclide. These facts would
help the better understanding of the reactor conditions in andafter the accident in addition to other information.

－ 124 －

23-FKP-10
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Chemical forms of radioactive Cs in soils originated from Fukushima Dai-ichi
nuclear power plant accident, as studied by extraction experiments
Masaaki Hirose1, Yoshikazu Kikawada1, Atsushi Tsukamoto2, Takao Oi1, Teruyuki Honda2, Katsumi
Hirose1, Hiroaki Takahashi3
1

Faculty of Science and Technology, Sophia University
Graduate School of Engineering, Tokyo City University
3
Graduate School of Engineering, Tohoku University

50

1M NH 4Ac0

0-1 cm1-2 cm

Cs-133
Cs-134
Cs-137

10

Cs-133
Cs-134
Cs-13720

Cs-133
Cs-134
Cs-1374030

0.11 M HAc

Cs-134
Cs-137

We first performed preliminary extraction experiments onsome soil samples with various extracting solutions. The
contents of Cs-133, the stable isotope of cesium, in thecentrifuged/filtered extract solutions were determined.
Based on the results of preliminary experiments, we thenperformed two-step sequential extraction on a soil sample
collected at Toride City, Ibaraki, Japan, which is locatedabout 200 km southwest of the FDNPP and is one of thesmall radioactive hotspots near Tokyo found after theaccident.
The soil core sample, collected with a core sampler (10 cm
in diameter and 10 cm in length) in August 2011, was cut
with 1 cm width layers. The contents of Cs in the surface
layer of the sample were Cs-133, Cs-134, and Cs-137 in the
3.8 µg/g, 1.1 Bq/g, and 1.3 Bq/g , respectively. Five grams ofthe dried soil (upper three layers) samples were subjected tosequential extraction with 200 mL of 1 M ammonium acetate
solution and then 0.11 M acetic acid for 24 hours each. The
contents of Cs-133 and radioactive Cs (Cs-134 and Cs-137)

Cs-133

II. EXPERIMENTAL

Cs-134
Cs-137

The FDNPP accident in March 2011 resulted inradiological contamination mainly by radioactive Cs widelyin Japan. It is highly probable that the behavior of radioactive
Cs newly deposited on soils due to the accident is different
from that of stable Cs that has existed in soils before theaccident, because of the difference in chemical forms
between them [1]. In this study, we discuss chemical forms ofradioactive Cs in soils originated from the FNPP accident
based on the results of extraction experiments conducted for
Cs on soil samples.

The preliminary experiments revealed that stable Cs in soil
was hardly extracted with Milli-Q water and 0.11 M acetic
acid, and that only the extractants prepared from ammonium
salts could partially extract Cs from the soil samples. This
indicates that stable Cs is predominantly extractable fromclay minerals with the extractants including ammonium ion
by ion exchange process.
Fig. 1 shows the results of the extraction experiments on
the Toride soil layer sample. About 10 to 20% of radioactive
Cs in the layer samples was extracted with 1 M ammonium
acetate solution, while only about 3% of the stable Cs, Cs133, was extracted. It is likely that the extracted radioactive
Cs was incorporated in ion-exchangeable sites of clay
minerals. Thus, radioactive Cs has apparently higher mobility
than Cs commonly existing in soil. The portion of theradioactive Cs extracted with ammonium acetate solution ishigher in deeper layers, which suggests that radioactive Cs
has migrated into the deeper layer of the soil via ionexchangeable sites of clay minerals. On the other hand, in thecase of acetic acid as extractant, a small amount of Cs-137
was extracted from only the surface layer (0-1cm).
As a whole, more than 70% of radioactive Cs was notextracted by either ammonium acetate solution or acetic acid.
A dominant part of radioactive Cs, which was not extracted
from present extractants, is probably strongly fixed tointerlayer spaces of 2:1 clay minerals.

Cs-133INTRODUCTION

III. RESULTS AND DISCUSSION

Cs-134
Cs-137I.

in each extract solution were determined with spectrometry
respectively.

Cs-133

We conducted extraction experiments on soil samples
contaminated with radioactive cesium originated from the
Fukushima Dai-ichi nuclear power plant (FDNPP) accident inJapan in March 2011. The experimental results suggested that the
majority of the radioactive cesium deposited on land surface was
first adsorbed on exchangeable sites of clay minerals, andeventually it was strongly fixed in interlayer spaces of some 2:1 clay
minerals. The experiment revealed that a very small amount of Cs137 extractable with acetic acid solution existed in the surface soil
layer.
Keywords: radioactive cesium, Fukushima Dai-ichi nuclear
power plant accident, sequential extraction, soil contamination.

Extraction rate (%)

22-3 cm0-1 cm1-2 cmDepth from the surface /cm

2-3 cm

Fig.1 Extraction rates of Cs in the Toride soil sample with NH4Ac-aq(left) and acetic acid (right).

REFERENCE[1]－ 125 －

Kaneyasu. H. et al, Environ. Sci. Technol. 46, 5720-5726, 2012.

23-FKP-11
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Thermal Oxidation of Cesium Loaded Prussian Blue as a Precaution for Exothermic
Phase Change in Extreme Conditions
Durga Parajuli, Hisashi Tanaka, Akira Takahashi, and Tohru Kawamoto
Nanosystem Research Institute, AIST, Japan

Abstract – Cesium adsorbed Prussian blue is studied for the thermaloxidation. The TG-DTA shows exothermic phase change of micro
aggregates of nano-PB at above 270 ºC. For this reason, Cs loaded
PB was heated between 180 to 260 ºC. Heating at 180 removed only
the water. Neither the oxidation of Iron nor the removal of cyanide
is observed at this temperature. Oxidation of cyanide is observed
upon heating above 200 ºC while loaded Cs is released after heatingat >250 ºC followed by washing with water. Thermal oxidation
between 200 to 220 ºC for more than 2 h showed control on
exothermic phase change and loaded Cs is also not solubilized.
Keywords – Prussian blue, Cesium, Exothermic Phase Change

I.

INTRODUCTION

Prussian blue (PB), ferric hexacyanoferrate (Fe-HCF), is
an inorganic complex, mostly known in the history for its
peculiar Cesium (Cs) selectivity.1 In reference to the PB
parent molecule, a number of transition metal
hexacyanoferrate are synthesized and named as PB-analogues.
The PB forms an open cage structure that possesses a typicalzeolytic characteristic, an adjective typically given to any
molecule capable of trapping other ions within its latticecavities.2 Interestingly, PB, different from the common
zeolytic materials, possesses unique selectivity for the Cs-ion.
Due to this structural coincidence, PB has become theultimate Cs-trapper. From Ni-HCF for Cs in alkaline
solutions to Cu-HCF for electrochemical removal of Cs or
Fe-HCF for neutral to acidic solutions, no materials showhigh Cs selectivity, faster kinetics, and high capacity like PBanalogues. However, based on the Sax’s Dangerous
Properties of Industrial Materials some concerns were raised
regarding the stability of used HCF analogues during longterm storage.3 Cash et. al. performed extensive study on
ferrocyanide storage tanks in Hanford site (USA) for
resolving such issues.4 Their report ruled out all these
postulations. Therefore, any speculations on the long-term
storage of PB are unlikely. Even so, to ensure the post-use
safety of the PB adsorbent for assured long-term storage, we
propose the thermal oxidation of the Cs loaded adsorbent
prior to the storage.

heated at different temperature. The oxidized sample waswashed with water and analyzed for the release of loaded Cs.
ICP-MS, TG-DTA, IR, Mossbauer, etc. were used for
different analyses.
III. RESULTS AND DISCUSSION
The phase change behavior of PB was studied by taking
micro aggregates of PB nanoparticles. The TG-DTA takenwith air, Figure 1, Shows the exothermic oxidation at about
272 ºC. Therefore, Cs loaded PB was heated at 180 ºC to 250ºC. No oxidation of iron or cyanide but only water removal
was observed at 180 ºC, while the loaded Cs is released uponwashing the PB oxidized at 250 ºC. Heating above 200 ºC is
necessary to induce the oxidation. But, the process may getvigorous when heated above 250 ºC. So, optimum oxidation
temperature is above 200 ºC and below 250 ºC. Exothermic
phase change was disappeared for a sample loaded with 0.2
wt% Cs when heated at 210 ºC for 3 h. Washing this sample
after oxidation, Cs release was not observed.

Figure 1. TG-DTA of Cs adsorbed PB taken in air. 10 mg, 10 ºC/min.

References[1][2]

II. EXPERIMENTAL[3]

As a parent molecule of number of analogues, PB itself isused for the thermal oxidation experiment. For this, PB isloaded with given amount of Cs from pure water or fly-ash
extracted solution containing Cs along with highconcentration other alkali metals, and other ions. Then it is[4]－ 126 －

M.T. Ganzerli Valentini, S. Meloni, V. Maxia, J Inorg. Nucl. Chem., 34,1427, 1972.
M. Ware, Prussian Blue: Artists’ Pigment and Chemist’s Sponge. J
Chem. Edu., 8,612, 2008
R. J. Lewis, Sr., "Sax's Dangerous Properties of Industrial Materials," Van
Nostrand Reinhold (1992).

R.J. Cash, J.E. Meacham, M.A. Lilga, H. Babad, Resolution of the
Hanford Site Ferrocyanide Safety Issue. Proceeding of the Waste
Management Symposium 1997.

23-FKP-12

Analysis of 134Cs and 137Cs distribution in soil of Fukushima prefecture and their
specific adsorption on clay minerals
A. Maekawa1, N. Momoshima2, S. Sugihara2, R. Ohzawa1, A. Nakama1
1

Graduate School of Sciences, Kyushu University, 6-10-1, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
2
Radioisotope Center, Kyushu University, 6-10-1, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan

Keywords – Radiocesium Interception Potential, Fukushima Daiichi Nuclear Power Plant accident

137Cs activity / Bq kg-1

0

2000

4000

6000

8000

Depth / cm

0-1
1-2

April 2011

2-3
3-4
4-5

137Cs activity / Bq kg-1

0

500

1000

1500

0-1

Depth / cm

Various kinds of radionuclides were released fromthe Fukushima Daiichi Nuclear Power Plant (FDNPP)
due to the accident that occurred in March of 2011. Of
the radionuclides released from the FDNPP, 134Cs and 137Cs
are the major radionuclides of concern in radiation dose
because of large amounts in deposition on surface soil andtheir long half-lives. Cs is known to be adsorbed specificallyon clay minerals in soil. The strong affinity of clay minerals
for Cs is considered to be due to the presence of the frayededge sites (FES). Cremers et al. (1988) proposed that thestrength of the affinity can be explained by the radiocesium
interception potential (RIP), which was defined by the
product of the FES capacity and Cs-K selectivity coefficienton the FES [1]. The RIP would be usable as an index of themobility of radiocesium in soil and expected to be used to
predict the downward migration of radiocesium.
We collected surface soil samples within 60 km from the
FDNPP and analyzed spatial and temporal radiocesium
distributions with a Ge semiconductor detector. No largechange in vertical distribution pattern of radiocesium has
observed on the samples collected in April 2011 and April
2012 at the same location, suggesting strong adsorption of134
Cs and 137Cs on soil (Fig. 1). To confirm the specificadsorption of Cs on clay minerals, we divided the soil into
different particle sizes by sieving and sedimentation method
and measured the activity in each size fraction. The activity
was highest in the clay fraction (< 2 �m) and it tended todecrease as the particle size increased. The RIP
measurement was carried out based on the procedure
adopted from Wauters et al. (1996) [2]. One g of soil was
equilibrated with carrier free 137Cs in a 100 cm3 of 0.1 mol
dm-3 CaCl2 and 0.5 mmol dm-3 KCl solution. Under theabove condition the amount of Cs adsorbed on the FES is
negligibly small compared to that of K. A known amount ofcarrier-free 137Cs was used for the equilibration experimentand the activity of 137Cs in the solution was measured with a
NaI scintillation detector for the determination of the solidliquid distribution coefficient for Cs (KdCs). The RIP can becalculated from the KdCs and the K concentration in solution.
The obtained RIP value ranged 200-1500 mmol kg-1 that
seemed to be high enough to adsorb 134Cs and 137Cs derived
from the accident. The relationship between the RIP and Cs
soil depth profile will be discussed.

1-2

April 2012

2-3
3-4
4-5

Fig. 1. Vertical distribution of 137Cs in soil collected at the same location(30 km west of the FDNPP) in 2011 and 2012. The concentrations differ but
the vertical distribution pattern was similar.

[1] A. Cremers, A. Elsen, P. De Preter, A. Maes, Nature 335, 247-249(1988)[2] J. Wauters, A. Elsen, A. Cremers, A. V. Konoplev, A. A. Bulgakov, R.
N. J. Comans, Applied Geochemistry 11, 589-594 (1996)－ 127 －

23-FKP-13

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Distribution of radionuclides in seabed sediments off Ibaraki coast after the
Fukushima Daiichi Nuclear Power Plant accident
1

M. Nagaoka1, H. Yokoyama1, H. Fujita1, M. Nakano1, H. Watanabe1, S. Sumiya1

Nuclear Fuel Cycle Engineering Laboratories, Japan Atomic Energy Agency, 4-33 Tokai-mura, Naka-gun, Ibaraki 3191194, Japan

Abstract – Various kinds of radionuclides were released into theatmosphere and the sea from the Fukushima Daiichi Nuclear
Power Plant of Tokyo Electric Power Co. (TEPCO) by theaccident and then reached to the neighboring prefectures.
Therefore the accident influence in Ibaraki prefecture wasinvestigated by measuring the concentrations of cesium-134,
cesium-137, strontium-90 and plutonium isotopes in seabedsediments. The values for 137Cs ranged from 6.1 to 300 Bq/kg (drywt) and the ratio of 134Cs/137Cs ranged from 0.48 to 0.77. The
highest point of 137Cs concentration was observed at thenorthernmost station and the concentration was similar to thatreported by MEXT [1].
Keywords – seabed sediments, Ibaraki coast, Fukushima Daiichi
Nuclear Power Plant accident, cesium-134, cesium-137

I.

137

Cs ranged from 6.1 to 300 Bq/kg (dry wt) and the ratio of
Cs/137Cs ranged from 0.48 to 0.77. The concentration of134
Cs and 137Cs before the accident at the sea area in thepast 10 years were < DL* and < DL* to 1.0 Bq/kg,
respectively. The highest 137Cs concentration was observedat the northernmost station near Kitaibaraki City and was
similar to that reported by MEXT [1]. The higher 137Csconcentrations were also observed along the coastal area of
Tokai-mura including the mouth of the Kuji River.
Therefore, the influence of the Kuji River on sea area
should be investigated in detail. Radioactivity
concentrations of 90Sr and plutonium isotopes are undermeasurements.
134* DL: detection limit (134Cs:1 Bq/kg, 137Cs:0.8Bq/kg)

INTRODUCTION(a)

Various kinds of radionuclides were released into theatmosphere and the sea by the Fukushima accident, andthen reached around the Tokai Reprocessing Plant (TRP)
located about 120 km south of the Fukushima Daiichi
Nuclear Power Plant. The influence of the radioactivity on
the environment should be investigated because we have
performed the routine environmental radiation monitoringaround TRP. In this research, strontium-90, cesium-134 andcesium-137 concentrations in the additional special seabedsediments were measured with plutonium isotopes (238Pu,
239+240Pu), to find out the accident influence on sea area.
Moreover, strontium-90/cesium-137 radioactivity ratio wascompared with the ratio before the accident. Finally, eachradioactivity distribution in sea area was arranged toacquire the influence of the accident.

137Cs �Bq/kg dry�(b)

50 Bq/kg dry
more than
100 Bq/kg dry
Takahagi City

JAEA

Hitachi City

Shin river
JAEA

Hitachikou
Hitachinaka
kou

Tokai-mura

Hitachinaka
City
Nakaminato

Fig.1 Distribution of 137Cs concentration in seabed sediments of(a) Ibaraki coast and (b) Tokai coast

IV. CONCLUSION
In order to identify the accident influence, distribution ofradionuclides in seabed sediments off Ibaraki coast wasinvestigated. Cesium-137 concentrations had more thanhundreds times higher than that before the Fukushima
accident. Furthermore, the Fukushima accident influence
was observed from the ratio of 134Cs/137Cs. The highest
point of 137Cs radioactivity was located at the northernmost
station.
[1]

III. RESULTS AND DISCUSSION

Kujiha
ma
Kuji
river

10 Bq/kg dry

II. METHODS
From May to July in 2012, fifty-one Seabed sediments
were collected by the Smith–McIntyre sampler set on amonitoring ship. The samples were dried at 105 °C for 3
days and then packed in measurement vessels. Cesium-134
and 137Cs radioactivity concentrations were measured byhigh-purity germanium semiconductor detectors for 10,000
sec. On the other hand, Strontium-90 and plutonium
isotopes were purified by chemical separation and werethen measured by a beta gas-flow counter and a silicon
semiconductor detector, respectively.

Kitaibaraki
City

Distributions of 137Cs concentration in seabed sediments
at each place are shown in Fig. 1(a), (b). Radioactivities of－ 128 －

MEXT,
http://radioactivity.mext.go.jp/ja/contents/6000/5704/2
4/229_so_0710.pdf, Accessed on March 28, 2013.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

23-FKP-14

Radiocesium Concentration Change in Tree Leaves Before and After Defoliation
1

Shigeo Uchida1, Keiko Tagami

Office of Biospheric Assessments for Waste Disposal, National Institute of Radiological Sciences

Abstract – Understanding the fate of radiocesium in a tree is ofgreat important to estimate the removal rates of radiocesium.
Defoliation is one of the important removal pathways, however,radiocesium might retranslocate from senesced leaves to othertree parts like potassium. In this study, several tree species were
measured the cesium-137 concentrations in leaves before andafter defoliation. It was found that a portion of radiocesium
retranslocate from senesced leaves to other tree tissues; thismechanism will extend radiocesium retention time in trees.
Keywords –defoliation

Cesium-137,

I.

Potassium-40,

retranslocation,

INTRODUCTION

Two years after the TEPCO’s Fukushima Daiichi
Nuclear Power Plant (FDNPP) accident, radiocesium(134+137Cs) is recognized as the only major contaminant in
the terrestrial environment. Decontamination of houses,
public places as well as some agricultural fields have beenproceeded, however, forests are difficult to clean up
because they occupies large areas in contaminated areasand countermeasures have not been established yet. Thus,
radiocesium will be recycled in natural forest ecosystems.
Under these circumstances, it is important to know the
reduction rate of radiocesium from a tree to understand thefate in forests after contamination. The most important
removal pathway is defoliation; the old leaves fell off withsome radiocesium in them so that radiocesium
concentrations could decrease with time [1]. However, as it
was found for potassium [2] retranslocate to developing
tissues or internal stores before defoliation would occur forradiocesium because both elements are in the same group.
The mechanism extends the radiocesium residence time intrees. However, there was no data on Cs retranslocationfrom senesced leaves to green leaves. In this study,
therefore, we measured concentrations of radiocesium
before and after defoliation to see whether the mechanism
was found or not.
II.

selected leave sample was decomposed with mineral acids
and the concentrations were measured by ICP-MS (Agilent
7500a) for Cs and ICP-OES for K (Seiko Vista-Pro).
III. RESULTS AND DISCUSSION
The retranslocate percentage (Tr) is defined as follows
Tr=(Agreen-Asenesced)/Agreenx100
Where Agreen is activity concentration of green leaves ofa tree (Bq kg-1-dry) and Asenesced is activity concentration of
fallen leaves of the tree (Bq kg-1-dry). The Tr values ofSomei-yoshino cherry trees (3 samples from different tree
stands) showed 19-49% for 137Cs while 16-40% for 40K.
Deciduous tree stands tended to show radiocesiumtranslocation (Tr=0-81%) however, no clear result was
found for evergreen tree stands because direct deposition
effect on senesced leaves remained. The stable isotope
determination results for K agreed well with 40K data,
however, the data for radiocesium and stable cesium did
not agree due to the above mentioned reason. The Tr valuesof stable Cs for deciduous tree ranged 0-63%, while less Cstranslocation was found for evergreen tree stands (0-17%).
The second year results will be added and discussed at
the presentation.
Acknowledgement: This study was partially supported by
the Agency for Natural Resources and Energy, Ministry of
Economy, Trade and Industry (METI), Japan.
REFERENCES
[1]

[2]

MATERIALS AND METHODS

Eight species of deciduous trees and evergreen trees
were studied in October to November 2011, within the
grounds of our institute (NIRS), Chiba Prefecture, Japan.
Tree leaves both just after defoliated (senesced leaves) andthe green leaves still remained on the tree branches werecollected on the same sampling day. They were dried at80��� ���� �� ����� ��� ������ ��� ������� ��������� �������� �����
sample mass was 8-22 g on dry weight basis. After drying,each sample was mixed well and transferred into a plastic
bottle to measure 137Cs and 40K concentrations with a Ge
detecting system (Seiko EG&G). In order to check thestable Cs and K concentration change, a 0.1-g amount of－ 129 －

Tagami, K., Uchida, S., Ishii, N., Kagiya, S.: Translocation ofradiocesium from stems and leaves of plants and the effect onradiocesium concentrations in newly emerged plant tissues. J.
Environ. Radioactiv. 111, 65-69 (2011).
Ares, A., Gleason, S. M.: Foliar nutrient resorption in trees species.
In: New Research on Forest Ecology, Eds. Archibald K.S., pp. 1-32.
Nova Science Pub. New York (2007).

23-FKP-15
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Distributions and Concentrations of Radionuclides in Giant Butterbur after the
Fukushima Nuclear Power Plant Accident
1

Keiko Tagami1, Shigeo Uchida1

Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences, Japan

Abstract – Distributions of radiocesium 137Cs) and radioiodine (131I)
in giant butterbur (Petasites japonicus) was studied to investigatetranslocation of these radionuclides. The concentration ratios (ondry weight basis) between petiole and leaf for the first samples (28March 2011) showed about 0.2 for both isotopes, however, the ratio
increased to ca 0.7 for 131I while that for 137Cs was ca. 0.4 by 5 May
2011. The newly emerged shoots showed the concentrations in
between.
Keywords – translocation, radioiodine, radiocesium, herbaceous
plantsI.

INTRODUCTIONRadioiodine and radiocesium released due to the
Fukushima Daiichi Nuclear Power Plant (FDNPP) accident
were deposited around Kanto Plain, mainly on 20-22 March2011 with rain [1]. Radionuclide behavior in herbaceous
plants after deposition will provide information ofradionuclide mobility and uptake from roots and throughplant surfaces after emergency situation. Previously, newly
emerged part concentrations were reported [2], however, thedistribution patterns between old plant parts, which directly
affected by deposition, and newly emerged plant part has notbeen reported yet.
In this study, we focused on giant butterbur (Petasites
japonicus), which is a herbaceous plant and had already beengrown at the time of FDNPP accident occurred. Distributionsof radioiodine and radiocesium in this plant will provide us
the fate differences between radioiodine and radiocesium
after deposition.
II. MATERIALS AND METHOD
Plant samples were collected from 28 March 2011 at NIRS,
about 210 km SSW from FDNPP. Newly emerged parts werecollected from 13 April to 5 May 2011. The sampled plantparts are shown in figure 1. Immediately after the collection,
each parts were cut and mixed well. The radioactivity
concentrations were measured with a Ge detecting system(Seiko EG&G). Concentrations of iodine-131 (131I) andcesium-137 (137Cs) in the ground were 4500 and 8300 Bq m-2
at 25 April 2011. About 200 days after the first sampling, theconcentrations of radiocesium in leaves and petiole samples
were collected again, however, due to the low concentrations,the samples were dried to reduce volume.
The samples collected between 28 March to 5 May 2011were measured in wet weight mass, thus, the concentration
was estimated to dry weight mass using the following data.

Figure 1. Schematic of giant butterbur sampling parts

III. RESULTS AND DISCUSSION
The average concentration ratios (on dry weight basis)
between petiole/leaf for 137Cs and 131I showed 0.42 (0.340.51) and 0.59 (0.40-0.76), respectively, for the samples
collected between 12 April to 5 May. The ratio for the firstsampling date were the same (ca. 0.2), thus these radionuclidetranslocation showed different increments in the petiole part.
The concentrations of 137Cs and 131I in newly emerged shoots
were between those of leaves and petioles. Compared to otherherbaceous plants, 137Cs concentration in giant butterbur
shoots was almost the same after 22 April, thus it was
assumed that the root uptake pathway became major by thattime. However, the concentration in shoots collected on 13
April was about 2.5 times higher than 22 April sample;
probably, translocation from leaf surface to newly emerged
shoots would partially affect.
Acknowledgement: This study was partially supported by the
Agency for Natural Resources and Energy, Ministry of
Economy, Trade and Industry (METI), Japan.
REFERENCES[1][2]－ 130 －

Ishii, N., Tagami, K., Takata, H. Fujita, K., Kawaguchi, I., Watanabe,Y., Uchida, S.: Deposition in Chiba Prefecture, Japan, of Fukushima
Daiichi Nuclear Power Plant Fallout. Health Phys. 104, 189-194 (2013).
Tagami, K., Uchida, S., Ishii, N., Kagiya, S.: Translocation ofradiocesium from stems and leaves of plants and the effect onradiocesium concentrations in newly emerged plant tissues. J. Environ.
Radioactiv. 111, 65-69 (2011).

23-FKP-16

��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The Behavior of Cs Adsorption of Microcapsule Beads Nano-Prussian Blue
Akiko Kitajima1, Hiroshi Ogawa1, Kazunori Yoshino2, Mikihiro Takasaki2, Hisashi Tanaka1 andTohru kawamoto1
Nanosystem Research Institute, AIST, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
2
Kanto Chemical Company Inc., Inari, Soka, Saitama 340-003, Japan

Abstract � A granular cesium adsorbent for column-type
decontamination has been developed using Prussian blue
nanoparticles with micro-capsule technique (MC-nPB). The MCnPB shows the extraordinary Cs-adsorption capacity, over120g(Cs)/Kg(Adsorbent). The lattice constant of MC-nPB was
expanded after Cs adsorbed, indicating that Cs cations areadsorbed in the nano-PB crystalline frameworks.
Keywords � Cesium, Cesium adsorbent, Nano-Prussian blue,
Microcapsule beads

compared to that of the MC-nPB. The lattice constants for
the MC-nPB, 7% Cs adsorbed and 15% Cs adsorbed were
determined as 10.167(4), 10.171(7) and 10.193(4) � ,respectively.

100
Adsorption rate / %I. � INTRODUCTION
Prussian blue is known as an excellent cesium-ion
adsorbent1-3. For the decontamination of the radioactive-Cs
from the aqueous solution, a column of the adsorbent isquite effective. For the purpose, we have developed the
granular adsorbent with Prussian blue nanoparticles by
microcapsule technique (MC-nPB). Here we show its quite
high adsorption capacity.

40
20
0
0

METHOD

10
Shaking time / h20

Figure 1 Relationship between Shaking time and Adsorption rate

Intensity/ arb. unit

(200)

The Cs adsorption properties of MC-nPB were
evaluated in a batch adsorption experiment. 12.5 mg of the
MC-nPBs were immersed in 10 mL of Cs solution andshaken at 25 �C for 24 h. (solid /liquid ratio = 800 mL/g).
The Cs+ concentration was determined using an inductively
coupled plasma mass spectrometer (ICP-MS).
The crystal structure of MC-nPB before and after the Csadsorbed is examined by an X-ray diffract meter (XRD).
The lattice constant a, b and c were estimated using XRD
spectra or miller indices (200) (220) (400) (420) (422) and(440) assuming a cubic structure. The lattice constant a, b
and c were refined with WPPF (Whole Powder Pattern
Fitting); Pawley Method.
III.

60

10

RESULTS

20

(400)

II.

80

(220)

1

30
40
2�/ �

(c)
(b)
(a)

50

60

Figure 2 XRD pattern of microcapsule beads nano-PB (a),7% Cs adsorbed PB (b), and 15% Cs adsorbed PB (c).

Figure 1 shows the Cs-adsorption isotherm of MC-nPB
with the 1 mg/L Cs-solution. Over 6 hours, the Csadsorption is almost complete. The adsorption rates at 6, 12,
and 24 hours are 96.0, 99.0 and 99.9 %, respectively. The
adsorption speed is roughly proportional to the solid/liquidratio.
With the solution with the high Cs-concentration until
500 mg/L, adsorption capacity is determined as the 120 g(Cs) /kg (adsorbent).
Figure 2 shows the XRD patterns of MC-nPB (a), thatafter 7% Cs-adsorbed (b) and that after 15% Cs-adsorbed(c). Accordingly to these results, a cubic structure shown ina stoichiometric PB was retained even after the Csadsorption. In addition, it was observed that the peaks for
the Cs 15% adsorbed PB were sifted to be lower degrees

REFERENCES
[1]
[2]
[3]

－ 131 －

H. Vandenhove, M. Van Hees, S. De. Brouwer, C. M.
Vandecasteele, The Science of Total Environment, 1996, 187, 237.
S. Taj,�D. Muhammad, M. A. Chaudhry, M. Mazha, Radional Nucl
Chem, 2011, 288, 79.
A. Kitajima, H. Tanaka, N. Minami, K. Yoshino and T. Kawamoto,Chem. Lett. 2012, 41,1473

23-FKP-17

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Transfer of Radiocesium from Soil to Cut Flowers

1,2

Yasukazu Suzuki , Hiroyuki Munakata1, Yutaka Yajima1, Yosihiro Tooyama3, Hirokazu Suzuki1,
Hirofumi Tsukada4, Kazuyuki Inubushi2
1

Fukushima Agricultural Technology Centre, 2 Graduate School of Horticulture, Chiba University3
Ken-poku District Agriculture and Forestry Office, Fukushima, Japan , 4Fukushima University

Abstract – Concentration and transfer factor of radiocesium,
which was derived from the Fukushima Daiichi Nuclear Power
Plant Accident, from soil to cut flowers was determined. Field
experiment was performed in Gray Lowland soil located in
Fukushima Prefecture from May to October of 2011 and sevenspecies of plants, gypsophila paniculata, sunflower,
chrysanthemum, gentian, lily, dahlia and eustoma, were cultivated.
Concentration of radiocesium (134+137Cs) in the soil was 18004400 Bq kg-1 and the range of the transfer factor in the plants
was 0.008-0.066, which was within one order of magnitude.
Keywords – cut flower, Fukushima Daiichi Nuclear Power Plant,
radiocesium, transfer factor

I.

INTRODUCTION

A huge amount of radionuclide was released into theenvironment at the Fukushima Dai-ichi Nuclear Power
Plant accident. Radiocesium, which is major radionuclide,
was deposited on the soil and agricultural products were
contaminated. Radiocesium is an important radionuclide
for the assessment of radiation exposure to the public andalso need to know the contamination level of agricultural
products for the public relief. Few data available on
behavior in soil-cut flower interactions. This study was
conducted to clarify the concentration and transfer factor ofradiocesium in cut flowers.
II. MATERIALS AND METHODS
Field experiment was performed in Gray Lowland soil
located in Fukushima Prefecture from May to October of
2011. The soils was sampling of 0–15 cm depth in five
points and mixing. Seven species of cut flowers such as
Table 1 Concentration and transfer factor of radiocesium in cut flowers

Cut flower

Gypsophila paniculata

Sunflower
Chrysanthemum
Gentian
Lily
DahliaEustoma

Samplingday
2011/8/18
2011/7/25
2011/8/17
2011/10/5
2011/9/5
2011/8/5
2011/8/16

soils
Cs

gypsophila paniculata (Gypsophila paniculata), sunflower(Helianthus annuus), chrysanthemum (Dendranthemagrandiflorum), gentian (Gentian triflora.), lily (Lilium ×
formolongo), dahlia (Dahlia pinnata.) and eustoma(Eustoma grandiflorum) were cultivated in the field
experiment. Cut flowers were harvested as when flowering.
After the plants maturing, they were collected from thefields. The samples were rinsed with water, and dried at
80°C for 3 d. The dried samples were pulverized withcutter blender and compressed into plastic vials (U-8). The
soil samples were collected after harvesting the cutting
flowers, air-dried at 25°C for 10 d, and passed through a 2mm mesh sieve. The soil samples were also compressed
into the plastic vials. The radioactivity of the samples wasmeasured with a germanium semiconductor detector with amultichannel analyzer, over a period of 2,000-48,000
seconds for the plant and 1,200 seconds for the soil samples.
III.

The concentration of radiocesium in the soil was 18004400 Bq kg-1. The concentration of radiocesium in cut
flowers was from 33 to 120 Bq kg-1 dry wt, which was 4.0
times differences between the eustoma and gypsophila
paniculata. The transfer factor of radiocesium in the sevenplant was 0.008-0.066 which was 8.3 times differences
between the eustoma and gypsophila paniculata. The
transfer factor in cut flowers was a relatively similar orderto the reported values in leafy vegetables.[1][2][1]http://www.maff.go.jp/j/press/syouan/nouan/pdf/110527-01.pdf(in Japanese)[2]http://www-pub.iaea.org/MTCD/publications/PDF/trs472_web.pdf

�Bq kg134

Cs

dry wt�

1800 ± 260

3500 ± 1100
2900 ± 310
3100 ± 170
3000 ± 350
4400 ± 880
4400 ± 450

Decay correction was done from sampling day. Average ± SD (n = 3).

Transfer factor

Radiocesium concentration

134+ 137-1

RESULTS AND DISCUSSION

Plants137
Cs

�Bq kg60 ± 32
39 ± 2120 ± 4.8
19 ± 4.6
32 ± 3.342 ± 3.3
13 ± 4.0－ 132 －

-1

134+ 137

Cs

dry wt�64 ± 3444 ± 30
24 ± 5.923 ± 3.933 ± 7.2
48 ± 6.4
19 ± 3.7120 ± 66
84 ± 5044 ± 1142 ± 8.0
65 ± 1190 ± 8.933 ± 7.7

0.066 ± 0.028
0.024 ± 0.013
0.016 ± 0.005
0.014 ± 0.003
0.022 ± 0.003
0.021 ± 0.006
0.008 ± 0.002

23-FKP-18
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

CLEVASOL, a novel radiation hard cation exchanger suitable
for treatment of liquid radioactive waste with high salinity
A. Yakushev1, A. Türler2, Z. Dvorakova3, K. von Bremen2
1

GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt, Germany
2
University of Bern, CH-3012 Bern, Switzerland
3
Neplachova 17, 37004 Ceske Budejovice, Czech Republic

Keywords – cation exchanger, ion selective, radiation resistant,radioactive waste treatment, water purificationI.

INTRODUCTION

CLEVASOL is a novel strongly acidic inorganic cationexchanger designed for the purification of aqueous solutions
from metal cations, and especially from caesium. This
macroporous cation exchange resin has an ultra-high capacity,
as well as a very high chemical stability and radiation
hardness. The resin is absolutely not soluble in aqueous
solutions at pH = 0÷14, and in common organic solvents. In
general, the selectivity increases in the order M+ < M2+ < M3+< M4+, but CLEVASOL has extremely high selectivity forheavy monovalent cations (caesium(I), silver(I), thallium(I)etc.) and for transition metal cations (e.g., Ni2+, Co2+, Mn2+).
High KD values for cations of d-transition metals increasesignificantly by adding chelating ligands to solution.
CLEVASOL has excellent kinetics resulting in high loading
capacity and minimal ionic leakage. This product is ideal foruse in radioactive waste treatment, water purification andnuclear medicine.
II. STRUCTURE OF CLEVASOLCLEVASOL has an ionic structure – cations as counterions are distributed inside of a resin grain. Solid crystal grainsof a salt containing the dodecahydro-closo-dodecaborateanion [B12H12]2- are polymerized by cross linking monomericanions [B12H12]2- to a polymeric anion [B12H(12-x)Lx]n2n-. Eachpolymeric anion is as big as a single crystal grain. The
monomer unit is a regular boron icosahedron with a highly
delocalized electron density. The icosahedron itself is aresonance hybrid involving both two-centre two-electron B-B
and three-centre two-electron B-B-B bonds. Each boron atom
contributes with two valence electrons to the B12 cage. The
position and distances between monomers are given by the
crystal structure of the initial salt.

yellow occurs by loading the resin in H+-form with metal
cations (Fig. 1).
The distribution coefficients (KD)for the following cations in nitricand/or hydrochloric acid media were
determined in batch and column
experiments: Na+, Cs+, Ag+, Tl+,
Mg2+, Ca2+, Sr2+, Ba2+, Ra2+, Mn2+,
Fe2+, Co2+, Ni2+, UO22+, Y3+, Ac3+,
Eu3+, Yb3+, Lu3+, Th4+ (see Fig. 2).
The KD values usually decrease withincreasing the acid or salt
concentration. For many cations KD
values obtained with CLEVASOL
are significantly higher then valuesof the common used cationexchanger AG 50W-X8. By adding
chelating ligands to solutions
containing cations of transition
metals, KD value remains very highFig. 1. Colour change from(~104) even at very high aciddark grey (H+-form) toconcentrations.
yellow (Na+-form).
CLEVASOL can find application
also in nuclear medicine, where ion exchangers are used toseparate or purify medical radionuclides. It is especiallysuited for the separation of heavy monovalent cations (Cs, Tl,Ag) from various cation mixtures. CLEVASOL can be also
employed for group separations of mono-, di-, and trivalentcations.
Columnexperiments
showedthatthechromatographic separation of divalent and trivalent cations
is feasible on CLEVASOL, even when one element is present
in macro amounts.



CLEVASOL is used usually as a solid cation exchanger
loaded with H3O+ ions. The determined total ion-exchange
capacity of the resin is 5.4±0.2 meq/g. We found that
CLEVASOL has a high stability against ionizing radiation.
Irradiating the resin with gamma-rays from 60Co, an integral
dose of ~6·106 Gray did not cause any changes in the ionexchange capacity. CLEVASOL is chemically stable and notsoluble in concentrated acids, bases, and in common organic
solvents. A change of CLEVASOL colour from dark grey to 

III. PROPERTIES OF CLEVASOL





















Fig. 2. Distribution coefficients of bi-, trivalent cations and Cs+ in acidsolutions.

－ 133 －

23-FKP-19
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Estimation of I-131/I-129 ratios and vertical distribution of radioiodine in soil
collected from Fukushima Prefecture
N. INAGAWA1, Y. MURAMATSU1, T. OHNO1, T. TOYAMA1, C. SATOU2, M. OUTSUKI3,
T. MATSUZAKI4
1

Gakushuin University
Fukushima Agricultural Technology Centre
3
Tohoku University
4
University of Tokyo

2

Keywords – I-131, I-129, I-131/I-129 raitos, vertical distribution ofradioiodine

I. INTRODUCTION
A severe nuclear accident occurred at Fukushima Daiichi
nuclear power plant in March 2011, resulting in the release ofenormous amounts of I-131 and Cs-137. Subsequently, soils
in Fukushima Prefecture were contaminated. Becauseradioiodine accumulates in thyroid glands in human body, it
is important to obtain data of I-131 in the environment at thetime of the accident. However, I-131 was below the detection
limit after a few months because its short half-life of 8.02
days. On the other hand, I-129 released simultaneously with
I-131 still remained in soil in Fukushima Prefecture, due to
its long half-life of 1.57 × 107 years. Therefore, we
determined I-129 in Fukushima soil samples in which I-131
concentrations were known, and calculated I-131/I-129 ratios
for radioiodine derived from the Fukushima accident.
II. EXPERIMENTALSThe soil sample collected in Fukushima Prefecture after
the accident was measured for I-131 and Cs-137 byGe-detector. Soil samples were dried and pulverized with ballmill. The powdered sample was placed in in a quartz tube andheated at 1000� to collect the evaporated iodine in alkaline
trap solution (TMAH). Stable iodine (I-127) concentrations in
the trap solution were measured by ICP-MS. Solvent
extraction was performed using remaining solution, andiodine was separated and purified. Silver nitrate was added toprecipitate AgI as a target for AMS and the I-129/I-127 ratios
were measured for about 150 samples. For the estimation of
I-129 concentrations the I-129/I-127 ratios and I-127
concentrations were used.

III. RESULTS AND DISCUSSION

The observed concentration of I-129 in soil samples
showed a wide range, (4.1×10 -5 to 6.3×10-2 Bq/kg). It isinterested to note that a good correlation was found between
the concentrations of I-131 and I-129. This finding suggests
the possibility to estimate previous I-131 levels in soil
samples through the analysis of I-129. We obtained anaverage I-131/I-129 ratio as (2.1 ± 0.7) × 107. However, due
to the variations in the data, it is possible that the ratios aredifferent according to the area.
We examined the depth distribution of I-129 and Cs-137 forinvestigating their behavior in soil. Most of the nuclides were
found to be retained in surface soil. If we compare the
distribution pattern for these two nuclides, we found that
I-129 moved deeper than Cs-137. We also examined different
soils such as wheat field, rice field and forest soils. It was
found that I-129 did not migrate deeper in rice field(uncultivated) because of its dense nature, while in wheat
field (uncultivated) I-129 penetrated deeper due to its highporosity. In case of forest soils, about 90% retained in thelayer of leaf litters.
18
131I ( ×105 Bq / kg )I-131 was released by the accident of Fukushima Daiichi Nuclear
Power Plant. However, due to its short half-life and there are notenough data for this nuclide to understand its dispersal. In this study
we determined I-129 (half-life: 1.57×107 years) in soil samples by
AMS for estimating I-131/I-129 ratios. We also studied vertical
distribution of radioiodine in soil and compared it with the profile ofradiocesium in soil.

15
12
9
6
y = 2.11×107x
R² = 0.97

3
0

0

2

4

129� ( ×10-2Bq / kg )6

8

Fig.1 Relationship between the concentration of I-129 andthat of I-131－ 134 －

23-FKP-20
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effects of soil types on the transfer of radiocesium to plant
K. ODA1, Y. MURAMATSU1, T. OHNO1, T. KOBAYASHI2, S. FUJIMURA2
1

Gakushuin University
Fukushima Agricultural Technology Centre

2

Following the accident of Fukushima Daiichi Nuclear Power Plant,
radiocesium was detected in agricultural crops cultivated in
Fukushima Prefecture. Although the activity levels in crops
significantly decreased in second year, some crops still exceeded theguideline (100 Bq/kg). In this study we cultivate agricultural crops
using different types of soils contaminated by the accident anddiscuss the mechanisms of transfer.
Keywords – radiocesium, soil-plant transfer, agricultural crops

I. INTRODUCTION
Agricultural fields in Fukushima Prefecture were
contaminated with radiocesium released from the accident ofFukushima Daiichi Nuclear Power Plant. From a perspectiveof agricultural safety, Cs-137 (half-life 30.1 y) and Cs-134(half-life 2.06 y) are very important. Following the accident,
radiocesium was detected in many agricultural crops. Morethan 2 years after the accident, however, some crops stillshow high concentrations. The mechanisms responsible forthe transfer of radiocesium from soil to plants are poorly
understood. Therefore, we investigated radiocesium andstable element concentrations in agricultural crops grown in
different types of soils. For the purpose of our investigation,soils were collected from the contaminated fields inFukushima Prefecture. We discuss mechanisms ofradiocesium transfer with special reference to the soil
characteristics in this study.
II. EXPERIMENTALS
Cultivation experiments using soil that was contaminatedwith radiocesium were carried out in Fukushima Agricultural
Technology Centre and the radiocesium concentrations ofboth soil and plant samples were determined by a Ge-detector
at Gakushuin University. Four different types of soil
collected in Fukushima Prefecture were used in our
experiments. The plant samples used in these experiments
are: komatsuna (a leafy vegetable) and rice plants. The plants
were cultivated in Wagner pots (3 L) in a greenhouse at
Fukushima Agricultural Technology Centre. Some soils weremixed with contaminated fallen leaves or humus in order toexamine whether there is a relationship between the transferof radiocesium and the organic content of the soils. The soil
and plant samples were decomposed with acid to determine
concentrations of stable elements by ICP-MS. In addition, we
operated extraction experiments with ammonium acetate toverify whether there is any correlation between the extractible
radiocesium and the transfer factor to plants.
III.

RESULTS AND DISCUSSIONRadiocesium concentrations in both the paddy rice and thekomatsuna harvested in this study were found to be
influenced by the soil types. The highest values for transfer
coefficient were observed in agricultural crops grown inbrown forest soils, while the plants cultivated in gray lowland
soil showed the lowest values.
In order to compare soils with different radiocesium levels,
we collected them from the top layer with high radiocesium
concentrations (upper 5 cm) and from the underlying soil
with lower concentrations (5–15 cm). We cultivatedkomatsuna and found that the transfer coefficients of plants
grown in the underlying soils are greater than the transfer
coefficients of komatsuna planted in the surface soils. Thismight be related to the speciation of radiocesium in the soils.
Deeper layers may have more labile, plant-available
radiocesium, while less labile particulate-bound radiocesium
from the accident may be more common in the surface soils.
Additionally, we also noted that the transfer coefficients ofkomatsuna cultivated with the underlying soils mixed withcontaminated fallen leaves or humus are higher than thetransfer coefficients of komatsuna grown with underlying
soils alone. Therefore, we speculate that the radiocesium thatexists in organic materials is more mobile, and is
subsequently more readily taken up by plants.
As a result of the analysis of stable cesium, we found that
komatsuna absorbed more radiocesium than stable cesium. It
would seem that stable cesium exists in a less labile form andis adsorbed tightly within the soils, particularly clay minerals.
The extraction experiments show that there is no clear
relationship between transfer coefficients and the proportionof radiocesium that is extractable along with potassium using
ammonium acetate. Further research should be done anothermethodologies for extracting plant-available radiocesium
from soil.

－ 135 －

23-FKP-21

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Temporal distribution of plutonium isotopes in marine sediments off Fukushima
and Ibaraki after the Fukushima Dai-ichi Nuclear Power Plant accident

Wenting Bu1,2, Jian Zheng*2, Tatsuo Aono2, Shigeyoshi Otosaka3, Keiko Tagami2, Qiuju Guo1, Shigeo
Uchida2
1

School of Physics, Peking University, China
National Institute of Radiological Sciences, Japan
3
Japan Atomic Energy Agency, Japan

2

Large amounts of radionuclides were released into theatmosphere as well as discharged into the sea as aconsequence of the Fukushima Dai-ichi Nuclear Power
Plant (FDNPP) accident caused by the earthquake andsubsequent tsunami on March 11, 2011. The radionuclide
contamination in the marine environment due to the
FDNPP accident is of great public and scientific concern.
Radiocesium (137Cs and 134Cs) were detected in thesediment traps in the deep sea in Pacific Ocean one monthafter the FDNPP accident, indicating the quickincorporating of radiocesium in seawater with thesediments.[1] In the coastal area of Fukushima and Ibaraki,
spatial and temporal distributions of radiocesium in themarine sediments from June 2011 to February 2012 were
determined.[2,3] Nevertheless, information about thetemporal distribution of Pu in the sediments off Fukushima
and Ibaraki after the FDNPP accident is limited.
Plutonium isotopes derived from the FDNPP accident
have been detected in the soil and liter samples in the 20-30
km zone around the FDNPP, revealing the release of Pu
from the accident.[4] In our previous works, we determinedthe distribution of Pu isotopes in the marine sediments off
Fukushima and Ibaraki collected from April 2011 to July
2012, and observed no detectable Pu contamination fromthe FDNPP accident.[5,6] However, as no information about
the Pu isotopes in the discharged liquids from the FDNPP
accident is available to date and the release of radionuclides
from the FDNPP site continued one year after the accident,
Pu contamination in the marine sediments off Fukushimaneeds continuous investigation.[7]In this work, we determined vertical distribution of Pu
activities and Pu atom ratios (240Pu/239Pu and 241Pu/239Pu) ina sediment core collected from the coastal areas off
Fukushima in January 2013. For the analysis of Pu isotopes,
ca. 2.0 g dried sediment sample was weighted out andspiked with 1 pg 242Pu as yield monitor. The extraction of
Pu was performed in a Teflon tube with 20 mL
concentrated HNO3 on a hot plate at 180-200ºC for at least
4 h. A two-stage anion-exchange chromatographic method
was employed for the separation of Pu and for the further
purification of Pu prior to the ICP-MS analysis. Combinedwith our previous results, the temporal distribution of Pu
isotopes in marine sediments off Fukushima and Ibaraki
will be discussed to understand the source and transport of
Pu in the sediments after the FDNPP accident.

Acknowledgments This work was supported by the
Agency for Natural Resources and Energy, the Ministry of
Economy, Trade and Industry (METI), Japan, and partly
supported by the Ministry of Education, Culture, Sports,
Sciences and Technology (MEXT) (24110004), Japan.
References[1] Honda, M. C., Kawakami, H., Watanabe, S. et al., Biogeosciences
Discuss., 10, 2455-2477, 2013.
[2] Otosaka, S. and Kobayashi, T., Environ. Monit. Assess, doi:10.1007/
s 10661-012-2956-7, 2012.
[3] Kusakabe, M., Oikawa, S., Takata, H. et al., Biogeosciences Discuss.,
10, 4819-4850, 2013.
[4] Zheng, J., Tagami, K., Watanabe, Y. et al., Sci. Rep., 2: 304,
doi:10.1 038/srep00304, 2012.
[5] Zheng, J., Aono, T., Uchida, S. et al., Geochem. J., 46, 361-369,
2012.
[6] Bu, W. T., Zheng, J., Aono, T. et al., Biogeosciences Discuss., 10,643-680, 2013.
[7] Kanda, J., Biogeosciences Discuss., 10, 3577-3595, 2013.

－ 136 －

23-FKP-22
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Evaluation of Iodine-129 mobility and deposition amount in the soil contaminated by
the Fukushima Daiichi nuclear power plant accident
Maki Honda1, Hiroyuki Matsuzaki2, Takeyasu Yamagata 3, Yoko (Sunohara)Tuchiya2, Chuichiro
Nakano2, Yuki Matsushi4, Yuji Maejima5, Hisao Nagai3
1

2

Graduate School of Integrated Basic Sciences, Nihon university, Japan
Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, Japan
3
College Humanities and Sciences, Nihon University, Japan
4
Disaster Prevention Research Institute, Kyoto University, Japan
5
National Institute for Agro-Environmental Sciences, Japan

Abstract – Iodine-129 depth profiles of 13 soil cores were analyzed
to evaluate the 129I distribution and mobility in soil. The cores were
sampled from various fields around the Fukushima Daiichi Nuclear
Power Plant (FDNPP). Four cores out of the 13 were collected fromalmost the same position in Kawauchi village crop field 20 km apartfrom FDNPP at different times between May 2011 and June 2012 toobserve the temporal variation of depth profile of 129I in soil. Clear
enhancement of the accidental origin 129I was observed but nopositive evidence of 129I migration was found. Other 9 cores werecollected from various fields including crop fields and man-madesoils within 30 km from FDNPP on June 2012. These cores showedlarge variation of depth profile of FDNPP origin 129I. The fractionof top 5 cm to the total inventory was varied from 56% to 100%.
Keywords – FDNPP accident, Iodine-129 concentration depth
profile, crop fieldI.

INTRODUCTIONFDNPP accident (on 11 March, 2011) released a large amount ofradionuclide into atmosphere such as 129I (T1/2= 1.57x107 y), 131I
(T1/2= 8.01d). Subsequently it caused extensive radioactive
contamination. Among them, 131I is absolutely essential radionuclide
for the estimation of primary dose. However the data on deposition
amount and distribution pattern of 131I most contaminated area, istotally lacking because of its short half-life. Through the 129I data,
the 131I levels at the time of accident can be estimated [2]. The
accidental origin 129I has also a great potential as a geographic andoceanographic tracer [3]. Predominant source of 129I in global
environment, including Japan, before FDNPP accident have been
two large nuclear reprocessing facilities at Sellafield and La Hauge.
They have released 129I totally over 1.03 TBq (7.35x1026 atoms) [4] toatmosphere. To evaluate the distribution and the mobility of 129I, it isessential to identify 129I of FDNPP origin from that of previously
existed. From this point, crop field is ideal because soil should havebeen tilled and well mixed by farmers to the depth of around 30cm
until just before the FDNPP accident. Therefore it is speculated thatthe crop field soil had been made homogeneous, so that the direct
accumulation from the accident should be clearly observed. Thiswas confirmed by the observations that depth profiles of 127I
concentration, as well as carbon content, of these soil cores wereroughly constant.
II. EXPERIMANTAL PROCEDURE
Collected column soil was cut into 1.5 or 3 cm layers. The soil
sample were first dried by oven (80�, 48h). Then homogenized

well. An amount of about 0.2 or 0.5 g was mixed with V2O5 in aceramic boat and placed in a quartz tube. The sample is then heatedat 990 � under a flow of oxygen gas and water vapor. The
evaporated iodine is collected with a trap solution (2% TMAH
solution). (Here, an aliquot was separated for ICP-MS for thedetermination of the stable iodine concentration.) Iodine in thealiquot of trap solution (2-9 mL) with 2-4 mg iodine carrier ispurified by a sequential solvent extraction and back extraction and a
finally extracted as AgI precipitation. Extracted AgI was dried welland pressed into a cathode of AMS system. 129I was measured at
MALT-AMS system, The University of Tokyo.
III. RESULTS AND DISCUSSION

The 129I depth profiles of four cores from Kawauchi villagecommonly showed particularly high concentration at the top mostlayer, steep exponential decrease as a depth and constant blow 10cm depth (Fig. 1). This enhancement in the top 10 cm layer can beconsidered as the direct accumulation from the FDNPP after theaccident. However no positive evidence of 129I migration was foundbecause there was only a small difference among these profiles
which can easily explained by the spatial variation of 129I deposition
amount suggested by other observation [1]. In any of the four cores,
more than 89% of FDNPP origin 129I was existed within top 5 cm
and 98% within top 10 cm. Other 9 cores showed larger variation of
depth profile of FDNPP
origin 129I. Especially thefraction of total inventory
existed within top 5 cm
were varied from 56% to100%. This large profile
variation for crop fieldand Man-made soil
should be controlled by
the soil properties such as
porosity. Sampling site
and/orshouldbecarefully chosen not tounderestimate the total
Fig. 1 Proportion of F1NPP generated 129I
deposition amount of 129I
per depth in Kawauchi village crop fieldoriginated from FDNPP.
[1]
[2]
[3]
[4]

－ 137 －

T. Ohno et al., J. Radiat. Res. 50, 325-332, 2009
S. K. Sahoo et al., Geochem. Cosmochim. Acta 63, 1927-1938, 2009
U. Rao et al., Geochem. Cosmochim. Acta 63, 1927-1938, 1999
UNSCEAR 2008, Annex C

23-FKP-23
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Vertical distribution of the Fukushima-derived radiocesium in the western North
Pacific in January and February 2011
Yuichiro Kumamoto1, Akihiko Murata1, Takeshi Kawano1, Michio Aoyama2
1

Japan Agency for Marine-Earth Science and Technology, Japan
2
Meteorological Research Institute, Japan

Abstract – The radiocesium in seawaters from surface to 800-m
depth at stations more than hundreds km away from the Fukushima
Dai-ichi nuclear power plants in the western North Pacific Ocean
were measured in January and February 2012. Activity of the
Fukushima-derived Cs-134 in the surface mixed layer (0 ~ 200-m
depth approx.) was highest (~ 20 Bq m-3) in the transition area
between the subarctic (north of 40°N approx.) and subtropicalregions (south of 35°N approx.), which was due to the directdischarge of radiocesium from the plants. In the subtropical region,
we observed Cs-134 maxima just below the mixing layer (200 ~ 300m depth approx.). The Cs-134 activities in the maxima corresponded
to those in the surface mixed layers in the transition area, which
implies that the Cs-134-rich waters in the transition area have beentransported southwardly to the subtropical region across theKuroshio Extension Current along isopycnal layers.
Keywords – Fukushima Dai-ichi nuclear power plants, radiocesium,
North Pacific OceanI.

INTRODUCTION

The massive Tohoku earthquake and consequent giant
tsunami of March 11, 2011 resulted in global releases ofradiocesium (Cs-134 and Cs-137) from the Fukushima Daiichi nuclear power plants (FDNPPs). In the North Pacific
Ocean, a large portion of Fukushima-derived radiocesium has
been settled in both through atmospheric deposition anddirect discharge of contaminated waters. The total amount of
the radiocesium derived from the direct discharge wasestimated to be about 4 PBq for Cs-137 (Kawamura et al,2011 [1]; Tsumune et al., 2012 [2]; Estournel et al., 2012[3]).
On the other hand, evaluation of the radiocesium derived
from the atmospheric deposition contains large uncertainty
mostly due to the restriction of available data in the vast
North Pacific Ocean. In particular, vertical distribution of the
Fukushima-derived radiocesium in the open ocean is hardly
known. We measured the radiocesium in seawaters fromsurface to 800-m depth at stations more than hundreds kmaway from FDNPPs in the western North Pacific Ocean in
January and February 2012.
II. METHODS

filtrated and acidified by nitric acid on board. Radiocesium inthe seawater was concentrated onto ammonium
molybdophosphate (AMP). The radiocesium in the AMP/Cs
compound was measured using a gamma-spectrometry withwell-type Ge detector. Detection limit of the radiocesium
measurement was 0.2 ~ 0.3 Bq m-3. Uncertainties for themeasurement was about 8 %. The radiocesium decay werecorrected to the sampling date.
III. RESULTS AND DISCUSSION
Before the FDNPPs accident, Cs-134 derived from thenuclear weapon tests and the Chernobyl accident was notdetected in the environment because of its short half-life(about 2 years). Therefore Cs-134 observed in the North
Pacific was derived from FDNPPs after the accident. Cs-134
was found in surface waters at all the stations from 20°N to
42°N about ten months after the disaster. Activity of Cs-134
in the surface mixed layer (0 ~ 200-m depth approx.) was
highest (~ 20 Bq m-3) in the transition area between thesubarctic (north of 40°N approx.) and subtropical regions(south of 35°N approx.). Those in the subarctic andsubtropical regions were less than 5 and 1 Bq m-3,
respectively. This meridional distribution was due to thedirect discharge of radiocesium into the transition area from
FDNPPs located at 37.4°N/ 141.0°E.
Below the surface mixed layer Cs-134 activity decreased
sharply and was not detected in deeper layers than 400-m
depth at stations in the subarctic region and transition area,
which is explained by vertical one-dimensional penetration ofradiocesium from the surface mixed layer to the deeper layers.
However, at stations in the subtropical region, south of theKuroshio Extension Current, we observed Cs-134 maxima
just below the mixing layer (200 ~ 300-m depth approx.). The
Cs-134 activities in the maxima corresponded to those in thesurface mixed layers in the transition area, which implies that
the Cs-134-rich waters in the transition area have beentransported southwardly to the subtropical region across theKuroshio Extension Current along isopycnal layers.
[1]

We conducted water sampling during a cruise of R/VMirai, Japan Agency of Marine-Earth Science andTechnology (MR11-08) along the 149°E meridional line
approximately. The seawater samples were collected into 20L cubitainers using a bucket and a conductivity-temperaturedepth rosette with Niskin water samplers. The sample were

[2]
[3]

－ 138 －

Kawamura, H., Kobayashi, T., Furuno, A., In, T., Ishikawa, Y.,
Nakayama, T., Shima, S., and Awaji, T., J. Nucl. Sci. Technol., 48,
1349–1356, 2011.
Tsumune, D., Tsubono, T., Aoyama, M., and Hirose, K., J. Environ.
Radioactiv., 111, 100–108, doi:10.1016/j.jenvrad.2011.10.007, 2012.
Estournel, C., Bosc, E., Bocquet, M., Ulses, C., Marsaleix, P., Winiarek,
V., Osvath, I., Nguyen, C., Duhaut, T., Lyard, F., Michaud, H., andAuclair, F.,J. Geophys. Res., 117, C11014, doi:10.1029/2012JC007933,
2012.

23-FKP-24

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effect of Application Timing of Potassium Fertilizer on Root Uptake of 137Cs in
Brown Rice
Takashi Saito1, Kazuhira Takahashi1, Tomoyuki Makino2, Hirofumi Tsukada3, 4,
Mutsuto Sato1, Kunio Yoshioka1
1

2

Fukushima Agricultural Technology Centre,
National Institute for Agro-Environmental Sciences
3
Institute for Environmental Sciences
4
Fukushima University

Abstract – We have already reported that potassium fertilizer iseffective to reduce radiocesium in brown rice. In this study, we
tried to find the most appropriate timing for potassium fertilizer
application during the rice cultivation period in terms of 137Csconcentrations in brown rice. The concentration of 137Cs in brownrice cultivated without application of potassium fertilizer was 32
Bq
kg-1, while that with application of basal fertilizer including
potassium was 5 Bq kg-1. The concentration of 137Cs in brown rice
was increased with the late application timing. Therefore,
application of potassium fertilizer in the early growing period
reduced the uptake of 137Cs by rice plant from contaminated soils
effectively.
Keywords –137Cs, Brown rice, Potassium fertilizer, Soil-to- brownrice transfer factor

I.

INTRODUCTION

After the accident of Fukushima Daiichi Nuclear Power
Plant, in 2011, the concentration of radiocesium in brownrice collected in some areas of Fukushima prefecture
exceeded the provisional regulation value for brown rice
(500Bq kg -1). It is reported that the concentration ofradiocesium in brown rice decreases with increasingexchangeable potassium concentrations in soil (Saito et al,2012). In terms of more positive application method ofpotassium fertilizer for reducing radioactive concentrationin rice, concentrations of 137Cs in brown rice according toapplication timing of potassium fertilizer were investigatedin the present study.

we collected soil from the vicinity of the rice plant. Afterthe soil samples were air-dried for 21 days, the soil in eachsample was properly mixed and sieved through a 2 mmsieve. Rice seeds were collected from the soil where thesoil was sampled. After threshing rice samples were passed
through a 1.80-mm sieve and grains remained on the sieve
were used for the analysis. The dried soil was compressed
into cylindrical polystyrene containers. The brown rice
samples were compressed into 0.7 L Marinelli beakers. The
concentration of 137Cs in the soil and brown rice were
measured using a Ge gamma- ray detector connected to a
multichannnel analyzer system by counting for 3600-7200s.
III. RESULTS AND DISCUSSIONSThe concentration range of 137Cs in the soils of theexperimental plot was 3262-3983 Bq kg-1. The 137Csconcentration in brown rice cultivated without potassium
fertilizer was 32 Bq kg-1, while that decreased to 5 Bq kg-1
with application of basal potassium fertilizer. On the other
hand, the 137Cs concentrations of brown rice to whichpotassium fertilizer was applied at 50, 70 and 80 d after
transplanting were 15, 23 and 36 Bq kg-1, respectively. As aresult, the concentrations of radiocesium in brown riceincreased with late application timing. These results showthat application of potassium fertilizer in the early growing
period decreases the uptake of 137Cs by rice plants fromcontaminated soils effectively.

II. MATERIALS AND METHODS
A field test was carried out in the northern part of
Fukushima Prefecture. Plowing, puddling and transplanting
were performed on April 20, May 4 and May 10, 2012,
respectively. The planting density was 17.1 hill m-2 (30×19.5 cm). The nitrogen and phosphorus fertilizer (g m-2)
were applied to each plot of paddy field in the proportion
6.0:10 (N-P2O5) on April 17, 2012. The potassium fertilizer
was applied to each plot of the field at a rate of 8.0 g m-2
before plowing, 50, 70 and 80 day after transplanting,respectively.
Rice straw had been applied to the test field every year.
The soil in the rice paddy field was classified as Gray
lowland soil. Soil samples (at the depth of 0-15cm) werecollected from each plot of experimental rice paddy field
after the cultivation of the rice plant on September 19, 2012.
In order to determine the soil-to brown rice transfer factor,

Fig.1 Concentrations of 137Cs in brown rice by differenceof application timing using potassium fertilizer[1]－ 139 －

Saito T et al : Effect of potassium application on root uptake ofradiocesium in rice, KUR Research Program for Scientific Basis of
Nuclear Safety, 165-170, 2012

23-FKP-25

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Low levels of 134Cs and 137Cs in bottom sediments along the Japanese Archipelagoside of the Sea of Japan after the Fukushima Dai-ichi NPP accident
M. Inoue1,*, S. Ochiai1, T. Murakami1, S. Oikawa2,
M. Yamamoto1, S. Nagao1, Y. Hamajima1, H. Kofuji1, J. Misonoo2
1

Low Level Radioactivity Laboratory, Kanazawa University
Marine Ecology Research Institute2

Abstract

38.5

We examined radiocesium concentrations in bottom sediment

5

0

0
2

0
0

2

0
0
2

0
0
5
1

samples collected along the Japanese Archipelago side of the Sea

1

Latitude (degree)of Japan before/after the Fukushima Dai-ichi Nuclear Power
Plant (FDNPP) accident. Low levels of 134Cs were detected in anarea located near estuaries. This was considered to be due to theriverine discharge rather than direct radioactive depositions tosea surface.

0

0

38.0
0
2

1500

0

0

37.0

� D2
�D1

0

0
2

Niigata� Agano

River

Agano
River
ShinanoRiver
Shinano
River

138.5

139.0

0

138.0

Sea of
Japan

�Da

0

50

Fukushima Dai-ichi Nuclear Power Plant accident

0

�Db

37.5
1

Key words- radiocesium; bottom sediment; riverine discharge;

0

0
0

139.5

Longitude (degree)

Fig. 1 sampling sites for sediment samples

I. INTRODUCTION
The FDNPP accident on March 11, 2011 resulted in134

in 2011) in contrary to the sediments at other coastal areas

Cs (half-life:

along the Japanese Archipelago side which were below theCs (30.2 y) to the atmosphere and to land anddetectable limit [1]. In estuary areas, particle materials playsea surfaces over a wide region of eastern Japan. We

important roles in the transportation of radiocesium. Due tothe widespread release of large amounts of
2.06 y) and137

Cs concentrations in sediment

the existence of the thermocline, the contamination of 134Cs

samples collected in the Japanese Archipelago side of thein sediment samples in area D could not be ascribed to the

Sea of Japan in May 2011, which indicated the slightcontribution

contamination of the FDNPP-derived radiocesium in a

downward water circulation, but to the transportation of thesediment sample from site D1 (Fig. 1) [1]. In the present

reactive fraction together with particle materials. Agano

analyzed thestudy,

we134

Cs andexamined137

radiocesium

concentrations

of

of

the

solublefraction

accompanying

River and Shinano River meet around area D. Detection of

sediments in area D and clarify delivery process of134radiocesium from the FDNPP.

introduction of contaminated riverine particles from theCs in samples collected in May 2011 suggests thatestuary may lead to radiocesium contamination in thesediment samples, showing immediate transportation

II. SAMPLES and EXPERIMENTAL
We collected a total of 11 bottom sediment samples(0–3 cm depths) at four sites in Niigata offshore (D) area(within 1–2 months) of radioactive particle materials to thebottom

of

this

area.

Furtherclarification

of
134

the

(230–530 m depths) during 2010–2012 (Fig. 1). Sedimentcontamination levels and delivery patterns forsamples were freeze-dried and crushed into a powder with137

an agate mortar after washing with distilled water (5–25 g-

sediment samples, including riverine sediments. This is andry). �-Spectrometry was performed on all samples using

operation that we are currently engaged in.

Cs andCs in this area can be achieved by obtaining additional

Ge-detectors designed for low-background counting andlocated at the Ogoya Underground Laboratory [2].

References[1] Inoue, M. et al. (2013) Appl. Radiat. Isot. (in press)

III. RESULTS and DISCUSSION
In area D,

134[2] Hamajima, Y. and Komura, K. (2004) Appl. Radiat. Isot. 61, 179-183

Cs was detected in bottom sediments

collected in 2011 and 2012 (e.g., 7.7 mBq/g-dry at site D2－ 140 －

23-NCP-01

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The heavy-ion reactions 238U + 238U and 238U + 248Cm and actinide
production close to the barrier revisited
1

J.V. Kratz1a, M. Schädel1b, H.W. Gäggeler1c

Gesellschaft für Schwerionenforschung mbH, 64291 Darmstadt, Germany
currently at Institut für Kernchemie, Johannes Gutenberg-Universität, 55099 Mainz, Germanybcurrently at Advanced Science Research Center, Japan Atomic Energy Agency, Tokai-mura,
Ibaraki 319-1195, Japanccurrently at Paul Scherrer Institut, 5232 Villigen, SwitzerlandaKeywords – Quasi-elastic and damped collisions/Sequential
fission/Total kinetic energy loss/Production of surviving heavy
actinides/Excitation functions/Survival probabilities

Recent theoretical work [1,2] has renewed interest inradiochemically determined isotope distributions inreactions of 238U projectiles with heavy targets that had
previously been published only in parts [3,4]. These data���� ������ ����������� ���� ������ ��������� ��Z) below theuranium target have been determined as a function ofincident energy in thick-target bombardments. These arecompared to predictions by a diffusion model [5] whereby
consistency with the experimental data is found in theenergy intervals 7.65 – 8.30 MeV/u and 6.06 – 7.50 MeV/u.
In the energy interval 6.06 – 6.49 MeV/u, the experimental
data are lower by a factor of 5 compared to the diffusion
model prediction indicating a threshold behaviour formassive charge and mass transfer close to the barrier. For
the intermediate energy interval, the missing mass between
the primary fragment masses deduced from the generalised
Qgg systematics including neutron pair-breaking corrections
and the centroid of the experimental isotope distributions as
a function of Z have been used to determine the average
excitation energy as a function of Z. From this, the Z
dependence of the average total kinetic-energy loss

independent of the bombarding energy indicating that thesame bins of excitation energy are responsible for the
production of these fissile isotopes. A comparison of thesurvival probabilities of the residues of equal charge andneutron transfers in the reactions of 238U projectiles witheither 238U or 248Cm targets [4] is consistent with this cutoff
as evaporation calculations assign the surviving heavy
actinides to the 3n and/or 4n evaporation channels.
[1]
[2]
[3]
[4]
[5]
[6]
[7]

T K E L has been determined. This is compared to thatmeasured in a thin-target counter experiment at 7.42
MeV/u [6,7]. For small charge transfers, the values ofT K E L of this work are typically about 30 MeV lower
than in the thin-target experiment with the difference
decreasing with increasing charge transfer developing intoeven slightly larger values in the thick-target experiment
for the largest charge transfers. This is the expectedbehaviour which is also found in a comparison of thepartial cross sections for quasi-elastic and deep-inelastic
reactions in both experiments. The cross sections forsurviving heavy actinides, e.g., 98Cf, 99Es, and 100Fm
indicate that these are produced in the low-energy tails of
the dissipated energy distributions, however, with a lowenergy cutoff on the order of 35 MeV. Excitation functions
show that identical isotope distributions are populated－ 141 －

V. Zagrebaev et al., Nucl. Phys. A787, 363c (2007)
V. Zagrebaev et al., Phys. Rev. C78, 034610 (2008)
M. Schädel et al., Phys. Rev. Lett. 41, 469 (1978)
M. Schädel et al., Phys. Rev. Lett. 48, 852 (1982)
C. Riedel et al., Z Physik A290, 385 (1979)
K.D. Hildenbrand et al., Phys. Rev. Lett. 39, 1065 (1977)
H. Freiesleben et al., Z. Physik A292, 171 (1979)

23-NCP-02

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Mechanism of Mo-99 Adsorption and Tc-99m Elution from
Zirconium-Based Material in Mo-99/Tc-99m Generator Column Using
Neutron-Irradiated Natural Molybdenum
Rohadi Awaludin1, Adang Hardi Gunawan1, Hotman Lubis1, Sriyono1, Herlina1, Abdul Mutalib1,
Akihiro Kimura2, Kunihiko Tsuchiya2, Masakazu Tanase3, Masahiro Ishihara2
1

Center for Radioisotope and Radiopharmaceutical, National Nuclear Energy Agency of Indonesia.
rohadi_a@batan.go.id
2
Neutron Irradiation and Testing Reactor Center, Oarai Research and Development Center, Japan Atomic Energy Agency
3
Chiyoda Technol Corporation, Japan
Keywords – adsorption mechanism/Mo-99/Tc-99m radionuclide
generator/neutron-irradiated natural molybdenum

It is expected that the use of fission product Mo-99 for
Tc-99m production can be replaced by neutron-irradiatednatural molybdenum. The challenge in using neutronirradiated molybdenum is that the Mo-99 has low specificradioactivity. Zirconium-based material has a great
opportunity as an adsorbent in Mo-99/Tc-99m radionuclide
generator using neutron-irradiated natural molybdenum
since the material can adsorb molybdenum with highcapacity. However, until now, there is still no data to
explain the mechanism of Mo adsorption and Tc-99m
elution process from the material. It is very important toinvestigate the mechanism for increasing the adsorption
capacity, increasing the Tc-99m elution yield as well as
reducing the Mo-99 breakthrough in Mo-99/Tc-99m
generator using irradiated natural molybdenum. In thisstudy, the Mo-99 adsorption and Tc-99m elution
mechanism were investigated using Scanning Electron
Microscope-Energy Dispersive X-ray Spectroscopy (SEMEDS) to analyze the elemental composition of the material
surfaces before Mo adsorption, after Mo adsorption andafter Tc-99m elution using saline solution. The results werecompared with the value of adsorption capacity of thematerial to irradiated natural Mo and elution yield of Tc99m. From the changes of elemental composition in thesurface, it was found that molybdate ions were adsorbed
into the adsorbent by ion exchange with Cl- ions in thematerial. It was also revealed that Tc-99m can be eluted
from the material column in high oxidation state (99mTcO4-)
since oxidizing agent was needed in the elution process. It
was considered that in lower oxidation state the Tc-99m
easily made coordination bonds with other elements in theadsorbent.

－ 142 －

23-NCP-03
APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013�����������������������������������������������������
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��������������������� �������� ���������������
�������������������� ������� ���������������

Abstract Ð We developed a new gas-filled recoil separator GARIS-II,
which consists of 5 magnets in a Q-D-Q-Q-D configuration, to study
on actinide-based fusion reaction. The solid angle of the separator
was determined to be 18.2 msr measured by a standard �-source of241
Am. Basic characteristics of the separator, such as a backgroundsuppression and transmission, was studied by using fusion products
via well-known nuclear reactions of 169Tm(40Ar,4n)205Fr and208
Pb(40Ar,3n)245Fm, respectively.
Keywords Ð gas-filled recoil ion separator, GARIS, new element,
superheavy element, SHE chemistry��������������������������������������������������������
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23-NCP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Purification of Scintillation Cocktails containing the alpha emitters americium andplutonium
E. Löfström-Engdahl*, G. Skarnemark, K. El Tayara, J. Eriksson, N. Halldin, J. Halleröd, M. Malmberg,
J. Mattiasson Bjugren
Nuclear chemistry, Department of Chemical and Biological Engineering,
Chalmers University of Technology, SE 412 96 Gothenburg, Sweden

ABSTRACT*Corresponding author, elinlo@chalmers.se

One efficient way of measuring alpha emitters is by the usage ofliquid scintillation counting (LSC). A liquid sample is placed in a

scintillation cocktail. In neither the americium nor thevial containing a scintillation cocktail. The alpha particles excite

plutonium system, adverse effects of increasing the volume

electrons in the surrounding liquid, and when they are de-excitedwere detected. The products of the process are a solid fraction

photons are emitted. The photons are detected and the activity canthat can be sent to final storage and a practically non-be quantified. LSC has a high efficiency for alpha radiation and isradioactive liquid fraction that can be sent to municipal

therefore a fast and easy way for measuring alpha emitting samples.

incineration.

One drawback is that it does not differentiate very well between
alpha energies; measurements of for example curium and plutonium
simultaneously are impossible and demand other techniques.

Liquid scintillation counting, Alpha emitting waste, Co-precipitation

Another drawback is the production of a liquid alpha active waste.
In Sweden alpha radioactive waste liquids with an activity oversome kBq per waste container cannot be sent for final storage. If,
however, the activity of the liquids could be reduced by precipitationof the actinides, it would be possible to send away the liquidsamples to municipal incineration. In this work a method for apurification of alpha active scintillation cocktails was developed.
The method was first tried on a lab scale, and then scaled up. Until
today (March, 2013) more than 20 liters of scintillation liquids havesuccessfully been purified from americium and plutonium at
Chalmers University of Technology in Sweden.

The four scintillation cocktails used were Emulsifier Safe®,
Hionic-Fluor®, Ultima Gold AB® and Ultima Gold XR®. The
scintillation cocktails could all be purified from americiumwith higher yield than 95 %. The yield was kept when theliquids were mixed. Also plutonium could be precipitatedwith a yield over 95 % in all cocktails except in HionicFluor® (>55 %). However, that liquid in particular could be
purified (>95 %) by mixing it with the three other cocktails.
Up-scaling was performed to a batch size of 6-8 L of

－ 144 －

23-NCP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Formation and stability of sulfides of the superheavy elements Cn and Fl
1

N.M. Chiera1,2, R. Eichler1,2*, A. Türler 1,2

Department of Chemistry & Biochemistry, University of Berne, Freiestrasse 3, CH-3012 Berne, Switzerland
Laboratory for Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, CH-5232 Villigen, Switzerland

2

First chemistry experiments with Cn and Fl revealed a
relativistic stabilization of their elemental state leading to amuch weaker metallic interaction with gold compared to theirlighter homologues in the groups 12 and 14 of the periodic
table [1,2]. Extrapolative predictions, in which
thermochemical state functions were correlated mutually,
showed that Cn and Fl may form stable sulfides. However,the stability trends in group 12 and 14 are predicted to be
opposite. Hence, FlS is expected to be more stable compared
to CnS. An experimentally exceptionally favourable case forcomparative studies of Cn and Fl is the possibility of asimultaneous production of both elements in Ca-48 induced
nuclear fusion reactions with Pu-242/Pu-244 [3]. The affinityof mercury towards sulfur is well known, and the formationof HgS is thermodynamically favored [4]. Hence, thischemical system is an ideal model system to investigate thekinetics and thermodynamics of the adsorption and reactionof a volatile noble metal with sulfur surfaces. For thispurpose the method of isothermal reaction chromatography isused. Here, first results from these investigations will bepresented. Some conclusions will be drawn, which areimportant for the preparation of further chemical
investigations of Cn and Fl.
[1] R. Eichler et al., Nature 447, 72 (2007)[2] R. Eichler et al., Radiochim. Acta 98, 133 (2010)[3] Y. Oganessian, J. Phys. G: Nucl. Part. Phys, 34 (2007)[4] M. Svensson, Sci. Tot. Env. 368, 418 (2006)－ 145 －

23-NCP-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Development of a Batch-Type Solid-Liquid Extraction Apparatus for Repetitive
Extraction Experiment of Element 104, Rf
Y. Kasamatsu1, T. Yokokita1, A. Kino1, K. Nakamura1, K. Toyomura1, Y. Komori1, N. Takahashi1, H.
Haba2, J. Kanaya2, M. Huang2, Y. Kudou2, T. Yoshimura3, A. Shinohara1
1

2

Graduate School of Science, Osaka University
Nishina Center for Accelerator-Based Science, RIKEN
3Radioisotope Research Center, Osaka University

Abstract – For the extraction of element 104, Rf, an automatic andrapid solid-liquid extraction apparatus by batch method was newly
developed. On-line solid-liquid extraction experiments using an
accelerator were performed in the TIOA/HCl system with 89m,gZr
and 175Hf produced in the nuclear reactions. As a result, thedistribution coefficients in equilibrium were obtained within 10 s in
7–11 M HCl. This indicates the applicability of the present
apparatus to Rf experiment.
Keywords – Solid-liquid extraction, Triisooctylamine (TIOA), Zr, Hf,
Superheavy element

Chemical properties of transactinide elements (Z �� �����
are expected to be characteristic due to strong relativistic
effects on their electronic shells. Therefore, transactinide
chemistry is very fascinating. It is, however, very difficult toperform chemical experiments of these elements because of
their short half-lives and low production rates in the nuclear
reactions. On-line chemical experiments on a “one-atom-at-atime” basis are required. In recent years, the fluoride complex
formation of Rf was successfully investigated under thecondition that chemical equilibrium is attained for its
homologues. To systematically study the complex formationof Rf, we are interested in the chloride complexation of Rf.
Purpose of the present study is to clarify the chloride
complex formation of Rf based on the extraction data inequilibrium and further to investigate time dependence of thechemical behavior of Rf for the first time. In our previous
work [1], solid-liquid extraction of Zr and Hf, thehomologues of Rf, using triisooctylamine (TIOA) from HCl
was performed by batch method. In this work, we newly
developed the automatic apparatus to perform batch-wisesolid-liquid extraction of transactinide elements rapidly andrepeatedly. On-line experiments using this apparatus wereconducted with 89m,gZr and 175Hf tracers produced at the AVF
cyclotron in RIKEN. We investigated the equilibrium time inextraction in several HCl concentrations by determining timedependences of the Kd values.
Schematic view of the solid-liquid extraction apparatus isshown in Fig. 1. Nuclear reaction products transported by thegas-jet system are deposited on the collection site of the
dissolution section and then dissolved with an aqueous
solution. The solution sample passes through two valves anda slider which moves horizontally to three positions, and thenenters a Teflon reactor containing TIOA resin, reactor 1 inFig. 1. After shaking the reactor using a vortex mixer, only

the liquid phase is pneumatically pushed out of the reactor,
and is subjected to the radiation measurement. To measure
the radioactivity on the resin, the control experiment without
the resin is performed using reactor 2. The present apparatus
is controlled by a computer through a LabVIEW system.
In the on-line experiment, 89g,mZr (T1/2 = 3.27 d, 4.18 min)and 175Hf (T1/2 = 70 d) were produced in the 89Y(p,n)89g,mZr
and 175Lu(p,n)175Hf reactions, respectively. Extraction
experiments were performed by the above operations with the
25–57 wt. % TIOA resin (2.6–3.8 mg) and 6–11 M HCl(160–23�����. Shaken time was varied to be from 10 s to 120
s. Remained Zr and Hf on the resin were eluted by washing�����������������������������������������������������3 and0.01 M HF three times. The TIOA resin was reused 3–6 times.
Each solution sample was a������� ��� �-ray spectrometry
using a Ge detector to obtain the Kd values by the equation Kd(mL/g) = [M]resin/[M]soln (M = Zr or Hf).
It was found that the Kd values are basically constant in thestudied time range, and are consistent with those obtained in
our previous batch experiment [1] in 7–11 M of HCl. This
result suggests that chemical reactions in the extraction reachthe equilibrium within 10 s for 89mZr and 175Hf under thepresent experimental conditions. It took about 35 s until theend of elution of the HCl solutions. These results suggest theapplicability of the present apparatus to Rf experiment.

Fig. 1 Schematic view of the solid-liquid extraction apparatus[1]－ 146 －

A. Kino et al., 4th International Conference on the Chemistry andPhysics of the Transactinide Elements, Sochi, Russia, 5-11 Sep. (2011).

23-NCP-07

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Coprecipitation of Zr, Hf, and Th with Sm Hydroxide for Chemical Study of Rf
K. Toyomura1, Y. Kasamatsu1, N. Shiohara1, T. Yokokita1, Y. Komori1, K. Nakamura1,
N. Takahashi1, T. Yoshimura2, H. Haba3, Y. Kudou3, H. Kikunaga4, T. Ohtsuki4, K. Takamiya5,
T. Mitsugashira6, and A. Shinohara1
1

Graduate School of Science, Osaka University

2

Radioisotope Research Center, Osaka University
3

Nishina Center for Accelerator-Based Science

4

Research Center for Electron Photon Science, Tohoku University
5

Research Reactor Institute, Kyoto University

6

International Research Center for Nuclear Materials Science, Institute for Material Research, Tohoku University

Abstract – The purpose of our study is to perform hydroxide

coprecipitation experiments of element 104, rutherfordium (Rf), toinvestigate its complex formation with hydroxide ions. In thiswork, we investigated the hydroxide coprecipitation behaviors of
the group-4 homologues Zr and Hf, and the pseudo homologue Th
in aqueous NH3 and NaOH solutions by coprecipitation methodwith Samarium (Sm) hydroxide. In addition, we developed thesemiautomatic and rapid suction filtration apparatus for
repetitive experiment of Rf, and tested its performance by on-line
experiments of Zr and Hf using an accelerator.
Keywords – Superheavy elements, Rutherfordium, CoprecipitationI.

INTRODUCTION

Elements with the atomic numbers Z � 104 are calledsuperheavy elements (SHEs). They have short half-lives
and are produced only by nuclear reaction with anaccelerator. Therefore, much repetition of rapid
experiments targeting one atom is required. This is why it
is difficult to perform experiments of SHEs, and theirchemical properties are hardly elucidated. So far, chemical
properties of SHEs have been studied mainly bychromatographic methods. Experiments of SHEs in morevarious chemical systems should be performed to study
their chemical properties in more detail. We have beendeveloping a new method to investigate chemical
properties of SHEs.
The purpose of our study is to perform coprecipitation
experiments of element 104, rutherfordium (Rf), toinvestigate its complex formation with hydroxide ions by
the coprecipitation method with samarium (Sm) hydroxide.
By this method [1], we can prepare a precipitate sample
which has good energy resolution in � spectroscopy in a
few min. Therefore, this method is expected to be
applicable to SHE chemistry that requires rapid operations.
In this work, we investigated the hydroxide coprecipitation
behaviors of the group-4 homologues Zr and Hf, and thepseudo homologue Th with Sm in aqueous NH3 and NaOH
solutions with various concentrations. In addition, wedeveloped a semiautomatic and rapid suction filtration
apparatus for repetitive experiments of Rf and tested its
performance by on-line experiments of Zr and Hf using an
accelerator.

II. EXPERIMENTS AND RESULTS
The Sm standard solution (1 M HNO3) with the volume of
20 �L containing 20 �g of Sm was added into the HClsolution containing 88Zr, 175Hf, and 228Th radiotracers. The
solution was stirred and then the basic solution (dilute andconcentrated aqueous NH3, and 0.1–12 M NaOH solutions)
was added. The solution was stirred for 10 s or 10 min. The
solution containing the precipitate was filtrated by suction
with a polypropylene membrane filter. The filtrate wascollected in a vial. Both the precipitate and filtrate weredried on the heater at 100°C. The precipitate, filtrate, andbeaker used were subjected to � and � spectrometry. The
precipitation yields of Zr, Hf, and Th were determined fromeach radioactivity. Above experiments were performedchanging conditions such as solution volume and filter sticksize to determine suitable conditions for Rf experiment.
The precipitation behaviors of Zr, Hf, and Th without Sm
were investigated using macro amounts of Zr, Hf, and Th
samples in the same conditions to coprecipitation
experiments with radioactive tracers.
As a result, the coprecipitation yields of Zr and Hf werelower as concentration of the hydroxide ions increases. On
the other hand, the precipitation yields of Th wereapproximately 100% under all conditions. We observed
clear differences in precipitation yields among theseelements, suggesting that it is possible to investigate thestability of complex formation with hydroxide ions by thismethod. Because precipitation yields of the samples stirred
for 10 s and 10 min were almost the same, it was found thatprecipitate is rapidly formed within 10 s. We were able toprepare a precipitate sample of Th with good energy
resolution in � spectrometry. These results are preferred in
Rf experiment. In the presentation, we will also report thedevelopment of the semiautomatic apparatus and results of
the on-line experiments using an accelerator, and propose
suitable conditions for Rf experiment.
[1]－ 147 －

H. Kikunaga et al.: Appl. Radiat. Isot. 67, 539 (2008).

23-NCP-08

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Development of modified epoxy paint films to reduce the volatile iodine source
term in the containments of LWRs during severe nuclear accidentsaSabrina Tietzea

PhD student, Severe Nuclear Accident Chemistry, Nuclear Chemistry Department, Department of Chemical andBiological Engineering, Chalmers University of Technology, Göteborg, Sweden, sabrina.tietze@chalmers.se

During a severe nuclear accident in a light water
reactor (LWR) significant amounts of iodine will be
released from damaged UO2 fuel into the containment.
Primarily released cesium iodide aerosols and elemental
iodine will partly dissolve in steam or the containment
water pools. The remaining gaseous species can undergo
complex reactions with released radiolysis- (e.g. ozone)
and pyrolysis products such as volatile short chainedorganics released from e.g. cable plastics to form under theconditions of a severe nuclear accident (high temperatures,
high radiation field) a series of different volatile iodine
species. While inorganic iodine oxide aerosols (IOx) arerather water soluble and are likely to deposit on metal
surfaces, organic iodides such as methyl- and ethyl iodide
are less reactive with metal surfaces and more hydrophobic
and thus are more likely to remain in gaseous phase.
While gaseous elemental iodine can be sufficiently trappedwith the currently used charcoal-, spray- and wet-scrubber
filter systems, the used filter materials are less selective fororganic iodides. Thus, both in case of a venting of thecontainment and in case of a failure of the containment
these highly volatile species are more likely to be released
into the environment and cause harm to the public. In caseof a Fukushima like containment pressure increase in a
nuclear power plant which is not equipped with an external
wet-scrubber filter system through which the vented air canbe filtered, significant amounts of both volatile inorganicand organic iodine species will be released into theenvironment.
In modern nuclear power plants bisphenol-A based
epoxy paints are commonly used as coatings within thecontainment. These aromatic rich paints withstand higher
radiation doses and thus they are expected to contribute lessto the formation of highly volatile organic iodides such as
methyl iodide than formerly used (partly) oil based paintfilms.
Experimental studies at Chalmers University ofTechnology on Teknopox Aqua VA epoxy paint, which isrecently used in Swedish and Finish nuclear power plants,
have shown that the paint can chemisorb significant
amounts of both inorganic- and organic iodine species. The
chemisorbed iodine will be partly washed out in steam or
can be revapourised under the increased temperature andgamma irradiation field during a severe nuclear accident.
Attempts are made at Chalmers University ofTechnology to develop a modified epoxy paint to increase
the retention of gaseous iodine species already inside thecontainment. For this purpose different organic andinorganic, irradiation stable, water insoluble and for
different iodine species reactive additives are tested using
e.g. a Co-60 gamma irradiator with a dose rate of 14 kGy/h.

－ 148 －

23-NCP-09

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

New insights into the formation and stability of
Molybdenum carbonyl compounds
1

I. Usoltsev1,2, Wang Yang3, R. Eichler1,2, A. Türler1,2, Qin Zhi3

Department of Chemistry & Biochemistry, University of Berne, Freiestrasse 3, CH-3012 Berne, Switzerland;Laboratory for Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, CH-5232 Villigen, Switzerland;
3
Institute of Modern Physics Lanzhou; Chinese Academy of Sciences, 509 Nanchang Road, CN-730000 Lanzhou, China
2

The “Ms. Piggy” 252Cf spontaneous fission (SF) source
installed at the University of Bern allows for production ofdifferent transition metal fission products with a wide
variety of half-lives. Volatile metal carbonyl compounds
were formed in situ and transported by flushing pure CO or
CO mixed with inert gas (N2, Ar, He) through the recoilchamber of this source at a flow rate of 1 l/min [1]. Thus,
these compounds are available outside of the source forradiochemical experiments. Our work focuses on thedecomposition or thermal stability of the formed complexes.
Therefore, the carbonyl complexes are transported trough a
decomposition column held at variable temperatures
between 25°C and 800°C. The surviving complexes aretrapped in a charcoal filter, which was monitored by a
HPGe gamma-ray detector. The fused silica decompositioncolumn (1 m, 4 mm i.d.) covered by selected stationary
surface materials was heated up within a steel cladding tube
by means of a resistance furnace. By performing a gamma
spectrometric measurement of the charcoal trap
decomposition curves for carbonyl complexes wereobtained. We will discuss here the results obtained for104
Mo. Several different surface materials were examined:
quartz, silver, gold, palladium, and PFA-Teflon®.
Formation and decomposition of the complexes has beenstudied also in dependence on the CO concentration and on
the inert gas used to dilute the CO. Thus, decomposition
curves were obtained for different isotopes and different
carrier gas mixtures, which allowed for determination of apseudo-reaction order on carbon monoxide in the metal
carbonyl formation. For the first time formation of nitrogencontaining carbonyl complexes with the neutral transition
metal atom Mo was observed. It was also shown that thebeta decay of the Mo central atom in the carbonyl complex
does not lead to the formation of volatile compounds of thedaughter nuclide Tc. Obtained results are discussed in thelight of upcoming decomposition studies of transactinide
carbonyl complexes.
[1]

Even J. et al: Inorg. Chem. 51, 6431 (2012).

－ 149 －

23-NCP-10

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Adsorption behavior of super-heavy elements (Z ������
on metal and inert surfaces
1

J. Anton1, T. Jacob1, V. Pershina2

Institut für Elektrochemie, Universität Ulm, Albert-Einstein-Allee 47, D-89069 Ulm, Germany
2
Gesellschaft für Schwerionenforschung, Planckstr 1, D-64291 Darmstadt, Germany

Investigation of chemical and physical properties of theheaviest elements (those beyond Lr) is a hot topic since
several decades. In this time period, many new elements
were discovered and after a proper characterization wereadded to the Periodic Table of the elements. The main
problem of such investigations, however, is the rather shorthalf-life of these elements, which requires the developmentof innovative experimental techniques. Nowadays theresearch focusses on the chemical properties of the element
114. So far, two gas chromatography experiments to study
the interaction strength of element 114 with a gold surface
have been performed with conflicting results. One
experiment [1] reported a weak interaction of element 114
with a gold surface, leading to adsorption only at very low
temperatures of approximately -90°C, while in the second
experiment [2] adsorption on gold has been observed at theroom temperature, indicating a much stronger bond
between element 114 and gold. To resolve this conflict,further experiments on chemical properties of the element
114 will be performed at GSI and PSI/JINR in the next two
years. For theoretical studies, standard quantummechanical packages that treat a system mostly non- or
only scalar-relativistically are not satisfactory: Due torather significant relativistic effects on the electron shells of
the heaviest elements a fully-relativistic four-component
description is required.
Recently, we have studied the adsorption behavior ofelements 112, Cn, and 114 and their lighter homologues Hgand Pb, respectively, on gold surfaces [3] by using acluster-approach [4]. We found that Hg/Cn and Pb/114
prefer different adsorption sites. Also, the adsorptionenergies of elements 112 and 114 are related to those of
their lighter homologues in a different way. Thus, Eb(Cn) is
only slightly (0.1-0.2 eV) lower than Eb(Hg), while Eb(114)
is much lower (1.4 eV) than Eb(Pb). This is due to the fact,that in element 112 both the relativistically stabilized 7s
and destabilized 6d AOs take part in the binding, while forelement 114 binding is mostly determined by the
relativistically stabilized 7p1/2 orbital. In contrast to Pb,
where 6p3/2 strongly contributes to the surface bond, the
7p3/2 participate much less due to its large relativistic
destabilization (the spin-orbit splitting between 7p1/2 and7p372 is about 3.5 eV). Furthermore, binding of element 114
to gold is similar to that of Cn, however, about 0.2 eVstronger. Our predicted sequence in the Eb values is Cn <Hg < E114 << Pb. Thus, we predicted that in thethermochromatography experiments, element 114 will
adsorb right at the beginning of the chromatography
column with the hot end of 35°C, at the position of Hg.
This prediction was recently confirmed experimentally [2].

In this talk we will present theoretical results on
adsorption energies and distances of the elements from 112
to 114 and their homologues on metal (gold) and inert(SiO2) surfaces.
Acknowledgment – J.A. gratefully acknowledges the support by
the Deutsche Forschungsgemeinschaft (DFG) and BMBF
[1]
[2]
[3]
[4]

－ 150 －

R. Eichler et al. Radiochim. Acta, 98, 133 (2010).
A. Yakushev, NUSTAR-SHE-11, GSI Scientic Report 2009.
V. Pershina, J. Anton, and T. Jacob, J.Chem. Phys., 131, 084713(2009).
J. Anton, B. Fricke, E. Engel, Phys. Rev. A69, 012505 (2004).

23-ACP-01

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Structural studies of the Eu(III) and U(VI) interactions with pentapeptides
A. Jeanson1, J. Roques1, S. Safi1, E. Simoni1, D. Aitken2
1

2

IPN - Université Paris Sud, 91406 Orsay Cedex, France
ICMMO - Université Paris Sud, 91406 Orsay Cedex, France

It is of great importance to assess the mechanisms
governing radionuclide impact on the environment(particularly the biosphere) and to unravel the molecular
processes underlying actinide transport and deposition intissues. But most data available on the interaction ofactinides with biological systems are based on
physiological or biokinetic measurements, with scarce
information on the microscopic factors such as structure of
the actinide coordination site within biological molecules(proteins, peptides...). These structural data are essential tounderstand structure, function and affinity interdependence,
which governs the organ deposition of such elements. In
this paper, we will present first results on the complexationof trivalent and hexavalent metals (in a first step, Eu3+ wasused as a surrogate to Am3+ and UO22+ represented the VI
oxydation state) with peptides containing various,
biologically relevant, geometrical constraints. The
pentapeptide sequences contain sequential differences thatinduce conformational change, but relatively close enoughso one parameter was varied at a time. We used the three
DGDGD, ADPDA and DPDPD peptides, since they are
differentiated by the number of proline (P) residues, thatinduce different angular strains. Both experimental(EXAFS, micro-calorimetry, laser fluorescence, ATRFTIR) and theoretical (DFT methodology) approaches havebeen performed in order to determine the structure of theobtained complexes and the consequences on their stability.

－ 151 －

23-ACP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Solubility of Amorphous UO2 and NpO2 in Nitrate Media
Containing Platinum Catalyst
1

Akira Kitamura1, Satoko Shimoda2

Japan Atomic Energy Agency, Tokai, Ibaraki 319-1194, Japan
Mitsubishi Materials Corporation, Naka, Ibaraki 311-0102, Japan2

concentration (mol dm-3)

10-4

no Pt - CFwith Pt - CF
no Pt - 0.45�m

10-5

with Pt - 0.45�m
no Pt - 10kDa
with Pt - 10kDa

10-6
10-7
10-8

DL

10-9
10-6

10-5

10-4
10-3
10-2
10-1
[NaNO3]ini (mol dm-3)

100

101

Fig. 1 – Solubility of UO2(am) as a function of NaNO3 concentration
with/without platinum black

10-4
concentration (mol dm-3)

Significant amount of nitrate salts are contained in a groupof TRU wastes which may be disposed under deep
underground together with high-level radioactive waste.
Nitrate may oxidize redox-sensitive elements, e.g., uranium
and neptunium. Although it was found that no effects ofnitrate on solubility of amorphous neptunium(IV) dioxide(NpO2(am)) was observed under anoxic conditions [1], it isstill concerned that some catalysts may promote redox
reactions between nitrate and elements reduced. Therefore,solubility of NpO2(am) was investigated under nitrate media
containing platinum catalyst. Similar experimental study wasapplied to amorphous uranium(IV) dioxide (UO2(am)) tocompare results with those for NpO2(am).
An oversaturation method was applied to prepare theUO2(am) and NpO2(am) using stock solutions of uranium(VI)and neptunium(V), respectively, with addition of the reducing
agent sodium dithionite (Na2S2O4). After removing thesolution containing Na2S2O4 and washing several times,
various concentration of sodium nitrate (NaNO3) solution
was added to UO2(am) and NpO2(am). A porous platinum
black powder was added to some samples as a catalyst. The
pH of solution was adjusted around 9, and no adjustment ofredox potential was carried out. After contacting from 2
weeks to 5 months, an aliquot of sample solution was pickedup, centrifuged (CF), filtered with 0.45 �m membrane, andfiltered with molecular weight cut-off of 104. All theexperimental procedures were performed in an argon-filled
glove box to avoid contamination of oxygen gas.
The obtained solubility values of UO2(am) and NpO2(am)as a function of NaNO3 concentration are shown in Figs. 1
and 2, respectively. Due to no dependences of nitrateconcentrations on solubility of UO2(am) and NpO2(am)containing platinum black powder, no redox effects of
NaNO3 on their solubility were found. On the other hand, it
was found that the obtained solubility values of UO2(am) andNpO2(am) containing porous platinum black powder werelarger than those without porous platinum black powder.
Considering with large difference of solubility by filtration
types, aqueous uranium and neptunium species may form
colloidal species in lower NaNO3 concentrations and bephysically absorbed into porous platinum black powder inhigher NaNO3 concentrations.
It was found that the oxidation state of uranium solid was
4 even after the solubility experiment using X-ray
diffractometry. According to thermodynamic calculations,the oxidation state of neptunium solid can also be 4.

no Pt - CFwith Pt - CF
no Pt - 0.45�mwith Pt - 0.45�m
no Pt - 10kDa
with Pt - 10kDa

10-5

10-6

10-7
DL
10-8
10-6

10-5

10-4
10-3
10-2
10-1
[NaNO3]ini (mol dm-3)

100

101

Fig. 2 – Solubility of NpO2(am) as a function of NaNO3 concentration
with/without platinum black[1]

M. Mihara et al., Proc. ASME 13th Intl. Conf. on Environmental
Remediation and Radioactive Waste Management (ICEM2010),
October 2010, Tsukuba, Japan, Paper No. ICEM2010-40040 (2010).

This work was performed in the project “TRU waste disposal
technology – Combined development of nitrate salt removal
technology and an assessment system for the impact of nitrateon the co-locational disposal of TRU waste and HLW” in FY
2012 funded by the Ministry of Economy, Trade and Industryof Japan.

－ 152 －

23-ACP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Apparent formation constants of actinide complexes with humic substances
determined by solvent extraction
Takayuki Sasaki1, Yury M. Kulyako2, Katharina Müller3, Taishi Kobayashi1,
Maxim Samsonov2, Boris F. Myasoedov2
1 Department of Nuclear Engineering, Kyoto University, Kyoto daigaku-Katsura, Nishikyo, Kyoto 615-8540, Japan
2
V.I. Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Kosygin str. 19, Moscow, Russia
Helmholtz-Zentrum Dresden-Rossendorf e.V., Institute of Resource Ecology, 510119, D-01314 Dresden, Germany

Abstract – Apparent formation constants of Pu(IV) with two kinds ofhumic substances (HSs) were determined in 0.1M NaClO4 at 25 �Cusing a back-solvent extraction method. The effect of solution
conditions, such as the pH, the initial metal and HS concentrations,and the ionic strength, on the formation constants was investigated.
The obtained data were compared with the other actinide series.
Keywords – Humic substances / Actinides / Apparent formation
constant / Solvent extraction

Organic substances may greatly affect the speciation andsolubility of tetravalent actinides in groundwater, dependingon the complex formation constants, pH, the ionic strength,
the organic ligand-to-metal concentration ratio, and so on. In
order to estimate how these parameters influence the apparent
solubility, reliable thermodynamic data on the interaction oftetravalent actinide ions with counter anions in aqueous
solutions are required in the safety assessment of geologicaldisposal. In the present study, we investigate the formation
constants of Pu(IV) with typical HSs in groundwater.
The formation constants were determined using thesolvent extraction method which was conducted in a similarmanner as described in a previous study [1,2]. The organic
phase of xylene containing thenoyltrifluoroacetone (HTTA)
without further purification and the aqueous phase containing
Pu at a pHc ~3 were placed in a polypropylene tube andshaken by hand for several minutes. The concentration ofPuIV(TTA)4 complexes extracted into the organic phase wasca. 10-6�-9 M, while the hydrophilic polymer/colloidal species
and species with other oxidation states such as PuIII,V(TTA)x
could not be co-extracted under the present condition. Soon
after, the organic phase was isolated and brought into contact
with fresh aqueous phases containing HS of pHc 4 to 8, andionic strength I = 0.1 M (NaClO4). In this back-extraction,
two kinds of humic acids were used. One is the purified
Aldrich humic acid (ALHA). The other is the Elliott soil
humic acid (1S102H, the International Humic SubstanceSociety) abbreviated to SHA. Back-extraction was performed
using a mechanical shaker at 25 ± 1 °C, and the pHc and Ehvalues were measured.
The Eh values were stable at around +0.5–+0.6V (vs.SHE)
throughout the measurement period at the examined pH
values. The predominant species of plutonium was tetravalentstate as discussed in ref. [1]. The concentration in both phases
was determined by alpha spectrometry (5.16MeV). Though
the recovery ratio for Pu was approximately 50% due tostrong adsorption of Pu on the polypropylene vessel wall, theratio was not dependent on the shaking time. Hence, thepresence of the adsorbed Pu was ignored in the analysis.
The apparent formation constant is expressed by thebinary or ternary complex, depending on the definition of thespecies.

�app,q �[M(OH) q L],
[M 4� ][OH]q [R � ]where q=0 or 1 is assumed in the present study. From thedifference of the distribution ratio between the presence (D)and absence (D0) of HSs,log ��
�

D0

� p
� q
� �
�
� � log � 1 � � � OH,p [OH ] � � app,q [OH ] [R ] ��D���
1 � � � OH,p [OH � ] p��

For A = 1 + � ßOH,p[OH]p,log D � log D0 � log( A � � app,q [OH � ]q [R � ]) � log A

where the �OH,p values at a given ionic strength calculated
from specific ion interaction theory (SIT). In Figure, thelog�app values for tetravalent Pu are higher than those for Th
due to an effect of actinide contraction.
30

log�app3

25

Pu(IV) SHA

20

Pu ALHA

15

Th ALHA, SHA

10

Np(V) ALHA, SHA

5
-7

-6

-5

-4
logCR�

-3-2

Fig. Comparison of the log�app (I=0.1 (NaClO4) and 25ºC) values for Pu– and
Th–OH–HS (as q=1) ternary complexes at pH 4 [1] and Np-HS binary
complexes at pH 6 [2] as a function of CR.
[1] T. Sasaki, S. Aoyama, H. Yoshida, Y.M. Kulyako, M. Samsonov, T.
Kobayashi, I. Takagi, B.F. Myasoedov, H. Moriyama, Radiochim. Acta, 100,
737-745 (2012).
[2] K. Müller, T. Sasaki, Radiochim. Acta, 101, 1-6 (2013).

－ 153 －

23-ACP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The solubility of Np(IV) under alkaline and anoxic conditions
Göran Källvenius1, Stefan Allard2, Christian Ekberg2
1

2

AB SVAFO, SE-611 23 Nyköping, Sweden
Chalmers University of Technology, Nuclear Chemistry, SE-41296 Göteborg, Sweden

The solubility of Np(IV) has been studied under alkaline (10 < pH< 14) and reducing conditions. Previously the solubility of Np(IV)has been studied under acidic and near neutral conditions, with justa few studies in the range of 11 < pH < 13. In these studies theanalysis technique used was liquid scintillation counting on 237Np,
resulting in a detection limit of about 10-8 M. The results from thesestudies have indicated solubility around or below this limit resulting
in a high degree of uncertainty. Another problem with the previous
studies is that they have been made on the amorphous hydroushydroxide which may not be a uniquely defined phase. This study
was initiated to test if the alkaline solubility of NpO2(c) would bewithin the detection limit using ICP-MS technique.
Experiments on Np(IV) in the form of NpO2(c) were performed in(Na+, OH-, ClO4-) media at 8 different pH values in the range of 10
to 14 and an ionic strength of 2 M. In trying to achieve reducing
conditions hydrogen atmosphere was used, and Pt(s) catalyst added
to the solutions. The neptunium concentration was determined using
ICP-MS technique thereby lowering the detection limit to between
10-12 and 10-11 M. In most of the studied pH region the solubility ofNp(IV) was found to be below the detection limit. However, at two
pH values, 10.4 and 13.5 the Np(IV) concentration was found to beat least 3·10-10 and 3·10-11 M respectively.
Np(IV), solubility, LSC, ICP-MS, detection limit－ 154 －

23-ACP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Separation of Am and Cm by Using TODGA and DOODA(C8) Adsorbents with
Hydrophilic Ligand-Nitric Acid Solution

1

Shigekazu Usuda1, Kei Yamanishi1, Hitoshi Mimura1, Yuji Sasaki2, Akira Kirishima3, Nobuaki Sato3,
Yuichi Niibori1

Department of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University
Research Group for Aqueous Separation Chemistry, Japan Atomic Energy Agency
3
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University
2

Abstract – Extraction chromatographic separation of Am and Cm
was studied by using TODGA and DOODA(8) adsorbents and nitricacid eluents containing hydrophilic ligands, DOODA(C2) and
TEDGA, respectively, in order to produce a synergistic effect inmutual separation properties.
Keywords – Chromatographic Separation of Am and Cm, TODGA
and DOODA(C8) Adsorbents, Hydrophilic Ligands

For an improved partitioning of high level radioactive
waste containing trivalent minor actinides (MA: Am, Cm)[1,2], extraction chromatographic separation of Am and Cm
was studied by using porous silica/polymer support (SiO2-P
particles), into which two lipophilic diamide-type extractants,
tridentate ligands TODGA (N,N,N’,N’-tetraoctyl-1,3oxapentane-1,5-diamide) and tetradentate ligands DOODA(8)(N,N,N’,N’-tetraoctyl-3,6-dioxaoctane-1,8-diamide)
wereimpregnated (TODGA and DOODA(C8) adsorbents,
respectively). For the TODGA and DOODA(C8) adsorbents,
nitric acid eluents containing hydrophilic ligands,
DOODA(C2) (N,N,N',N'-tetraethyl-3,6-dioxaoctanediamide)
and
TEDGA
(N,N,N',N'-tetraethyl-diglycolamide),
respectively, were selected as masking agents in order toproduce a synergistic effect in mutual separation of trivalentlanthanides (Ln) and/or MA.
Mutual separation properties of Ln were preliminarily
investigated in both separation systems by batch and column
methods, especially paying attention of separation between
Nd and Sm. In nitric acid solution, the uptake of Ln onto the
TODGA and DOODA(C8) adsorbents increased with nitricacid concentration. While the distribution coefficient (Kd)values of Ln for the TODGA adsorbent increased with atomic
number of Ln, those for the DOODA(C8) adsorbent
decreased with atomic number of Ln [3]. In nitric acidsolution containing hydrophilic ligands, the Kd (Ln) values
onto the TODGA and DOODA(C8) adsorbents decreased
with concentration of DOODA(C2) and TEDGA ligands [4].
Relative separation factors (SF) of Ln (Nd~Tb) for the
TODGA/DOODA(C2) system were almost the same degreeirrespective of DOODA(C2) concentration, but those for the
DOODA(C8)/TEDGA system were enlarged in lower
TEDGA concentration. Consequently satisfactory eluent
concentration of hydrophilic extractant and nitric acidconcentration for each adsorbent was determined to be 0.05

M DOODA(C2)-0.1 M nitric acid eluent for TODGA
adsorbent and 0.005 M TEDGA-3 M nitric acid eluent for
DOODA(C8) adsorbent. Chromatographic separations of Ln(Nd~Tb) by both systems were effectively performed (SF(Nd/Sm): 4.2 for the TODGA system and 2.7 for the
DOODA(C8) system and peak resolution (R) of Nd/Sm: 2.5
for the TODGA system and 2 for the DOODA(C8) system).
In this presentation, separation of MA(III) in both systems
was demonstrated using not only Am-241 and Cm-243 but
also Eu-152 for comparison between MA and Ln
adsorbabilities. In the TODGA system, SF (Am/Cm) was
considerably large (4.2), but chromatographic development
was not sufficient and R (Am/Cm) was ca. 0.9 since the Kd(Am) value was unexpectedly small (0.7~0.8). In the
DOODA(C8) system, SF (Am/Cm) was not so large (2.3) andR (Am/Cm) was ca. 1.2 because of adequate developed
elution. It seems that the DOODA(C8) system is better than
the TODGA system for practical use from a viewpoint of 3 M
nitric acid eluent. On the other hand, the latter was superior to
the former from an angle of mutual separation of Ln (Nd~Gd).
In near future, the optimum elution condition will be searched
for more effective separation of MA in pursuit of higher peak
resolution between Am and Cm (R�1.5).
A part of this study is the result of “Development ofmutual separation technology of minor actinides by the novelhydrophilic and lipophilic diamide compounds” entrusted to“Japan Atomic Energy Agency” by the Ministry of Education,
Culture, Sports, Science and Technology of Japan.
[1]

[2]

[3]

[4]

－ 155 －

Y. Sasaki, Y. Kitatsuji, Y. Tsubata, Y. Sugo, Y. Morita, “Separatiion of
Am, Cm and lanthanides by solvent extraction with hydrophilic andlipophilic organic ligands,” Solvent Extraction Research andDevelopment, Japan, 18, p.93-101 (2011).
Y. Sasaki, Y. Kitatsuji, Y. Sugo, Y. Tsubata, T. Kimura and Y. Morita,“Actinides extractability trends for multidentate diamides andphosphine oxides”, Solvent Extraction Research and Development,
Japan, 19, p.51-61 (2012).
K. Yamanishi, H. Mimura, S. Usuda, Y. Sasaki, Y. Morita,“Adsorption properties of lanthanoids for SiO2-polymer adsorbents
impregnated with extractants”, Extended Abstracts of IEX 2012 (TheInternational Ion Exchange Conference, 19-21 September 2012,
Queens’ College, University of Cambridge, UK).
K. Yamanishi, H. Mimura, S. Usuda, Y. Sasaki, Y. Morita, “Separationof lanthanoids by SiO2-P adsorbent impregnated with extractants”,
Proceedings of WM2013 Conference (The annual Waste Management
Symposia, 24-28 February, 2013, Phoenix, Arizona USA).

23-ACP-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Growth of uranyl hydroxide nanowires and nanotubes with electrodeposition method
Lin Wang, Li-Yong Yuan, Zhi-Fang Chai, and Wei-Qun Shi*

Key Laboratory of Nuclear Analysis Techniques, Institute of High Energy Physics, Chinese Academy of Sciences
Email: shiwq@ihep.ac.cn
Abstract –Actinides nanomaterials have great potential applications
in fabrication of novel nuclear fuel and spent fuel reprocessing in
advanced nuclear energy system. [1-2] However, the relative researchso far still lacks systematic investigation on the synthetic methods
for actinides nanomaterials. In this work, we use track-etchedmembranes as hard templates to synthesize uranium based
nanomaterials with novel structures by electrodeposition method.
Through electrochemical behavior investigations and subsequent
product characterizations such as energy dispersive spectrometer(EDS), fourier transform infrared spectroscopy (FTIR), the chemicalcomposition of deposition products have been confirmed as theuranyl hydroxide. More importantly, accurate control ofmorphology and structures (nanowires and nanotubes) could beachieved by carefully adjusting the growth parameters such as
deposition time and deposition current density. It was found that thepreferred morphology of electrodeposition products is nanowire
when a low current density was applied, whereas nanotubes could
be formed only under conditions of high current density and theshort deposition time. The mechanism for the formation of
nanowires in track-etched membranes is based on the precipitationof uranyl hydroxide from uranyl nitrate solution, according to theprevious researches about obtaining nanostructures of hydroxides
from nitrate salt solutions. [3-4] And we have concluded that theformation of nanotubes is attributed to the hydrogen bubbles
generated by water electrolysis under the condition of over-potential
electro-reduction. The conveying of hydrogen bubbles plays the roleof dynamic template which can prevent the complete filling of uranylhydroxide in the channels. Additionally, we transform the chemicalcomposition of deposition products from uranyl hydroxide totriuranium octoxide by calcining them at 500 and 800 degree
centigrade, respectively, and SEM results show the morphologies ofnanowires and nanotubes are maintained very well. Our work
provides new idea for synthesizing one-dimension uranium based
nanomaterials. Further investigations are needed to unveil the sizeand shape effect on the physical and chemical properties of thesenanowires and nanotubes, and to demonstrate their potential
applications.

Figure 1. Growth of uranyl hydroxide nanowires/nanotubes withelectrodeposition method. Top left, scheme of electrodeposition system; top
right, result of elemental analysis for nano-structured products; down left,
SEM images of uranyl hydroxide nanowires with diameters of 400 nm; down
middle, SEM image of uranyl hydroxide nanowires with diameters of 50 nm;
down right, SEM images of uranyl hydroxide nanotubes.

REFERENCES
[1]
[2]
[3]
[4]

Keywords – uranium based nanomaterials, uranyl hydroxide,
electrodeposition, track-etched membranes, template method,
nanowires, nanotubes.

－ 156 －

T. E. Albrecht-Schmitt, Angewandte Chemie-International Edition,
2005, 44, 4836-4838.
P. C. Burns, K. A. Kubatko, G. Sigmon, et al., Angewandte ChemieInternational Edition, 2005, 44, 2135-2139.
L. Gonzalez-Rovira, J. M. Sanchez-Amaya, M. Lopez-Haro, et al.,Nanotechnology, 2008, 19, 495305.
D. Z. Zheng, J. Y. Shi, X. H. Lu, et al., CrystEngComm, 2010, 12,4066-4070.

23-ACP-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Adsorption Behavior of Neptunium Ions on Pyridine Resinin Hydrochloric Acid Solutions
Yu Tachibana1, Yusuke Tomobuchi1, Masafumi Inaki1, Yuki Yamazaki1, Tatsuya Suzuki1,
Tomoo Yamamura2
1

Department of Nuclear System Engineering, Nagaoka University of Technology,
2
Institute of Material Research, Tohoku Univeristy

Abstract - The adsorption behavior of neptunium ions on pyridine
resin in hydrochloric acid solutions has been studied at room
temperature. Neptunium has many kinds of valence states of ions;mainly tetravalent, pentavalent, and heptavalent ions. We controlled
the neptunium valence states and confirmed the valence states inhydrochloric acid solution by a UV-vis. spectrometry. The
adsorption study on the neptunium ions which has the confirmed
valence states, using pyridine resin was studied by batch-wise
experiments. The distribution coefficients of neptunium on pyridine
resin in hydrochloric acid solution were obtained.

Adsorption behavior was investigated by batch-wise
experiments at room temperature. The neptunium with thecontrolled valences in a hydrochloric solution was added tothe hydrochloric acid solution of adjusted concentrations. 0.1
g of pyridine resin was added to 1.0 mL of a neptunium
solution. Adsorptions of neptunium ions on pyridine resin
were evaluated by comparison of activity of neptunium
before and after adding the pyridine resin.
III. RESULTS

Keywords – neptunium, pyridine resin, nuclear fuel reprocessing

The noble nuclear reprocessing process based on
chromatography in hydrochloric acid solutions has beendeveloped [1]. This pyridine resin is used as the adsorption
medium. In our previous works, the adsorption behavior ofmany elements was investigated, and the reprocessing
process with nuclide separation system has been proposedfrom these results [2]. However we have not obtained theadsorption behavior of neptunium ions on pyridine resin inhydrochloric acid solution. It is well known that theneptunium has many valance states in solution. Thus, we
controlled the valence states of neptunium, and obtained theadsorption behavior of each valence state of neptunium.

We confirmed the methods of neptunium valence control.
Distribution coefficients of neptunium with each controlledvalence in hydrochloric acid solutions were obtained.
Distribution coefficients of heptavalent neptunium are shownin Fig. 1. In this experiment, the neptunium-239 obtained by
milking of americium-244 decay was used. The gamma-ray
spectrometry was used for measurement of neptunium
activity. We found that the heptavalent neptunium is strongly
adsorbed on pyridine resin in higher concentratedhydrochloric acid solution, and this behavior is similar to
heptavalent uranium.

Distirbution coefficient

I. INTRODUCTION

II. EXPERIMENTAL
1. Confirmation of valance states of neptunium
An ultraviolet-visible absorption photospectrometry(Lambda750, Perkin Elmer) was used for confirmation ofvalence states of neptunium. The wavelength of absorption
peaks used for confirmation of Np(IV), Np(V), and Np(VI)species are about 750 and 960 nm, 980 nm, and 1230 nm,
respectively.
Neptunium we used was confirmed to consist of pentavalentand heptavalent ions in original solution. In addition, we also
confirmed that the neptunium can be controlled to be
heptavalent by twice treatments of evaporation to dryness
with the concentrated nitric acid solution and the perchloric
acid solution. Tetravalent condition was confirmed to be able
to be obtained by adding 0.5 M of hydroxylaminehydrochloride to the original solution. It was confirmed that
Np(V) species are able to be obtained by adding peroxide toNp(VI) solution.
2. Adsorption experiments

10

3

10

2

10

1

10

0

0

4

8

12

HCl / mol/L
Fig. 1 Distribution coefficients of heptavalent neptunium on pyridine resin inhydrochloric acid solution.

REFERENCES[1][2]－ 157 －

S. Koyama, et al ., J. Nucl. Sci & Technol. 43 (2006) 681.
T. Suzuki, et al., Prog. Nucl. Energy. 50 (2008) 476.
T. Suzuki, et al., Energy Procedia 7 (2011) 421., etc.

23-ACP-08

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

A method for 237Np determination with liquid scintillation counting in theexperiment of neptunium sorption onto bentonite
LI Ping, LIU Zhi, GUO Zhijun, WU Wangsuo*

Radiochemistry Laboratory, School of Nuclear Science and Technology, Lanzhou University, Lanzhou 730000, China

5000

background counting rate (cpm)

3000

10

Background Sample
Mixed Sample

5

2000

0

40

80

120

160

200

1.0

1.5

2.0

2.5

3.0

measurement at a PSA-level=38.

[1] Thakur P, Mulholland G P. Determination of 237Np in environmental
and nuclear samples: A review of the analytical method [J]. Appl Radiat
Isotopes, 2012, 70: 1747-1778.
[2] Aupiais J, Dacheux N, Thomas A C, Matton S. Study of neptunium
measurement by alpha liquid scintillation with ��������������-���������� [J].
Anal Chim Acta. 1999, 398: 205-218.

1000
0

0

0.5

Fig. 2 Influence of bentonite on LSC

sample counting rate (cpm)

4000

1000

m (tracer) /g

6000
5000

2000

0.0

7000

15

3000

0

25

20

m/V=0.2g/L pH=2.0
m/V=1.0g/L pH=2.0
m/V=1.0g/L pH=8.8
m/V=10.0g/L pH=8.5

4000

Counting rate (cpm)

Among various analytical methods developed andused for the determination of neptunium (alpha
spectroscopy, Neutron Activation Analysis (NAA), High����������� �-Spectroscopy (HRGS), Inductively Coupled
Plasma Mass Spectrometry (ICP–MS), luminescencemethod and Liquid Scintillation Counting (LSC) etc.), The
Liquid Scintillation Counting (LSC) method does not
require extensive sample preparation and is very sensitive
for alpha-decaying radionuclides such as 237Np[1].
However, direct determination of 237��� ����� ���� �-active
daughter 233Pa is difficult.
In this study, a new method was developed for thedetermination of 237Np with liquid scintillation counting(LSC), ���� ���� ��������������� ��� �������� ���� ����� ����function of pulse shape analysis (PSA) without a pure ���������� ��� �� ����� �� �������. Before we use the PSA
technique to discriminate ���, an approach was developed
to set the optimum PSA by measuring a ������������������
sample and a background sample. The mathematic
treatment of neptunium peak indicated that at the selected
PSA-level (38), we detected ~86% of the total �emission[2]. It is suitable for the sample determination in
the sorption experiments at this PSA-level with LSC.
Moreover, we confirmed that, at m/V(bentonite) = 0~10g/L
the suspension in sample did not influence LSC
determination obviously. Thus, we could detect 237Np
samples containing bentonite suspension directly with LSC
by setting PSA-level=38.

240

PSA-level

Fig.1 Count rate of a mixed sample and abackground sample as a function of the PSA-levelused.

－ 158 －

23-ACP-09

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa,Japan, 22-27September 2013

Determination of Stability Constants for the Thorium Iminodiacetic acid
Complexes

D. Rama Mohana Rao, R. M. Sawant, B. S. Tomar.
Radioanalytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085

INTRODUCTION
The complexation of actinides with various naturally
present and anthropogenic organic ligands plays a vital rolein understanding their speciation and migration in theenvironment. Thermodynamics of complexation ofactinides with various organic and inorganic ligands havebeen reported in the literature. To know the binding natureand the effect of hetero atom present in the ligand on
complexation with actinides, we initiated the study todetermine the thermodynamic parameters for complexationof actinide ions with carboxylates containing hetero atom
like nitrogen, sulphur, etc. As a part of this study, in thepresent paper the stability constants for the complexation ofthorium with iminodiacetic acid have been reported. The
complexation of thorium with iminodiacetic acid have also
been reported in the literature [1] which show the formationof MLH and ML complexes whereas in our study wedetermined for the completely deprotonated ligand metal
complexes ML and ML2.
EXPERIMENTAL
The details on the preparation and standardization ofTh(IV) solution was given elsewhere [2]. The iminodiacetic
acid (IDA) was procured from sigma Aldrich and was usedas such. Carbonate free NaOH was used for the electrodecalibration. Potassium hydrogen phthalate as a primary
standard has been used to standardize the NaOH. The
ligand solution was prepared by adding known amount ofstandardized NaOH to iminodiacetic acid solution. The
acidic metal ion solution was titrated with the ligand
solution to determine the stability constants of the Th(IV) –Iminodiacetate complexes. The data collection was stopped
before the appearance of turbidity and the collected data
was analyzed by Hyperquad software.
RESULTS AND DISCUSSION
There is always a competition from H+ during thecomplexation of metal with a ligand containing dissociable
proton. Therefore, in order to determine the stability
constants of the metal ligand complexes, knowledge of the
protonation constants is essential. The protonation
constants of iminodiacetate ion were taken from ourprevious experiment results [3]. During the titration ofacidic metal ion solution with the buffered ligand solution,
following reaction can occur in the reaction vessel.

Th 4� � nL2� � ThL(n4�2 n ) �The overall stability constant for the complex formed bythorium can be given by� MLn �[ThL( 4�n ) � ][Th 4� ][ L2� ]nFigure:1 shows the speciation diagram for thecomplexation of thorium with iminodiacetic acid alongwith the fitted data of pH. Under the experimental
conditions, ML and ML2 complexes are observed
predominantly �����������������������������������������areshown in the table 1. The log � for the complex ML wascomparable with literature value ����� �� ������� [1]. The
higher values of ������indicate the role of chelation in thesecomplexes. Studies on the coordination structure in thesecomplexes are in progress.
3.0
Free Metal

2.5

100

ML2

Obs pH80

Cal pH

ML% Formation Relative to M

Keywords:Thorium, Iminaodiacetic acid, stability constantsH � � L2� � HL�
H � � HL� � H 2 L

60

2.0
pH

Abstract: Potentiometric method of determining the stability
constants was employed to study the complexation of thorium withiminodiacetic acid. All the stability constant values have been
determined at temperature of 298 K and in 1 M NaClO4 medium.
The f������������������������������������������������������������
literature for ML2 complex. Under our experimental conditions
1:1 and 1:2 complexes are found to be formed and no partially
protonated ligand metal complexes such as MLH, ML2H wereobserved. The d������������������������������������2 complexes
are 10.78 ± 0.03 and 19.81 ± 0.07 respectively.

40

1.5

20

1.0
0

0

5

10
15
Volume of IDA/cm3

20

Figure:1 Speciation diagram of complexation of thorium withiminodiacetic acid along with the fitted data of both calculated andobserved pH. ([Th] = 3*10-3 M, [H] = 0.0890 M and [IDA] = 0.2997 M,[H] = 0.2987 M, initial volume = 25 cm3, I = 1 M NaClO4, T = 298 K).
Table: 1 stability constants of thorium complexes with IDA ([Th] = 3*10-3
M, [H] = 0.0890 M and [IDA] = 0.2997 M, [H] = 0.2987 M, initial volume= 25 cm3, I = 1 M NaClO4, T = 298 K)
S.No.
Reaction
�����
2
Th
+ IDA
������������������
10.78± 0.033Th+ 2 IDA�����������������2]
19.81± 0.07

Reference
1.
2.

3.

－ 159 －P di Bernardo, A. Cassol, G. Tomat et al, J. Chem. Soc.,
Dalton trans., 733 (1983)“Thermodynamics of Complexation of Actinides andLanthanides with Ligands”, Ph. D. Thesis by Neetika Rawat
submitted to Homi Bhabha National Institute, Mumbai, March2011.
D. Rama Mohana Rao, R. M. Sawant, B. S. Tomar, “Study ofComplexation of Uranyl with iminodiacetic acid byPotentiometry”, NUCAR 2013, Govt. Model Science College(A), R. D. University, Jabalpur, M. P. February 19-2013.

25-ACP-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Time-resolved laser fluorescence spectroscopy combined with parallel factor
analysis: a robust speciation technique for UO22+
1

Takumi Saito1, Noboru Aoyagi2, Takaumi Kimura2

Nuclear Professional School, School of Engineering, The University of Tokyo
2
Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

Speciation is a key issue for the fate of actinides and fission
products in natural environments. Time-resolved laser
fluorescence spectroscopy (TRLFS) is a popular speciation
technique for fluorescent metal ions and can be further extended
by combining multivariate data reduction methods such asparallel factor analysis (PARAFAC). This study demonstrates theapplicability of TRLFS combined with PARAFAC for the
speciation of UO22+ in solution as well as on mineral surface.
Uranium, time-resolved laser spectroscopy,
speciation, adsorption, complexation

I.

PARAFAC,INTRODUCTION

Chemical speciation governs the reactivity andmigration of radionuclides released from nuclear waste
disposal or an accident of a nuclear power plant inenvironments. Various analytical techniques are used forthis purpose. Preferably, such speciation techniques shallpossess all of the following capabilities: (i) discriminationof species by their different chemical and/or physicalproperties, (ii) quantification, and (iiii) structural
determination of the species. Time-resolved laser
fluorescence spectroscopy (TRLFS) is a particularspeciation technique for fluorescent actinide ions such as
UO22+ and Cm3+. The above three characteristics are wellbalanced in TRLFS; the discrimination and quantificationof species can be achieved, based on their
excitation/emission spectra and decay lifetimes; theconcentrations of the species are proportional to theirfluorescence intensities. The favorable characteristics of
TRLFS as a speciation technique largely rely on theinherent multi-dimensional nature of its data, which makes
the combination of multivariate statistics method suitable
for the data reduction. Parallel factor analysis (PARAFAC)
is a multi-model factor analytic method, which can only beapplied for data having more than three dimensions. It has
been shown that combining TLRFS with PARAFAC
provides robust speciation capability for the speciation of
Eu3+, a chemical homologues of the trivalent actinide ions[1-3]. In this study, the applicability of TRLFS-PARAFAC
for the speciation of UO22+ is firstly demonstrated.
II. EXPERIMENTAL
A set of the time-resolved fluorescence spectra of UO22+
complexed with orthosilicate (H2SiO4) or adsorbed on�����������-Al(OH)3) surface were obtained with a TRLFS
system equipped with the forth harmonics of Nd:YAG laser.
The complexation of UO22+ with H2SiO4 was studied as afunction of the H2SiO4 concentration at different pH; theadsorption of UO22+ on gibbsite as a function of pH at thedifferent concentrations of UO22+. The entire data set ineach series was processed by PARAFAC, using the N-way
toolbox for MATLAB®[4].
III.

RESULTS AND DISCUSSION

Three species were found for the complexation of UO22+
with H2SiO4 at pH 4, exhibiting the characteristic
fluorescence spectra (Figure 1) and decay curves. The
fluorescence intensity profiles, which approximated theconcentration profiles of the species as a function of the
H2SiO4 concentration, were used to determine the stability
constants of the complexation.
Three surface species of UO22+ on gibbsite wereobtained from the TRLFS data set by applying PARAFAC.
Based on the fluorescence spectra, decay lifetimes, and thedependence of the intensity profiles on pH and the UO22+
concentration, these species likely corresponded to mononuclear surface complexes with and without hydrolysis anda multi-nuclear surface complex.
IV.

CONCLUSION

It was shown that the combination of TRLFS with
PARAFAC was capable of discriminating the contributionof multiple species of UO22+. The obtained spectra, decay
curves, and intensity profiles were invaluable to understandand model the underlying speciation both in solution andon mineral surface.

Figure 1. Fluorescence spectra of the three UO22+ species with H4SiO4obtained from a series of TRLFS spectra by PARARAC.

REFERENCES
[1]
[2]
[3]
[4]

－ 160 －

Saito, T., et al., Environ. Sci. Technol. 2010, 44, 5055–5060.
Ishida, K. et al., J. Colloid Interface Sci. 2012, 374, 258–266.
Lukman, S., et al., Geochim. Cosmochim. Acta 2012, 88, 199–215.
Andersson, C. and Bro, R., Chemometr. Intell. Lab. 2000, 52, 1–4.

23-ENP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of 55Fe and 89,90Sr in liquid samples using Sr and/or Pb resins for themutual separation of Fe and Sr
Marijana Nodilo, ���������������, Željko Grahek

Division for marine and environmental research, Rudjer Bo��������������������������������Croatia
Abstract. The determination of 55Fe and strontium isotopes iscomplicated and time-consuming, especially the determination of
89,90
Sr. In the last decade, a number of methods have been developed
for radioactive strontium isolation and determination in various
types of samples. On the other hand, only few methods for 55Fe
determination are developed, mainly in liquid radioactive waste
samples. Since strontium isotopes are highly radiotoxic fission
products (especially 90Sr with long half-life), they are an interesting
subject for various investigations, from their distribution andbehavior in natural systems to the influences on the human health. In
distinction from strontium isotopes, 55Fe is an activation product,
low energetic emitter with approximately 2.74 year half-life. As
such, it is not as interesting as strontium, but environmental
concerns prompted the responsible institutions in the radiologicalmonitoring program to include 55Fe determinations in theirprocedures. In almost all published methods, isolation anddetermination of 89,90Sr and 55Fe are separated. Therefore, the aim of
the paper is to present a method for the isolation of 55Fe and 89,90Srfrom liquid sample in one step by using Sr and/or Pb resin andmixture of nitric and hydrochloric acid, because Fe and Sr can bebound on Sr resin from mixture of HNO3+HCl as shown earlier.1
Namely, Sr and Pb resins were primarily developed as Sr, Pb
specific resins which enable very efficient separation of Sr and Pb
from other elements as well as for their mutual separation. The main
focus in the literature was directed on their application in thedetermination of 89,90Sr and 210Pb in different kinds of samples,2,3
while determination of 55Fe was not in focus from above mentioned
reason. Therefore, it will be shown how Fe and Sr can be bound andmutually separated (and from many other elements) on Sr and Pb
resin column. It will be shown that binding strength and selectivity
on both resins depend on concentration of HCl and HNO3. Bychanging the eluent composition, separation of Fe from Sr, as well
as Pb from Fe and Sr ions, can be achieved on both resins. Based onthese results, methodology for rapid determination which involves,binding of Fe and Sr on the column from the mixture of HNO3+HCl,elution of Sr with HCl, Fe with H2O and detection on LSC is created.
It will be shown that 55Fe and 89,90Sr can be easily separated on bothresins from different types of samples with almost same efficiency.
Methodology is tested by determination of 55Fe and 89,90Sr in
proficiency testing samples and radioactive waste samples andobtained results will be presented and discussed in detail.

Table 1. Distribution coefficients of elements on Pb resin
Kd [mLg-1]

Pb

resin

Sr

Mn

Fe

Ni

Pb

-

-

-

-

322
218

4 M HCl
6 M HCl
6 M HCl + 1 M HNO3

58,91

-

220
442
796

-

68,7
8,94
3,54

6 M HCl + 3 M HNO3

101,12

-

210

-

-

6 M HCl + 5 M HNO3

105,66

-

102,5

-

-

5 M HNO3

108,42

-

-

-

>399

0,5 M HCl
2 M HCl

Figure 1. Distribution coefficients of elements in mixture of 6M HCl and
HNO3 on Sr resin

Keywords: Sr and Pb resin, Iron-55, Strontium-89, 90, separation

Figure 2. Separation of Sr and Fe from other elements on Pb resin column[1][2]－ 161 －

��� �������� ��� ����������� ��� �������� ��� ���������� �����������
separation of Fe and Sr from liquid samples by using Sr resin and rapid
determination of 55Fe and 89,90Sr. Appl. Radiat. Isot. In press
Horwitz E.P., Dietz M, Chiarzia R, Novel Strontium-Selective
Extraction Chromatographic Resin. Solvent Extraction & Ion Exchange,
10 (1992) 313-336.

23-ENP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Implementation of Dry Cow Dung Powder for Biosorption of 90Sr(II) from SimulatedRadioactive Waste
Roshan P. Khilnani, Hemlata K. Bagla

Department of Nuclear and Radiochemistry, K. C. College, Mumbai – 20, India.
Abstract – 90Sr is one of the major fission product found in the radioactive waste. The anthropogenic activities such as nuclear weapon
testing, reprocessing of liquid spent fuel etc. are major sources of 90Sr in our environment. Some of the well-established processes such as
chemical precipitation, membrane process, liquid extraction and ion exchange have been applied as a tool for the removal of this metal ion.
All the above methods are not considered to be greener due to some of their shortcomings such as incomplete metal ion removal, highrequirement of energy and reagents, generation of toxic sludge or other waste materials which in turn require further treatments for theircautious disposal. The present investigation entails the biosorption studies of 90Sr(II) from simulated radioactive waste employing dry cow
dung powder (DCP) as an indigenous, inexpensive and, eco-friendly material without any pre or post treatments. As DCP is easily available,
it is superior to other processed natural adsorbent considering their cost, time and energy efficiency. The Batch experiments were conductedemploying 90Sr as a radiotracer and the effect of process parameters such as pH, temperature, amount of resin, time of equilibration,
agitation speed and distribution co-efficient have been studied for simulated reactor and reprocessing waste with and without carrier. The
efficiency of adsorption was found to be more than 70%. The prime amenity of using DCP over other biosorbents is that it doesnot require
any degree of physical and chemical enhacement for optimization of the method and inturn adds to the economy of entire adsorption process.
Thus use of DCP manifests the principles of Green Chemistry and proves to be an eco-friendly alternative for the remediation of radiotoxic
90
Sr(II).
Keywords – Biosorption, Strontium, Dry cow dung powder, Simulated radioactive waste－ 162 －

23-ENP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Application of Simplified Desorption Method to Sorption Study: (1) Sorption ofAmericium (III) on Bentonite and Its Major Components
1

Naofumi Kozai1, Toshihiko Ohnuki1

Japan Atomic Energy Agency, Tokai, Ibaraki, 319-1195 Japan

Abstract – To elucidate the sorption behavior of americium on
bentonite, which is a mixture of montmorillonite clay, quartz and soon, simplified desorption experiments were applied to the solid
phases collected after the sorption experiments. Almost 100% of
Am was sorbed on bentonite and montmorillonite at pH from 2 to 8.
A fraction of the Am sorbed on the solid phases was desorbed bytwice treatment with a 1M KCl aqueous solution, and the residual
Am was completely desorbed by twice treatment with a 1M HClaqueous solution. The desorption behaviors of Am from bentonite
and montmorillonite were very similar to each other andsymmetrical at pH 7. Most of the Am sorbed below pH 7 wasdesorbed with 1M KCl solutions and that above pH 7 was notdesorbed with 1M KCl but with 1M HCl solutions. The trend in the
KCl-desorbable fraction vs. pH is very similar to the abundance
ratio of cationic Am species (Am3+) and so is the trend in the KClnondesorbable fraction to that of the hydrolyzed species of Am.
Keywords – Americium, sorption, desorption, pH, montmorillonite,bentonite, quartzI.

product from this bentonite. An Am (III) nitrate stock
solution was diluted with 0.01 M NaClO4 to yield a working-10
solution having an Am concentration of about 5x10 M.
For the sorption experiments, the initial pH of the Am
solution was adjusted over a range of 1.8 to 10. A weighed3
amount (0.06 g) of sold phases was soaked in 6 cm aliquotsoof the Am solution and stored at 20 C. This solid-solution
mixture was agitated once a day. After 10 days, asupernatant was collected by centrifugation.
Desorption experiments were conducted in two steps.
3
First, 6 cm of 1 M KCl solution was added to the solid
phases collected after the sorption experiments. After 2 days,
the KCl solution was separated by centrifugation. Second,
desorption with a 1 M HCl solution was undertaken in thesame way as the desorption with a 1 M KCl solution. The
desorption with each solution was carried out twice toconfirm complete desorption of Am.
III. RESULTS AND DISCUSSIONINTRODUCTION

Sorption is one of the key mechanisms to control thesubsurface environmental behavior of the radionuclides. It is
known that sorption behavior of elements on solid phases
may vary depending on the concentration of the element [1].
Thus, for the environmental study, it is desirable to examine
sorption behaviors at tracer concentrations (nanomolar orless). To date it is however impossible to apply any
instrument analysis except radiation measurements to theanalysis of the tracer level radionuclides on solid phases.
To analyze the tracer level neptunium sorbed on clays, a
simplified desorption method sequentially using two kinds ofdesorption agent solutions was effective [2]. This paper
applies the desorption method to the sorption study of Am on
bentonite and discuss the sorption and Am species. Bentonite
is a clay found ubiquitously in soil environment. Its main
component is montmorillonite, and minor components arecalcite, dolomite, quartz, pyrite, cristobalite, zeolite, etc.
Owing to high cation exchange capacity of montmorillonite,bentonite clay plays a very important role for migration ofradionuclides in the subsurface environment.
II. EXPERIMENTAL
Tsukinuno montmorillonite (Kunipia F®, Kunimine
Industries Co. Ltd.) was used after the montmorillonite was+converted to homoionic Na forms (Na-montmorillonite).
Tsukinuno bentonite (Kunigel V1®, Kunimine Industries Co.
Ltd.) was used with no pretreatment. Kunipia F is a purified

In the examined final pH range (2 – 8), almost 100% of
Am was sorbed on bentonite and montmorillonite. All of the
Am sorbed on bentonite and montmorillonite were desorbedby the two step desorption procedures. The desorption
behaviors of Am from bentonite and montmorillonite werevery similar to each other. Most of the Am sorbed below pH
5 was desorbed by the twice treatment with 1M KCl solutions.
The KCl-desorbable fraction of Am sharply decreased withincreasing pH above pH 5 and most of the Am sorbed above
pH 7 was not desorbed with 1M KCl solution but with 1M
HCl solution. The trend in the KCl-desorbable fraction vs. pH
is very similar to the abundance ratio of cationic Am species(Am3+) and so is the trend in the KCl-undesorbable fraction
to that of the hydrolyzed species of Am. It is intuitively
understand that the Am desorbable from the bentonite with
KCl solution is the Am sorbed on the montmorillonite
fraction in the bentonite.
This paper further discuss the sorption behavior of Am on
bentonite with the result of blank experiments to examine thesorption on the reaction vessels and with that of sorption anddesorption experiments on quartz, which is the second major
mineral in the bentonite.
[1][2]－ 163 －

Ohnuki T et al., J. Nucl. Sci. Technol., in press.
Kozai N et al., Radiochimica Acta, 75, 149-158 (1996).

23-ENP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effect of aging on availability of iodine in grassland soil collected in Rokkasho, Japan
Akira Takeda, Hirofumi Tsukada, Yuichi Takaku, Shun’ichi Hisamatsu
Department of Radioecology, Institute for Environmental Sciences

Abstract – In the laboratory, we investigated the time-dependentchanges in the availability of I in soil over the course of 23 months.
Stable I was added as iodide or iodate to a soil sample collectedfrom a grassland area in Rokkasho, Japan. Whether I was added as
iodide or iodate, its water solubility, and soil-to-grass transfer
factor decreased drastically over the course of 4 months after
addition and then slightly decreased thereafter.
Keywords – iodate, iodide, radioiodine, soil-to-plant transfer

I.

INTRODUCTION

The first commercial nuclear fuel reprocessing facility inJapan, located in Rokkasho, Aomori Prefecture, isundergoing its final testing using actual spent nuclear fuel.
Iodine-129 (half-life, 1.6 × 107 y) is discharged from thefacility, and the radiation dose to the public resulting fromdischarge of this radionuclide must be assessed. Some of the129
I discharged to the atmosphere is deposited on the land
surface and retained in surface soil. The mobility of I in soil
is expected to decrease with time after its deposition, andinvestigation of the time-dependent changes in I mobility insoil is necessary for the better prediction of long-term I
behavior in the surface soil environment. We conducted alaboratory study of the changes in the water solubility andphytoavailability of trace I added to soil collected from
Rokkasho.
II. MATERIALS AND METHODS
A soil sample was collected from the surface of a pasture
field in Rokkasho, Japan. Aliquots (200 g) of the dried soil
sample were placed in plastic pots, and a solution of NaI or
NaIO3 was added to the soil in each pot at a concentration of
20 mg-I kg-1-soil. The pots were stored in an artificial climate
chamber for about 23 months. The water content of the soil
was adjusted to 60% of its maximum water-holding capacity
every 2 weeks. The soil in the pots was stirred every 4 weeks.
As controls, pots of soil without added I were treated thesame way.
Soil samples were collected from the pots at 0, 2, 9, 29, 64,
113, 204, 372, and 687 d after addition of the I solution. The
soil samples were extracted with deionized water, at a 1:10
w/v ratio of soil to water, for 1 h at 20°C. The supernatants
were separated from the soil by means of high-speed
centrifugation and then filtered through a 0.22-��-pore
membrane filter.
Orchardgrass (Dactylis glomerata) was cultivated in thepots 2–29 d, 37–64 d, 86–113 d, 117–204 d, 345–372 d, and
660–687 d after the addition of I. The cultivation experiments

were carried out in triplicate for each time period. Twenty
germinated seeds were sown in each pot. The water content
of the soil was adjusted with deionized water to 60% of
maximum water-holding capacity of the soil three times aweek during the cultivation period. The aboveground parts ofthe plants were sampled at 28 d after sowing. The plant
samples were freeze-dried and finely ground. Iodine in theplant samples was extracted with tetramethyl ammoniumhydroxide at 60ºC overnight. The concentrations of I in thesoil and plant extracts were determined by inductively
coupled plasma mass spectrometry. Concentrations of added I
in the soil extract and plant were calculated by subtracting the
I concentrations in the control samples, to which I had notbeen added.
III. RESULTS AND DISCUSSION
The water-solubility of I in the soil decreased with timeafter its addition. Soon after addition, 98% of the I added as
iodide and 54% of the I added as iodate were extracted withwater. In contrast, the extraction yield of the added I at 113 dafter addition was 2%, and no difference was observed
between the chemical forms of the added I. The extraction
yield of the added I was nearly constant thereafter, and was
1.5% at 687 d after the addition.
The concentration of added I in the orchardgrass plants
was relatively lower in the later stage compared to soon after
addition of I to the soil. The soil-to-plant transfer factor,
which is defined as (concentration of added I in theaboveground part of the plant)/(concentration of added I in
the soil) (mg kg-1 dry plant)/(mg kg-1 dry soil), decreased withtime after the addition: from 0.80 to 0.042 for the soil withadded iodide, and 1.3 to 0.041 for the soil with added iodate
over the course of the experiment (Fig. 1). The decreasing
trend was similar to that for the water extractability from thesoil.

Fig. 1 Time-dependence of soil-to-plant transfer factor of I after its addition
to the soil. Error bars indicate standard deviations (n = 3). Orchardgrass wascultivated for 28 d in each pot experiment. The plotted transfer factors arevalues for the end of each cultivation period.
This study was performed under a contract with the government of Aomori
Prefecture, Japan.

－ 164 －

23-ENP-05

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Study on 14C spatial distribution around Qinshan nuclear power plant in China
1

2

Zhongtang Wang1, Dan Hu2, Qiuju Guo1

State Key Laboratory of Nuclear Physics and Technology, Peking University Beijing 100871,China.
Radiation Monitoring Technical Center of Ministry of Environmental Protection, Hangzhou 310012, China

Abstract –To understand the spatial distribution of 14C discharged
by Qinshan nuclear power plant (NPP), where two heavy water
reactors (Plant III) are on commercial operation, bothexperimental investigation and model prediction (Gaussian plumemodel) were carried out by this work. Twenty one moss samples
were collected in five different wind directions near Qinshan NPP,
and analyzed by accelerator mass spectrometry (AMS). The 14C
specific activities in moss samples ranged from 265.6 to 233.0
Bq/kg C (the background is 233.8 ±1.1 Bq/kg C), decreasing withincreased distance from the stacks of Plant III. Simulation of 14C
spatial distribution in air was calculated by using a Gaussian
plume model, which was based on monthly meteorological data,
14
C discharge record, local dispersion parameter and otherparameters. A good fit was found between the predicted andmeasured values, indicating that the spatial distribution of 14C
follows a Gaussian model. It can be concluded furthermore, thatthe influence of the Hill Qinshan (located at W of Plant III, 170
meters high) on 14C’s distribution is quite limited at this site compared to meteorological influences.
Key words: Qinshan NPP; 14C; Gaussian plume model－ 165 －

23-ENP-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Atmospheric deposition of radionuclides (7Be, 210Pb, 134Cs, 137Cs, and 40K) during
2000–2012 at Rokkasho, Japan, and impact of the Fukushima Dai-ichi Nuclear
Power Plant accident
Naofumi Akata1, Hidenao Hasegawa1, Hitoshi Kawabata1, Hideki Kakiuchi1, Yuki Chikuchi2
Nagayoshi Shima3, Toshitaka Suzuki4, Shun’ichi Hisamatsu1
Institute for Environmental Sciences
2
Aomori JGC PLANTECH
3
Fukushima University
4
Yamagata University

Keywords – atmospheric deposition, Rokkasho Village, Fukushima
Dai-ichi Nuclear Power Plant accident

I.

INTRODUCTION

Natural and anthropogenic radionuclides are useful tracers
for studying processes in the atmospheric environment.
Atmospheric deposition of radionuclides has been measured
at many sites for geochemical studies and radiation protection.
We have been measuring atmospheric deposition ofradionuclides in the village of Rokkasho, Aomori Prefecture,
Japan, since 2000 [1, 2]. In this study, we report the impact of
the accident at the Fukushima Dai-ichi Nuclear Power Plant(FDNPP) on the atmospheric deposition of radiocesium(134Cs and 137Cs) in Rokkasho.
II. EXPERIMENTAL
Atmospheric deposition samples were collected on theroof of a building at the Institute for Environmental Sciencesin Rokkasho (40° 57� N, 141° 21� E), approximately 13 m
above ground level. Bulk atmospheric deposition samples
were collected biweekly in a polyethylene basin from March
2000 until March 2006, and samples were collected monthly
after April 2006. Each sample was passed through a Powdex
resin (Ecodyne Co., USA) column to separate ionicradioactive species and particulates from the sample. The
homogenized resin was dried and packed into a plastic casefor �-ray spectrometry. The concentrations of �-ray-emitting
radionuclides, including 7Be, 210Pb, 137Cs, and 40K, in thesample were measured with a low-energy photon
spectrometer with a Ge detector. After the accident at the
FDNPP, 134Cs concentrations were also measured.

III. RESULTS AND DISCUSSION
Annual deposition of 137Cs from 2001 to 2010 ranged from0.04 to 0.69 Bq m-2 with a mean value of 0.21 Bq m-2. We
have already reported that recent background 137Cs deposition
was affected by Asian dust [1]. On 11 March 2011, large
amounts of radiocesium were released into the atmospherefrom the accident at the FDNPP. After the accident, monthly
radiocesium deposition increased, reaching a maximum in
April 2011. Thereafter, monthly 137Cs deposition decreased
rapidly until September 2011 (apparent half-time ~0.8 month)and more gradually (half-time ~0.7 y) from September 2011
until December 2012. Annual deposition of 137Cs was 86.9
Bq m-2 in 2011 and 1.89 Bq m-2 in 2012. Monthly 137Cs
deposition has dropped almost to the pre-accident level,although 134Cs is still detectable.
Cs and 134Cs deposition (Bq m-2 month-1)

Abstract – Radionuclides, including radiocesium (134Cs and 137Cs),
were measured in atmospheric deposition samples collected in
Rokkasho, Aomori, Japan, from 2000 to 2012. After the accident at
the Fukushima Dai-ichi Nuclear Power Plant, radiocesium
deposition rapidly increased and reached a maximum in April 2011.
Since then, monthly radiocesium deposition has gradually decreased.
Monthly 137Cs deposition has almost reached pre-accident levels,
although 134Cs is still being detected.

137

1

1.0E+02: 137Cs134: Cs

1.0E+01

1.0E+00

1.0E-01

1.0E-02

1.0E-03

2000

2002

2004

2006
Year

2008

2010

2012

Fig. 1 Monthly atmospheric deposition of 137Cs and 134Cs in Rokkasho

REFERENCES
[1]

[2]

Akata, N., Hasegawa, H., Kawabata, H., Chikuchi, Y., Sato, T.,
Ohtsuka, Y., Kondo, K. and Hisamatsu, S. (2007) Deposition of 137Cs
in Rokkasho, Japan and its relation to Asian dust, Journal ofEnvironmental Radioactivity, 95, 1-9.
Akata, N., Kawabata, H., Hasegawa, H., Sato, T., Chikuchi, Y., Kondo,
K., Hisamatsu, S. and Inaba, J. (2008) Total deposition velocities andscavenging ratios of 7Be and 210Pb at Rokkasho, Japan, Journal ofRadioanalytical and Nuclear Chemistry, 277, 347-355.

This study was performed under a contract with the government of Aomori Prefecture, Japan.

－ 166 －

23-ENP-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effect of Aging on Water Extractability of Radioactive Iodine and Cesium from Soil
Hirofumi Tsukada, Akira Takeda, Shunichi Hisamatsu

Department of Radioecology, Institute for Environmental Sciences
Abstract – Water extractabilities of radioactive 125I and 137Cs fromsoil were determined by tracer experiments. Career free 125I (iodide
or iodate) or 137Cs was spiked to soil samples, which were thenstored in an artificial climate chamber where a wetting-and-drying
treatment was repeated. Extraction yield of 125I at 4 h after spiking
with iodide was higher than that with iodate, and then both yields
decreased with aging independent of the chemical forms. Chemical
form of 125I in the water extracts at 29 d was predominantly iodide,regardless of whether the spiked form was iodide or iodate. Water
extraction yield of 137Cs immediately decreased after spiking in thesoil, which was 0.015 at 4 h, and then less than 0.001 at 320 d after
spiking.
Keywords – radioactive
extractability, aging

I.

125

I, iodide, iodate,137

Cs, water

INTRODUCTION

Aging of radionuclides in soils after deposition can play animportant role in the change of the physicochemical form,
which is an important factor in determining the fate ofradionuclides in the environment. Radioactive iodine andcesium were the major radionuclides released from the
Fukushima Daiichi Nuclear Power Plants after the accident inMarch 2011. Water extractable forms in soil make up themost mobile fraction, which can migrate and be taken up by
plants. In the present study, water extractabilities ofradioactive 125I (iodide and iodate) and 137Cs were determinedat different elapsed time intervals.

min. Chemical forms of 125I in the water extracts were also
determined at 2 and 29 d after spiking by using an anion
exchange disk (3M, Empore Anion-SR®). Radioactivity ofthe extract and disk samples were measured with NaI(Tl)detectors.
III. RESULTS AND DISCUSSION
Water extraction yield of 125I at 4 h after spiking withiodide was 0.87, which was higher than that with iodate(0.33), and both yields after spiking decreased to 0.033-0.034
at 320 d independent of the spiking chemical forms (Fig. 1).
Content of 125IO3- in the water extract at 2 d after spiking withiodate was 28%, and that it decreased to 1% at 29 d. Iodine125 in the water extract at 2 and 29 d after spiking withiodide existed as 125I-. This suggests that the chemical form of125
I in the water extracts was predominantly iodide excluding
the time just after spiking, regardless of whether the spiking
form was iodide or iodate.
Water extraction yield of 137Cs in the soil immediately
decreased after spiking, from 0.015 at 4 h to 0.0075 at 30 d.
After that, the yield was gradually decreased from 0.0012 at
120 d to less than 0.001 at 320 d, and was 0.00050 at 1110 d
after spiking. It is well known that radioactive Cs is strongly
fixed in clays, and that its mobility is limited.
The results show that transferability of radioactive iodine
and cesium in soil immediately decreases in early stage after
deposition.

II. MATERIALS AND METHODS
Volcanic ash soil (Andosol), which is a typical upland soil
in Japan, was collected from the surface of a grassland in
Aomori Prefecture (40°52’23”N, 141°16’57”E). The soil wasdried at 50°C and passed through a 2 mm sieve. Career free125
I (iodide or iodate) or 137Cs of 10 kBq was spiked to 1 g ofsoil sample. Iodate solution was prepared by the oxidation ofiodide solution by adding bromine water. The samples werestored in an artificial climate chamber (17°C, 60% relative
humidity, 30 klx, 12 h of daylight), and wetting-and-drying
treatments were repeated by adding 1 ml of deionized water
every 2 weeks. The soil samples were extracted with
deionized water for 1 h at room temperature with a 1:10 ratioof soil weight to extract. The samples were extracted from 4 h
to 320 d after spiking for 125I, and 4 h to 1110 d for 137Cs. The
extracts were filtered through a 0.22 �m pore membrane filter(Millipore, Steriflip®) after centrifugation at 10,000 rpm for 5

Fig. 1 Time dependecy of water extractabilities of 125I (iodide and iodate)and 137Cs from soil. Error bars indicate one standard deviation (n=3).
This study was performed under a contract with the government of Aomori
Prefecture, Japan.

－ 167 －

23-ENP-08

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013���������������������������������������������������������������������������������
������������������
Yoshihito Ohtsuka, Yuichi Takaku, Shun’ichi Hisamatsu
Department of Radioecology, Institute for Environmental Sciences��������� –� ��� ��������� ���������� ���������� �������������� ����������� ����� ��� ���������� �������� ��� ��� ���������� ��������
���������� ��� ����������� �������� ��� ���������� �������� ������� ���������� ����������� ��������� ���������� ����� ������� ���� ������ �����
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INTRODUCTION

Protection of the environment from radiation andassessing effects of radiation on nonhuman species havebeen discussed by international organizations such as theInternational Commission on Radiological Protection [1].
Many researchers have reported concentrations of artificial
radionuclides in animals living in terrestrial environments
contaminated by the nuclear accidents at Chernobyl and
Fukushima [e.g., 2, 3]. However, few studies havecompared background radiation doses with artificial
radionuclide doses.
In this study, samples of an earthworm species and 11
arthropod species were collected in coniferous forests
around the nuclear fuel reprocessing plant currently underconstruction in Rokkasho, Aomori, Japan, and the internal
background dose rates of natural radionuclides were
determined.

concentration in the samples of all the arthropods, except
for a millipede and a Japanese ground beetle. The mean210
Po concentration in the earthworm samples was 0.10 Bq
g-1-wet, and the mean 210Po concentrations in thearthropods varied widely, from 0.0042 Bq g-1-wet in a
longhorn beetle to 0.24 Bq g-1-wet in a millipede.
The internal dose rates were calculated by using themeasured concentrations of 210Pb, 210Po, 232Th, 238U, and40
K, and the dose coefficients for the earthworm and thewoodlouse reported by the Framework for Assessment ofEnvironmental Impact [4]; the dose coefficients for the
woodlouse were applied to all the arthropods. The meaninternal dose rate for the earthworm was calculated to be
0.35 Gy h-1, approximately 90% of which was due to210
Po. The dose rates for the arthropods ranged from 36
nGy h-1 to 0.79 Gy h-1, with the actual value depending
mainly on the 210Po concentration. The contribution of210
Po to the dose rate of the arthropods varied from 36% to95%.

II. MATERIALS AND METHODSOne species of earthworm and 11 species of arthropods
were collected monthly in coniferous forests in Rokkasho
from June to October 2008; the animals were collected withfalling traps buried in the ground in four areas (Fig. 1).
After being washed with pure water, the animals were
freeze-dried. For each animal species, a composite sample
was prepared from the dried animals for each sampling siteand each collection month. The composite samples wereanalyzed for 210Po, 210Pb, 238U, 232Th, 40K, and 87Rb by -rayand -ray spectrometry, and ICP-AES and ICP-MS.

Fig. 1 Sampling areas for earthworms and arthropods,
along with the distribution of coniferous forests in
Rokkasho, Aomori, Japan.
This study was performed under a contact with thegovernment of Aomori Prefecture, Japan.
REFERENCES[1]

III. RESULTS AND DISCUSSION
Polonium-210 was the natural radionuclide with thehighest concentration in the earthworm samples, whereas
40
K was the radionuclide present at the highest

[2]
[3]
[4]

－ 168 －

International Commission on Radiological Protection (2007) The
2007 recommendation of the Internal Commission on RadiologicalProtection, Publication 103.
J. W. Mietelski et al. J. Radioanal. Nucl. Chem., 262, (2005) 645.
T. Fukuda et al., PLOS ONE, 8, (2013) e54312.
Framework for Assessment of Environmental Impact (2003) The EC
5th Framework programme, Contact FIGE-CT-2000-00102.

23-ENP-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

An EXAFS Study on the Effect of Natural Organic Matter and Mineralogy
Composition on Cesium Mobility in Environment
Qiaohui FAN, Masato TANAKA and Yoshio TAKAHASHI
Department of Earth and Planetary Systems Science, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama,
Higashi-Hiroshima, Hiroshima 739-8526, Japan(Corresponding mail: fanqiaohui@gmail.com)
Abstract: The sorption of Cs was clearly inhibited in the ternary
clay+HA+Cs system (the addition sequence of reagent) with respect
to the blocking to the access of frayed edge sites (FESs) andinterlayer sites by HA for both illite and vermiculite. Both innersphere complexes (ISCs) and outer-sphere complexes (OSCs) of Cs+
have attribution to its adsorption on illite (non-expansion). However,on vermiculite (intermediate expansion), the partially dehydrated
Cs+ was liable to be present as ISCs associated with the siloxanegroup of the ditrigonal cavity in the SiO4 sheet. However, nearlycomplete OSCs were observed at the planar sites of montmorillonite(high expansion).
Keywords: Cesium, EXAFS, Clay mineral, Mobility, Naturalorganic matter

Introduction
There is a consensus that radiocesium (RCs) strongly andselectively interacts with the phyllosilicate fraction of soil,
sediment, and suspended particles such as illite, vermiculite,
and montmorillonite. Natural organic matters (NOMs)
normally play various important roles in the environment
because of its correlations with soil properties and Cs
bioavailability. Herein, the speciation of Cs on clay minerals
in presence of humic acid (HA) were investigated by batch
experiment, modified sequential extraction [1] and Cs LIIIedge EXAFS approaches.
Experimental
IMt-1 illite (Cambrian shale, Silver Hill, Montana) andSWy-2 montmorillonite (Mont) from the University ofMissouri were purchased from The Clay Minerals Society.
Vermiculite (Verm) from Kent, Connecticut was supplied by
Ward's Natural Science Establishment, Rochester, NY, USA.
Cs LIII-edge extended X-ray absorption fine structure(EXAFS) spectra were collected at BL-12C and BL-9A
stations at KEK Photon Factory (Tsukuba, Japan). EXAFS
analysis was performed using REX 2000 (Rigaku Co. Ltd)and FEFF 7.0 [2].
Results and Discussion
Cesium sorption on vermiculite increased significantly
over the pH range of 3.0 to 7.0, whereas weak pH
dependence was observed for Cs sorption on illite. The pH
dependence can be ascribed to the competitive sorption with
proton, wherein the available exchange site for Cs increases

with pH increasing. In Verm+HA+Cs system, Cs sorption isclearly depressed, but this inhibition becomes weaker withincreasing pH. A similar phenomenon could also be found in
the illite+HA+Cs system.
EXAFS analysis demonstrated that Cs speciation strongly
depends on mineralogy and NOMs. The increase in pH from
3.0 to 7.0 increases ISCs from 42% to 80% for illite.
However, in vermiculite system, ISCs mostly dominate Cs
fixation and weakly depend on pH. Vermiculite with a 1.4 nm
layer distance is enough to the entrance of Cs+ and to form
the ISCs associated with the siloxane groups of ditrigonalcavities even at low pH. XRD patterns showed that thecharacteristic peak of vermiculite (6.1o) shifted to a large
angle after Cs adsorption at low Cs concentration even in thepresence of HA and disappears at high Cs concentration. The
dehydrated Cs+ replacement of Mg2+ or K+ causes the partial
collapse of vermiculite layers at low Cs coverage andcomplete collapse at high Cs coverage, which is a more stablestate to Cs [2]. However, no such change was observed in theillite systems. The negative charge of montmorillonite with a
2.0 nm layer distance (high expansibility) is mainly derived
from the isomorphic substitution of Mg2+ for Al3+ in theoctahedral AlO6 sheet, which drives hydrated Cs+ to form
OSCs in the interlayer sites.
EXAFS analysis indicates that HA molecules could
efficiently block the accesses to FESs and interlayer even at
relative large layer distance such as vermiculite (1.4 nm) to
reduce Cs sorption to a large extent. Obviously, the OSCs
proportion increase in the illite+HA+Cs system, because thecoated HA molecules make Cs form OSCs throughelectrostatic attractive force, which was also consistent withthe sequential extraction results.
Conclusion
The strong retard Cs in soil or sediment could attribute to
the ISCs related to the FESs and interlayer of illitic clay
minerals. However, the presence of NOMs could provoke Cs
mobility largely by the indirect effect, i.e., the blocking effect.
Reference
[1]
[2]
[3]

－ 169 －

Rigol A., Roig M., Vidal M. and Rauret G. Environ. Sci. Technol. 33(1999) 887-895.
Zabinsky S. I., Rehr J. J. and Ankudinov A. Phys. Rev. B 52 (1995)
2995-3009.
Kogure T., Morimoto K., Tamura K., Sato H. and Yamagishi A. Chem.
Lett. 41 (2012) 380-382.

23-ENP-10
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Using Factorial Design to the Robustness Analysis of the Classic Sample Preparation
Method for 90Sr Determination in Tea Leaf
Chi-Chang Liu1*, Wen-Hsien Tsai1, Ming-Chi Horng1, Ching-Chung Huang1, Yuh-Wern Wu2
1

2

Radiation Monitoring Center, AEC, Taiwan, ROC
Department of Chemical Engineering, I-Shou University, Taiwan, ROC

Abstract
The classic sample pretreatment method for 90Sr determination based on a series of precipitations including the separation of Sr from Ca byfuming nitric acid is the standard and popular method around world. To select a best set of operational conditions for such an analyticalmethod with numerous of experimental steps is a difficult task. Even when the optimum values of these factors are found, practically it isdifficult in accurately controlling them and sometimes leads to wide variations of results. Procedures for optimization of factors bymultivariate techniques have been encouraged, as they are faster, more economical and effective, and allow more than one variable to be
optimized simultaneously for sample preparation. However, the application of these techniques for the robustness analysis in the method forradiochemical analysis has been limited. In this study, a robustness test was performed to provide a better insight into which critical process
affect 90Sr determination in the sample preparation method. To assess method robustness, the empirical optimum procedures set for thismethod have been test by slightly modified and were evaluated using the factorial design approach at two levels. The evaluated sensitivity ofparameters includes pHs in precipitation procedures, concentration of fuming nitric acid, and times for reactions. The result allows us toanalyze the influence of significant factors upon the 90Sr radioactivity and the recovery of carrier and to establish intervals that ensure therobustness of our method.
Keywords 90Sr, robustness, factorial design, fuming nitric acid method[1][2]

Y. Vander Heyden, A. Nijhuis, J. Smeyers-Verbeke, B. G. M. Vandeginste, and D. L. Massart, “Guidance for robustness/ruggedness tests in method
validation,” Journal of Pharmaceutical and Biomedical Analysis, vol. 24, no. 5-6, pp. 723–753, 2001.
D.G. Montgomery, Design and Analysis of Experiments, 7th Edition, John Wiley and Sons, New York, 2009.

－ 170 －

23-ENP-11

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

A simple method for dehydrogenase assay of soil microorganisms to evaluate thebiospheric behavior of C-14 originated in transuranic waste
Kayoko Iwata, Nobuyoshi Ishii, Keiko Tagami, Shigeo Uchida

Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences
Abstract – When carbon-14 (14C) that originated in transuranic(TRU) waste reaches the ground surface in low molecular weightorganic forms, it is reported that soil microbial activity has
influence on 14CO2 gas production. This study aims to develop a
simple method to determine soil microbial respiratory activity,
which results can be applied to evaluate their correlations with
14
C gasification ratios. Respiratory activity was measured using
2-(p-iodophenyl)-3-(p-nitrophenyl)-5-phenyltetraxolium chloride(INT). Agricultural soil samples were incubated at a solid: liquidratio of 1 to 10, often used in the gasification ratio experiments.
Primarily, INT incubation time, INT-formazan extraction method,and storage time for the extracted INT-formazan were examined.
Keywords – C-14, Soil microbial activity, CO2 production

I.

INTRODUCTION

Carbon-14 (14C) is one of the important radionuclides intransuranic (TRU) waste, which are concerns to humandose assessment due to its relatively long half-life (5730 y)and potential for migration to the biosphere. It was reported
that 14C released from TRU waste is partially released as
low molecular weight organic forms, such as acetic acid,formic acid, and methanol. These forms have low
adsorption properties and are expected to pass throughbarrier materials. However, there is little information
available on the fate of organic 14C after reaching the
ground surface. Although it has been showed that soil
microbial activity influences CO2 gas production [1], few
studies have been conducted to estimate the gasification
ratio using soil microbial activity as an indicator.
Understanding the relationship between soil microbialactivity and CO2 gas production may enable to estimate
gasification ratio of 14C in different soil in the future.
Since CO2 gas production is influenced by microbial
decomposition of organic 14C, microbial respiratory activity
is involved. However, the microbial respiratory activity
determination method corresponding to the 14CO2 gas
production study has not been developed yet. Therefore,
this study was conducted to develop a suitable and easily
replicable method to determine soil microbial respiratory
activities, which results can be applied to evaluate thecorrelation with 14C gasification ratio. For the microbialactivity determination, electron transport system (ETS) was
measured by dehydrogenase assay using the redox dye 2(p-iodophenyl)-3-(p-nitrophenyl)-5-phenyltetraxolium
chloride (INT) as the substrate, which is reduced to INTformazan by the dehydrogenase enzyme. In the method
development, primarily three points were examined—INT
incubation time, extraction method, and storage time for the
extracted INT-formazan.

II. MATERIALS AND METHODSAgricultural soil samples that were air-dried and sieved
through a 2-mm mesh were incubated beforehand at asolid: liquid ratio of 1 to 10 (0.5 g to 5 mL), which iscommonly used in the experiments to determine 14CO2
gasification ratio, so as to share the method [2]. After the
incubation, 4mL of supernatant was discarded, and INTaqueous solution (0.05%) was added to the sample. INT
incubation time was evaluated up to four hours bycomparing the amount of extracted INT-formazan detectedwith a spectrophotometer at 480 nm. INT-formazan
extraction methods using methanol as the extractant werealso evaluated, regarding the volume of methanol andextracting time. Storage time of extracted INT-formazan
before absorbance reading was assessed by keeping
samples in the dark at 4� or room temperature (approx.
20�).
III. RESULTS AND DISCUSSION
Based on the experiments, three hours was chosen for
INT incubation time because resultant INT-formazan
increased over time for the first three hours and then started
to be stabilized. As regards INT-formazan extracting
method, our experiment showed that mixing samples with
8mL of methanol vigorously for one minute was sufficient.
Extracted INT-formazan was stable in both conditions atleast for 24 hours. Because our method considered themethod of gasification ratio experiments, it enables theevaluation of correlation between soil microbial activity
and gasification ratio.
This work was partially supported by the Agency for
Natural Resources and Energy, the Ministry of Economy,
Trade and Industry (METI), Japan.
REFERENCES[1][2]－ 171 －

Koga, K. The roles of soil microbes in the global environment. Netsu
Sokutei 34 (2): 77-86, 2007
Ishii, N., Koiso, H., Takeda, H., Uchida, S. Partitioning of 14C into
solid, liquid, and gas phases in various paddy soils in Japan. J. Nuc.
Sci. Technol. 47: 238-243, 2010

23-ENP-12

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effect of humic acid on the sorption of selenium (VI) on ferric oxide hydrate
N. Guo, Z. L. Niu, Y. L. Ye, R. Zhang, Z. J. Guo

School of nuclear science and technology, Lanzhou University, Lanzhou, China, 730000
Abstract – Selenium-79 (T1/2= 6.5×105 a) is one of thelong-lived fission products, which is chemically andradiologically toxic, and one of the main radionuclides of
special concerned in the disposal of high level nuclear
waste. In this paper we studied the effect of humic acid
(HA) on the sorption of selenium (VI) on ferric oxide
hydrate (HFO) via batch-type experiments. We researched
the effects of contact time, pH, ion strength, concentrationof Se (VI) and HA on the sorption of Se (VI) and found thatthe equilibrium time of the Se (VI) sorption on HFO wasaround 3 h, the sorption decreased with the increasing pH
and increased with the decreasing ion strength. The sorbed
amount decreased with equilibrium concentration inaqueous phase, and the sorption isotherms were fitted toLangmuir equation to figure out the max sorbed amountwhich was 3.82×10-4 mol/g. HA significantly suppressed
the sorption of Se (VI).
Keywords – selenium, sorption, ferric oxide hydrate, humic
acid

10000

Kd(mL/g)None HA
25mg/LHA

1000

100

3

4

5

6

pH

7

8

9

10

Fig 1. Effect of HA on the sorption of Se (VI) on HFO: CSe = 1.5×10-4 mol/L, I = 0.1 mol/L (NaCl), T = 25±1 �－ 172 －

23-ENP-13
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Uranyl ions Adsorption to Na-GMZ and Interactions with FA Adsorption:
experiments and modeling
Ye Yuanlv, Guo Zhijun*, Wu Wangsuo

Radiochemistry Laboratory, School of Nuclear Science and Technology, LanzhouUniversity, Lanzhou, 730000, China

Abstract –In this work, data for the interactions betwee fulvic acid(FA) with uranyl ions at the surface of Na-GMZ are presented. U
adsorption to Na-GMZ in the presence of FA can be well predictedwith the SCD model (surface and complex distribution). According
to the model calculations, the nature of the interactions between FA
and U at Na-GMZ surface is mainly surface complex.
Keywords –Uranyl ions, Na-GMZ, FA, Surface Complex Model

U(VI) sorption %INTRODUCTION

In the enviromnent, an important factor of radionuclide
mobility is their interaction with mineral–water interfaces. To
predict radionuclide mobility, it is necessary to understandfundamental processes such as surface precipitation andsurface complexation. Studies of uranium sorption onto
mineral surfaces have great practical importance for risk
assessment.what’s more, in recent years it has been revealed
that many groundwaters in granitoidic environments contain
excessive amounts of dissolved U[1].In addition to the effects
for sorption, NOM may influence U(VI) distribution via
some other mechanisms. In addition, some studies also
postulated that U(VI) can form organic complexes with NOM
possibly via metal ion bridging The formation of organic
U(VI) complexes at the mineral surface or in the solution
may decrease or increase U(VI) solubility in groundwater[1-2].

60

40

20

0
2

3

4

5

6

7

8

pH

Figure 1 Adsorption curves of U(VI) vs. pH on Na-GMZ , C[U(VI)]=1.003E-4 mol/ L,m/ V = 20 g/ L , T = 22±1 �, I =0.1 mol/ L (NaCl).
100

exist FA
exist FA model
no FA
no FA model80

A. Uranyl ions Adsorption to Na-GMZ and Interactions with
FA Adsorption
Figures 1 and 2 show the two relatively gentle sorption edges
from pH 2 to 8. It is also seen that FA causes a relative
enhancement in the U(VI) sorption at pH<6. U adsorption to
Na-GMZ in the presence of adsorbed FA can be well
predicted with the SCD model (surface and complex
distribution) U adsorption to Na-GMZ in the presence ofadsorbed FA can be well predicted with the SCD model(surface and complex distribution).

=AlO(UO2)+=X(UO2)2=AlO(UO2)3(OH)5modeling
experiment data

80

U(VI) sorption %

I.

100

60

40

20

0
2

3

4

5

6

7

8

pH

Figure. 2 Adsorption curves of U(VI) vs. pH on Na-GMZ inthe absence and presence of FA, C[U(VI)] =1.012E-4 mol/ L,
C[FA] =10 mg/L, m/ V = 20 g/ L , T = 22±1 �, I =0.1 mol/
L (NaCl).
[1][2]* coresponding author:Guo Zhijun email:Guohij@lzu.edu.cn－ 173 －

Gustafsson, J.P., Dassman, E. and Backstrom, M. (2009) Towards a
consistent geochemical model for prediction of uranium(VI) removalfrom groundwater by ferrihydrite. Applied Geochemistry 24(3), 454462
Weng, L.P., Van Riemsdijk, W.H. and Hiemstra, T. (2008) Humic
Nanoparticles at the Oxide-Water Interface: Interactions with
Phosphate Ion Adsorption. Environmental Science & Technology
42(23), 8747-8752.

23-ENP-14
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Foliar uptake and translocation of stable cesium and iodine by radish
Hidenao Hasegawa1, Hirofumi Tsukada1, Hitoshi Kawabata1, Yuichi Takaku1, Shun’ichi Hisamatsu1
1

Institute for Environmental Sciences

Abstract – We studied foliar uptake of Cs and I by radish (Raphanus
sativus L. cv. Redchim) by applying droplets of a solution of Cs (asCsCl or CsNO3) or I (as NaI or NaIO3) on an upper leaf surface.
The uptake of Cs decreased with increasing CsNO3 concentration in
the applied solution. Approximately 80% of applied Cs wasabsorbed no matter what the initial concentration of the applied
solution. The uptake of I in either form was independent of theconcentration of the applied solution. Approximately 80% of appliedI- was absorbed, whereas 90% of IO3- remained on the surface.

(Fig. 1). When Cs was applied as a CsNO3 solution, the Cs
absorption ratio decreased with increasing Cs concentrationin the applied solution. In contrast, when Cs was applied as a
CsCl solution, the absorption ratio was nearly constant. There
was a clear difference in I absorption ratio between NaI and
NaIO3. This result suggests that the chemical form of I
strongly affected the absorption ratio of I.

INTRODUCTION

Absorption ratio of Cs (%)

I.

CsCl

100

Keywords – foliar uptake, translocation, cesium, iodide, iodate

Direct deposition of radioactive materials onto crops is an
important pathway for radiation dose assessment ofradionuclides released from nuclear facilities. Cesium andiodine radioisotopes are transferred into agricultural products
both by direct deposition from the atmosphere onto the plants
and by absorption from the soil via the roots. We havealready reported that foliar uptake of stable Cs is higher fromdroplets of a CsCl solution than from droplets of a CsNO3
solution. In this study, we investigated the concentration
dependence of the foliar uptake of Cs from a CsCl or CsNO3
solution applied as droplets onto the leaf surface of radish
plants (Raphanus sativus L. cv. Redchim). A similar
experiment was carried out with NaI and NaIO3 solutions.

CsNO3
CsNO3

80
60
40
20
0
0.0001 0.001 0.01

0.1

1

10

Cs concentration in applied solution (g L-1)

NaI

100

Absorption ratio of I (%)

II. MATERIALS AND METHODS
Details of radish plant cultivation and the method for
applying the solutions to leaf surfaces are described
elsewhere [1]. A solution of CsCl or CsNO3 at aconcentration of 0.001, 0.01, 0.1, or 1 g Cs L-1 was applied tothe upper surface of radish leaves (Raphanus sativus L. cv.
Redchim) 28 d after germination. A solution of NaI or NaIO3
at a concentration of 0.2, 0.5, or 1 g I L-1 was also applied in asimilar manner. The plants were harvested 4 d after theapplication of test solutions and were divided into leaves, root
tubers, and lateral roots. The leaves were washed with asolution containing detergent. The washing solution, leaves,and root tubers were analyzed for Cs and I by means of
inductively coupled plasma mass spectrometry.

NaIO3
NaIO3

80
60
40
20
0
0

0.2

0.4

0.6

0.8

1

1.2

I concentration in applied solution (g L-1)
Fig. 1 Absorption ratios of Cs and I into radish plants from upper leaf
surfaces

REFERENCES

III. RESULTS AND DISCUSSION
We determined the absorption ratios of Cs and I,
calculated as (amount of Cs or I detected in the inner leaf orroot tuber)/(applied amount of Cs or I), and we plotted theratios against the Cs or I concentration of the applied solution[1]

H. Hasegawa, H. Tsukada, H. Kawabata, Y. Chikuchi, Y. Takaku, S.
Hisamatsu, J. Environ. Radioact., 100 (2009) 54.

This study was performed under a contract with the government of Aomori
Prefecture, Japan.

－ 174 －

23-ENP-15
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The rapid determination of radiostrontium from a large amount of seawater(within 72hrs) for an emergency situation
Hyuncheol Kim*, Kun-Ho Chung, Hyo-Kook Park, Jong-Myoung Lim, Mun-Ja Kang
Environmental Radioactivity Assessment Team, Korea Atomic Energy Research Institute989-111 Deadeok-daero, Yuseong-gu, Daejeon, 305-353, Korea

Abstract – This paper describes the results of the development of an
automated radionuclide separator from a large seawater sample. It
consists of two parts, which are a concentration part with a cationexchange resin (Dowex50Wx8, Sigma-Aldrich) and a purification
part with Sr resin (Eichrom Technology). The volume of raw
seawater sample was reduced by about 25% at the concentration
part, and radiostrontium was purified at the Sr-resin part. The
chemical yield ranged from 92% to 96%. This automated system cansimultaneously execute four samples. Using liquid scintillation
counting (LSC) and Cherenkov counting, the analysis of Sr-89/90
from seawater could be completed within 3 days.
Keywords – radiostrontium, seawater, automated system, rapid
determination

sample, which did not affect the Sr recovery by Sr resin. The
Sr recovery was quantitative for Ca levels of up to 320mg,
which was higher than that of Ca in the elution sample. About
99% of Sr in seawater from 1L to 10L was collected by theconcentration part. A pre-concentration of Sr from 10L
seawater was completed within 5hrs.
We prepared a Sr resin column using a benchmark glasscolumn (Omnifit Ltd.) in the purification part. The amount of
Sr resin depends on the sample size because the level of Sr inseawater is around 8ppm. All procedures were automaticallycompleted by MARS Sr-sw. It took 4hrs to complete thepurification of Sr from 10L of seawater The Sr recovery was
about 93%.

Radiostrontium is one of the main fission products and canbe released into the environment through nuclear test or NPP
accidents. During emergency situations such as FDNPP, aradionuclide analysis should be completed in a short time tosupport rapid decision making and maintain public safety.
The determination of radiostrontium following traditional
methods involves a significant number of separation steps
such as precipitation which are time-consuming and labor
intensive. This paper describes Modular AutomatedRadionuclides Separator Sr-seawater (MARS Sr-sw) whichallows the purification of radiostrontium from four seawater
samples at the same time within 3 days. MARS Sr-sw canreduce the analytical time and labor intensity.
MARS Sr-sw was based on column chromatography. It
consists of a concentration part and purification part, whichcontain a control module, a pump module, a valve module,
and four column modules. We developed the control software
using LabVIEW (National Instrument). The operational
procedure is shown in figure 1.
In the concentration part, Dowex50Wx8(100~150um) wasused to concentrate a large seawater sample, the volume ofwhich was reduced from 20% to 30%. Seawater consists ofmany cations, such as Ca2+, Mg2+ and Sr2+. However, theselectivity of Sr for Dowex50Wx8 is relatively higher thanthat of Ca or Mg, which are dominant ions in seawater. It
enables Sr concentration from seawater without significant
loss of Sr. In a Sr breakthrough test, 500g of Dowex50Wx8
can isolate 99% of Sr from 10L seawater (0.16mg Sr/g ofDowex50Wx8). The low level of Ca was found in the elution

Concentration part2M HCl (3CV)
DIW (5CV)
2M NaOH (3CV)
DIW (5CV)

Purification part
8M HNO3(5CV)

conditioning

conditioning

loadingloading

DIW (3CV)

rinsingrinsing

8M HNO3(3CV)
3M HNO3+0.05M oxalic acid (2CV)
8M HNO3 (3CV)

5M NaCl (4CV)

elutionelution

DIW(4CV)

SrCO3 bycentrifuge

SrCO3 bycentrifuge

LSC analysis

Figure 1 Procedure of MARS Sr-sw (CV: column volume)

This study suggests that MARS Sr-sw can complete thedetermination of radiostrontium from a large amount ofseawater within 3 days using LSC and Cherenkov counting
which provide spectral information. It allows theidentification of Sr-89/90. The remarkable aspects of MARS
Sr-sw are the automation and capability to handle multiple
samples at the same time.
[1]

[2]

Chung, G.H., Choi, S.D., Choi, G.S., Kang, M.J. Design andperformance of an automated radionuclide separator: its application on
the determination of 99Tc in groundwater. Applied Radiation andisotopes (in press)
Vajda, N. and Kim, C.H. Determination of radiostrontium isotopes: A
review of analytical mehtodoly. Applied Radiation and isotopes, 2010.
2306-2326.

*Corresponding author. E-mail: hckim3@kaeri.re.kr－ 175 －

23-ENP-16
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Peak Tailing Correction in Measurement of 222Rn/220Rn Activity Concentration with
��Spectrum Method
1

Lei Zhang1�Qiuju Guo2, Ruoyun Ma2, Lu Guo2

Solid Dosimetric Detector and Method Laboratory, Beijing, 102205, China
State Key Laboratory of Nuclear Physics and Technology, School of Physics, Peking University, Beijing 100871, China

2

Abstract – �������������������������������������������������������
for 222Rn/220Rn concentration measurement. The peak tailing from����� ������� �� ��������� ��� ���� ������� ������� �nfluences the������������ �������������� ��� �������� �� ��������� �������� ����theory of peak tailing was analyzed and a series of calibrating
experiments was carried out. For a commercial radon monitor ERS2, the experiment values of peak tailing correction factors C5 and K4
is 15.25%±0.24% and 36.23%±0.68%, the calibration factors of222
Rn and 220Rn(KFRn and KFTn) is 2.08±0.02 Bq•m-3/cph and5.23±0.28 Bq•m-3/cph. After peak tailing correction, themeasurement results agree with reference value very well.
Keywords – 222Rn/220Rn; �����������������; peak tailing correction
factor; calibration factors－ 176 －

23-ENP-17
�����������������������������������������������������������������������
������������������������������������������������������������������

������������������������������������������������������������������������������������������������ �����������������������������������������������

������������������������������������������������������������������������������������������
Abstract Ð The increasing number and size of marine reserves comes with additional challenges and responsibilities
concerning environmental monitoring, including sediment chemistry. The characterisation of sediments can shed light on past
events like anthropogenic contamination and natural events as well as provide information to guide mineral exploration.
However, the costs associated with the monitoring of sediment chemistry are high and traditional methods can disturb the
sediment and influence the results. Here we present original results of X-ray fluorescence measurements performed underwater,
in-situ, using an autonomous underwater vehicle in the Derwent Estuary, which is located in South East Tasmania Australia
and has a long history of contamination from heavy metals. To demonstrate the capability of performing in situ, underwater
analysis of sediments we analysed three distinctive sites on the Derwent estuary floor. XRF spectra with good signal-to-noise
ratios have been recorded. The results show spatial variation of zinc, lead and iron concentration. The contamination of heavy
metals we found reflects proximity to potential sources and patterns of the hydrodynamics of the estuary. We suggest that XRF
in submersible autonomous platforms could be used to perform an initial, cost effective, assessment of heavy metals
contamination of sediments to guide comprehensive surveys.
Keywords Ð XRF, Sediments, AUV

XRF spectra recorded underwater. Typical least-squares fitted XRF spectrum record at site D (Ralphs Bay) at
10m-depth. The broader line between 10 keV and 30 keV overlaps Lead, Bromine and Strontium signals and arecaused by bremsstrahlung from the XRF housing (high density polypropylene).

－ 177 －

23-RPP-01

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Development of the in-line, multiple elution cartridge-based radioisotope
concentrator device for increasing 99mTc and 188Re concentration of commercial
radionuclide generator eluates
Le, Van So1,2*; Morcos, Nabil1; McBrayer, James1; Bogulski, Zac1; Buttigieg, Charles1; Phillips,
Graham1
1

CYCLOPHARM Ltd, NSW, Australia
2
MEDISOTEC, NSW, Australia

I. INTRODUCTION
Tc is used in approximately 85% of diagnostic imaging
procedures in nuclear medicine world-wide. 188Re is
important radio-therapeutic radionuclide. The expansion of99m
Tc and 188Re application depends on the generator
availability. However, the cost-effective utilisation of 99mTc
and 188Re generators and the quality of SPECT imaging
diagnosis and radiotherapy are controlled by the 99mTc and188
Re generator operation/elution management, which isdetermined by the 99mTc and 188Re concentration in thegenerator eluate. Generally 99mTc and 188Re eluates areproduced from the generators in fixed volume and the99m
Tc and 188Re concentration of the eluates decreases withthe life time of the generators due to radioactive decay ofparent nuclides 99Mo and 188W, respectively. Consequently,
the useful life time of the generator is also a function ofavailable 99mTc and 188Re concentration of the eluate. The
injection dose activity of 99mTc- and 188Re-based
radiopharmaceuticals delivered in 1 mL solution (99mTc- or
188
Re- concentration, mCi/mL) is an important factor in
determining the useful life time of the 99mTc and 188Re
generators and the quality of 99mTc based SPECT imaging
diagnosis or 188Re –based radiotherapy, respectively. So,
the radioisotope concentrator device should be developed
to increase the concentration and quality of injectable 99mTc
and 188Re eluates and the life time of the generators.
99m

II. METHODS
A multi-elution, radioisotope concentrator device [1], inline eluted via evacuated-vial and through disposable sterile
filters was developed to increase the concentration of 99mTc
or 188Re in the elution of aged commercial 99mTc or 188Re
generators. The increase in 99mTc concentration in theeluate enhances the utilisation of technetium in Technegas
generator-based lung perfusion (100-250 mCi/mL) andother SPECT (20-30 mCi/mL) imaging studies. A selfshielded radioisotope concentrator device (Fig. 1a) was
created based on a newly developed sorbent/concentrator
column which selectively retains 99mTcO4- ions fromdownstream of 10 mL 99mTc solution eluted from thegenerator. The eluate is freed from Cl- and MoO4- ions bypassing through a competitive ion-selective column. 99mTc
is then eluted from the concentrator column with 1.0 mL
saline into an evacuated vial through a millipore filter andready for injection. The design of the device in form of adisposable cartridge was optimised to make elution processeffective, simple, sterile and radiation safe. Gentech 99mTc
generator of 110 GBq activity eluted with 10 mL saline waschosen to test our radioisotope concentrator device.

III. RESULTS
As a result obtained from our project, the 99mTc eluate wasconcentrated more than 10-fold with a 99mTc recovery yieldof > 85% using this radioisotope concentrator device. 5 or
10 repeated elutions were successfully performed with eachcartridge coupled to the 10 mL or 5 mL saline solution
eluted generators, respectively. So, each cartridge can beeffectively used for one week in the hospital environment
for radiopharmaceutical formulation. The useful lifetime of
the 99mTc generator was significantly extended from 10-20
days for the generators of 300-3000 mCi activity,
respectively. The 99Mo impurity in the 99mTc solution eluted
from the Gentech generator was totally eliminated by thisradioisotope concentrator device (Fig. 1c).
IV. CONCLUSION
We conclude that the radioisotope concentrator device
functioned well and is robust in operation. This device will,
to some extent, mitigate the global 99mTc crisis. This
concentrator device is under patent-pending.

Fig. 1. Radioisotope concentrator device withstandard accessories (a) and the radioisotope
concentrator device coupled with 99mTc generator for
in-line elution/concentration of 99mTc eluate (b).

REFERENCE[1] Le V.S, McBrayer J., Morcos N. (2012) Australian Patent
AU2012904683APSORC’13 Body Text

－ 178 －

23-RPP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Production and Preclinical Evaluation of Diagnostic and Therapeutic Radionuclides
in Tumor-Bearing Mice: Recent Developments at Paul Scherrer Institute
A. Türler1,2, M. Behe3, M. Bunka1,2, H. Dorrer1,2, A. Hohn3, K. Johnston4, U. Köster5, C. Müller3,
J. Reber3, R. Schibli3, N.T. van der Walt6, K. Zhernosekov1,2
1

Laboratory of Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, Villigen-PSI, Switzerland
2
Laboratory of Radiochemistry and Environmental Chemistry, University of Bern, Bern, Switzerland
3
Center for Radiopharmaceutical Sciences ETH-PSI-USZ, Paul Scherrer Institute, Villigen-PSI, Switzerland
4
Physics Department, ISOLDE/CERN, Geneva, Switzerland
5
Institut Laue-Langevin, Grenoble, France
6
Faculty of Applied Sciences, Cape Peninsula University of Technology, Bellville, South Africa

Abstract – At PSI we have initiated a close collaboration of theLaboratory of Radiochemistry and Environmental Chemistry andthe Center for Radiopharmaceutical Sciences to bring novel
diagnostic and therapeutic radiopharmaceuticals to the point ofclinical trials. Pre-clinical studies using tumor-bearing mice wereconducted at PSI and ETH Zürich. At the university hospital in Bernthe required infrastructure for clinical trials was established.
Keywords – theranostics, diagnostic radionuclides, 44Sc, 152Tb, 155Tc,
therapeutic radionuclides, 149Tb, 161Tb, DOTA-folate conjugate,
targeted radionuclide therapy,

I.

INTRODUCTIONRadiopharmaceuticals which comprise metallic radionuclides are valuable diagnostic and therapeutic tools in
nuclear oncology. Several clinics worldwide have started
targeted radionuclide therapies based on 177Lu- or 90YDOTA-TOC, a somatostatin receptor targeting peptide totreat metastatic gastro-entero-pancreatic neuroendocrine
tumors. For diagnostic purposes 177Lu can be replaced withthe short-lived positron emitter 68Ga available from a68
Ge/68Ga generator system.
Further development and implementation of suchinnovative radiometallated drugs depend, however, directlyon the availability of radiometals. Compared to otherlanthanides, the element Tb comprises a quadruplet ofclinically attractive radionuclides, such as 152Tb and 155Tb,
with suitable decay properties for PET and SPECT imaging,and, 149Tb and 161Tb, suitable for targeted alpha- and betaradionuclide therapy. To assess the diagnostic and therapeutic
features of these four radioisotopes we employed the folic
acid/folate receptor (FR)-targeting strategy.
In addition, we investigated the use of 44Sc (t1/2 = 3.97 h,
E+av = 632 keV) as a valuable alternative to short-lived 68Ga
(t1/2 = 68 min, E�+av = 830 keV) for imaging of cancer prior
to 177Lu-based radionuclide therapy. The aim of the study was
the preclinical evaluation of a folate conjugate labeled withcyclotron-produced 44Sc and to compare these data with thoseof the 177Lu-labeled match.

A. Production of Radionuclides
The neutron deficient 149Tb, 152Tb, and 155Tb wereobtained in several beam times at CERN-ISOLDE byspallation of a Ta target with 1 GeV protons followed bymass separation. The low energy isobaric ion beams were
implanted in Zn covered Au foils.
A production facility for up to 20 GBq of n.c.a. 161Tb was
established at PSI. Samples of enriched 160Gd were irradiatedat PSI-SINQ, FRM-II Munich, or ILL Grenoble. It waspossible to routinely produce 161Tb of excellent radionuclidic
purity and highest specific activity (i.e. >3700 GBq/mg), sothat labeling of i.e. DOTATATE was possible with a molar
161
Tb:DOTATATE – ratio of 1:3.5 with 99.41 % yield.
44
Sc was produced via the 44Ca(p,n)44Sc-nuclear reaction
at the PSI Injector 2 cyclotron using highly enriched 44Catargets. Separation from the target material was carried out by
a semi-automated process using extraction- and cationexchange chromatography.
B. Preclinical Evaluation
A summary of results obtained in in-vivo experiments withall four Tb-isotopes is shown in Figure 1.
Control�Treated

149Tb-therapy

with alphaparticlestutu

152Tb-PET

in vivoapplication

tu

tu

Tumor
KidneyControl�Treated
Tumor

Kidney

tu

tu

tu

tu
161Tb-therapy

with low energy
beta particles

155Tb-SPECT

in vivoapplication

Figure 1: Left-hand side: treatment of tumor bearing mice withTb (�-particle therapy) and 161Tb (�-particle therapy) DOTA-FOLATE.
Right-hand side: PET and SPECT images of tumor bearing mice with 152Tb
and 155Tb DOTA-FOLATE, respectively.
149

[1]

－ 179 －

C. Müller et al., J. Nucl. Med. 53, 1951-1959 (2012).

23-RPP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201399

Mo production by 100Mo(n,2n)99Mo using accelerator neutrons

Nozomi SATO1, Masako KAWABATA1, Yasuki NAGAI1, Kazuyuki HASHIMOTO1,
Yuichi HATSUKAWA1, Hideya SAEKI1, Shoji MOTOISHI1, Tadahiro KIN2, Chikara KONNO3,
Kentaro OCHIAI3, Kosuke TAKAKURA3, Futoshi MINATO4, Osamu IWAMOTO4,
Nobuyuki IWAMOTO4, and Shintaro HASHIMOTO4
1

Nuclear Engineering Research Collaboration Center, Japan Atomic Energy Agency
2
Faculty of Engineering Sciences, Kyushu University
3
Fusion Research and Development Directorate, Japan Atomic Energy Agency
4 Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

Abstract – We proposed a new route to produce a medical
radioisotope 99Mo by the 100Mo(n,2n)99Mo reaction using
accelerator neutrons. A high-quality 99Mo with a minimum level ofradioactive waste can be obtained by the proposed reaction. The
decay product of 99Mo, 99mTc, is separated from 99Mo by the
sublimation method. The proposed route could bring a major
breakthrough in the solution of ensuring a constant and reliablesupply of 99Mo.
Keywords – 99Mo radioisotopes, diagnosis, accelerator neutrons,
neutron induced reaction, SPECTI.

of 2 cm was irradiated by neutrons. The sample was placed 2
cm downward from the natC or 9Be target.
The 99Mo harvest frequency, determined by the ratio, R =99
N( Tc)/N(99mTc), is also important. Here, N(99Tc) andN(99mTc) are the numbers of 99Tc (T1/2 = 2.1 � 105 y, uselessin diagnostic use), and 99mTc. The calculated R values were
1.2, 3.0, and 11 for one, two and six-days of irradiation. The
harvest frequency will be every two or three days byconsidering the available amounts of 100Mo and the 99Mo
decay during the 100Mo sample irradiation.
III. EXPERIMENT AND RESULTINTRODUCTION

99m

Tc (half-life, T1/2 = 6.0 h), the daughter nuclide of 99Mo
(T1/2 = 66 h), is the most common radioisotope used indiagnosis, and its use accounts for 80% of all nuclear
medicine procedures worldwide.1) 99mTc has a versatile
chemistry that allows it to be incorporated into all sorts ofmolecules, and because of the short half-life of 99mTc, 99mTc
is routinely produced in 99Mo/99mTc generators. 99Mo has
been mostly produced by the fission reaction of highly
enriched 235U in research reactors. However, an unscheduled
shutdown of some of these reactors has recently caused acrisis shortage of 99Mo worldwide, which triggered
widespread discussions on the 99Mo supply.2) The 99Mo
production using a charged-particle induced nuclear reaction,such as the 100Mo(p,pn)99Mo, 100Mo(d,p2n)99Mo, and100Mo(p,2n)99mTc reactions, has been investigated.3) We
proposed a new route to produce 99Mo using fast neutrons
from an accelerator,4) and we have been carrying out
important steps necessary to obtain high-quality 99mTc.
II. 99MO PRODUCTION BY ACCERELATOR NEUTRONSIntense neutrons with an average energy of 14 MeV arenecessary to produce a large amount of 99Mo by the100
Mo(n,2n)99Mo reaction. Neutrons can be produced fromthe natC(d,n) or 9Be(d,n) reactions at deuteron energy of 40
MeV. The production yield of 99Mo was estimated using theevaluated cross section of 100Mo(n,2n)99Mo,5) and the neutron
intensity. Typically, we assumed a metallic 100Mo sample(251 g, 100% enriched) with a radius of 2 cm and a thickness

99

Mo was produced by irradiating an enriched 100MoO3
sample with �14 MeV neutrons from the 3H(d,n)4He reaction
at the Fusion Neutronics Source (FNS) facility of Japan
Atomic Energy Agency (JAEA). Gamma-rays from the decayof 99mTc and 99Mo were clearly observed. Yields of impurity
isotopes, such as 97Zr and 97Nb, were much smaller than thatof 99Mo.
To separate high-quality 99mTc from the produced 99Mo,
we used the sublimation method, which is based on adifferent volatility of Tc2O7 and MoO3.6) The irradiated100
MoO3 sample was placed in a furnace, and heated so as toform gaseous materials containing vaporized 99mTc2O7 in a
stream of oxygen carrier gas. 99mTc was condensed at the exitof the furnace, and was eluted with a saline solution. As aresult of the �-ray measurement of the separated 99mTc, theupper limits of �-rays from any impurity isotopes were foundto be very small. A sublimation method allows us to recycle
any irradiated enriched 100Mo. Labeling efficiency, an
important factor in the compounding and dispensing ofradiopharmaceuticals, was shown to be higher than 90% by
formulating a radiopharmaceutical.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]

－ 180 －

F. F. Knapp, Jr. and S. Mirzadeh: Eur. J. Nucl. Med. 21 (1994) 1151.
J. R. Ballinger: J. Labelled Compd. Radiopharm. 53 (2010) 167.
K. Bertsche: Proceedings of IPAC’10, Kyoto, Japan. (2010) 121.
Y. Nagai and Y. Hatsukawa: J. Phys. Soc. Jpn. 78 (2009) 033201.
K. Shibata, et al.: J. Nucl. Sci. Technol. 48 (2011) 1.
C. Perrier and E. Segre: J. Chem. Phys. 5 (1937) 712.

23-RPP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Production and Separation of 64Cu and 67Cu using 14 MeV Neutrons
Masako Kawabata1, Kazuyuki Hashimoto1, Hideya Saeki1, Nozomi Sato1, Shoji Motoishi1, Kosuke
Takakura2, Chikara Konno2 and Yasuki Nagai11

1,2

Nuclear Engineering Research Collaboration Centre, 2Fusion Research and Development Directorate
Japan Atomic Energy Agency (JAEA), 2-4 Shirane, Shirakata, Tokai, Naka-gun, Ibaraki, 319 1195, Japan

Abstract –64Cu and 67Cu were produced from 14 MeV neutron
irradiated natural ZnO and enriched 64ZnO targets via 64Zn(n,p)64Cu and 67Zn(n,p)67Cu reactions. The ZnO disc targets were
irradiated for 6 hours by 14 MeV neutrons, which are generated bybombarding a tritiated titanium target with deuteron beam at the
Fusion Neutronics Source (FNS) at Japan Atomic Energy Agency(JAEA). After irradiation, ion chromatographic separations werecarried out to obtain purified no-carrier-added Cu radionuclides.
Elution pattern clearly showed separation of 64Cu and 67Cu giving ayield of > 90%, and a very low radionuclide impurity ratio of 65Zn
within the purified 64Cu.

with 20 ml of 2 M HCl and passed through an AG1-X8
column (0.8� � 12.0 cm) to remove traces of Zn followed by
a washing with 10 ml 2 M HCl [10]. The drop rate wasregulated to be 1 ml/min throughout the separation. The
purified 64,67Cu solution was evaporated and dissolved in 1 ml
0.4 M ammonium acetate (pH5.5), filtered, and then reactedwith TETA (1,4,8,11-tetraazacyclotetradecane-1,4,8,11tetraacetic acid) solution for 2 hours [11]. The labeling yield
was determined by silica gel TLC / 1:1 methanol-10 �
ammonium acetate.

Keywords – 64Cu, 67Cu, radioisotope production, 14 MeV neutrons,
nuclear medicine,III. RESULTS & DISCUSSIONI.

INTRODUCTION

64

Cu (T1/2 12 h, E.C.= 43%, �+ = 18%, �- = 40%) and 67Cu
(T1/2 62 h, �- = 100%) [1] have attracted attention inradiopharmaceutical applications for their unique decay
properties and chemical characteristics [2]. Being a positron
and a beta emitter, 64Cu is a strong candidate for the agents ofboth positron emission tomography imaging and targetedradiotherapy. 67Cu, a longer-lived beta emitter can be used forradiotherapy to treat small tumors with a diameter of 2-3 mm[3]. Cu radionuclides can be produced either with cyclotrons
by bombarding Ni or Zn targets with proton beams, e.g.
64
Ni(p,n)64Cu, 68Zn(p,�n)64Cu, 68Zn(p,2p)67Cu, or in a nuclear
reactor by bombarding a target with thermal neutrons [4,5].
The studied methods using cyclotron generated proton beams,
however, include relatively expensive targets, unwanted
radionuclides or complex chemical separation [5-8]. The
current study investigates a production route of 64Cu and 67Cu
from 64Zn(n,p)64Cu and 67Zn(n,p)67Cu reactions, by
irradiating natZnO or 64ZnO with 14 MeV neutrons [9], and asubsequent chemical separation.
II. EXPERIMENTAL
nat

ZnO and 64ZnO (99.935% enriched 64Zn) disc targets(20� � 5 mm, 5 g) were individually irradiated by 14 MeV
neutrons at FNS in JAEA for 6 hours. The average neutron
flux was ca. 1.0 � 1011 n/s generated via 3H(d,n)4He reaction.
The irradiated target was dissolved in 20 ml of 36 wt% HCl
after which the pH was adjusted to 3.5-4.0 with 10 M NaOH.
The sample was passed through a Chelex-100 exchange
column (1.1� � 11.5 cm) followed by washing with 100 ml of
0.001 M HCl to remove Zn [10]. The 64,67Cu was then eluted

The production of 64, 67Cu by irradiating nat, 64ZnO with 14
MeV neutrons reduced the consequent chemical separation
process because of fewer side products (e.g. only 65Zn ifenriched 64ZnO is used), which saves considerable time incomparison with 64, 67Cu production by proton-irradiation [8,10]. The time required for the column separation process was
3 hours and could be shortened further if the system was fully
automated. Over 95% of the 65, 69Zn side products wereseparated by the ion exchange Chelex-100 column, which canbe recovered as Zn(OH)2 by alkaline precipitation anddecomposed to ZnO upon heating [8]. Radioactivity of 0.79
MBq/g 64Cu, 6.3 kBq/g 67Cu from natZnO and 2.5 MBq/g 64Cu
were obtained from 64ZnO at the end of bombardment. A
high separation efficiency was observed from the Chelex-100(98%) and the AG1-X8 (95%) based on the 64Cu yield of two
experiments, with the final product having a 65Zn
radionuclide impurity below the detection limit of gamma-ray
spectrometry. The labeling efficiency of Cu-TETA forclinical radiotherapy applications was found to be good at
94.4%.
REFERENCES
[1]
[2]
[3]

Monographie BIPM-5, Table of radionuclides, Vol. 2, 2004
Blower P.J, Lewis J.S. et al., Nucl med biol, 23, 957, 1996
Ting G.,Chang,C.-H. et al., J Biomed Biotechnol, 2010, ID953537,
2010[4] Qaim S.M., Radiochim Acta, 100, 635, 2012[5] Novak-Hofer I. and Schubiger P.A., Eur J Nucl Med, 29(6), 821, 2002
[6] McCarthy D.W., Shefer R.E. et al., Nucl med biol, 24, 35, 1997
[7] Le,V.S., Pellegrini P. et al, J Radioanal Nucl Ch, 277(2), 451, 2008[8] Katabuchi T., Watanabe S. et al., J Radioanal Nucl Ch, 277(2), 467,
2008[9] Kin T., Nagai, Y. et al., J Phys Soc Jpn, 82,034201-1, 2013[10] Schwarzbach R., Zimmermann K. et al., Appl Radiat isot, 46(5), 329,
1995
[11] Sun X., Wuest M. et al., J Biol Inorg Chem, 8, 217, 2003

－ 181 －

23-RPP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Novel radiochemical separation of arsenic from selenium for 72Se/72As generator.
Ewelina Chajduk1, Halina Polkowska-Motrenko1, Aleksander Bilewicz1
1

Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland

Keywords–
selenium-arsenic
separation,
chromatography, PET, 72Se/72As generator

extraction

The potential usage of arsenic isotopes for nuclear
medicine has been reported recently. One of theway for obtaining appropriate radioarsenic species
is using radionuclide generator, where As isformed by the radioactive decay, eg.72Se� 72As. A
new radiochemical separation scheme based on
extraction chromatography for isolation As fromSe is presented. The distribution coefficients of As
and Se on prepared sorbents were determined inorder to find the best condition for separation ofboth elements. Batch experiments were verified bycolumn studies.
Elaborated radiochemical
separation scheme insures high selectivity andradionuclide purity of separated arsenic fraction,
whereas examined sorbents have been found tohave a very high selectivity with reference toselenium (IV). Arsenic is easily eluted by diluted
HCl and NaCl solutions. Proposed approach
insures high selectivity and radionuclide purity ofseparated arsenic fraction; it is also characterizedby high elution efficiency (>95 %) using small
volume (2 mL) of 0.9 % NaCl with very low
breakthrough (<0.01 %) of selenium.
Acknowledgments: This work was partly supportedby the grant of Polish Ministry of Science andHigher
Education,
Poland,(Nr2713/B/H03/2011/40)－ 182 －

23-RPP-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Training Program of Synthesizing a Radiopharmaceutical in KAERI
1

S. Yang1, Y. H. Chung2

Advanced Radiation Technology Institute, Korea Atomic Research Institute, Jeongeup, 580-185, Korea
Department of Chemistry, Hallym University, 1 Hallymdaehak-gil, Chuncheon 200-702, Korea; yhchung@hallym.ac.kr

2

Radiopharmaceuticals have widely been used in diagnosesof various medical conditions. Medical facilities using
radiopharmaceuticals such as 2-deoxy-2-[18F]fluoroglucose(18F-FDG) have increased in number in Korea. 18F-FDG isabsorbed into cells such as brain and kidney along withcancer cells. Without the hydroxyl group replaced to 18F it
fails to undergo glycolysis in the cell and cannot leave it
before its radioactive decay, which provides a quantitative
distribution of glucose uptake and phosphorylation in cells.
As 18F-FDG is used in many medical facilities, a reliable
quality control system is needed in its synthesis in addition
to technical staff who can handle the process. KAERI
recently started to operate its own 30-MeV cyclotron at
Jeongeup, where 18F-FDG is to be produced. A month-longtraining program is planned for college undergraduates andgraduates to learn synthesis of 18F-FDG and its handling,which would fill national future demand of skilled technicalpersonnel.

－ 183 －APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201323-RPP-07

��������������������������������������������������������������������������
���������������������
Yumi Sugo, Ichiro Sasaki, Shigeki Watanabe, Yasuhiro Ohshima, Noriko S. Ishioka
Quantum Beam Science Directorate, Japan Atomic Energy Agency

Abstract Ð 64Cu was produced by the cyclotron using
64
Ni(p,n)64Cu nuclear reaction. MARSGL peptide has high affinity
to HER2/neu overexpressing in various cancer cells. In this study,
64
Cu-DOTA-MARSGL was designed and synthesized as a novel
PET imaging probe for HER2/neu overexpressing tumors.

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Keywords Ð 64Cu, Positron, DOTA, Peptide, HER2/neu

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Copper-64 is an attractive radionuclide for positronemission tomography (PET) imaging as well asradiotherapy due to its half-life (T1/2=12.7 h) and decay
characteristics (�+ 17.4%, �- 39%). MARSGL (H-Met-AlaArg-Ser-Gly-Leu-OH) is a linear peptide having highaffinity to HER2/neu overexpressing in various cancer cells[1].
1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetic
acid (DOTA) is a macrocyclic ligand for various metal ions.

EDCIáHCl, HOBt

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Cu was produced by the AVF cyclotron of Takasaki
Ion Accelerators for Advanced Radiation Application
facility at Japan Atomic Energy Agency using the nuclear
reaction of 64Ni(p,n)64Cu. Radiochemical separation of 64Cu
was carried out by chelating ion-exchange method [2].

Cu-labeling of DOTA-MARSGL was carried out inacetate buffer. The formation of 64Cu-DOTA-MARSGL
was determined by reversed-phase TLC and HPLC.

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In this study, we designed Cu-labeled MARSGL
peptide conjugated with DOTA as an imaging probe for
HER2/neu overexpressing tumors.

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Protected MAR(Pbf)S(tBu)GL-Trt(2-Cl) resin was
prepared by solid-phase peptide synthesis using automatic
peptide synthesizer (Aapptec, Titan 357). As shown in
1,4,7,10-tetraazacyclododecaneFig.1,
tri-tert-butyl
1,4,7,10-tetraacetate was allowed to react with the peptide
resin by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimidehydrochloride(EDCIáHCl)and1-hydroxy-1Hbenzotriazole (HOBt) in dimethylformamide. And then thecleavage and the deprotection were performed at the sametime using trifluoroacetic acid (TFA), 1,2-ethanedithiol(EDT), and triisopropylsilane (TIS).

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TFA:EDT:H2O:TIS=94:2.5:2.5:1
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Fig. 1 Synthesis of DOTA-MARSGL by solid-phase conjugation.

REFERENCES[1][2]

In order to evaluate the usefulness of 64Cu-DOTAMARSGL peptide as a PET imaging probe, in vitro
stability and affinity to HER2 are under investigation.

－ 184 －

M. Houimel et al., Int. J. Cancer, ��, 748 (2001).
Sh. Watanabe et al., Nucl. Med. Biol, ��, 587 (2009).

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23-RPP-08

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Molybdenum Isotope Fractionation in Ion Exchange Reaction
by using Anion Exchange Chromatography
Masafumi Inaki1, Yu Tachibana1, Masao Nomura2 and Tatsuya Suzuki1
Department of Nuclear System Safety Engineering, Nagaoka University of Technology
2
Reserch Laboratory for Nuclear Reactors, Tokyo Institute of Technology

Abstract – The molybdenum isotope fraction in ion exchange
reaction in hydrochloric acid solution was investigated by using
the anion exchange chromatography. We confirmed that theheavier isotopes are enriched in solution phase.
Keywords – technetium-99m, molybdenum-99, molybdenum
isotope, isotope enrichment

I.

INTRODUCTION
99m

Technetium-99m ( Tc) is one of the most importantradioisotopes in nuclear medicine. 99mTc is generated frommolybdenum-99 (99Mo). Now, 99Mo is mainly produced byfission of highly enriched uranium-235 (HEU). However,the supply of 99Mo becomes unsteady, since the reactors
for the generation of 99Mo become older. In addition, theuse of HEU causes the problem of nuclear proliferation.
Thus, new production technologies for 99Mo and 99mTc by
non-use of HEU are required and investigated [1,2]. The
typical technologies use the molybdenum targets, such as
100
Mo(n, 2n)99Mo [3], 100Mo(p,x)99Mo or 99mTc [4],98Mo(n,�)99Mo [5]. These methods are required theenriched molybdenum isotopes. We are investigating themolybdenum isotope separation by chemical exchange. In
the present work, the molybdenum isotope fractionation by
ion exchange is studied. The geochemists have also muchinterest in the molybdenum isotope fraction in chemical
reaction, recently [6,7]. Our study may help theunderstanding of molybdenum fraction in nature.
II. EXPERIMENTAL
1. Materials
Na2MoO4·2H2O supplied by Junsei Chemical Co., Ltd.
was used. The purity of Mo(VI) was more than 99.0 %. The
acidic concentrations of the solutions dissolved Mo speciesof 0.1 M(M = mol/L) were adjusted to 0.1, 0.5, 1.0, 2.0, 4.0,
6.0, 9.0, and 11.2 M using HCl. The high-porous
benzimidazole-type anion-exchange resin embedded inhigh-porous silica beads which has two functional groups
consisted of 4-(1-methylbenzoimidazole-2-yl)phenyl and 4(1,3-dimethyl-benzoimidazole-2-yl)phenyl was used for
Mo isotope fractionation.
2. Chromatography Experiments
Five columns connected in series were used for theisotope fractionation chromatography. Each column has thediameter of 0.8 cm and the length of 100 cm. Total volumeof the resin packed into these columns was 84.8 mL. The
temperature of columns was kept at 308 K. The
breakthrough experiments using 0.1 M of Mo species
dissolved in 0.10 - 11.2 M HCl were performed. The flowrate was controlled at 0.35 mL/min by using the highpressure pump made of Nihon Seimitsu Kagaku Co., Ltd.
The Mo isotope ratios were measured using ICP-MS(7700x,
Agilent). Mo concentrations in samples for isotope ratio
measurements were adjusted at ca. 1.0 ppb (ppb = ng/g),
and all sample solutions was used as 2.0 % HNO3.
III. RESULTS AND DISCUSSION
The breakthrough experiments for Mo isotope
fractionation were carried out under conditions, [Mo]T =0.1 M(subscript T means total concentration), [HCl]T = 0.1- 11.2 M, and Temp. = 308 K. The typical result of Mo
isotope fractionation was shown in Figure 1. As shown in
the figure, it was found that heavier isotopes are
disproportionately distributed into a solution phase. The
hexavalent molybdenum in solution is known to have many
type of chemical species, such as oxoacid ions, complexes,
and their combines. Mo isotope fractionations are attributed
to the chemical exchange among their species.
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Figure 1. Molybdenum breakthrough curve and molybdenum isotope
fractionation by anion exchange chromatography using 2 M HCl solution.

ACKNOWLEDGEMENT
This work was partially supported by the Grant-in-Aid
for Challenging Exploratory Research (KAKENHI No.
24656567).
[1]
[2]
[3]
[4]
[5]
[6]
[7]

－ 185 －

IAEA Nuclear Energy Series No. NF-T-5.4 (2013)
IAEA TecDoc 1065 (1999)
Y.Nagai, Y. Hatsukawa, J. Phys Soc. Jpn. 78(2009)33201
K. Gagnon, et al. Nucl. Medicine & Biology 38(2011)907.
A. Kimura, et al, IOP conf. Series : Mat. Sci & Eng. 18(2011)42001
T. Kashiwabara, et al. Geochem. J. 43(2009e31.
J. Barling, A.D.Anbar Earth & Planetary Sci. Lett. 217(2004)315.

23-APP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The Mechanism of Oxidized Multi-walled Carbon Nanotubes across Placental
Barrier and Its Effects on Pregnany
QI Wei1, BI Juanjuan1, WANG Jing1, LI Zhan2, LIU Peng1, WU Wangsuo1*
Radiochemical Laboratory, Lanzhou University, Lanzhou, Gansu, China, 730000
2
Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou, Gansu, China, 730000
1

Abstract
The mechanism of nanoparticles across placental barrier wasstudied post injected intravenously with solution of oxidized multiwalled carbon nanotubes (oMWCNTs) labeled by technetium-99m
into pregnant mice, the rate and mechanisms of abortion were also
investigated via measuring content of progesterone and estradiol inmaternal serum. The results indicated that oMWCNTs could acrossplacental barrier and enter into fetus body, and caused highdistribution of fetal lung, and then eliminated gradually; oMWCNTs
could decrease level of progesterone and increase level of estradiol
in serum, that depended on exposure dosage and time, but weakened
with the extension of gestational ages; the abortion rate ofprimiparous, second-parous and fourth-parous pregnant micecaused by oMWCNTs was 70%, 40% and 50%, respectively, andalso the maternal body weight growth were inhibited until
gestational age of 13, 10 and 11 days, respectively. Therefore,
oMWCNTs can damaged normal pregnancy, and that was more
serious for primiparous.
Keywords: oMWCNTs; placenta; biodistribution; abortion rate;
progestational hormone.

Table 1.The statistics of abortion rates after exposure oMWCNTs (n=10).

GroupFirstoMWCNTsFirst-control
SecondoMWCNTs
Second-control
FourthoMWCNTs
Fourth-control

Ectroma(colpobleeding)

Average weightchange before andNormalparturition after production
/g

Total
abortion
rate

7

3

8.57±8.95*

70%

1

9

20.73±9.00

10%

4

6

13.99±9.44

40%

0

10

15.83±4.24

0

5

5

11.18±5.82

50%

3

7

12.72±5.7830%*p<0.05, group vs. normal.

Figure. The exposure time of oMWCNTs effects on the progesterone in themice at gestational age of 18 days (n=4-5, *p<0.05, group.vs normal,&
p<0.05,group vs. Et-500ug).

*Corresponding author: WU Wangsuo, Tel & Fax:(+86)09318913594, Email address: wuws@lzu.edu.cn,－ 186 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

23-APP-02

Prompt Gamma Test of a Large Volume Lanthanum Bromide Detector
Naqvi, A. A*1 , M. A. Gondal1; M. Raashid1; Khateeb-ur-Rehman1, M. Dastegeer1
1Department of Physics,
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
Abstract – Response of a large LaBr3:Ce detector has been tested
over broad range of gamma rays using prompt gamma ray
neutron activation analysis technique,. Due to its larger size,

the detector has poorer energy resolution a 76 mm x 76 mm(diameter x height ) cylindrical LaBr3:Ce detector

Keywords – Large LaBr3:Ce detector, performance tests using
prompt gamma rays, portable neutron generator, chlorine,
mercury and cadmium contaminated bulk water samples

I.

INTRODUCTION

The application of Prompt Gamma-ray Neutron Activation
Analysis (PGNAA) technique is growing further due to thefabricationofradiation

hardenedlanthanum-halide(LaBr3:Ce and LaCl3:Ce ) gamma ray detectors. Although
LaCl3:Ce detectors and LaBr3:Ce detectors have a fast risetime, excellent light output and energy resolution but they
have intrinsic activity, which increases with detector
volume.

This may limit their utilization in PGNAA

application. King Fahd University of Petroleum andMinerals , Dhahran, Saudi Arabia

has acquired acylindrical 100 mm x 100 ( diameter x height ) LaBr3:Ce
detectorfor

its

promptgamma

rayprogram.

A prompt gamma ray neutron activation analysis setup has
been developed using a MP320 D-D reaction-based
portableneutrongenerator

toanalyzeelemental

concentration of bulk samples. Response of the cylindrical
100 mm x 100 mm (diameter x height) LaBr3:Ce detector
has been measured for detection of chlorine, mercury andcadmium contaminatedbulk water samples, Comparedwith performance of a smaller 76 mm x 76 mm LaBr3:Ce
detector reported earlier [ 1], the larger volume LaBr3:Ce
detector has higher intrinsic activity and poorer energy
resolution. Results of the study will be presented.
[1]

Performance test of the large volume detector
were carried out over broad range of gamma rayenergies emitted in thermal neutron capture inbulk samples.

－ 187 －

Naqvi A. A., M.S. Al-Anezi, Zameer Kalakada, Faris A. Al Matouq,
M. Maslehuddin , M. A. Gondal , A. A. Isab, Khateeb-ur-Rehman.

and M. Dastageer Response Tests of a LaCl :Ce Scintillation3

Detector With Low Energy Prompt Gamma Rays From Boron andCadmium. Applied Radiation and Isotopes, Vol.70 (2012) pp. 882887.

23-APP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Radiation-Induced Reactions in D, L-�-Alanine Adsorbed in Solid Surfaces
E Aguilar, A. Negrón-Mendoza, and C. Camargo

Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Mexico DF 04510, Mexico

Abstract
The aim of this work is to study the behavior under irradiation of D,
L and D-L �-alanine adsorbed in solid surfaces, as possible phasein the chemical evolution that may have occurred on the primitive
Earth or in extraterrestrial environments and to evaluate thecontribution of solids (a clay mineral) as shields for the adsorbed
amino acids against a external energy source. The results show that
�-alanine is adsorbed in the surfaces as function of pH and its yieldof decomposition in mineral suspension is lower than the system
without the solid surface. These results show the importance of
nuclear techniques in these types of studies.
Keywords – �-Alanine, chemical evolution, gamma radiation, clay
mineralI.

III.

EXPERIMENTAL PROCEDURES

The solid surface was sodium montmorillonite of Wyoming
bentonite. Aqueous solutions of �-alanine were tested (racemicand pure enantiomeric forms) at concentrations of 0, 01 M anddifferent pH values (2, 4, and 6). The oxygen was removed bypassing argon through the solutions. The irradiations werecarried out in a 60Co- gamma source. The radiation doses werefrom 0 to 91 kGy. The analyses were made by high pressureliquid chromatography with a Chiral column (ChirobioticT®),
coupled to light scattered detector (ELSD). The solid phase

RESULTS

The adsorption data shows that the �-alanine (D and L or
D; L) is absorbed readily in the clay. The adsorption occurs toa maximum degree at low pH. At basic pH the adsorption
was very low. The gamma irradiation of samples show low
yield of recovery of the amino acid without clay. The
summary of the recovery percent is in Table I.
Table I Survival Percent of �-Alanine after irradiation

INTRODUCTION

The emergence of life on Earth needed a physical andchemical preamble. There is a large variety of experimental
data to support the hypothesis for the abiotic formation oforganic compounds [1, 2]. Although much knowledge has
been obtained, many questions remain. One important factor
in chemical evolution is related to the importance of randomchemical synthesis/decomposition versus more selective
pathways forming compounds of biological relevance. It is
important then to explore chemical mechanisms able to narrow
the variety of prebiotic chemical compounds liable to be usedin the construction of primitive living systems. We study asimple chemical system: an amino acid adsorbed in a clay
mineral and exposed to ionizing radiation.
Our interest is twofold: (1) to evaluate the role that a solid
surface plays to protect the compound adsorbed in the solid. (2)To show experimentally that biased reactions might haveoccurred in geologically relevant conditions on the primitive
Earth, for example to study if there is a preferential destruction
by ionizing radiation of one of the optical isomers of �-alanine.
II.

was analyzed by X-ray, IR and electron spin resonance. The
experiment was carried out 15 times to check the repeatabilityof the results.

IV.

REMARKSIt was observed that the presence of mineral drasticallydecreases the damage to that amino acid by action of the
gamma radiation. The observed general tendency shows theL-�-alanine as the most resistant to ionizing radiation,
especially when is radiated in enantiomerically pure solutions,the difference is very slight, but this small difference may be
amplified with time and by other mechanism. This resultshows the important role of minerals in chemical evolution
processes.
ACKNOLEDGEMENTS
This work was supported by PAPIIT Grant No. IN1107123 and the CONACyT Grant No. 168579/11. The technicalsupport from C. Camargo, B. Leal, and F. García-Flores is
acknowledged.
REFERENCES[1][2]－ 188 －A. Negrón Mendoza, S. Ramos-Bernal and G. Mosqueira, Int. J.
Astrobiol. 3, 295-300, 2005
. S. L. Miller and L. Orgel, The Origins of Life on Earth, Prentice-Hall,
Inc. New Jersey, 1974.

23-APP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201336

Cl determination in steel radioactive waste

F. Goutelard1, P. Perret1, C. Hamon1, R. Brennetot1, C. Andrieu2
1

Operator Support Analyses Laboratory, Atomic Energy Commission, CEA Saclay, DEN/DANS/DPC/SEARS/LASE,
Building 459, PC171, 91191 GIF SUR YVETTE CEDEX, FRANCE

2

Electricité de France, EDF – CIDEN / Département Etudes - Division Déconstruction/Groupe Inventaire et Agréments, 154
Avenue Thiers, CS 60018, 69458 LYON CEDEX 06

Abstract – APSORC’13 Abstract
Within the framework of the nuclear power plants
dismantling, approximately 3600 tons of metallic radioactive
wastes will be generated. Located near the reactor core,some of them are highly activated and 36Cl produced from thenatural stable isotope 35Cl, due to high mobility and long halflife, becomes one of the radionuclides that significantly
control the ultimate disposal. In steel materials,
concentrations between 0.15 and 12.9ppm have beenreported [1, 2]. Depending on neutron flux intensity, 36Cl
activity calculated for a stable chlorine concentration of
1ppm varies from 0.03 to 91 Bq/g, while the upper
acceptance limit for medium activity waste is 5 Bq/g. 200
steel samples have already been collected in nuclear plants
under dismantling. Without further available data on stablechlorine content, 36Cl has to be measured.
French standard methods [3] dedicated to 36Cl measurement
in wastes does not describe this first step in details and theradiochemical method includes no more than 3mmole ofstable chlorine used as carrier and chemical yield tracer.
36
Cl is measured by liquid scintillation. A radiochemical
process dedicated to 36Cl measurement in steel radioactive
waste, has been developed in order to� ensure a detection limit far below 5Bq/g,
� treat a great flow of samples.
Furthermore, it must be adapted to as well as carbon thanstainless steel samples. And, as 36Cl is an activated product, a
total dissolution must be guaranteed.
A dissolution mixture of nitric and chlorhydric acid needed toassure a complete dissolution specially for stainless steel
samples has been optimized in order to minimize the quantityof chlorine added. Nevertheless, 25mmole of chlorine are
required to dissolve 0.2g of stainless steel, while 15mmole
are necessary for 1g of carbon steel. As a result, thefollowing separation steps have to be adapted. The
experimental set-up for the dissolution step is a three-neckflask, containing the sample and KCl as chloride source.
After gently added nitric acid, nitrogen is bubbled in thesolution in order to carry on the gas Cl2, in a trapped bottle.
With this process, only volatile radionuclides such as 14C,
129
I… are trapped.

In order to sort the samples, an aliquot of the bubbler
solution is directly analyzed. For sample with an activity
higher than 3Bq/g, the radiochemistry is carried on to isolate
36
Cl in a pure fraction in only two days. The recovery yield isdetermined at the different stages of the radiochemical
procedure,measuringstablechlorinebyionic
chromatography.
The method has been evaluated in terms of recovery yield andlimit of detection according to the French AFNOR NFT90210 standard [4]. Thus, a limit of quantification of 0,15Bq
has been experimentally verified. Considering the mass
analyzed and the limit of quantification the limit of detectionis 3 times lower than this limit of quantification, leading to alimit of detection at 0,3Bq/g and 0,15 Bq/g for stainless steel
and carbon steel samples respectively.
Results on activated steel will be presented.

[1] C.S. Sastri, G. Blondiaux, P. Mijller, H. Petri
Determination of chlorine in metals and ceramics materials
by low energy deuteron activation analysis, Nuclear
instruments and methods in physics research B, vol.119,1996
p425-428.
[2] NIREX report 772, T/REP/20021/P/08 (date d’émission :31/03/1997).
[3] Norme NF M 60-332, Détermination du chlore-36 dansles effluents et déchets par scintillation liquide, mai 2009.
[4] Norme NF T 90-210, Protocole d’évaluation initiale desperformances d’une méthode dans un laboratoire, mai 2009.

－ 189 －

23-APP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Naturally Occurring Radioactive Materials(NORM) in Malaysian Oil Sludge
Samples
1
1

2

Mohamed B.A. Teiara and 2Sukiman B. Sarmani

Department of Physics, University of Al-Zaituna, Tarhruna, Libya
School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan,
Malaysia, Bangi, 43600, Malaysia

It was in the early 70’s, when concern was started
regarding the presence of NORM associated with the oil &gas production. During 1980’s a lot of work has been
devoted to the hazards arising from the measured elevatedconcentration of NORM in this field. Recently, mostpublications concern about the effect of NORM on
personnel and environment. It was the scope of this paper
to analyze the sludge waste resulted from the Malaysian oil
fields for the presence of Naturally Occurring Radioactive
Materials (NORM) and investigated the hazardous risk
associated. This can be also used in future as a reference
data to monitor any level changes. About 30 dried sludge
samples were characterized using gamma-ray spectroscopy
based on a well shielded HPGe detector for thedetermination of the activity concentrations of 238U, 232Th,
their important progenies and 40K. The range of activity
concentrations were (10.1 – 51.0) Bq/Kg for 226Ra (186keV), (6.2 – 34.8) Bq/Kg for 214Pb (352keV), (4.7 – 17.7)
Bq/Kg for 208Tl (583 keV), (5.8 – 40) Bq/Kg for 214Bi(609keV), (5.45 – 15.7) Bq/Kg for 228Ac (911keV) and(9.2 – 46) Bq/Kg for 40K (1460keV). The radiation doses
resulted from the sample total activities were measured andcompared with standard dose limits which would be
investigated in the full manuscript.

－ 190 －

23-APP-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

On the Use of 233U and 237Np as Radiotracers for Redox Potential Measurements
Stellan Holgersson

Chalmers University of Technology, Department of Chemical and Biological Engineering, Nuclear Chemistry, Kemivägen 4,
SE41296 Göteborg , Sweden
Abstract
Reduction/oxidation(redox)potential
measurements
inenvironmental samples are usually made with electrodes. However,these have certain weaknesses in terms of stability and memory
effects. Alternative methods for determination of redox are thereforeof interest and the use of radioactive tracer elements may be one
such method, which is the subject of this investigation. It issuggested that the actinides are particularly appropriate for use as
indicators of redox, provided that their different redox states can beseparated in a fast and reliable way. A literature survey show thatsolvent extraction is an established method for separation of tracer
amounts of actinides into their redox states and three of the mostcommonly used extraction reagents of the beta-diketone type were
investigated:
thenoyltrifluoroacetone (TTA), dibenzoylmethane(DBM) and 4-benzoyl -3-methyl-1-phenyl pyrazol-5-one (PMBP). U
and Np were reduced to tetravalent state, which was confirmed with
spectropscopic measurements. Extraction curves in the pH range
0.6-7 were then measured for An(IV),(V) and (VI) . It was found that
0.5M DBM in chloroform and 0.05M PMBP in xylene gave the best
separation factor (SF=1700 resp. 1100) for actinide (IV)/(VI) and(IV)/(V) oxidation state separation, respectively, when pH ofaqueous phase was in the region 1-2. Actinide tracer was used forredox determinations of prepared samples with an artificial
groundwater, with or without addition of grains of rock and pyrite
and also a Fe(II)/Fe(III) redox-buffer. Comparison with electrode(Pt/Ag/AgCl) measurements gave values that were considerable
lower: for example 30mV for a non-redox-buffered synthetic
groundwater measured with actinide speciation, compared with
about 300mV with electrode. The actinide speciation reflects aslower response to redox changes and a preservation of an earlier
redox state of the groundwater, while the electrode responds seems
to respond fasterto changes but is thereby also more sensitive toundesirable Eh drift. It was also found that U and Np redox
speciation method also have a limited working range of about 100>Eh<100 mV so an absolute correspondence between themethods may therefore be impossible to attain if Eh is outside thisrange.
Keywords – Redox potential measurements, Groundwater, Uranium,
Neptunium, Solvent extraction－ 191 －

23-APP-07

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Analysis of 129I/127I ratios from underground fluids collected in Japan
N. Okabe1, Y. Muramatsu1, M. Arai1, H. Matsuzaki2, M. Takahashi3, K. Kazahaya3
1

Gakushuin University, Japan
University of Tokyo, Japan
3
AIST, Japan

2

Keywords – I-129, dating, underground fluids

1.

INTRODUCTION

There are many isotopes of iodine. Specialty, the longlived iodine isotope, 129I is produced by the spallation of
atmospheric and by spontaneous fission 238U. 129I and thestable isotope 127I are in steady state before being released
and mixed with anthropogenic 129I. So this ratio wasmeasured in order to provide an estimation of the age of
iodine.
The purpose of this study is to understand the origin ofhigh salinity groundwaters related to the geological settingsof the area. In this study we analyzed 129I (half-life 15.7m.y.) in the fluids in older to estimate the age of the
dissolved iodine in hot spring waters collected from various
places in Hokkaido. It is known that several hot springs in
Hokkaido, the northern Japanese island, contain highconcentrations of halogens including iodine. However, theorigin of the salts in these springs is not well known. We
analyzed I, Br and Cl concentrations.

(0.3-0.4×10-12, Tomaru et al. 2009) and Satsuma-Iwojima(0.78×10-12, Snyder et al. 2002). Considering the 129I
systematics (Fehn et al. 2004), iodine age in Hokkaido
samples of the lowest 129I/127I ratios is estimated to be 6070 Ma. This indicates that the iodine-rich fluids are likely
be derived from old marine sediment, which was later
uplifted to form older rock formations in the present day
coastal region of Hokkaido.

0.100
0.093
0.064
0.094
0.068

※Values are sample of
129I/127I ratio（×10-12）

0.075 0.100
0.051

0.051
0.094

0.075

0.064

0.068

0.082

2. Samples and Analytical method

3.

Results and discussion

Fig. 1 Mapping of location of low 129I/127I ratio samples in Hokkaido

4Ⅵb
129I/127I ( 10-12 )Hot springs and groundwaters were collected in Hokkaido.
In the sampling interpretation of sample types weconsidered the classification based on Matsunami et al(1999).
Concentrations of Cl in the hot spring samples were
determined by an ion chromatography. Concentrations of I
and Br were determined by ICP-MS.
The 129I/127I ratios were determined by accelerator mass
spectrometry (AMS). Samples were precipitated as AgI(target cell) after separated iodine, and analyzed by AMS at
MALT (Micro Analysis Laboratory, Tandem accelerator,
University of Tokyo).

Ⅶb
Ⅶc

0.4

Ⅷ
Ⅸ
Ⅹ

In the Hokkaido hot spring samples, the relationshipbetween iodine concentration and 129I/127I ratios isclassified in 2 types. In general, if iodine concentrations
increase, 129I/127I ratios are higher. But, a part of sample
didn’t show this trend.
129 127
I/ I ratios ranged between 0.05×10-12 and 0.38×10-12
in Hokkaido hot springs samples. Samples collected from
north-western area showed very low 129I/127I ratios of 0.05
×10-12 to 0.1×10-12. Low values are also observed along
the longitude 141-142. These values are markedly lower
than the 129I/127I ratios observed in iodine-rich fluids inother areas in Japan, such as Chiba (0.18×10-12), Niigata－ 192 －

0.04
0.001

0.01
1/I ( μM-1 )0.1

Fig. 2 Iodine concentrations vs. 129I/127I ratios

Ⅺa

23-APP-08
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Radiocarbon Dating of Ancient Japanese Calligraphy Sheets: Checks with AncientDocuments of Known Age and Its Application to Kohitsugire Calligraphies
Hirotaka Oda1, Kazuomi Ikeda2, Hiroaki Yasu3, Shoji Sakamoto4
1

Center for Chronological Research, Nagoya University
2
Faculty of Letters, Chuo University
3
Taga High School
4
Degital Archives Research Center, Ryukoku University

Abstract – Radiocarbon ages of ancient documents, sutras andbooks of known age were measured by AMS. The calibrated
radiocarbon ages corresponded to the years in which they were
written. The result shows that Japanese paper is suitable forradiocarbon dating. Radiocarbon dating on ancient calligraphies of
unknown age clarified their historical ages and academic value.
Keywords – AMS, Radiocarbon dating, Ancient calligraphy.

I.

radiocarbon ages of the documents correspond to thepaleographical ages. Although ancient Japanese paper can beconsidered as a wooden sample, it was made from short-lived
branches of trees. In addition, old paper is not used for
calligraphy because it repels India ink and is unsuitable for
elegant handwriting. The result indicates that ancientJapanese paper is suitable for radiocarbon dating.

INTRODUCTION

Kohitsugire are ancient paper sheets or fragments
containing elegant calligraphy. They were originally pages ofancient manuscripts. The old manuscripts written before the14th century hardly remain as complete books; therefore,
kohitsugire potentially has high academic value. However,among kohitsugire attributed to famous calligraphists,many copies and counterfeits written several
centuries later are in circulation. Therefore, in this study,
we measured radiocarbon ages of kohitsugire by accelerator
mass spectrometry (AMS). In the first, we measured ancient
documents, sutras and books of known age for check of themethod. Then, we applied to kohitsugire calligraphies of
unknown age to determine their historical ages and academic
value.
II. EXPERIMENTAL
Paper samples were cut from the margins of kohitsugire. A
kohitsugire is commonly mounted on other paper sheets thatform a lining. The samples were soaked in distilled water topeel the surface sheet of the calligraphy from the mounts. The
surface sheets were first washed in distilled water with anultrasonic cleaner and then treated with 1.2N HCl and 1.2N
NaOH solutions (60-70°C). After re-treating with 1.2N HCl
and rinsing with distilled water, they were combusted using
CuO (850°C, 3h) to form CO2. The CO2 was reduced tographite by H2 (650°C, cat-Fe, 6h). The radiocarbon ages
were measured by AMS.

Fig. 1. Result on the known-age documents

IV. RESULTS AND DISCUSSION: KOHITSUGIRECALLIGRAPHIES
We applied to kohitsugire of unknown age to clarify their
historical ages and academic value. For example, Fig. 2 is
kohitsugire attributed to Nakatomi no Kamatari (614-669).
However, radiocarbon dating indicated that it was written in
the 14th century and is not his genuine handwriting.
According to legend, calligraphy of Fig. 3 is Shibunritsu sutrabrought from China by the priest Ganjin (688-763). Althoughradiocarbon dating cannot show that the legend is true or not,it indicated that it is old sutra written in the 7-8th centuries as
the legend.

III. RESULTS AND DISCUSSION: THE KNOWN-AGE
DOCUMENTS
The results of the known-age documents, sutras and books
were plotted on the calibration curve (Fig. 1). The obtained－ 193 －

Fig. 2. Kohitsugire attributed to
Nakatomi no KamatariFig.3 Shibunritsu sutra

23-APP-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013µ-XRF study on Wiangkalong pottery
1

K. Won-in1, S. Tancharakorn2, W. Tanthanuch2, P. Dararutana3

Department of Earth Sciences, Faculty of Science, Kasetsart University, Bangkok 10900 Thailand
2
Synchrotron Light Research Institute, Nakhon Ratchasima 30000 Thailand
3
The Royal Thai Army Chemical School of the Royal Thai Army Chemical Department, Bangkok 10900 Thailand

Abstract- It was proved that non-destructive andnon-sampling methods were used to analyze thecomposition of the archaeological objects. It was
well-known that differences of them found in
Thailand such as glasses, potteries and metal
wares. Due to the complex nature of materials andobjects, extremely sensitive, spatially resolved,
multi-elemental
andversatile
analytical
instruments are needed. In this work, micro-beam
X-ray fluorescence spectroscopy (µ-XRF) based onsynchrotron radiation was firstly used tocharacterize the elemental composition of ancientWiangkalong pottery. Wiangkalong was one ofmajor ceramic production cities in northern ofThailand, once colonized by the ancient Lanna
Kingdom (1290 A.D.). Potteries were producedwith shapes and designs as similar as those of theChinese Yuan and Ming Dynasties. The results
showed the variations in elemental composition of
the body matrix, the glaze and the painting. µ-XRF
was successfully to characterize the elemental
composition of this ancient pottery.
Keywords – Wiangkalong pottery, µ-XRF[1][2]

Praichanjit, S. (2011). Archaeology of Ceramics in Lanna NorthernSiam, Samaphun Publishing Co.Ltd., Bangkok.
Won-in, K., Pongkrapan, S, Dararutana, P., Thawwornmongkolkij, M.
and Wathanakul, P. (2010). Raman spectroscopic study of ancientpotteries in Thailand: Wiangkalong pottery, 5th Mid-European Clay
Conference; August 25-29, 2010: Budapest, Hungary.

－ 194 －

Poster Session 2
Tuesday, 24 September 2013
18:50 ~ 20:00

Scientific Topics (Abbrev.)

1. Fukushima issues (FK)
2. Education in nuclear and radiochemistry (ED)
3. Nuclear forensics (NF)
4. Nuclear energy chemistry (NE)
5. Nuclear chemistry (NC)

6. Actinide chemistry (AC)
7. Environmental radiochemistry (EN)
8. Radiopharmaceutical chemistry and Nuclear medicine (RP)
9. Nuclear probes for materials science (NP)
10. Activation analysis (AA)
11. Application of nuclear and radiochemical techniques (AP)－ 195 －

24-FKP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of short-lived 241Pu in environmental samples
by inductively coupled plasma mass spectrometry
Jian Zheng*, Keiko Tagami, Shigeo Uchida

Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences

Plutonium isotopes have been released into the environment mainly from the atmospheric nuclear
weapons tests in last century, the discharges from nuclear fuel reprocessing facilities, and the nuclear
accidents, such as the Chernobyl and the Fukushima Daiichi Nuclear Power Plant (FDNPP) accidents [13]. Accurate determination of Pu isotopic composition is important for the source identification ofradioactive contamination in the environment since Pu isotopic composition is characteristic for various
Pu sources. Among Pu isotopes (238Pu, 239Pu, 240Pu, and 241Pu) observed in the environment, the shortlived 241Pu (t1/2 = 14.4 y), a beta emitter, is a sensitive indicator for the identification of any newcontamination of Pu isotopes resulted from nuclear power plant accident. For 241Pu originated from theglobal fallout, the activity of 241Pu in the environment is quite low due to the dacay with time. The
activity ratio of 241Pu/239+240Pu is ca. 1.2 in 2011 for the global fallout-sourced Pu isotopes. Therefore,
higher activity ratio of 241Pu/239+240Pu in the environment will provide evidence of additional Pu input.
Due to its short half-life and beta emission, determination of 241Pu in environmental samples has beena great analytical challege. Conventional technique is the low level liquid scintillation counting, which
requires tedious sample preparation and long measurement time (typically 13-24 h). In the past years, wehave developed sensitive analytical method using inductively coupled plasma mass spectrometry for thedetermination of 241Pu in various environmental samples, such as atmospheric fallou material, marine
sediments, and seawater reference material [4-6]. In this work, we report the determination of 241Pu in
environmental samples, such as litter, soil and marine sediments collected in Fukushima Prefecture after
the FDNPP accident in 2011. Fig. 1 shows the results of 241Pu activity in litter and surface soils collected
in 20-30 km zone of the FDNPP, and in Cities of Mito, Kamagaya and Chiba. High activities of 241Pu
ranging from 4.5 to 34.8 mBq/g were detected in the J-Village surface soil (0-2 cm) and two litter
samples. This finding of high 241Pu activities in environmental samples after the FDNPP accidnet
provided evidence of the release of Pu isotopes from the accident.

－ 196 －

千 葉

Chiba

濃 度 範 囲 （ 推 定 ）
鎌 ヶ 谷

N.D.

Kamagaya

2011年 に お け る

N.D.

水 戸

J-village

N.D.

Mito

サ ン プ ルSamples

Jビ レ ッ ジ

S3土 壌

S3 Soil

S2土 壌

S3落 葉 層S2落 葉 層S2 LitterS1土 壌

S1落 葉 層

N.D.

N.D.

S3 Litter

N.D.

0.1

S2 SoilN.D.

S1 SoilN.D.:
Not detected

G 241
lo b a l f a llo u t

Global fallout
source in 2011
241
Pu
Pu activity range

濃 度 範 囲 （ 推 定 ）1963年 に お け る

1963 Global fallout
241
Pu
Pu activity range
G lo
b a l f a llo u t
241

1S1 Litter[1] J. M. Kelley, L. A. Bond, T. M. Beasley. Sci. Total Environ.
237/238 (1999) 483-500.
[2] M. E. Ketterer, K. M. Hafer, J. W. Mietelski. J. Environ.
Radioact. 73 (2004) 183-201.
[3] J. Zheng, K. Tagami, Y. Watanabe et al. Sci. Rep. 2:304;
DOI:10.1038/srep00304. 2012[4] J. Zheng, M. Yamada. J. Oceanogr. 64 (2008) 541-550.
[5] J. Zheng, M. Yamada, Appl. Radio. Isot. 70 (2012) 19441948.
[6] Y. S. Zhang, J. Zheng, M. Yamada et al. Sci. Total Environ.
408 (2010) 1139-1144.

10

241

References

100

241Pu
P u 濃 activity
度（m B q (mBq/g)/g )Acknowledgement: This study was partially supported by the
Agency for Natural Resources and Energy, Ministry of
Economy, Trade and Industry (METI), Japan.

Figure 1. Results of activities of 241Pu detected in theenvironmental samples collected after the FDNPP accident.

APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-02

������������������������������������������������������������������������
��������������������������������������������Hiroshi Ogawa, Akiko Kitajima, Hisashi Tanaka, and Tohru Kawamoto

Nanosystem Research Institute, Advanced Industrial Science and Technology (AIST), Tsukuba, 305-8568, Japan.
Abstract Ð Amount of Cs adsorption in PB column was
numerically evaluated based on extended Langmuir formula andone-dimensional adsorption model. The extended Langmuir
formula successfully reproduced the experimental Kd distribution
coefficient of Cs adsorption that cannot be explained bytraditional Langmuir model. The time-variation of the Cs
adsorption in column experiment was also explained by onedimensional adsorption model.
Keywords Ð Cs decontamination, Cs adsorption, extended
Langmuir formula, column experiment, simulationI.

INTRODUCTION

The accident of the Fukushima-daiichi nuclear plant inMarch, 2011 has caused heavy radioactive pollution insurrounding regions.
Decontamination of radioactive
elements, especially Cs-134 and Cs-137, is an urgent issue.
One of the most effective procedures for the Csdecontamination from contaminated water is to use
Prussian-Blue (PB) as a Cs adsorbent [1,2]. In this paper,
the authors propose a numerical method for expecting theamount of Cs reduction by PB adsorbent based on extended
Langmuir formula and one-dimensional adsorption model.
II. METHOD
The Langmuir formula is extended as,
w = �i � Ni wi ,wi = Ki c (wimax Ð wi),

(1)
(2)

where w is the total amount of the adsorbed Cs in theadsorbent, Ni the number of adsorption site, wi the amountof the adsorbed Cs at i-th adsorption site, Ki the equilibrium
constant between liquid and adsorbent at the i-th site, wimax

Fig. 1 Experimental and calculated Kd values of the adsorbent usedin this study.

the saturation value of the Cs adsorption at the i-th site, andc the Cs concentration in the liquid.
Time-variation of Cs reduction in a column experiment
was calculated by one-dimensional adsorption model as,dc (x, t) / dt« = Ð c (1 Ð � (x, t)) / � max �,(3)where x, t, t«, � (max), and � are the one-dimensional positionin the column, wall-clock time, contact time of the waterwith the adsorbent, (maximum capacity of) Csconcentration in the adsorbent, and time constant of Csconcentration reduction, respectively.
The column and shaking experiments were carried out
by using granular adsorbent with PB nanoparticle suppliedby Kanto Chemical Co. Inc. [2]III. RESULTSIn Fig. 1 the experimental Kd values are shown as afunction of initial Cs concentration in comparison with theresults of Langmuir fittings of Ni = 1 and 2. Large
discrepancy is found in the case of Ni = 1 (dashed line)
especially at high Cs concentration. The fitting is, however,drastically improved if the second adsorption site isincluded (solid line).
Figure 2 gives the comparison between experimental
and calculated time-variation of Cs concentration incolumn experiment. Our one-dimensional model gives
time-variation of the Cs concentration after column
adsorption accurately. It is expected that precise simulationof the Cs adsorption in actual plant will be possible bycombining extended Langmuir formula and onedimensional adsorption model.
[1][2]

Kitajima et al., Chem. Lett., 41, 1403 (2012).
Kitajima et al., in APSORC 13 abstract.

Fig. 2 Experimental and calculated (solid lines) time-variation of Cs
concentration in liquid after column adsorption.

－ 197 －

24-FKP-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Secular distribution of radioactive concentration in the atmosphere at Fukushima,
Hitachi and Marumori
ZiJian Zhang1, Shunsuke Kakitani1, Kazuhiko Ninomiya1, Naruto Takahashi1, Yoshiaki Yamaguchi2,
Takashi Yoshimura2, Kazuyuki Kita3, Akira Watanabe4, Atsushi Shinohara1
1

Graduate School of Science, Osaka University, 2 Radioisotope Research Center, Osaka University,
3
Faculty of Symbiotic Systems Science, Fukushima University,
4
College of Science, Ibaraki University

Abstract - Our group started gamma ray measurement of air dust
sample after the Fukushima Dai-ichi nuclear power station
accident. Air dust filters was collected at Hitachi, Fukushima andMarumori. The activity of Cs-134 and Cs-137 was determined by
germanium semiconductor detector. The radiocesium activity
concentration in air dust(Bq/m3) after October 2011 were stableand 6.2×10-6 at Hitachi, 3.0×10-4 at Fukushima and 1.3×10-4
at Marumori.
Key word –radioactive cesium, air dustI.

INTRODUCTION

On 11th March 2011, the earthquake occurred and alarge tsunami destroyed coasts of Eastern Japan. As a result,the nuclear accident of Fukushima Dai-ichi nuclear power
station (in the following FD-NPS) was arisen. The accident
caused massive release of radioactivity into the atmosphere.
Many material transportation models were used for
simulating the behavior of radioactive nuclides inenvironment. From these simulations, we can estimate theamount of radioactive deposition to land and sea, andcalculate the internal exposure. However, there are someunclear points about nuclides transportation in theenvironment, and the accuracy of precision simulation was
limited by these problems. We need accurate measurement
data of radioactive nuclides in the atmosphere. Our group
started collection of air dust after the accident of FD-NPS
at three locations. In this study, we discuss about theseculer distribution of radioactive concentration in theatmosphere.

the concentration in April. The average of radiocesium
activity concentration after October 2011 were 6.2×10-6
Bq/m3 at Hitachi, 3.0×10-4 Bq/m3 at Fukushima and 1.3×
10-4 Bq/m3 at Marumori. Ratios of Cs-134/Cs137 wereabout 1 in three locations. There are many studies thatobserve the same results in environmental samples.
The activity concentration of beryllium-7 was always
about 10-3 Bq/m3. The seasonal variation was likely someprevious report [1]. Beryllium-7 is known for attaching toaerosol and being transported to all over the world. We
could not find out some correlation between Be-7 and Cs137. Therefore, main sources of Cs-137 in environment
behave differently with cosmic ray radionuclides. We
suggest that most of radiocesium in the atmosphere comefrom some local sources, likely releasing from soil andforest.

II. MEASUREMENTOur group has been collecting air dust in Fukushima
City, in 68 km east of FD-NPS, Hitachi, in 87 km south andMarumori, in 50 km north. Sampling duration was 3-4 days.
All gamma ray measurements were carried out at Osaka
University in low background condition with 1-2 days.
Radioactivities in air (Bq/m3) of I-131, Cs-134 and Cs-137
were determined. We also measured Be-7 that is one ofindex of cosmogenic radionuclides, to discusstransportation process of Cs-137.
III.

Fig.1. Cs-134, Cs-137 and Be-7 activity concentration. Upper one isdata of Hitachi and Under one is data of Fukushima

RESULT AND DISCUSSION

The time variation of activity concentration in Hitachi
and Fukushima is shown in Fig.1. In Hitachi, activity
concentrations for Cs-134 and Cs-137 were very high at
April 2011(�Bq/m3).They were rapidly decrease with time
passing, and in October, they were about one-thousandth of－ 198 －

[1]R.Winkler and F.DIETL, Atmospheric Environment 32,
No6, 983-991(1998)

24-FKP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Concentration of 137Cs in atmospheric coarse and fine particles collected in
Fukushima
Kyo Kitayama1, Hirofumi Tsukada1, Kenji Ohse1, Chika Suzuki1, Akira Kanno1, Kencho Kawatsu1,
1

Fukushima University Future Center for Regional Revitalization

Keywords – 137Cs, fine particle, coarse particle, Fukushima city,
Date city

INTRODUCTION

300
250
200
150
100
50
0
2012/8/1

2012/9/1

2012/10/1

2012/11/1

2012/12/1

2013/1/1

2013/2/1

2012/9/1

2012/10/1

2012/11/1

2012/12/1

2013/1/1

2013/2/1

350

RESULTS AND DISCUSSION

Total concentration of 137Cs in coarse and fine particles inFukushima was ranged from 84 to 347 µBq m-3 with anaverage of 182 µBq m-3 (Fig. 1-a). The total 137Csconcentration of Date was in the range of 103 to 311 µBq m-3
where the average was 173 µBq m-3 (Fig. 1-b). The range of

300
250
200
150
100
50
0
2012/8/1

METHODCoarse and fine particles were collected from two sites
such as 62 km (Fukushima) and 55 km (Date) distant from
Fukushima Dai-ichi Nuclear Power Plant from August 2012
to January 2013. Fukushima is in the urban site and Date is in
the rural site. Coarse and fine particles were divided at 50 %cutoff diameter of 1.1 �m with an Andersen sampler (AH600,
Tokyo
Dylec),
andwerecollectedon
polytetrafluoroethylen filters at flow rate of 566 L min-1. The
filters were exchanged every two weeks.
The sampled filters were cut into small pieces andcompress into a plasitic bottle. Radioactivety of 137Cs in thesamples was measured for 0.5-2 days by Ge detector.
III.

350

b) Date city

On 11 March, 2011, the Fukushima Dai-ichi Nuclear
Power Plant accident was caused by the tsunami following
the earthquake to release radioactive nuclides into theatmosphere. Cesium-137 is a major radionuclide released into
the environment and is important to estimate radiation dose
for the public. In order to estimate radiation dose frominhalation, the particle size distribution of 137Cs in theatmosphere is required. In this study, concentration of 137Cs
in atmospheric coarse and fine particles was determined in
Fukushima city and Date city.
II.

400

137Cs activety concentration / µBq m -3

I.

a) Fukushima city
137Cs activety concentration / µBq m -3

Abstract – Concentration of 137Cs in atmospheric coarse and fineparticles was determined in Fukushima city and Date city collected
every 2 weeks from August 2012 to January 2013. Total average
concentration of 137Cs in Fukushima and Date were 182 and 173
�Bq m-3, respectively and the range was within a factor of 2. The
concentration of 137Cs in the coarse fraction was higher than that in
the fine fraction except for one sample collected in Fukushima city.
The variation of 137Cs concentration in the fine fraction was smaller
than that in the coarse fraction and the concentration ratio of 137Cs
in the fine fraction to that in the total was approximately 1/3.

Fig. 1 Concentration of 137Cs in atmospheric coarse and fine particles.
Error bars indicate one sigma of deviation.

the concentration of 137Cs in the total particles was within afactor of 2. Tsukada et al. (2012) reported that 137Csconcentration in Fukushima city was 164 mBq m-3 in early
April 2011 and the value decreased to one thousandth in
September 2011. The observed values in the study also
maintained a similar order of magnitude to the value in
September 2011.
The concentration of 137Cs in the coarse fraction was
higher than that in the fine fraction except for one sample
collected in Fukushima. The variation of 137Cs concentrationin the fine fraction was smaller than that in the coarse fraction
and the concentration ratio of 137Cs in the fine fraction to thatin the total was approximately 1/3. However, massconcentration ratio in the fine fraction to the total wasapproximately 1/2. It may attribute that the sources of coarse
and fine particles were different.
[1]－ 199 －

Tsukada H. et al. (2012) Atomic Energy Society of Japan, Hiroshima.

24-FKP-05
APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013����������������������������������������������������������� ������������������������
��������������������������
����������������������������������� ��������������� ������������������������������������������������������������
���������������������������������������������������������� ������������������������
�������������������������������������� ������������������������������������������������������������������
������������������������������������������������������������������������������������������� �������������������������
������������������������
����������������������������� ��������������������������������������������������������������������
Abstract Ð Copper hexacyanoferrate (CuHCF) is known as a good
adsorbent for Cs. We developed water-dispersible CuHCF ink by
nanoparticulation and surface treatment, and fabricated the thinfilm of CuHCF on metal electrodes. Cs adsorption/desorption canbe controlled electrochemically using this thin film CuHCF
electrode, repetitively. Cs sorption capability under coexisting otherions were examined for alkali metals, alkali earth metals, transition
metals, etc, and determined to be few affected.
Keywords Ð Copper hexacyanoferrate, Prusian blue analogues,
Nanoparticle ink, Electrochemical adsorption/desorption, Cs
adsorption, Nuclear waste water, Fukushima daiichi nuclear
disaster��

desorption, ������� ������������� ����������������������� ������������������ ����������������������������������������������
���� ����� ��� ����� ���� ������ ����������� ����� ������ ��� ������������� ���� ��� �������������� ����� ������ ��� ���� ����������������������������������������������� ���������������
����������� ��� ��� ���� ����� ���� ������� ���� ���������������� ������������ ����������� ��� ������ ����� ������ ���� ��� ��������� �������������������������������������������� �����������������������
�����������������������������������������������������������������
����� ����������������������������������� 18��������

������������

���� ������������ ������� ����� ��� ������ �T��� �� ����� ������� ������� ��� ����� �������� ��� ������������ �������� ��� ������� ���������������� ��������� ���������� �������� ����� ����� ����� ������
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���������������� ��������������������������������������������
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����� ������� ��� ���������� ��� ����������� ������������������� �������������������������������������������������������
���������������������� �������� ���� ��� ��������� �����������
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II. ������������ ���������
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������ ��������������� ��������� ���� ������ ���������� ���� �����
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���� ����������� ��������� ���������� ��� ���� ����� ��� ���� �������� �� ���� ���. After executing 5 cycle adsorption and������������������������������������������������������
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－ 200 －

24-FKP-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of 129I in Fukushima Soil Samples by ICP-MS
Takeshi Ohno1, Yasuyuki Muramatsu1, Hiroyuki Matsuzaki2
1

2

Faculty of Science, Gakushuin University
School of Engineering, The University of Tokyo

Abstract – A method was developed for the determination of 129I in
soil samples, which uses a ICP-MS with an octopole reaction system,
permitting the investigation of radioiodine released by the
Fukushima Daiichi nuclear power plant (FDNPP) accident. The
determination of 129I by ICP-MS is capable of providing a highsample throughput compared to other methods.
Keywords – Radioiodine, Fukushima Daiichi nuclear power plant
accident, 129I, ICP-MS, Octopole reaction systemI.

INTRODUCTION

The accident at the Fukushima Daiichi nuclear power
plant (FDNPP) resulted in a substantial release ofradionuclides into the environment, including atmospheric ofradioiodine and radioceium.1, 2 The distribution of radiocesium has been studied, and a map of the radiocesium
contamination was made. On the other hand, 131I could only
be determined within a couple of months, due to its short halflife (8 days), resulting in a lack of data on the deposition ofthis nuclide. Because iodine is an essential element, andplays an important role in thyroid development, radioiodinethat is ingested readily and becomes enriched in the human
thyroid. In the event of a nuclear plant accident, an effective
dose estimation of released 131I is important.
Another iodine isotope, 129I (half-life: 1.57 × 107 y), wasreleased simultaneously with 131I, although the amount wasvery small. To reconstruct the early distribution of 131I in theenvironment, 129I has been used as a follow-up tracer due to
its much longer half-life. The determination of 129I in soils inFukushima is of importance to investigate the distribution ofradioiodine released from the FDNPP. Recent advances in
inductively coupled plasma mass spectrometry (ICP-MS)
using a octopole reaction cell have enabled us to determine
the long-lived radionuclide 129I in soil samples.3
II. EXPERIMENTAL
The analytical method used in this study is based on themethod for AMS measurements.4 Soil samples (about 2 g)
were mixed with V2O5 in a ceramic boat before being placedin a quartz tube. The sample was heated at 1000°C in a tube
oven for 30 min under a flow of oxygen with water vapor.
The iodine released by heating was collected with a trap
containing 10 ml of a solution of 1% TMAH. The iodine
fraction was then purified by a combination of solventextraction and back extraction using carbon tetrachloride as
the solvent. The back-extracted solution was concentrated toabout 1 mL on a hotplate at 100°C. The purified samples

were subjected to measurements of 129I/127I by the ICP-MS.
Any mass-discrimination effect in the mass spectrometer wasmonitored using NIST SRM 3231 Level 1.
III. RESULTS AND DISCUSSION
In order to improve the precision and accuracy of theI/ I isotopic ratio measurements, interfering signals, suchas 129Xe+, must be reduced. In this study, 129Xe+ was
suppressed by O2 as a reaction gas using the following
reaction: Xe+ + O2 � Xe + O2+. The oxygen flow rate was
optimized while aspirating an iodine solution (10 ppb,
129 127
I/ I=10-13) so as to maximize the 127I intensity/background(m/z = 129) ratio. When increasing the oxygen flow ratefrom 0 L/min to the optimum value at 0.8 mL/min, a twenty129
I
background-equivalentfold
improvementofconcentration was observed.
We investigated the production ratio of 127IH2+/127I+ while
aspirating iodine solution (100 ppm, 129I/127I=10-13). The
results demonstrated that the production ratio of 127IH2+/127I+
in the ICP-MS was about 3 × 10-8. The contribution from thisinterference could be corrected by subtracting of 127IH2+
according to the production ratio. The production ratio wasmonitored before and after measuring the samples, and thecontribution of 127IH2+ was subtracted from the signal
intensity of 129I when calculating the 129I/127I isotopic ratios.
In order to confirm the applicability to measurements of
the 129I/127I ratios of soils we measured 129I in six samples
which were collected from an orchard in Ohkuma-machi(about 5 km from the FDNPP), a rice paddy in Iitate-muraand Namie-machi (about 30 km from the FDNPP) and an
orchard in Koriyama-shi (about 60 km from the FDNPP).
The measured 129I/127I ratios in the samples by ICP-MS areconsistent with the value determined by AMS within theanalytical error, suggesting the applicability of this method tomeasurements of 129I/127I in Fukushima soil samples. Our
results indicate that 129I can also be determined outside of the
30 km districted area, i.e. 60 km or more from the FDNPP.
This method could provide a powerful tool for theinvestigation of the radioiodine contamination.
129 127

[1]
[2]
[3]
[4]

－ 201 －

M. Chino, H. Nakayama, H. Nagai, H. Terada, G. Katata, and H.
Yamazawa, J. Nucl. Sci. and Tech., 2011, 48, 1129.
N. Kinoshita, K. Sueki, K. Sasa, J. Kitagawa, S. Ikarashi, T. Nishimura,
Y.-S. Wong, Y. Satou, K. Handa, T. Takahashi, M. Sato, and T.
Yamagata, PNAS, 2011, 108, 19526.
T. Ohno, Y. Muramatsu, C. Toyama, K. Nakano, S. Kakuta, and H.
Matsuzaki, Anal. Sci., 2013, 29, 271.
Y. Muramatsu, Y. Takada, H. Matsuzaki, and S. Yoshida, Quarter.
Geochronol., 2008, 3, 291.

24-FKP-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Measurement of soil-to-crop transfer factor of tellurium for estimation of potential
radiotellurium ingestion from crops
Guosheng Yang, Keiko Tagami*, Jian Zheng, Shigeo Uchida

Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences

0.10

Transfer factor

The Fukushima Daiichi Nuclear Power Plant (FDNPP)
accident discharged large amounts of radionuclides into theenvironment, including 127mTe (T1/2=109 d), 129mTe (T1/2=33.6d), 131mTe (T1/2=30 h) and 132Te (T1/2=3.204 d) [1]. Since
relatively long-lived 127mTe could transfer from soil to crops
through roots, people would ingest 127mTe; however, theisotope is a beta-emitter and the concentration data in foodcrops were unavailable. Now, 127mTe has been decayed out
and it is difficult to measure 127mTe in crops samples.
However, it is still important to estimate how much amountof 127mTe might have been ingested from food for public
safety purpose. The soil-to-crop transfer factor (TF) is a
useful tool to estimate Te concentrations in crops.
Unfortunately, the TF data of Te are scarce in the world [2]and there are no data for crops native to Japan.
In order to obtain the TF data of Te for crops, we
focused on stable Te as an analogue of radioactive Te. We
measured 79 soil and associated crop samples collectednationwide to calculate TFs of Te. Te concentrations in soil
and crop samples were measured by using sector field
inductively coupled plasma mass spectrometry (SF-ICP-MS)
after aqua regia digestion and appropriate dilution to reducethe matrix effect [3]. The Te contents in Japanese soil andcrops ranged from 12.6 to 479 ng g-1 (mean: 55.3 ng g-1) andfrom 0.06 to 3.8 ng g-1 (mean: 0.7 ng g-1), respectively. The
Te concentrations in soil were higher than previous report inJapan (10–109 ng g-1), while Te contents in plant samples
were much lower than those (18–33 ng g-1) in Japanese plants[4]. Then, TF values from 8.7 × 10-4 to 1.1 × 10-1 (mean: 1.8
× 10-2) were obtained for the first time in Japan (Figure 1),
which were relatively low compared to those reported by
IAEA-TRS-472 (0.1–1) [2]. These data could be used toestimate the internal radiation dose from 127mTe after the
FDNPP accident.

0.08

0.06

0.04
Arithmetic mean:
0.02

0.02

0.00

a
Le

fy

V

e ta
eg

ble

l
r
e
e
e
be llium um tabl tabl erea
g
Tu
e
e
A
C
e
g
g
L
Ve t Ve
o
uit
Fr
Ro

Figure 1. The variations of soil-to-crop transfer
factors of Te from different crop groups in Japan.
Bars show maximum and minimum values. Boxes
show the 75% and 25% values.

Acknowledgement: This work was partially supported by the
Agency for Natural Resources and Energy, the Ministry of
Economy, Trade and Industry (METI), Japan.
[1]
[2]
[3]
[4]

METI (Ministry of Economy, Trade and Industry), Data on the amountof released radioactive materials, http://www.meti.go.jp/press/2011/08/
20110826010/20110826010-2.pdf. 2011.
IAEA. Handbook of Parameter Values for the Prediction ofRadionuclide Transfer in Terrestrial and Freshwater Environments.
Technical Reports Series No. 472, IAEA, 2010.
G. Yang, J. Zheng, K. Tagami, S. Uchida, Direct determination of
tellurium in Japanese soil and plant samples by sector-field inductively
coupled plasma mass spectrometry (submitted).
T. Asami, Metal pollution in Japanese soils (in Japanese), Heiwa
Kogyo Co., Ltd., Tokyo, Japan, 2010, p. 447.

* Corresponding author. Tel: +81 43 206 3268; fax: +81 43 206 3267. E-mailaddress: k_tagami@nirs.go.jp (K. Tagami).

－ 202 －

24-FKP-08
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Retention of radiocesium incorporated in tree leaves contaminated by fallout of theradionuclides emitted from the Fukushima Daiichi Nuclear Power Plant
1

Kazuya Tanaka1, Hokuto Iwatani2, Aya Sakaguchi2, Yoshio Takahashi2, Yuichi Onda3

Institute for Sustainable Sciences and Development, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima,
Hiroshima 739-8530 Japan2
Department of Earth and Planetary Systems Science, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama,
Higashi-Hiroshima, Hiroshima 739-8526 Japan
3 Graduate School of Life and Environmental Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8572,
Japan
Abstract – We analyzed fresh and dead leaves collected in forests inFukushima after the Fukushima Daiichi Nuclear Power Plant(FDNPP) accident using autoradiography. We examined how
strongly radiocesium was incorporated in contaminated leaves of
Cryptomeria japonica, Quercus serrata and Pinus densiflora. Morethan half of radiocesium in the contaminated leaves remained in leaf
tissues after leaching treatment using pure water, surfactant andacetone.
Keywords – Fukushima, radioactivity, radiocesium, tree leaves,autoradiography

I.

INTRODUCTION

A large amount of radionuclides was emitted by the
Fukushima Daiichi Nuclear Power Plant (FDNPP) accident.
Tree canopies and underlying litters above the soil layers are
critical parts when forests are directly contaminated by falloutof radionuclides. Considering cycles of radiocesium inecosystems, it is very important to know the distribution ofradionuclides that were deposited directly on litters orintercepted by tree canopies [1-3]. In this study, weinvestigated the distribution of radioactivity in various
samples of fresh and dead leaves contaminated by the falloutof radionuclides after the FDNPP accident, and examined
how strongly radiocesium was incorporated in the leaves [4].
II. SAMPLES AND METHODS
We collected fresh and dead leaf samples (Cryptomeria
japonica, Quercus serrate and Pinus densiflora) from
Kawamata Town in Yamakiya District, in the northern part of
Fukushima Prefecture on December 15, 2011. Leachingexperiments were carried out to examine how strongly
radiocesium was incorporated in leaf tissues. Leachingexperiments consisted of three steps using leachates in theorder of pure water, 0.14% of fatty acid potassium salt
(surfactant) solution and 100% acetone. Leaf samples were
immersed in each leachate and sonicated in an ultrasonicwater bath at room temperature for 30 min. Leaf samples
before and after each treatment were analyzed using
autoradiography. All the samples were treated in the same
way to obtain comparable autoradiographs. Reduction ofradioactivity by each leaching treatment was evaluated using

the differences in signal intensity of autoradiographs before
and after leaching treatments.
III. RESULTS AND DISCUSSION
It was clearly observed in autoradiographs that both freshand dead leaves of C. japonica were contaminated byradionuclides (134Cs and 137Cs). Contamination of the fresh
leaves was possibly attributed to interception of radionuclides
by tree canopies, whereas the dead leaves indicated the direct
deposition of radionuclides by fallout and/or washout ofradionuclides intercepted by tree canopies. Fallen leaves of Q.
serrata, which started growing after the FDNPP accident, did
not show radioactivity. This means that significant amountsof translocation from other parts to new leaves did not occur.
Fallen leaves of Q. serrata collected from a litter showed hot
spots originating from direct fallout. Needles of P. densiflora
were also contaminated by fallout. Leaching with pure water
removed soluble fractions of radiocesium and radiocesiumbearing particles from the surface of the contaminated leaves,
but significant amounts of radioactivity remained. Thissuggests that foliar absorption occurred in both fresh anddead leaves. The surfactant was used to remove the wax
coating from leaf surfaces. This treatment showed that 10 to
20% of radiocesium was removed as a wax fraction of leaf
surface. However, the further treatment using acetone did noteffectively removed radiocesium. After the three stepleaching experiments using pure water, surfactant andacetone, more than half of radiocesium remained in thecontaminated leaves. In conclusion, our results indicate thatradiocesium in the contaminated leaves is strongly fixed inleaf tissues and is not readily released unless leaf tissues aredecomposed.
REFERENCES
[1]
[2]
[3]
[4]

－ 203 －

Desmet G, Myttenaere C (1988) J Environ Radioact 6:197-202
Bunzl K, Schimmack W, Kreutzer K, Schierl R (1989) Sci Total
Environ 78:77-87
Ronneau C, Sombre L, Myttenaere C, Andre P, Vanhouche M, Cara J(1991) J Environ Radioact 14:259-268

Tanaka K, Iwatani H, Sakaguchi A, Takahashi, Y, Onda Y (2013) J
Radioanal Nucl Chem 295:2007–2014

24-FKP-09

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Decontamination of Radioactive Cesium in the Soil
Makoto YANAGA, Ayumi OISHI

Department of Chemistry, Graduate School of Science, Shizuoka University

Abstract – Decontamination of radioactive cesium from theagricultural soil was attempted by extraction method using
potassium solution. The result of experiments using the soil
artificially contaminated with 137Cs showed that radioactive
cesium was extracted by potassium solution. However, theextraction rate decreased when time after contamination passed.

70
60
50
抽出率(%)

Keywords – Decontamination, Radioactive cesium, Nuclear
power plant accident, soil

I.

Pure water
1M KNO3
1M KI
2M KI

INTRODUCTION

40
30
20

A huge amount of radioisotopes was released by the
Fukushima Daiichi Nuclear Power Plant accident in March
2011. The radioactive materials released in the atmosphere
contaminated not only air but also the earth surface.
Decontamination of the radioactive cesium from the soil is
one of the current serious problems. In the present work,
the decontamination of radioactive cesium from soil,
especially agricultural soil, was attempted using thecontaminated soil which was made artificially.
II. EXPERIMENTAL

10
0

0

2

4

6

Time
after contamination / week
汚染させてからの経過時間(週)Fig. 1 Time variation of removal rate of 137Cs from the gardening soil.

On the other hand, when time after soil was
contaminated by radioactive cesium passed, in the case ofany solution used in the present work, the removal rate
decreased. It is thought that cesium ion moved to the sitethat is strongly combined with cesium ion in minerals.

Many commercial plastic containers usually for storingand preserving food were prepared. About 400 grams ofcommercially obtained mixture of many kinds of soil, used
for gardening, was put into each plastic container. Then, 5
ml of 137Cs solution (1 kBq/ml) was dropped in eachcontainer. After selected time (from several hours todozens of weeks) was passed, one container was opened
and homogenized in another container.
The homogenized soil was separated to by 60 grams,
and each radioactivity was measured. Then, 200 ml of purewater, 1M KNO3, 1M KI, or 2M KI solution was poured
into the beaker which soil was in and the mixture wasstirred. After two days standstill, radioactivity of eachextract was measured.
III. RESULTS AND DISCUSSION
Relation between the removal rate and time after
contamination is shown in Fig. 1. As shown in Fig. 1, it
was hardly extracted in pure water. The extraction rate for
1M KI solution and the 1M KNO3 solution was about thesame, and the extraction rate for the 2M KI water solution
was higher than them. This indicates that radioactive
cesium in the soil was extracted by ion exchange withpotassium.

－ 204 －

24-FKP-10
APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013��������������������������������������������������������������
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��������������������������������������������������������������������������

Abstract Ð Altitude distributions of radioactive cesium (134Cs and
137Cs) fallout at Mt. Fuji due to Fukushima No.1 nuclear power
plant accident have been investigated. Radioactive cesium from
Fukushima No.1 nuclear plant is found to reach at the height of
2700 m. It is inferred that some amounts of radioactive cesium are
attributable to the global fallout due to the nuclear weapons tests inthe atmosphere.
Keywords Ð radioactive cesium, altitude distribution, Mt. Fuji��������������

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－ 205 －

24-FKP-11
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Isotope Compositions of Strontium in Environmental Samples
in Fukushima Prefecture
Y. Shibahara1, S. Fukutani1, T. Fujii1, T. Kubota1, M. Yoshikawa2, T. Shibata2, T. Ohta3, K. Takamiya1,
N. Sato1, M. Tanigaki1, Y. Kobayashi1, R. Okumura1, H. Yoshinaga1, H. Yoshino1, A. Uehara1,
S. Mizuno4, T. Takahashi1, and H. Yamana1
1

Research Reactor Institute, Kyoto University
Institute for Geothermal Sciences, Kyoto University
3
Faculty of Engineering, Hokkaido University
4
Nuclear Power Safety Division, Fukushima Prefectural Government2

Abstract – Strontium was recovered from environmental samples inFukushima prefecture. The isotopic composition of 84Sr, 86Sr, 87Sr,
88Sr, and 90Sr was evaluated by mass spectrometry and �
spectrometry. The source of radioactive strontium released during
the Fukushima Daiichi nuclear power plant accident was discussed.
Keywords– strontium-90, strontium isotope ratio, mass spectrometry

On the accident of Fukushima Daiichi nuclear power plant,huge amount of fission product containing radioactive
strontium were widely released. The most importantradioactive strontium are 89Sr and 90Sr, whose half-lives are
50.5 days and 28.90 years, respectively. The cumulative
yields of thermal neutron induced fission of 235U are 4.73%(89Sr) and 5.77% (90Sr) [1]. As shown in Fig. 1, the isotopic
composition of Sr via fission of uranium and plutonium [1]are totally different from the natural abundance. The
information on the origin of radioactive strontium releasewould also be obtained from the analytical data.

Isotopic abundance (%)

100
80

Fission Products
Naturally occuring isotopes

60
40
20
0
84

85

86

87

88

89

90

Mass number

Fig. 1 Isotopic abundances of Sr. The sum of cumulative fission yields of Sr
isotopes from 235U by thermal neutron irradiation [1] was set to 100% forcomparing them with the natural abundance. The natural abundance of 84Sr is
0.56%. The fission yields of 84Sr and 86Sr are less than 10-4%.

precision isotopic analysis in parallel. The isotopic
composition of 84Sr, 86Sr, 87Sr, 88Sr, and 90Sr was evaluatedEnvironmental samples (soils, plants, and so on) were
immersed in concentrated HNO3 and heated at 413 K. Afterevaporation of HNO3, diluted HNO3 was added and this wasused as the source material. Strontium was recovered fromthe samples by extraction chromatography with UTEVAresin and Sr-resin following ion-exchange chromatography
with ion-exchange resin. Concentration of recovered
strontium was analyzed with a quadrupole inductively
coupled plasma mass spectrometer, and that of 90Sr was
analyzed by �� ��������etry. Correlation between 90Sr and137
Cs was also checked. These samples were supplied for
TIMS.
Isotopic ratios of Sr were measured with a TIMS (TritonT1, Thermo Fisher Scientific). About 100 ng of strontium
was loaded on a rhenium single filament with TaO activator.
The isotopic reference material SRM987 was used as thestandard. Our analytical result of SRM987 agreed with the���������� ������ ������� �� analytical error. As a possible
source of 89Sr and 90Sr, on the other hand, 10 mg of UO2 ofnatural uranium was irradiated at the Kyoto University
Research Reactor. Similar to the environmental samples,strontium was recovered from UO2 irradiated and analyzed.
Since the amounts of 89Sr and 90Sr were much smaller thanthose of stable Sr isotopes, their mass spectra were obtainedwith a secondary electron multiplier detector. The isotopic
data obtained are discussed by conjunction with the results of� spectrometry.
[1] K. Shibata et al., J. Nucl. Sci. Technol.. 48, 1 (2011).

The purpose of the present study is to enhance the analysis
of Sr isotopes in environmental samples in Fukushima
prefecture for safety assessment about 90Sr dose. Generally,
concentration of 90Sr is determined by � spectrometry. Since
this method gives no data of stable isotopes, the thermal
ionization mass spectrometry (TIMS) was applied for high－ 206 －

24-FKP-12

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Distribution of radioactive caesium in the North Pacific one year and a half after
the Fukushima Dai-ichi Nuclear Power Plant accident
K. Tsujita1, A. Hasegawa1, N. Harada2, T. Yamagata2, H. Nagai2, M. Aoyama3
1

Graduate School of integrated Basic Sciences, Nihon University
2
College of Humanities and Sciences, Nihon University
3
Geochemical Research Department, Meteorological Research Institute

Abstract – In stations off Fukushima, 137Cs concentration insurface seawater were 3.9±0.2 and 2.7±0.2 mBq/kg. Between
stations off Fukushima and open ocean station (K2; 47°N, 160°E),
average 137Cs concentration was 2.9±0.2 mBq/kg. From 160°E to
170°W along 47°N in the North Pacific, average 137Csconcentration was 4.9±0.2 mBq/kg. It was higher than that off
Fukushima, and 134Cs was also detected. Thus, the effects of the
Fukushima Dai-ichi Nuclear Power Plant accident were observed.
But it was not observed in Bering Sea and east of 170°W.
Keywords – Fukushima Dai-ichi Nuclear Power Plant; 137Cs;
Cs; North Pacific

134

I.

INTRODUCTION

On 11 March 2011, the accident occurred at the
Fukushima Dai-ichi Nuclear Power Plant (F1NPP) due tothe Tohoku earthquake and tsunami. A large amount of134
Cs (T1/2=2.06 y) and 137Cs (T1/2=30.07 y) were released
to the environment. The estimated total amounts of 137Cs
released from the F1NPP reactors to the atmosphere andocean were 15 [1] and 3.5±0.7 PBq [2], respectively. In thisstudy, we measured the distributions of 134Cs and 137Cs inseawater off Fukushima and in the North Pacific toinvestigate the spread of the radionuclides about a year anda half after the accident.

km south (BD-01) and 250 km east (BD-04) of F1NPP
were 1.4±0.1 and 1.3±0.1 mBq/kg, respectively. It wasalmost same as those before the accident (1.5 mBq/kg) [5].
Between off Fukushima and open ocean (47°N, 160°E,
BD-05~07), average 137Cs concentration in surface water
was 2.9±0.2 mBq/kg, still high compared to that before theaccident (1.8 mBq/kg) [6]. From 160°E to 170°W along
47°N (BD-08~14), average 137Cs concentration was 4.9±0.2
mBq/kg. It is higher than those off Fukushima. For all
stations of high 137Cs concentration, 134Cs were also
detected. In those regions the effects of the F1NPP accident
were observed. In Bering Sea and east of 170°W (BD15~17), 137Cs concentration in surface water were equal toor lower than those before the accident and 134Cs were notdetected. In those regions the effects of the F1NPP accident
were not observed.

�������
Dutch
Harbor
BD-10

BD-12

SB-1

BD-08
BD-07
BD-06

BD-15

BD-09
S1 BD-11 BD-13

Vancouver������
BD-16

BD-14

BD-05

mBq/kg
BD-17

BD-02 BD-03
BD-04
�� BD-01
Tokyo

II. EXPERIMENTAL
Seawater samples (20 L) were collected with anunderway pump and a large-volume water sampler during
the KH-12-4 cruise (23 Aug. to 3 Oct. 2012). The sample
was acidified to pH1.8 by adding concentrated nitric acid,stirred for 1 hour after adding 200 mg of stable cesium,then stirred again for 1 hour after adding 4 g of ammonium
phosphomolybdate (AMP). The sample was settled for 12hours and filtrated to collect AMP-Cs compound onto amembrane filter (0.45 �m). The AMP-Cs compound was
dried for 12 hours at 100 °C, transferred to a counting tube,
then measured 134Cs (E�=604 keV, 795 keV) and 137Cs(E�=661 keV) gamma rays using a well-type HPGe
detector.

Fig.1 The surface 137Cs concentration in the North Pacific and the KH-124 cruise track

REFERENCES
[1]

[2]
[3]
[4]
[5]
[6]

III. RESULTS AND DISCUSSION
In regions off Fukushima, 137Cs concentration in surface
water from BD-02 and 03 located 30 km east of F1NPP
were 3.9±0.2 and 2.7±0.2 mBq/kg, respectively. The 137Csconcentrations reduced by two orders of magnitude fromthose observed in MR-11-03 cruise (Apr. 2011) [3] and
KOK cruise (Jun. 2011) [4]. For distant stations about 190－ 207 －NERH (Nuclear Emergency Response Headquarters, Government ofJapan) (2011) Report of Japanese Government to the IAEA
Ministerial Conference on Nuclear Safety—The Accident at
TEPCO’s Fukushima Nuclear Power Stations.
D. Tsumune et al., J. of Environ. Radioact., 111 (2012) 100e108.
M. C. Honda et al., Geochemical J., 46 (2012) e1- e9.
N. Harada, Bachelor thesis (2011).
K. Buesseler et al., Environ. Sci. Technol., 45(2011) 9931-9935.
K. Hirose et al., Deep-Sea Res. II, 50 (2003) 2675-2700.

24-FKP-13
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Image analysis for the study of radiocesium distribution in coniferous trees:
two years after the Fukushima Daiichi Nuclear Power Plant accident
Haruka Minowa

Radioisotope Research Facility, The Tokyo Jikei University School of Medicine
Abstract – The accident at the Fukushima Daiichi Nuclear Power
Plant in March 2011 resulted in the deposition of radioactive fallout
over wide area in eastern Japan. Environmental samples were
examined with an imaging plate to investigate the characteristics
and the behavior of fallout deposits. In the autoradiographs, socalled “hot particles” were evident in many samples. There were no
particulate contamination on new leaves which grown after theaccident. The state and adsorption amount of fallout was different
depending on the locality and the timing of sampling. The results ofthis study confirm that deposition on the leaves and the barks would
remain several years and radiocesium concentration would bedecrease with the growing of new leaves.
Keywords – radiocesium, autoradiography, coniferous treeI.

INTRODUCTIONRadioactive fallout from the March 2011 disaster at the
Fukushima Daiichi Nuclear Power Plant (NPP) spread acrossmuch of eastern Japan. Deposition of fallout on land wasaffected by rain, wind, and geographical features [1]. The
purpose of this research is to investigate the characteristics
and behavior of the fallout. Because it was early spring ineastern Japan at the time of the accident, many trees werebare of leaves except for evergreen trees include coniferous
trees. Radioactivity on the perennial leaves of coniferous
trees would be an appropriate indicator for the monitoring of
the radionuclides in the environmental system.
II. SAMPLES AND METHODS
Samples were collected at Naraha-machi, Hirono-machi
and Iwaki city in Fukushima prefecture, which are locatedapproximately 20 to 50km in south or southwest side from
Fukushima Dai-ichi NPP. It was considered that the dried
deposition were more principal than the wet deposition inthese area [2]. As a typical coniferous tree, Pine trees (Pinus
thunbergii,
Pinus
densiflora),
Japanesecypress(Chamaecyparis obtusa), Japanese cedar (Cryptomeria
japonica), and Chinese juniper (Juniperus chinensis) wereselected.
Samples were flattened and covered with a wrapping filmand exposed to an imaging plate BASIII 2040 (Fujifilm Co.,Tokyo, Japan) for time periods ranging from overnight to one
week. Autoradiographs were scanned using an image
analyzer Typhoon FLA7000 (GE Healthcare Japan Co.,Tokyo, Japan).

III. RESULTS AND DISCCUSION
Autoradiographs are shown in Figure 1 and 2. Samples
were collected from Naraha-machi at Nov. 2012. It wasobserved that the fallout seemed to be granular, so-called “hotparticles”. These radioactive particles had not moved fromthe initial site of adhesion on the leaf despite repeatedexposure to rain. Particulate contaminations were distributed
only the bottom leaves spread before the accident and did notseen in the top leaves grown after the accident. This confirmsthat particulate deposition on the leaves and the barks would
remained several years and radiocesium concentration would
be decrease with the growing of new leaves.

Fig. 1. Leaves of Juniperus chinensis from Naraha-machi at Nov. 2012.
Particulate contaminations were seem only on the bottom leaves and notseem on the top leaves.

Fig. 2. Tree barks of Chamaecypars obtusa from Naraha-machi at Nov 2012.
Heterogeneously contaminations were visible throughout on the bark.
[1][2]－ 208 －

Kinoshita et al. (2011) PNAS 108, 19526-19529
Katata et al. (2012) J. Environ. Radioact. 109, 103-113

APSORC’13 – 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-14

Distribution of Iodine-129 in off Fukushima and the North Pacific one year and ahalf after the Fukushima Dai-ichi Nuclear Power Plant accident
A. Hasegawa1, T. Yamagata2, H. Nagai2, M. Aoyama3, H. Matsuzaki4
1

Graduate School of integrated Basic Sciences, Nihon University
2
College of Humanities and Sciences, Nihon University
3
Geochemical Research Department, Meteorological Research Institute4
School of Engineering, the University of Tokyo

Abstract – High 129I concentrations were observed in samples
from stations off Fukushima (BD02, 03) located 30 km away from
Fukushima Dai-ichi Nuclear Power Plant (F1NPP). In thesestations, 129I inventory down to 100 m water depth was notdecrease since three month after the F1NPP accident. In adjacentstations off Fukushima (BD01, 04), 129I concentrations were
almost identical to those observed in seawater collected in the
Kuroshio region before the F1NPP accident. In the North Pacific(BD05~17), 129I concentrations in surface seawater were 2 times
higher than those in the Kuroshio region.
Keywords – Iodine-129, seawater, Fukushima Daiiti Nuclear
Power Plant, North PacificI.

INTRODUCTION

The Fukushima Dai-ichi Nuclear Power Plant (F1NPP)
was damaged by the great earthquake of magnitude 9.0 andthe associated tsunami on 11 March 2011. As a result,Many radionuclides such as, 134Cs (2.06 yr), 137Cs (30.2 yr),131
I (8.01 d), 129I (1.57 x 107 yr) were discharged from
F1NPP into the ocean. These nuclides were transported by
the Oyashio current and the Kuroshio current, andsupposed to spread along the Kuroshio extension. Many
data for 137Cs discharged into ocean from F1NPP inseawater has already reported[1][2] but few data for 129I
have reported[3][4].
A large amount of 129I discharged from nuclear
activities such as, weapons testing until the 1970’s, nuclear
power plant accidents, nuclear fuel reprocessing plants, into
the environment. As a result, most of 129I present in theenvironment is anthropogenic, and 129I concentrations inseawater are higher than pre-nuclear activities. Due to the
F1NPP accident, 129I concentration in seawater may
enhanced. In this study, we measure of 129I concentration inseawater, to investigate the influence of the F1NPP
accident in the North Pacific.

back-extracted into aqueous layer. Finally, silver nitride
solution was added to make silver iodide precipitation. The
129 127
I/ I ratios of samples were measured by Accelerator
Mass Spectrometry (AMS) at MALT, the University ofTokyo. All measured ratios were normalized to thestandard reference material having 129I/127I=63.6 x 10-12(SPuredue2).
III. RESULTS AND DISCUSSION
129

I concentrations in surface seawater in the Western
North Pacific (BD05~09) and Eastern North Pacific(BD11~17) were almost constant (12.7~17.1 x 106
atoms/kg). On the other hand, 129I concentrations in stations
off Fukushima were higher than those in the North Pacific.
Maximum 129I concentration 71.4 x 106 atoms/kg wasobserved at BD03 (about 30 km away from F1NPP). 129I
inventory down to 100 m water depth at BD03 was 35.3 x1011 atoms/m2, which is comparable to those observed threemonth after the F1NPP accident (KOK cruise). Therefore,
the effects of the F1NPP accident still remain in this region.
In other stations off Fukushima (BD01 and BD04), 129I
concentrations were almost identical to those observed inseawater collected in the Kuroshio region before the
F1NPP accident (KT-09-13). In the North Pacific(BD05~17), 129I concentrations were 2 times higher thanthose in the Kurosio region. It considered with high 129I
concentration seawater inflow from the Bering Sea.

Vancouver
BD07

BD15
BD11

Tokyo
BD05

II. EXPERIMENTAL PROCEDURE

BD09
BD14

BD17

BD01～04

Seawater samples (1L) were collected with an underway
pump and a large-volume water sampler during the cruiseof the R/V Hakuho-maru in 23 Aug. to 3 October 2012
(KH-12-4). The cruise track and positions of the station are
shown in Fig. 1. First, seawater samples were filteredthrough a membrane filter (0.45 m), them iodine carrier (I: 1 mg) were added to filtered seawater samples. Secondly,
separation of iodine from seawater samples has carried out
solvent extraction and back-extraction. The moleculariodine extracted into carbon tetrachloride (CCl4), thenFig. 1 The KH-12-4 cruise track and sampling stations[1] http://www.mri-jma.go.jp/Topics/hotyouhi/houtyouhi_sea.html[2] P. P. Povinec et al., Biogeosciences Discuss, 10, 6377-6416, 2013[3] T. Suzuki et al., Biogeosciences Discuss, 10, 1401-1419, 2013
[4] X. Hou et al., Environ. Sci. Technol. 47, 3091-3098, 2013

－ 209 －

24-FKP-15
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Agricultural Implications for Fukushima Nuclear Accident
Tomoko M. Nakanishi
Graduate School of Agricultural and Life Sciences, The University of Tokyo
Abstract – The overview of our research projects for
Fukushima is presented including how they were
derived. Then, where the fallout was found, right after
the accident, is briefly summarized for soil, plants, trees,
etc. The time of the accident was late winter, there werehardly any plants growing except for the wheat in thefarming field. Most of the fallout was found at thesurface of soil, tree barks, etc., which were exposed tothe air at the time of the accident. The fallout found was
firmly adsorbed to anything and did not move formonths from the site when they first touched. Therefore,
the newly emerged tissue after the accident showed very
low radioactivity. The fallout contamination was not
uniform, therefore, when radiograph of contaminatedsoil or leaves were taken, fallout was shown as spots.
Generally, plants could not absorb radiocesium
adsorbed to soil. Some of the results we obtained will
be presented.

animals, fish, etc. Our activities were classified into
several groups as follows but most of them weredeveloped based on voluntary activities.
Research projects
Influence of fallout (distribution & movement)
1. crop plants and soils
2. stock raising & dairy products
3. fishery
4. environment, including wild life
5. radiation measurement & radiochemistry
6. science communication
Research sites

Keywords – Fukushima nuclear accident, research inagiriculture, research project, research site, fallout, theway of contamination
Introduction
After the accident of Fukushima Daiichi nuclear
power plant, thousands of measuring data have been
piling up, especially in the web sites of government
agencies. However, most of them are two kinds of thedata. One is the radio activities of the places, including
soil, air dust or sea water and the other is themeasurement of the foods. These are just the monitoringdata and it is difficult to find out the research data
related to agriculture, such as, how much amount ofradioactivity was found or estimated when the plants
were grown in the contaminated field or how much
radioactivity was accumulated in mountains and what
about the contamination of river water coming from themountain, etc.
Research groups
Right after the accident, about 40 academic staffs in
our Graduate School had started the research project for
Fukushima in plants, soil, animals, fish, etc. Our
activities were classified into several groups as follows
but most of them were developed based on voluntary
activities. research project for Fukushima for plants, soil,

Results & discussion
The Cs movement in soil showed that Cs is so firmly
adsorbed on soil and there was no further washout of Cs
by rain, therefore, Therefore, it was suggested that thisthin contaminated surface soil can thus be collected andburied on site, leaving the land safe to work again, as
the radionuclides are unlikely to be leached from thesoil. The downward movement of the radiocesium insoil was further monitored. The study of fruit tree
showed that Cs was transferred from bark surface tofruits and there was not any radiocesium taken up fromroots. Animals are now investigated how radiocesium is
distributed among the tissues. We have now expanded
our investigations into a long-term study that will also
cover trees and fisheries.
Reference
Agricultural Implications for Fukushima Nuclear
Accidents. Nakanishi, T.M. and Tanoi, K. ed. Springer(2013)－ 210 －

24-FKP-16
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Concentration of Radiocesium in Rice, Vegetables, and Fruits Cultivated in
Evacuation Area at Okuma Town, Fukushima
Kenji Ohse1, Kyo Kitayama1, Seiich Suenaga2, Kiyoyuki Matsumoto2, Akira Kanno1, Chika Suzuki1,
Kencho Kawatsu1, Hirofumi Tsukada1
1

Fukushima Future Center for Regional Revitalization, Fukushima University
2
Okuma Government Office

Abstract – Rice, vegetables, and fruits were cultivated in theevacuation area at Okuma town, and the radiocesium concentrationof the crop samples cultivated in contaminated and decontaminatedsoil was compared. Decrease of the concentration in every crop bydecontamination was observed. The TF of brown rice was higher
than previous reports.
Keywords – evacuation area, test cultivation, radiocesium

I.

INTRODUCTION

Okuma Town which Fukushima Daiichi nuclear power
plant locates, the whole region contaminated severely byradioactive nuclides including 134Cs and 137Cs and was
designated the evacuation area. The prospect for reactivate of
agriculture was not found in the regions. However, in order toobtain the scientific data for recultivation in the future, test
cultivations of several crops in the contaminated anddecontaminated soils and collected fruits grown in the town
were carried out. In this study, the concentration and translate
factor of radiocesium in rice, vegetables, and fruits cultivatedin the contaminated and decontaminated sites are reported.

the weighted average of the concentration for the depth of 15
cm was 31.6, 7.46, 15.4, 13.7, and 14.8 kBq kg-1,. The
concentration of radiocesium in the decontaminated uplandsoil decreased 1/4 by removing the soil of 0-15 cm depth.
However, the radiocesium concentration in decontaminatedpaddy soil was slightly decrease compared to the contaminated paddy soil because the paddy field was disturbed byanimals and radiocesium mixed in deeper before cultivation.
The radiocesium concentration in crops and their transfer
factor (TF) were shown in Table 1. The concentration ofradiocesium in every crop cultivated in the decontaminatedfield was lower than that cultivated in the contaminated field.
The concentration of radiocesium in eggplant and pumpkin of
edible part cultivated in the decontaminated field was lower
than standard limit (100 Bq kg-1). However, the TF values of
the crops cultivated in the contaminated fields were within afactor of 3 to those cultivated in the decontaminated fields.
More techniques are required to decrease the radiocesium
concentration in crops.
Table 1 Concentration and translate factor of radiocesium in crops.
Crop

date

II. MATERIALS AND METHODS

contaminated field

Sampling

Cs-134

Cs-137decontaminated field
TF(Bq kg-1 fresh weight)

Cs-134

Cs-137

TF(Bq kg-1 fresh weight)

rice plant

Test cultivation site, which had paddy and upland field,
was located about 6 km far from Fukushima Daiichi Nuclear
Power Plant. Each paddy and upland field was divided into
two parts, which was contaminated and decontaminated byremoving surface soil. Several crops including rice plant,
eggplant, green soybean, sweet potato, pumpkin, and cabbage
were cultivated in both sites. After harvest, the crops were
washed and separated in several parts. They were dried andpulverized to powder. An ancient black rice plant was also
harvested from other paddy field. Soil samples werecorrected for the depth of 30 cm, cut into sections 0-2, 2-5, 510, 10-15, 15-20, 20-25, 25-30 in depth, oven dried andsieved 2 mm mesh. 134Cs and 137Cs in the samples were
determined by germanium semiconductor detector.
III. RESULTS AND DISSCUSSION
The abundance of radiocesium in the soils at contaminatedupland, decontaminated upland, contaminated paddy,
decontaminated paddy and ancient black rice paddy field was
3680, 877, 1820, 1640, and 1070 kBq m-2, respectively and－ 211 －

brown rice 3-Oct-12
rice hull 3-Oct-12
reaf and straw 8-Aug-12
reaf and straw 3-Oct-12
ancient black ricebrown rice 3-Oct-12
rice hull 3-Oct-12
reaf and straw 22-Aug-12
reaf and straw 3-Oct-12

117
264
89.0
185

195
438
132
300

0.02030.04560.01440.0315

82.7
197
39.2
113

139
322
57.5
187

0.01620.03790.0071
0.0219

258
474
178
285

424
762
271
464

0.04610.08350.03030.0506

58.5
32.4
69.1
161

90.0
52.9
116
262

0.00470.00270.00590.0134

7.01
7.39
12.2
46.4

11.0
11.5
20.4
77.1

0.00240.00250.00440.0166

161
240
302
627

257
395
492
992

0.01320.02010.0251
0.0512

69.4
97.0
91.8
136

116
158
153
226

0.02490.03420.03290.0486

151
223
171
215

261
356
284
361

0.01300.01830.01440.0182

84.4
68.6
101
137

139
115
163
226

0.03000.02460.03540.0487

113
145
191
143

184
234
319
234

0.00940.01200.01610.0119

13.4
16.0
14.6
41.7

21.7
24.5
22.6
62.8

0.00470.00540.00500.0140

250
375

402
634

0.0206
0.0319

148
321

241
520

0.05220.1129eggplant
edible part 8-Aug-12
edible part 3-Oct-12
stalk 3-Oct-12
reaf 3-Oct-12
green soybean
bean 3-Oct-12
pod 3-Oct-12
stalk 3-Oct-12
reaf 3-Oct-12
sweet potato
edible part 3-Oct-12
coat 3-Oct-12
vine 3-Oct-12
reaf 3-Oct-12
pumpkinedible part 3-Oct-12
coat 3-Oct-12
gut 3-Oct-12
vine and reaf 3-Oct-12
cabbagehead 3-Oct-12
un-head reaf 3-Oct-12

24-FKP-17
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Isotopic U, Pu, Am and Cm signatures in environmental samples fromthe Fukusima Dai-ichi Nuclear Power Plant accident
Masayoshi Yamamoto1, Aya Sakaguchi2, Shinya Ochiai1,Takahiro Takada1, Seiya Nagao1, Peter Steier3
1

Low Level Radioactivity Laboratory, KINET, Kanazawa University, Nomi, Ishikawa 923-1224, Japan
2
Graduate School of Science, Hiroshima University, Higashi-Hiroshima, 739-8526, Japan
3
VERA-Laboratory, Faculty of Physics, University of Vienna, Währinger Str. 17, A-1090 Vienna, Austria

Abstract – Alpha-ray spectrometry and AMS measurementsof U, Pu Am and Cm isotopes isolated from black materialsof roadsides collected at areas within the 20-km exclusion
zones (Minami-Souma, Namie, Futaba and Okuma Towns)
and Iitate Village are reported. For most of the samples, lowlevels of 236U, 238Pu, 239,240Pu, 241Am, 242Cm and 243,244Cm
were successfully determined. The results provide a coherent
isotopic data set, indicating that traces of U and transuranic
nuclides were released into the environment without theirlarge fractionations, probably with forms of fine particles.
These data are also very important in order to check thevalidity of estimation of fuel compositions in the FDNPP.
Keywords – FDNPP accident, 236U, transuranic elements, blackmaterials of roadside, alpha-ray spectrometry, AMS

contaminated with extremely high levels of radionuclides
released. They seemed to be suitable for getting information
on isotopic composition of trace amount of U and transuranicelements. The samples were mainly collected from areas
within the 20-km exclusion zones (Minami-Souma, Namie,
Futaba and Okuma Towns) in Sep.- Nov., 2012. Also were
samples taken from Iitate Village heavily contaminated. The
collected samples were air-dried, and sieved through a 2-mm
mesh to remove pebbles and big plant remains, andpulverized in an agate mortar to obtain homogeneous samples.
After chemical separation of each element, Pu (238Pu and239,240Pu), 241Am and Cm (242Cm and 243,244Cm) were
determined by alpha-ray spectrometry, respectively.
Uranium-236 was determined by AMS installed at VERALaboratory, University of Vienna (Vienna, Austria).

I. INTRODUCTION

III. RESULTS AND DISCUSSION

In the Fukushima Dai-ichi Nuclear Power Plant (FDNPP)
accident which occurred in connection with the M9 Great
East Japan Earthquake and subsequent tsunami on 11 March
2011, large amounts of radionuclides, especially volatile ones
such as 131I, 134Cs and 137Cs, have been accidently released
into the environment from the FDNPP. By broadly survey ofthese nuclides and researches, whole picture about levels andspreading areas of contaminants has been becoming clear,
together with the situation of plant accident. However,information on releases of U and transuranic nuclides as
refractory elements in fuel core was extremely limited due tothe difficulties of analyzing these nuclides. In this paper, weintended to clarify a full picture about these elements released
into the environment. For this purpose, 236U, Pu isotopes(238Pu, 239Pu and 240Pu), 241Am and Cm isotopes (242Cm and
243,244Cm) were measured for roadside dust collected at the
Fukushima areas heavily contaminated. Their released levels
and isotopic compositions will be discussed, compared withthe fuel compositions in FDNPP estimated by Nishihara et al.
(2012).

The collected black materials samples were found to becontaminated with extremely high levels of 134Cs and 137Cs
over 1000 kBq/kg by the FDNPP accident. More than 100
samples from areas within the 20 km-exclusion zones were
determined for 238Pu, 239,240Pu, 241Am. 242Cm and 243,244Cm by��ray spectrometry. Furthermore, in some samples, 236U was
successfully determined by AMS.
The results provided a coherent isotopic data set as
follows: 1) traces of 239,240Pu (range: 0.0n-1.8 Bq/kg) andhigh levels of 238Pu/239,240Pu activity ratios (range; ca.1-2.7,
but mostly around 2.1-2.4) were detected; for samples
showing 238Pu/239,240Pu ratios of more than 2 ( most (or all) of
Pu detected is due to the accident); 2) 241Am/239,240Pu activity
ratios were in the range from 0.32-0.75 with the mean valueof 0.53 ± 0.12 (n=35); 3) 242Cm/243,244Cm activity ratios(decay-corrected to 11 March, 2011) were 25.1±8.9 (n=61)
on average; 4) 242Cm/239,240Pu activity ratios (decay-corrected
to 11 March, 2011) were 33.6±10.6 (n=52) on average; and5) 236U/239,240Pu activity ratios were in the range of (1.9618.4) x10-4 with the weighted mean value of 7.87x10-4 (n=12).
When these activity ratios are compared with those of fuelcompositions in the FDNPP estimated by Nishihara et al(2012) of the JAEA group, fairly good agreement was found,indicating that traces of U and transuranic nuclides, probably
with forms of fine particles, were released into theenvironment without their large fractionations.

II. MATERIAL AND METHODS
The road dusts, called "Black Materials", whose color isapparently black, are browned in a corner and/or dip ofresidential streets and roadside by wind and rain. Thesematerials are composed with fine aerosol particles, fine carcut asphalt materials, residue of lichens, soil and so on, andK. Nishihawa et al. (2012), JAEA-Data/Code, 2012-018.

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APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Influence of the Fukushima Daiichi nuclear disaster on the tritium concentrationin the precipitation of Kanazawa city
Yoshimune Yamada1, Kaeko Yasuike1, Toshiyuki Kawabata2, Akihiro Fujii2, Hitoshi Kakimoto2
1

2

Faculty of Pharmaceutical Sciences, Hokuriku University, Kanagawa-machi, Kanazawa, 920-1181, Japan
Ishikawa Prefectural Institute of Public Health and Environmental Science, Taiyogaoka, Kanazawa, 920-1154, Japan

Abstract – The variation in tritium concentration in the
precipitation of Kanazawa city was measured the day after the
Fukushima Daiichi nuclear disaster, which occurred on 11 March,
2011. The most interesting result in the period from March toAugust 2011 is that a secondary peak of 4.6 Bq/L was observed on
22 March after the maximum peak of 15.0 Bq/L on 16 March. This
fact suggests that a sudden release of a large amount of tritiumfrom the Fukushima Daiichi nuclear power plant occurred
between 21 March and 22 March, followed by the release from 11
March to 15 March. Another interesting result is that dramaticincreases in the tritium concentration of 131.6 Bq/L and 99.9
Bq/L were observed on 30 May and 13 June in the variation
patterns of the tritium concentration in the precipitation of
Kanazawa city. These increases may have been caused by windblowing down from the upper atmosphere during a storm. A large
amount of tritium which had been released by hydrogen
explosions from the Fukushima Daiichi nuclear reactors wasconsidered to exist in the bulk air in the upper atmosphere.

rainfall in a stainless tray of 560 mm x 405 mm, and thendistilled after the addition of KMnO4 and Na2O2 to remove
any acidic contaminants. The counting source for a liquid
scintillation spectrometer was prepared by mixing 40 mL of
distilled water with 60 mL of cooled sol-gel emulsifier-type
scintillating cocktail, ULTIMA GOLD LLT �PerkinElmer
Inc.� in a 100 mL Teflon vial. It was allowed to standunder cool, dark conditions for three days before counting
to suppress chemical luminescence. The tritium activity
was measured under temperature-stabilized conditions at
12°C using a low background liquid scintillation counter,
Aloka LB-5. The counting was carried out for at least fourcycles of 1,150 min (50 min x 23) run. The backgroundcount rate was 2.22-2.48 cpm at an efficiency of 30.030.8 %, which was determined by the external standard
channels ratio method.

Keywords – Tritium, Fukushima Daiichi nuclear disaster,precipitation of Kanazawa city

III. RESULTS AND DISCUSSIONI.

INTRODUCTION

Tritium distribution in nature is mainly the result ofcontinuous production by cosmic rays in the upper
atmosphere and prolonged exposure from thermonuclear
bomb tests carried out during the 1950’s and early 1960’s.
The tritium concentration of the precipitation in
Ishikawa Prefecture, Japan, showed the highest annually
averaged value of 74.1 Bq/L1 in 1963, which corresponded
to the year of the maximum fallout of tritium in thenorthern hemisphere. After the maximum, it decreased year
by year for the past four or five decades, and returned tolevels lower than 1 Bq/L in 2007.
Tritium is generated by various nuclear reactions andpresents as tritiated water (HTO), tritiated hydrogen gas(HT) and other chemical forms in nuclear reactors. A large
amount of tritium was released from the Fukushima Daiichi
nuclear power plant caused by the damage of the nuclear
reactors in consequence of the Great East Japan Earthquakeon 11 March 2011. In this paper, the variations in tritium
concentration in the precipitation of Kanazawa city arereported for the period from March to August 2011. Thiswas done to determine the influence of the tritium released
into the environment by the Fukushima Daiichi nuclear
disaster on the tritium concentration in the precipitation of
Kanazawa city.
II. MATERIAL AND METHODS
The precipitation of Kanazawa city (36.52oN, 136.71oE)
Ishikawa Prefecture, Japan, was collected during every

The first rainfall in Kanazawa city after the occurrenceof the Fukushima Daiichi nuclear disaster was observed on
15 March 2011 (from 15:50) and it changed to intermittent
snow the next day. The tritium concentration in the
precipitation of Kanazawa city (36.52oN, 136.71oE)
Ishikawa Prefecture, Japan was at levels of 0.35-0.54 Bq/L
during the period from February to early March in 2011. It
began to increase following the snow of 4:10-9:00 on 16
March, and through to a maximum peak of 15.0 Bq/L after
the snow of 9:00-19:00 on 16 March. It decreased to thenormal level of 0.5 Bq/L in the rainfall of 9:00-13:30 on 21
March, and thereafter increased again rapidly to 4.6 Bq/L
in the sleet from 19:10 on 22 March to 9:00 on 23 March.
These facts suggests that a sudden release of a large amountof tritium from the Fukushima Daiichi nuclear power plant
occurred between 21 March and 22 March, followed by theaccidental or uncontrolled release of tritium from 11 March
to 15 March.
A dramatic increase in tritium concentrations of 131.6
Bq/L and 99.9 Bq/L was observed in the rainfalls of 9:3013:40 on 30 May and those from 21:30 on 13 June to 9:00
on 14 June in the variation patterns of tritium concentrationin the precipitation of Kanazawa city, although no marked
change was observed in the period from April up to the endof May. This may have been caused by the wind violently
blowing down from the upper atmosphere during a storm.
A large amount of tritium which had been released byhydrogen explosions from the Fukushima Daiichi nuclear
reactors is considered to exist in the bulk air in the upper
atmosphere.
[1]－ 213 －

Y. Yamada, K. Yasuike, K. Komura, J. Nucl. Radiochem. Sci., 6,
17-20 (2005)

24-FKP-19

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Sediment transport processes in reservoir-catchment system inferred fromsediment trap observation and fallout radionuclides
1

Shinya Ochiai1, Seiya Nagao1, Masayoshi Yamamoto1, Taeko Itono2, Kenji Kashiwaya3

Low Level Radioactivity Laboratory, Institute of Nature and Environmental Technology, Kanazawa University, Japan
2
Graduate School of Natural Science & Technology, Kanazawa University, Japan
3
Institute of Nature and Environmental Technology, Kanazawa University, Japan

Abstract – Sediment trap observation of 210Pb, 137Cs, and 134Cs in
an artificial reservoir located in central Japan indicates that thedischarge rate of these radionuclides from the catchment islargely influenced by the precipitation, with high precipitation in
typhoon and snow season. The annual discharge rate of 134Cs
from the catchment is larger than that of 137Cs, suggesting that
FDNPP-derived 134Cs is concentrated at the erodible surface soil
and it is a major sediment source for the annual timescale. The
137
Cs/210Pbex activity ratio was high during rainy season andtyphoon season, corresponding to the change in 10 mm/h excess
rainfall. The soil erosion during the heavy rainfall may extend tothe high 137Cs accumulated part in the catchment where is not
erodible in the normal condition. This result suggests that heavy
rainfall affects the source of eroded sediment and the erosion
process in the catchment.
Keywords – sediment transport, sediment trap,
Fukushima Dai-ichi NPP

I.

210

Pb,

134,137

Cs,

INTRODUCTION

The sediment transport processes in the catchment areimportant to understand the landform development andmaterial transport to downstream rivers, lakes and ocean.
The fallout radionuclides 137Cs and 210Pb have been widelyused to investigate soil erosion and sediment transport
processes. 210Pb is continuously supplied on the soil
through atmospheric deposition, while the supply of 137Cs
is negligible at the present and its distribution has beenchanged by downward migration and erosion during thepast several decades. Additionally, 134Cs was newly
accumulated on the surface soil by the Fukushima Dai-ichi
Nuclear Power Plant (FDNPP) accident in 2011. The
difference in horizontal and vertical distribution of theseradionuclides in the catchment may provide the informationon the eroded sediment sources and its response toerosional forces (e.g., hydrological and geomorphologicalconditions).
This study aims to investigate the sediment transport
processes in the reservoir-catchment system based on thecontinuous sediment trap observation and these fallout
radionuclides.
II. SAMPLES AND METHOD
Study site is an artificial reservoir Takidani-ike for
agricultural irrigation located in Ishikawa Prefecture incentral Japan. Sediment trap observations have been
performed since 2000 in Takidani-ike. Deposited sediments
collected monthly using a sediment trap on the bottom wereoven dried at 110°C to obtain their dry weights andsedimentation rates. Samples collected during the period
from February 2010 to December 2011 were used for theradioactivity measurements. Soil samples were also
obtained in the catchment using a steel tube (30 cm length)
to estimate inventory of the radionuclides. The activity
concentration of 210Pb (peak energy: 46 keV), 214Pb (352keV), 137Cs (661.6 keV), and 134Cs (604.7 keV) were
determined by gamma-ray spectrometry using low
background Ge detectors. The activity of excess 210Pbex was
estimated by subtracting the activity of 214Pb from that of210
Pb.
III. RESULTS AND DISCUSSION
Sedimentation fluxes of 210Pbex and 137Cs in Takidaniike range 3.5–80 and 0.1–2.6 Bq/m2/day, respectively, andwere high during autumn and winter than in spring andsummer. 134Cs was first observed just after the FDNPP
accident and showed the similar seasonal fluctuation
ranging n.d.–0.15 Bq/m2/day. These fluctuations
correspond to the changes in precipitation, with highprecipitation in typhoon and snow season, indicating thatthe discharge of these radionuclides from the catchment islargely influenced by the precipitation.
Based on the average sedimentation flux, the annual
210
Pbex, 137Cs, and 134Cs discharge rates from the catchment
were estimated as 222, 7.1, and 0.62 Bq/m2/year,
respectively. These values correspond to 0.72, 0.25, and
4.2 %/year of the inventory of 210Pbex (31 kBq/m2), 137Cs(2.8 kBq/m2), and 134Cs (14.7 Bq/m2). The annual discharge
rate of 134Cs is much larger than that of 137Cs, suggestingthat FDNPP-derived 134Cs was accumulated at the erodible
surface soil and it is a major sediment source for the annual
timescale.
The 137Cs/210Pbex activity ratio of the trap samples
temporally changes from 0.02 to 0.045, and was highduring rainy season and typhoon season. This fluctuation
well corresponds to the change in 10 mm/h excess rainfall(total rainfall exceed 10 mm/h for each sampling interval)
reflecting the heavy rainfall events. This fluctuation may
result from the soil erosion at the high 137Cs accumulatedpart in the catchment during the heavy rainfall where is not
erodible in the normal condition. This result suggests thatheavy rainfall affects the source of eroded sediment and theerosion process in the catchment.

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24-FKP-20

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Transfer of Radiocesium to Crops Cultivated in Fukushima
1

Shinji Sugihara1, Toshio Hara2, Akihiro Maekawa3, Noriyuki Momoshima1

Radioisotope Center, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Iizuka, Fukuoka 820-8555, Japan
3
Graduate School of Sciences, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
2

Abstract – Several kinds of crops were cultivated by using thecontaminated soil in the field of Fukushima Prefecture and theradioactivity of soil and crops was measured. The soil-to-crops
transfer factor of a radiocesium was calculated, and a different
value was calculated by corps and the part of crops. But the levelof the calculated value is almost equal to already reported.
Keywords – Transfer factor, Radiocesium, Crop, Fukushima Daiichi Nuclear Power Plant

I.

INTRODUCTION

A large amount of radioactive materials were discharged
into the atmosphere during the Fukushima Dai-ichi Nuclear
Power Plant accident. As a consequence, a wide region ofJapan has been contaminated by mainly radiocesium.
As part of the proof examination of the revival model
after the Fukushima nuclear disaster, several kinds of crops
were cultivated and the effect of decontamination anddesalinization of the contaminated farmland were inspected.
The soil-to-plant transfer factor (TF) of radiocesium isextremely variable among soils.
Radionuclides can reach the human body throughseveral food chains in the environment. A lot of data in thetargeted environment such as TF is necessary to evaluate
the influence on the human body.

The radioactivity of the sunflower (Helianthus annuus)
grown at the field in A area was measured similarly.
III. RESULTS AND DISCUSSION
Figure 1 shows the depth distribution of the Cs in thesoil before the ploughing of A area. Cs that deposited tosurface on the field by the Fukushima nuclear disasterremained in the surface layer after two years passed, andmost was detected within 5cm in depth. The radiation dose
rate at A area was 1.14 �Sv/h by 1m on the ground. The Cs
concentration was about 1/3 of that of A area, and the dose
rate was 0.71 �Sv/h on B area.

II. METHOD

Fig.1 Depth distribution of Cs in A area before the ploughing

The cultivation examination ground was set by twoplaces (A area: Harashita, B area: Kekaya) in Tomioka,
Fukushima Prefecture. B area had received the flood
damage of the tsunami. After the disaster, the area was left
because these areas were specified for the no-go zone
though both areas were originally rice fields. The radiation
measurement, the ploughing and the sowing were done inMay, 2013. Crops were sorghum (Sorghum bicolor), corn
(Zea mays), rapeseed (Brassica napus) and Sugar beet
(Beta vulgaris ssp). Sorghum and corn were harvested in
the middle of November, 2013 at A area. Because thecultivation period was different, the flowering of therapeseed was difficult. Only the sugar beet grew and it
harvested in December, 2013 though sorghum and corn
were fruitless on B area due to the salt damage. The
radioactivity of the soil before and after the ploughing andthe harvested crops sample was measured. The soil sample
was cut at intervals of 1cm. The samples of Crops weremade separately for the leaf, the stalk and the seed. A dry
sample was put in the U8 container, and the Cs
concentration was measured with the Ge solid state detector.

Soil-to-crop transfer factor (TF) was calculated as theratio of the radionuclide concentration in crops (Bq/kg dryweight) to its concentration in soil (Bq/kg dry weight).
Both the dry weight and the fresh weight were used as forthe numerator, and the dry weight was used here. TF
differed according to the part of the crop, and existed in therange of 0.01 to 0.1. Because TF of the seed was small, theseed might be able to use as fodder.
It will be necessary to obtain the basic data for therevival by changing the kind of the soil and crops inaddition and accumulating the vast scope of data in the
future.

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24-FKP-21

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Dynamics of radiocesium in bamboo forests
after the accident of Fukushima Daiichi nuclear power plant
Tsutomu KANASASHI, Mitsutoshi UMEMURA, Yuki Sugiura , Chisato TAKENAKA
Graduate School of Bioagricultural Sciences, Nagoya University
Abstract – To understand the dynamics of radiocesium in bamboo
forests, we compared the 137Cs concentrations in one-year old
bamboo with older ones. The leaves from one-year bamboo
contained 137Cs at similar concentration to those of older
bamboos. Since bamboo shoot of 2012 also contained 137Cs,
cesium should be actively transported in bamboo body.
Keywords – bamboo, radiocesium, leaves, branch, shootI.

INTRODUCTION

The accident of Fukushima daiichi nuclear power planton 2011 caused serious problems through the deposition ofradionuclide in a large area of Fukushima prefecture.
Bamboo forests, which have been familiar to peoples as
producing area of various livelihoods like bamboo shoots,
were also contaminated with radionuclide, especially 137Cs.
The decontamination of 137Cs from bamboo forests has
been expected but supposed to be difficult because of theexistence of a large amount of subterranean stems. In orderto design an effective decontamination procedure of 137Cs
and resume the usage of bamboo forests in Fukushima, it isessential to understand the dynamics of 137Cs in bamboo
forests. We aimed to clarify the absorption and transport of137
Cs in bamboo by comparing the 137Cs concentration in
one-year old bamboo with older one.

From these data, the radioactivity at site A was almost athird of those at sites B and C. In addition, at the sites A
and B, the concentrations of 137Cs in soil layer were higher
than those in litter layer, whereas the activity of litter was
almost twice of that of soil layer at site C. Theseobservations suggested that the degree of 137Cs infiltration
into root system were different among three sites.
The concentrations of 137Cs in leaves and branches
collected at site A were shown in Fig.1. The 137Csconcentration in leaves from one-year bamboo, which
sprouted on 2011 after the accident, was not so different
from the values of leaves in the other samples (2 to 11years old bamboos), whereas the data in branch of one-year
bamboo was quite low comparing with those of the otherbamboos. Since the bamboos older than one year adsorbed
137
Cs on their surface at the accident of FNPP, thedifference of concentrations among branches with various
aged bamboo should reflect the direct deposition. On thecontrary, the similar concentrations of 137Cs in leaves of
one-year bamboo with the others might indicate the uptakeof 137Cs through root system. The same results wereobtained from the data of site B and C. The bamboo shootsprouted on 2012 also contained 137Cs at the same level asleaves.
Table 1. Acticity of Cs-137 in litter and soilat three moso forests (kBq/m2)
A
B
C

II. MATERIAL & METHODS
Bamboo samples were collected from three moso
bamboo (Phyllostachys pubescens) forests in Fukushima
prefecture during spring season of 2012. At one site (siteA), since the age of each bamboo could be defined, notonly an one-year old bamboo, which sprouted after theaccident of FNPP, but also 2,4,5,10,11-years old bamboos
were collected. At the other two sites (sites B and C),
three one-year old bamboos and three bamboos older than
one year were sampled. A bamboo shoot was alsocollected at site C. Litters and soils were collected fromthree sites.
Each bamboo was divided into stem, branch and leaves.
For the samples from site C, branch and leave samples
were prepared from top and middle parts of a stem.
Every plant samples were pulverized after drying. The
activity of 137Cs was counted by a Ge- semiconductor
detector (Seiko EG & G). Each counting was continued
until the count error becomes below 10%.
III. RESULTS & DISCUSSION

Litter

44

161

254

Soils

66

186

132

Figure 1. Concentration of 137Cs of leaves and branches in various agedbamboos

Table 1 shows the concentration of 137Cs per area inlitter and soil layers at three moso bamboo forest sites.
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24-FKP-22

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Reaction Behavior of Uranium and Zirconium Oxides in Oxidative and Reductive
Conditions
Nobuaki Sato, Kohei Fukuda and Akira Kirishima

Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,
2-1-1, Katahira, Aoba-ku, Sendai,980-8577, Japan

To investigate the treatment of fuel debris formed in the damaged reactors at Fukushima Daiichi NPP, study on
the reaction behavior of main constituents in the reactor is essential. The main component in the damaged
reactor is the mixture of uranium and zirconium since there are the fuel and cladding. As for the reaction
between fuel oxide and fission products in oxidative condition, the phase relation of the oxides in the U3O8 andNd2O3 system was reported [1]. Then the reaction behavior of the uranium and zirconium oxides at elevatedtemperatures in oxidative and reductive atmospheres was studied by XRD method. After the heat treatment of
the mixture of UO2 and ZrO2 with a Zr amount of 50 mol % under vacuum at elevated temperature, the UO2solid solution phase such as ZryU1-yO2+x seemed to be formed at temperatures lower than 1273 K. However,phases similar to U3O8 structure appeared in the temperature range from 1073 K to 1473 K. Over thistemperature, a new phase similar to the UO2 phase seemed to be formed showing the decomposition of U3O8
phase at high temperature. When the mixture of zirconium to uranium oxides was treated by mechanochemical
method under reducing condition , the X-ray pattern of the products showed that they were the same fluorite
structure and the lattice parameter of linearly decreased with increasing zirconium ratio. This suggests that theUO2 and ZrO2 form the solid solution from low Zr/U ratio to high one. These results were also discussed withthe phase diagram.
Keywords: Fuel debris, Uranium oxides, Zirconium, UO2 solid solution, Phase relation[1] N. Sato, G. Shinohara, A. Kirishima and O. Tochiyama, High Temp. Mat. Proc., 29 (2010) 461–468.

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24-FKP-23

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Radiocesium in zooplankton in seawaters off Miyagi, Fukushima, and Ibaraki
Prefectures
1

H. Takata1, M. Kusakabe2, S. Oikawa1

Central Laboratory, Marine Ecology Research Institute2
Head Office, Marine Ecology Research Institute

Abstract – Zooplankton samples in seawaters were collected off
Miyagi, Fukushima, and Ibaraki prefectures from May 2012 toJanuary 2013. Activity concentrations of 134Cs and 137Cs inzooplankton varied from 0.1to 9.1 Bq/kg-wet weight, and from
0.1 to 12.8 Bq/kg-wet weight, and were higher in May 2012 thanin the other sampling months. We also estimated the zooplanktonto-water activity ratio of 137Cs to be 20-754 L/kg.
Keywords – zooplankton, radiocesium, concentration ratio,
Fukushima Dai-ichi nuclear power plantI.

INTRODUCTION

The East Japan earthquake and tsunami of March 11,
2011, resulted in unprecedented radioactivity releases fromthe Fukushima Dai-ichi nuclear power plant (FDNPP) to
the Northwest Pacific Ocean. Radionuclides (e.g., 134Cs (t1/2=2 y), and 137Cs (t1/2=30 y)) originated from the FDNPP
migrated horizontally (e.g., Aoyama et al., [1]); however,the vertical transport mechanisms for radiocesium in the
coastal areas off Japan are not fully understood.
Zooplankton activity such as excretion and verticalmigration can be one of candidates to play an importantrole in vertical transport of man-made radionuclides (e.g.
Fowler et al. [2]).
We report here the results from a radiochemical analysisof zooplankton for raiocesium (134Cs and 137Cs) collected in
the waters off Miyagi, Fukushima, and Ibaraki prefecturesin 2012 and 2013.

12.8 Bq/kg-wet weight for 134Cs and 137Cs, respectively
during May 2012 to January 2013 (Fig. 1). In addition,
relatively high activity concentrations of radiocesium wereobserved near off Ibaraki prefecture during May 2012
cruise, and near off Fukushima prefecture during January
2013 cruise (Fig. 1). The variation in activity
concentrations would be due to changes in activity
concentrations of radiocesium in their ambient waters.
However, there was no significant correlation between
radiocesium activity concentration in the ambient water andin the zooplankton.
Another possible reason is probably due to the differencein the composition of zooplankton at each station; however,so far it is unclear as to the relationship between planktonic
species and their 137Cs contents.
We also estimated the zooplankton-to-water activity ratioof Cs to be 20-754 L/kg; most of them are higher than theone (40 L/kg) published by the IAEA[3].
137

II. MATERIALS AND METHODS
Zooplankton were collected at seven stations during fourcruises (May 2012, Aug. 2012, Oct. 2012, and Jan. 2013) atthe depths of around 20-80 m with a large ring net (160 cm
mouth diameter, 0.5 mm mesh) during daytime by a 30-min
horizontal towing. To ensure sufficient amounts of sample
for radionuclide analyses, 2–3 hauls per station werecombined into one sample. After the collection, samples on
the mesh were transferred to plastic buckets. A small
amount of samples were preserved immediately in 5% (v/v)
formalin–seawater buffered with borax for microscopic
observation, and the rest of the sample was stored in afreezer at -20oC.
Zooplankton samples were weighed (wet weight),
ovendried (105 C), and weighed again to obtain dry weight.
The activity of radiocesium in dried samples was measured
with coaxial type Ge detectors for a few hours. The
radioactivities of 134Cs and 137Cs in the samples weredecay-corrected to the sampling date.
oIII. RESULTS AND DISCUSSION
Activity concentrations of radiocesium in zooplankton
ranged from 0.1 to 9.1 Bq/kg-wet weight, and from 0.1 toFig. 1 Activity concentrations of 137Cs in zooplankton at 7stations during
each sampling cruise.

REFFERENCES[1]

Aoyama, M., Uematsu, M., Tsumune, D., and Hamajima, Y.:
Surface pathway of radioactiveplume of TEPCO Fukushima NPP1
released 134Cs and 137Cs, Biogeosciences Discuss., 10, 265–283,
doi:10.5194/bgd-10-265-2013, 2013.
[2] Fowler, S.,W., Buat-Menard, P., Yokoyama, Y., Ballestra, S., Holm,E., and Nguyen, H.,V.: Rapid removal of Chernobyl fallout from
Mediterranean surface waters by biological activity, Nature 329, 56–
58, 1987.
[3] IAEA: Sediment distribution coefficients and concentration factors
for biota in the marine environment, Technical Report Series no. 422,
IAEA, Vienna, 1–95, 2004.
This work was part of a research project contracted from the Ministry of
Education, Culture, Sports, Science and Technology, Tokyo, Japan.

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24-FKP-24

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Plutonium isotopes and 241Am in surface sediments off the coast of the Japaneseislands after the Fukushima accident
S. Oikawa1, T. Watabe2, H. Takata1, J. Misonoo2, M. Kusakabe2
1

Central Laboratory, Marine Ecology Research Institute2
Head Office, Marine Ecology Research Institute

Abstract – We determined concentrations of Pu isotopes and241
Am in surface (upper 3cm) bottom sediments collected in a sea
area along the coast of the Japanese islands after the Fukushima
Dai-ichi Nuclear Power Plant (FDNPP) accident. The
concentration in the sediments collected immediately after theaccident was at almost the same levels as those obtained before
the accident.
Keywords – plutonium; 241Am; bottom sediment; Fukushima Daiichi Nuclear Power Plant accident

I.

INTRODUCTION

As a result of the FDNPP accident on March 11, 2011, alarge amount of 131I (half-life: 8 d), 134Cs (2 y), 137Cs (30 y)and other radionuclides were released into the atmosphere.
In addition, a remarkable amount of radionuclides was also
released directly from the plant as the leakage of coolant
seawater poured into the reactor. Comprehensive survey
projects were immediately initiated after the accident forclarifying the distribution of radionuclides especially withhigh volatility such as 131I, 134Cs and 137Cs in theenvironment. However, a survey of actinides derived fromthe accident in the marine environment has been yet to be
sufficient to evaluate their impact. This paper represents theresults of a nationwide survey project to figure out theextent of the accident impact in the levels of Pu isotopes
and 241Am in the bottom sediments collected from the 15
sampling areas. And a comparison was made of the preaccident data to the post-accident ones.

clayey sediment collected in the Aomori area and thelowest of 0.42 Bq/kg-dry in the sandy sediment in the
Ehime area. Although the 241Pu was detected from somesamples having relatively high 239+240Pu concentration (ca.
>0.7 Bq/kg-dry), the 241Am was detected from all of thesediments. The 241Pu/239+240Pu activity ratio found in thesediments varied among the sites even if the sediments
collected in the same period of time and ranged from 0.75
to 1.2. The 241Am/239+240Pu activity ratio in the sediments
were nearly constant (ca. 0.6), and the 240Pu/239Pu atom
ratios were also nearly constant (ca. 0.24) throughout thenationwide sites. The concentrations of Pu isotopes and241
Am, and their ratios found even in the sediments taken in
the vicinity of the FDNPP accident have no significant
differences between prior to and after the accident. Thus,
our nationwide survey results showed that the accident at
the FDNPP did not contribute so greatly to the inventory of
Pu isotopes and 241Am even in the coastal area off
Fukushima Prefecture.

II. MATERIALS AND METHODS
The radioactivity survey project was implemented innationwide 15 sampling areas (Fig. 1). Bottom sediment
samples were collected by a box-type sampler, which
retrieves a 1600 cm2 of sediment from the ocean floor
without disturbing their surface. The upper 3 cm of thesediments were taken for analysis. Plutonium and 241Am
analysis was performed using 50 g aliquot of dried sample,
and alpha spectrometry and beta counting method was used
to measure 239+240Pu (alpha), 241Pu (beta) and 241Am (alpha).
We also used SF-ICP-MS to measure 240Pu/239Pu atom ratio.
III. RESULTS AND DISCUSSION

Fig. 1 Locations of sampling areas.
REFERENCES[1]

The activity concentrations of 239+240Pu found in thesesurface sediment samples collected in May-July 2011,
immediately after the accident ranged from 0.42 to 3.7
Bq/kg-dry, which was comparable to those reported byZheng et al. [1] and Oikawa et al. [2]. The highest 239+240Pu
activity concentration of 3.7 Bq/kg-dry was found in the[2]

Zheng, J. et al., Distribution of Pu isotopes in marine sediments in
the Pacific 30km off Fukushima after the Fukushima Daiichi nuclear
power plant accident. Geochem. J. 46, 361-369 (2012).
Oikawa, S. et al., Plutonium isotopes concentration in seawater andbottom sediment off the Pacific coast of Aomori sea area during
1991-2005. J. Environ. Radioact. 102, 302-310 (2011).

This work was a part of a research project contracted from the Ministry of
Education, Culture, Sports, Science and Technology, Tokyo, Japan.

－ 219 －

24-NEP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

A theoretical study of actinide and lanthanide extraction withcarbamoylmethylphosphine oxide ligands
Cong-Zhi Wang , Jian-Hui Lan , Yu-Liang Zhao , Zhi-Fang Chai , Wei-Qun Shi*

Nuclear Energy Nano-Chemistry Group, Key Laboratory of Nuclear Analytical Techniques and Key Laboratory For
Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing
100049, China
E-mail: shiwq@ihep.ac.cn
Abstract – With the development of nuclear energy, safe disposal of
the spent nuclear fuel especially high level liquid waste (HLLW)
generated during the PUREX (Plutonium Uranium Extraction)
process has become the key factors affecting the sustainable
development of nuclear energy. The n-octyl(phenyl)-N,N-diisobutylmethylcarbamoyl phosphine oxide (CMPO) used in the so-called
TRUEX (Transuranium Extraction) process was found to possess
excellent extracting ability for actinide and lanthanide cations inacidic media.1,2 In this work, The UO22+, NpO2+, Pu4+, Am3+ andEu3+ extraction complexes with CMPO and diphenyl-N,N-diisobutyl
carbamoyl phosphine oxide (Ph2CMPO) have been investigated bydensity functional theory (DFT) in conjunction with relativistic
small-core pseudopotentials. For most extraction complexes, the
CMPO and Ph2CMPO molecules are coordinated as bidentate
chelating ligands through the carbonyl oxygen and phosphoric
oxygen atoms. The metal-ligand bonding is mainly ionic for all ofthese complexes. The neutral UO2L2(NO3)2, NpO2L2(NO3),
PuL2(NO3)4, AmL3(NO3)3 and EuL3(NO3)3 complexes are predicted
to be the most thermodynamically stable molecules according to themetal-ligand complexation reactions. As reported in the literature,3-5
the extractability of these actinides decrease in the order of Pu4+>
UO22+> Eu3+ � Am3+> NpO2+. In addition, hydration energies may
play an important role in the extractability of CMPO and Ph2CMPO
for these actinide ions. In most cases, the complexes with CMPO
and Ph2CMPO ligands have comparable metal-ligand binding
energies, i.e., the substitution of a phenyl ring for the n-octyl at thephosphoryl group of CMPO has little influence on the extraction ofthese actinides and lanthanides.

Fig. 1 Extraction complexes of UO22+, NpO2+, Pu4+, Am3+ and Eu3+ from
nitric acid solutions with CMPO
[1]
[2]
[3]
[4]
[5]

Keywords – actinide, lanthanide, extractant, relativistic quantum
chemistry－ 220 －

Horwitz, E. P.; Kalina, D. G.; Diamond, H.; Vandegrift, G. F.; Schulz,
W. W. Solvent Extr. Ion Exch. 1985, 3, 75.
Horwitz, E. P.; Kalina, D. G.; Diamond, H.; Kaplan, L.; Vandegrift, G.
F.; Leonard, R. A.; Steindler, M. J.; Schulz, W. W. DE85 010251, 1985.
Visser, A. E.; Jensen, M. P.; Laszak, I.; Nash, K. L.; Choppin G. R.;
Rogers, R. D. Inorg. Chem. 2003, 42, 2197.
Wisnubroto, D. S.; Nagasaki S.; Enokida Y.; Suzuki A. J. Nucl. Sci.
Technol. 1992, 29, 263.
Mathur, J. N.; Murali, M. S.; Natarajan P. R. Taianta 1992, 39, 493.

24-NEP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The role of microorganisms during the wet nuclear fuel storage in Slovak Republic
1

Martin Pipíška1, Lenka Tišáková2, Miroslav Horník1, Jozef Augustín1

Department of Ecochemistry and Radioecology, University of SS Cyril and Methodius, J. Herdu 2, Trnava, SK-917 01,
Slovak Republic (pipiska@ucm.sk)
2
Institute of Molecular Biology, Slovak Academy of Sciences, SK-845 51, Bratislava, Slovak Republic

Abstract
The role of short-term and long-term effects of microbialactivity on the wet disposal of spent nuclear fuel in storage
facilities is relatively discussed question. Deionized water instorage pools serves as a coolant and, at the same time, as aprotection against radiation. However, microorganisms havebeen shown to survive and grow in high levels of radiationand in highly pure water and they can tolerate both high andlow osmolarity and extreme pH and temperature values �1, 2�.
This work is focused on a characterization of bacterial
contamination in pool water of the Interim spent nuclear fuelstorage (ISFS, JAVYS Inc.) in Slovakia. The ISFS consists of
4 interconnecting pools: 3 fuel storage pools and 1 reserve
pool built from austenitic steel and permanently filled with
deionized water (Fig 1). The mean specific radioactivity of����� ������ ���� �� ��������� ���� ����×10 5 Bq/L�� ���� �� ���������
53
3.7 ×10 Bq/m . Tritium participated by the activity 1.3 ×105
Bq/m3 and contribution of radionuclides increased in theorder: 60Co < 134Cs < 3H < 137Cs. From the microbiologicalpoint of view, the pool water represents oligotrophic
environment which enables the growth of mesophilic bacteria,
where chronic radiation exerts selective pressure, alteringboth the diversity and abundance of bacteria.

the water from the bottom of the pool SP 3 and SP4 to SP6
fluctuated between 100 and 5 500 CFU/L, although
noticeable higher values were observed in August andOctober 2011 and from April to June 2012. Observed higher
values up to 250 000 CFU/L can be caused by manipulation
procedures such as filling the new fuel assemblies ormanipulation in filtration units and by the facility
reconstruction. In our primary screening 7 different bacterial
isolates from spent nuclear fuel pools were obtained. Only 4
isolates showed stable growth on DEV nutrient agar.
Subsequently, these isolates were identified by 16S rDNA as
Kocuria palustris, Micrococcus luteus, Ochrobactrum spp.
and Pseudomonas aeruginosa.
In laboratory experiments, the bioaccumulation of 137Cs
and 60Co by isolated bacteria were also studied �3�. The
maximum specific uptake of Cs+ after 48 h cultivation inmineral medium (MM) reached 7.54 ± 0.48 µmol/g dw.
(Ochrobactrum spp.), 19.6 ± 0.1 µmol/g dw. (M. luteus) and20.1 ± 2.2 µmol/g dw. (K. palustris). The maximum specificuptake of Co2+ after 24 h cultivation in MM reached 31.1 ±3.5 µmol/g dw. (Ochrobactrum spp.), 86.6 ± 12.2 µmol/g dw.
(M. luteus) and 16.9 ± 1.2 µmol/g dw. (K. palustris).
Analyzing of bacterial communities inhabiting anenvironment exposed to radiation gives opportunities to findbacterial strains with interesting properties such asradioresistance and radionuclide sequestering, able to survive
in extremely nutrient deficient environment. We found thatbacteria K. palustris, Ochrobactrum spp. and M. luteus
isolated from ISFS pool water effectively accumulate both137
Cs and 60Co under growth conditions indicating that thesebacteria affect the fate of radionuclides in pool water.
Presented results should serve also as the basis for further
studies relating to the microbial safety of wet nuclear waste
storage in Slovak Republic.
Keywords spent nuclear
bioaccumulation, 60Co, 137Cs

fuel,storagepools,

bacteria,

References
Fig. 1 Circulation system of pool water in spent nuclear fuel storage facility
at ISFS. Samples of water were collected from fixed 6 sampling points: SP1
and SP2 – near the water surfaces, SP3 – from the bottom, SP4, SP5 andSP6 – after filtration unit, after catex and anex columns, respectively.

Bacterial content in pool waters is kept on very low levelby extremely low concentration of solutes in deionized waterand by both the efficient water and air filtration systems.
During the monitoring from 2009 to 2012, bacterial densities
in the water samples from the surface of pools (SP1, 2) were
within the range from 50 to 4 525 CFU/L. Viable counts in[1] Wolfram JH, Dirk, WJ (1997) Biofilm development and the survival of
microorganisms in water systems of nuclear reactors and spent fuelpools. In: Wolfram JH, Rogers RD, Gaszó LG (Eds) Microbial
degradation process in radioactive waste repository and in nuclear fuelstorage areas. Dordrecht, Kluwer Academic Publishers, pp. 139-147[2] Diósi G, Telegdi J, Farkas G, Gazso LG, Bokori E (2003) Corrosion
influenced by biofilms during wet nuclear waste storage. Int Biodeterior
Biodegrad 51: 151-156[3] Tišáková L, Pipíška M, Godány A, Horník M, Vidová B, Augustín J(2013) Bioaccumulation of 137Cs and 60Co by bacteria isolated fromspent nuclear fuel pools. J Radioanal Nucl Chem 295: 737-748－ 221 －

24-NEP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Single centrifugal contactor test of a proposed group actinide extraction process forpartitioning and transmutation purposes
1

Emma Aneheim1,2, Christian Ekberg1, Giuseppe Modolo3, Andreas Wilden3

Nuclear Chemistry, Department of Chemical- and Biological Engineering, Chalmers University of Technology, SE41296
Gothenburg, Sweden
2
Targeted Alpha Therapy group, Department of Radiation Physics, Sahlgrenska Academy at Gothenburg University, SE41345
Gothenburg Sweden
3
Forschungszentrum Jülich GmbH (FZJ), Institut für Energie- und Klimaforschung, Nukleare Entsorgung und
Reaktorsicherheit (IEK-6), 52428 Jülich, Germany
Partitioning and Transmutation (P&T) is one of the future strategies
for handling of used nuclear fuel. Within P&T, compared toconventional reprocessing, not only uranium and plutonium are to
be recycled, but also the rest of the actinides present in the used fuel.
By doing this, the idea is to decrease the storage time needed for the
residual waste as well as to lower the strain on the final repository.
Group Actinide Extraction (GANEX) is a process scheme for P&T
where the actinides are extracted as a group directly from thedissolution liquor, after removal of bulk uranium. A solvent intended
for GANEX purposes, utilizing two well-known extractants (tri-butyl
phosphate and bis-triazine,bi-pyridine) in cyclohexanone has
previously been intensely investigated. The extraction system has inbatch tests been found to extract the actinides as a group and, withsome modifications, separate them from most of the fission products.
The solvent was also found to be resistant both towards strong nitricacid and irradiation up to ca 200 kGy. Due to these positive findings,
the extraction system has in this work been used in a single
centrifugal contactor test on a simulated high active raffinate
solution, spiked with radiotracers. The kinetics of the system wasfound to be relatively slow in the equipment of choice, especiallyregarding the stripping. However, it was still possible to recover
more than 87% of all actinides in one extraction step with a flowrateof 30ml/h.
Keywords – GANEX, TBP, BTBP, Centrifugal contactor－ 222 －

24-NEP-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Application of Flow Analytical Methods for Determination of Radionuclides in Cooling Water
and Wastes from Nuclear Plants
Anna Bojanowska-Czajka1�������������������1, Marek Trojanowicz1
1

Institut of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland

I.

INTRODUCTION

include determinations of such radioisotopes as
Sr, 99Tc, 226Ra or 231,240Pu and 241Am. For
design of flow-injection setups different
configurations of instrumentation can be
employed, including FIA, SIA, and also multisyringe and multi-pumping devices. Most
commonly both in environmental samples or
cooling waters from nuclear plants those isotopes
are determined in trace or ultra-trace levels,
hence, in flow systems especially efficient
preconcentration steps are developed. As themost efficient is considered extraction
chromatography, but among other methods
possible for this purpose are sorption on solid
sorbents including recently also nanostructured
materials, and precipitation or co-precipitation
processes. Those operations can be especiallyefficient in flow conditions, hence construction ofsuch monitoring systems is very advantageous formonitoring of selected radionuclides in nuclear
power reactors.
90

Flow analytical systems can be described asmeasuring devices, in which all operations ofsample pretreatment and detection of analyte arecarried out in flowing streams. This concept ofanalytical measurements is widely employed inprocess
analysis,andforlaboratory
measurements was primarily developed forclinical analysis. In last decades these methods
have gained a lot of interest especially forenvironmental applications [1]. This is proved byvast number of research papers and developed
methods, increasing number of commerciallyavailable instruments and increasing number ofmethods, which are recognized by national andinternational authorities as standard methods.
The methodology of flow-injection
analysis (FIA), being developed since 1970-ties,
has gained numerous technical modifications
such as e.g. systems with sequential injection ofsample and reagents into a single line system(named as sequential injection analysis - SIA),
flow measurements with direct injection to thedetector sensing surface (named as batch
injection analysis – BIA), or application in flowinjection systems with a moveable solid particles,
also named as bead-injection analysis. [2].
Commonly, as major advantages of flow methodsof analysis are considered possibility of efficient
on-line methods of sample processing prior to thedetection step, and improvement of precision andefficiency compared to batch procedures. Fromthe point of view of application of flow analysis
in determination of trace level of selectedradionuclides especially valuable is possibility ofeffective on-line preconcentration of trace
analytes [3], and carrying out elemental
speciation analysis.
Flow methods are mainly developed fornon-gamma or low-energy gamma emitters withapplication for detection of individual
radioisotopes mainly �� and �-spectrometry (gasproportionalcounters,
liquid-scintillation
counters) [4]. Some developments reported so far

APSORC’13 HEADING (WITHOUT NUMBER)
[1]
[2]
[3]
[4]

M. Trojanowicz (Ed.), Advances in Flow Analysis, Wiley-VCH,
Weinheim, 2008.
M. Trojanowicz, Flow Injection Analysis. Instrumentation andApplications.
World
Scientific
Publishing,
Singapore,
2000APSORC’13 Reference
Z. Fang, Flow Injection Separation and Preconcentration, VCH,
Weinheim, 1993
Y. Fajardo, J. Avivar, L. Ferrer, E. Gomez, M. Casas, V. Cerda,
Trends Anal. Chem., 29 (2010) 1399.

Acknowledgments:
Research task No. 8 „Study of processes occurring underregular operation of water circulation systems in nuclear
power plants with suggested actions aimed at upgrade ofnuclear safety" financed by the National Research andDevelopment Centre in the framework of the strategic
research project entitled „Technologies Supporting
Development of Safe Nuclear Power Engineering”.

－ 223 －

24-NEP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of low level 99Tc in the primary coolant water by ICP-MS. Analysis ofpotential interferences.
Ewelina Chajduk1, Sylwia Witman-�����1, Halina Polkowska-Motrenko1
1

Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland

Keywords – technetium-99, primary coolant water, inductively
coupled plasma mass spectrometry (ICP-MS)

Development Centre in the framework of the strategic
research project entitled „Technologies Supporting
Development of Safe Nuclear Power Engineering”.

Tc-99 is produced by the fission of U-235 and Pu-239.
Information on technetium and other fission and activation
product content in the primary coolant and at various
locations in the purification system can be of considerable
value in assessing fuel integrity and performance of
purification

systemcomponent.

Nowadays,mass

spectrometry methods are complementary to radiometrictechniques for radionuclide determination. Using inductively
coupled plasma mass spectrometry (ICP-MS) for long-lived
radionuclides

improves detection

limit

and

accuracy.

However, in accurate measurements by ICP-MS method, thecontribution of isobaric interferences from atomic- andmolecular ions created by plasma gas and/or solvent usedshould be defined and appropriate ways of their elimination
should be introduced. During the determination of Tc-99, thefollowing interferences can be taken into account: 99Ru+,64

Zn35Cl+, 98Mo1H+, 198Hg2+, 198Pt2+, 157Gd40Ar2+, 40Ar218O1H+

etc. In this work, possibility of presence isobaric inferences
has been investigated. From obtained results, it could beconcluded, that some of interference examined can berecognized as insignificant.

However, a careful chemical

separation of Tc species before the measurements, for theremoval of interfering elements, such as Ru traces, as well as
for the high recovery of Tc is necessary.
Acknowledgments:
Research task No. 8 „Study of processes occurring underregular operation of water circulation systems in nuclear
power plants with suggested actions aimed at upgrade ofnuclear safety" financed by the National Research and－ 224 －

24-NCP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Extraction of Homologous Elements of Dubnium and Seaborgium from HCl Solution
T. Yokokita1, K. Nakamura1, A. Kino1, Y. Komori1, K. Toyomura1, Y. Kasamatsu1, N. Takahashi1,
T. Yoshimura2, K. Ooe3, Y. Kudou4, K. Takamiya5, A. Shinohara1
1

Graduate School of Science, Osaka University
Radioisotope Research Center, Osaka University
3
Faculty of Science, Niigata University
4
Nishina Center for Accelerator Based Science, RIKEN
5
Research Reactor Institute, Kyoto University
2

Abstract – We aim at studying aqueous chemistry of element 105,
dubnium (Db), and element 106, seaborgium (Sg). In this work, we
carried out extraction experiments of Nb, Mo, Ta, W, and Pa which
are homologous elements of Db and Sg by batch method. These data
are significant to investigate the chemical properties of Db and Sg
and to determine the experimental conditions of these experiments.
Keywords – Hydrochloric acid, Niobium, Molybdenum, Tantalum,
Tungsten, ProtactiniumI.

INTRODUCTION

It is predicted that the chemical properties of transactinide
elements, atomic numbers Z � 104, show some difference
from periodicity in the Periodic Table due to increasingly
strong relativistic effect. These elements are produced only
by nuclear reactions with very low production rates as one
atom at a time, and their half-lives are short, �s to ca. 1 min.
Therefore, we must repeat rapid chemistry by such as
partition method and alpha-particle measurement. In thesestudies, the complex formation and chemical species of thetransactinides were investigated based on the comparison of
their chemical behaviors with those of lighter homologues
and pseud homologues. To the chemistry of element 104 (Rf),
105 (Db), and 106 (Sg), we have studied extraction
experiments of homologous of Rf, Db, and Sg. Moreover, wehave developed rapid extraction apparatuses. In thispresentation, we report on solid-liquid and liquid-liquid
extraction of Nb, Mo, Ta, W, and Pa as homologous elementsof Db and Sg in HCl solution. For Db only one result
obtained in HCl solution, so far, and Sg is expected to show
different behavior with oxidation states.
II. EXPERIMENTAL
We carried out extraction experiments using carrier-freeradiotracers of 95Nb, 99Mo, 179Ta, 181W, and 233Pa. Two kindsof macro amounts of Mo(V) samples were used; one is[MoCl5] and the other is prepared by electrochemical
reduction of Na2[MoO4] solution. Macro amounts of W(V)
was prepared by reducing Na2[WO4] containing 181W tracer
by SnCl2. Liquid-liquid extraction was performed by mixing
1–2 mL of the 0.1–11 M HCl solutions containing RI tracers
or Mo(V) or W(V) with the same volumes of Aliquat 336 inchloroform or carbon tetrachloride solutions. The mixture

was mechanically shaken at 25 °C. After centrifuging thesolution, both the phases were pipetted in separate tubes andthen subjected to �- or X-ray spectrometry. The quantity of
Mo(V) was determined by thiocyanate method. In solidliquid extraction, cation-exchange resin (DOWEXTM 50W×8)
or MCI GEL CHP20/P30 powder sorbed by Aliquat 336 and
0.5–1 mL of 0.1–11 M HCl solution containing 95Nb, 179Ta,
and 233Pa tracers was mixed. The aqueous solution was
pipetted into another tube and the sample was subjected to �or X-ray spectrometry. In all solid-liquid extraction, control
experiments without the resin were performed to determine
the radioactivities on the resin indirectly. We also carried out
solvent extraction with a flow-type extraction apparatus.
Distribution ratio (D) and distribution coefficient (Kd) were
determined from radioactivity of RI tracer or concentration of
Mo(V).
III. RESULTS AND DISCUSSION
In the results of the cation-exchange of Nb, Ta, and Pa, theKd value was in the sequence of Ta > Pa > Nb. In the liquidliquid extraction and solid-liquid extraction of the anioniccomplexes of Nb, Ta, and Pa using Aliquat 336, the D value
and Kd value were in the sequence of Pa > Nb > Ta. FromHCl concentration dependences of the Kd and D values, Nb
forms neutral and anionic complexes in 0.1–4 M and 5–11 M
HCl, respectively. The Ta forms cationic and neutral
complexes in 0.1–5 M and 6–11 M HCl, respectively. The Pa
forms cationic, neutral, and anionic complexes in 0.1–1 M,
1–3 M, and 4–11 M HCl, respectively. Based on thecomparison with these elements, we are planning toinvestigate the chloride complex formation of Db. In theliquid-liquid extraction of group-6 elements using Aliquat
336, the D values of Mo(VI) were higher than those of W(VI).
The D values of Mo(V) were higher than those of Mo(VI).
The D values of Mo(V) obtained by the reduction of Mo(VI)were in good agreement with those obtained with [MoCl5].
These results suggest that reduction behavior of Sg can beobserved by solvent extraction in Aliquat 336/HCl system. In
contrast, the D values of W(VI) and W(V) were similar toeach other. This suggests that the behavior of W(V) is similarof that of W(VI). The alternative interpretation is that W(VI)
could not be reduced or W(V) was rapidly oxidized torecover W(VI) species.

－ 225 －

24-NCP-02

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Evaluation of Stopping Powers of Superheavy Ions in Al and U
Y. H. Chung

Department of Chemistry, Hallym University, 1 Hallymdaehak-gil, Chuncheon 200-702, Korea
yhchung@hallym.ac.kr
Electronic and nuclear stopping powers of superheavy ionswith Z>120 in Al and U were estimated in the energy rangeof 0.01-0.20 MeV/u. In the previous study [1], thecorresponding stopping powers of a superheavy ion with
Z=120 and A=300 in several media were estimated using
stopping powers of ions with 6�Z�92 obtained from SRIM[2]. Results were compared with those deduced from
Northcliffe and Schilling’s stopping-power tables [3]. In
the lower energy regime the contribution of nuclear
stopping powers is substantially significant in both media
while it is not negligible even in the higher energy regime.
[1] Y. H. Chung, Int. J. Mod. Phys. E 19, 1117 (2010).
[2] http://www.srim.org.
[3] L. C. Northcliffe and R. F. Schilling, Nuclear Data Tables A 7, 233(1970).

－ 226 －

24-NCP-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Separation of tungsten from LEU fission-produced 99Mo solution to improve
technological performance in both the processes of 99Mo and 99mTc generator
production
Van So Le1 , Cong Duc Nguyen2
1

Medisotec, NSW, Australia
ChoRay Hospital , HCM, Vietnam

2

I. INTRODUCTION99
Mo is a parent nuclide of the 99mTc radioisotope generator
which is used in diagnostic imaging procedures in nuclear
medicine world-wide. The 99Mo production is mainly basedon the 235U fission using HEU and/or LEU targets and on
the 98Mo (n, �� 99Mo reaction. The conversion of present
HEU-based technology to those using LEU requires a 5-6
fold increase in total uranium target weight. Consequently,
LEU target possibly contains approximately five times
more W contaminant than HEU target, assuming the same
purity of the both types of the targets. The large amount of
W is seriously challenging the performance of both theprocessing of 99Mo stock solution and the 99mTc generator
production. So the development of the method of W
separation from LEU-produced 99Mo solution should be
addressed.
II. METHODS
A 99Mo/188W-spiked simulator of the fission 99Mo solution
containing (0.05 mg Mo + 0.06 mg W) per mL and thecontaminant ions was used for W/Mo separation method
development. The element composition of the simulator
solution is mimicked based on an elemental analysis resultof a real 99Mo solution sample which is obtained from thechemical processing steps in which a base-dissolutionprocessed 99Mo solution of LEU (20% 235U) target ispassed through anion exchange (AG-1 X8 and AGMP) andChelex resin columns to remove the majority of fission
products.
Kd values of molybdate and tungstate ions adsorption
on the acidic alumina in the above mentioned simulator
solution of variable acidity were first studied as describedin the literature [1]. The separation process was thenperformed using a chromatographic column of 1.0 g acidic
alumina sorbent, on which a given amount of the simulator
solution was loaded. The elution of 99Mo-molybdate ions

was performed by sulphuric and/or nitric acid solutions
with an acidity optimised based on the Kd measurement
results. Tungstate ions were then striped out of the column
with 5 mL 1.0 M NH4OH solution. The elution fractions of
5 mL were collected and their 99Mo/188W radioactivity wasmeasured using an Ortec gamma-ray spectrometer coupledwith HpGe detector.
III. RESULTS
The Kd values versus acidity of H2SO4 solutions and theelution profile of 99Mo/W separation are shown in Fig.1
and Fig. 2, respectively. Based on the obtained results it isstated that the separation of 99Mo from W contaminant canbe effectively performed using a small acidic alumina
column and H2SO4 eluant. This process can beconveniently integrated with the base-dissolution
technology process of LEU target-based 99Mo production.
This additional alumina column separation step, following
the step of AG-1 X8/AGMP anion exchange and Chelex
resin column separation, is proposed to eliminate or reduce
W contaminant content from 99Mo solution. A typicaldesign of a chromatographic column loaded with 5-10 gacidic alumina and the elution of 99Mo with 50-70 mL 4 M
H2SO4 solution can be effectively used to remove morethan 80% W contaminant content (~ 100 mg W) from a3665 Ci activity (E.O.B) 99Mo solution (~ 70 mg Mo)
produced using 18.4 g 235U LEU target neutron-activatedfor 120 hours in the OPAL reactor. The 99Mo recovery
yield is >96 %.
REFERENCE[1] Le, VS, Morcos N. (2008) New SPE column packing material:
Retention assessment method and its application for the radionuclide
chromatographic separation, J Radioanal nucl Chem, 277: 651-661－ 227 －

24-NCP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effecting Separation of Fission Products from the Actinides By Direct Reaction with
Diketones
Daniel B. Rego, Paul M. Forster, Kenneth R. Czerwinski
University of Nevada, Las Vegas

Abstract – The use of diketone ligands, such as
hexafluoroacetylacetone (Hhfac) and tetramethylheptandione(Htmhd), can react in solvent -free and solvent-minimal routes toeffect separation fission products from uranium matrices without
any pre-preparation of the isotopes in question, and provides a pathto drastically simplify the separations process and limits thepotential for contamination and waste formation due to extensive
handling, while increasing the rapidity of separation and isolation oftarget elements. In particular, the reactivity cesium, barium,
strontium, silver, and lead [1] with Hhfac can allow for rapid
separations from uranium matrices such as oxide mixtures, in somecases in a matter of minutes.
Keywords – Fission Products, Uranium, Cesium, Strontium,
Volatility, Separations.

I.

INTRODUCTION

Current radioelement separations necessitate the dissolutionof solids in either an acidic aqueous solution or a molten salt.
The resulting solutions must be manipulated through a variety
of means to achieve the desired separation.
These
manipulations can involve a complex set of conditions (e.g.,the UREX+ suite of separations). Volatile dikeotones, suchashexafluoroacetylacetone(Hhfac)andtetramethylheptandione (Htmhd), have been used to react
with, and isolate with crystalline purity, fission products [2,3]and actinides [4,5] such as uranium (figure 1) and neptunium.

Ball and stick diagram of UO2(hfac)2(H2O).
Initial studies have focused on characterizing thecoordination with the diketone ligands. The use ofcoordinating ethers to help break up matrices in order tomaximize volatility has been examined and can increase thevolatility and separatability of species from uranium
matrices: For example, cesium hexafluroacetylacetonate
forms an extended polymeric structure with extensive Cs-O
and Cs-F coordination; in contrast, the use of diglyme or 18crown-6 reduces this extensive cross-coordination
significantly.

Direct separation of reactive species from uranium containingoxide mixtures has been demonstrated. The additional abilityof exploiting differences in volatility of these diketone
complexes themselves serves as a secondary method ofseparating the isotopes in question with limited handling andprocessing. [6] The flexibility of this system can allow for
customization to fit specific scenarios and situations. Single
solvent extraction from solid material, or volatilization oftreated solid samples, are utilizable routes. An additionalroute is that these metal complexes are often used as metal
vapor deposition precursors. [7] Thus, a pure metal could beobtained directly from vapor phase volatile complexes
formed directly in the reaction mixture from the oxides andvaporous ligands in situ, which would allow for the potential
combination of separations with metal formation in a single
step.

[1] (a) Evans, W. J.; Rego, D. B.; Ziller, J. W. Polyhedron 2006, 25, 26912697. (b) Malandrino, G.; Nigro, R. L.; Rossi, P.; Dapporto, P.; Fragalá, I. L.
Inorg. Chim. Acta 2004, 357, 3927. (c) Rego, D. B. Lanthanide Reduction
Chemistry of the LnZ3/M and LnZ2Z�/M Systems and Related Coordination

Chemistry Dissertation, University of California, Irvine, 2007.
[2] (a) Evans, W. J.; Giarikos, D. G.; Johnston, M. A.; Greci, M. A.; Ziller, J.
W. J. Chem. Soc., Dalton Trans. 2002, 520-526. (b) Fragalà, L.; Maladrino,G.; Benelli, C.; Castelli Chem. Mater. 1998, 10, 3434. (c) Fragalà, L.
Maladrino, G.; Incontro, O.; Castelli, F. Chem. Mater, 1996, 8, 1292.
[3] (a) Krisyuk, V.V.; Sysoev, S. V.; Fedotova, N. E.; Igumenov, I. K.;
Grigorieva, N. V. Thermochim. Acta 1997, 307, 107-115. (b) Drake, S. R.;
Hursthouse, M. B.; Abdul Malik, K. M.; Miller, S. A. S. Inorg. Chem. 1993,
32, 4653-4657. (c) Darr, J. A.; Poliakoff, M.; Blake, A. J.; Li, W.-S. Inorg.
Chem. 1998, 37, 5491-5496. (d) Strasser, A.; Vogler, A. Inorg. Chem. Comm.
2004, 7, 528-530. (e) Azad Malik, M.; O’Biren, P.; Motevalli, M.; Jomes, A.
C.; Leedham, T. Polyhedron 1999, 18, 1641-1646. (f) Fenton, D. E.;
Newman, R. J. Chem. Soc., Dalton Trans. 1974, 655-657. (g) Cotton, F. A.;
Holm, R. H. J. Am. Chem. Soc. 1960, 82, 2979-2983.
[4] (a) Nikitenko, S. I.; Moisy, Ph.; Tcharushnikova, I. A.; Blanc, P.; Madic,
C. Ultrasonics Sonochemistry, 2000, 7, 177-182. (b) Danford, M. D.; Burns,
J. H.; Higgins, C. E.; Stokely, J. R., Jr.; Baldwin, W. H. Inorg. Chem. 1970,
9, 1953-1955. (c) Morris, M. L.; Moshier, R. W.; Sievers, R. E. Inorg. Chem.
1962, 1, 411-412.
[5] (a) Giarikos, D.G. Dissertation. University of California, Irvine, 2003. (b)Yamamura, T.; Shiokawa, Y.; Yamana, H.; Moriyama, H. Electochim. Acta
2002, 48, 43-50. (c) Kramer, G. M.; Dines, M. B.; Kaldor, A.; Hall, R.;
McClure, D. Inorg. Chem. 1981, 20, 1421-1426. (d) Kramer, G. M.; Dines,
M. B.; Hall, R. B.; Kaldor, A.; Jacobson, A. J.; Scanlon, J. C. Inorg. Chem.
1980, 19, 1340-1347.
[6] Sedai, B.; Heeg, M. J.; Winter, C. H. Organometallics, 2009, 28, 10321038.
[7] Lin, W., Warren, T.H., Nuzzo, R.G., and Girolami, G.S.: J. Am. Chem.
Soc., 115 (24), 11644–11645 (1993).

－ 228 －

24-NCP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Muonic Atom Formation by Muon Transfer Process in C6H6 / C6H12 + CCl4 Mixtures
M. Inagaki1, K. Fujihara1, G. Yoshida1, K. Ninomiya1, Y. Kasamatsu1, A. Shinohara1, M. K. Kubo2,
W. Higemoto3, Y. Miyake4, T. Miura5
1
Graduate School of Science, Osaka University
Colleage of Liberal Arts, International Christian University
3
Advanced Science Research Center, Japan Atomic Energy Agency
4
Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK)5
Radiation Science Center, High Energy Accelerator Research Organization (KEK)2

Abstract – Negative muon transfer process in the mixtures of C6H6 /C6H12 + CCl4 was studied. The muonic Cl X-ray structure of C6H6 +CCl4 mixture sample was similar to that of pure CCl4 sample.
However, the muonic Cl X-ray structure of C6H12 + CCl4 mixture
sample was different from that of pure CCl4 sample. This result canbe explained by assuming that the number of muons transferred tochlorine atoms in C6H6 + CCl4 mixture sample is smaller than thatin C6H12 + CCl4 mixture sample. This fact suggests that the muontransfer rate for carbon atoms of C6H6 is higher than that for
carbon atoms of C6H12.
Keywords – Muonic Atom, Exotic Atom, Muon Transfer, Muonic XrayI.

INTRODUCTION

A muonic hydrogen is one of the simplest exotic atom thatconsists of a muon and a proton. The charge of a proton isstrongly shielded by a muon in the muonic hydrogen because
the mass of a muon is 206 times larger than that of anelectron. The muonic hydrogen can diffuse in the substancelike a neutron and transfer the muon to the other heavier
atoms. This process is known as muon transfer process. The
transfer process occurs also in the case of a pionic hydrogen,which consists of a pion and a proton.
It is reported that the structure of molecule affects theformation or transfer process of the exotic atom. This effect iscalled as chemical effect. In the previous study on piontransfer process, we investigated the chemical effect in
mixtures of C6H6 / C6H12 + CCl4. The pion transfer rate forcarbon atoms of C6H6 is twice higher than that for C6H12 [1].
In this study, we examined the chemical effect on the muontransfer in the same sample system.

III. RESULTS AND DISCUSSION
The experimental muonic Cl X-ray structure (muonic Xray intensity ratios) in pure CCl4, C6H12 + CCl4 (33%)
mixture and C6H6 + CCl4 (33%) mixture samples are shownin Fig. 1.
The relative intensity of Cl (5–3) / Cl (4–3) and Cl (4–2) /Cl (3–2) in C6H12 + CCl4 mixture sample was smaller thanthat in pure CCl4 sample. The difference indicates that initialstate (principal and angular momentum quantum number) of
the muon captured by chlorine atoms in C6H12 + CCl4
mixture sample is different from that in pure CCl4 sample.
Because the muon transfer occurs in C6H12 + CCl4 mixture
sample while no muon transfer in pure CCl4 sample, it seems
that the muon transfer process changes the initial state of themuon captured by chlorine atoms in C6H12 + CCl4 sample. On
the other hand, although the muon transfer also occurs in
C6H6 + CCl4 sample, the muonic X-ray structure of that was
similar to pure CCl4 sample. This can be explained byassuming that the number of muons transferred to chlorine
atoms in C6H6 + CCl4 sample is smaller than that in C6H12 +CCl4 sample. This fact suggests that the muon transfer rate
for carbon atoms of C6H6 is higher than that for carbon atomsof C6H12. Despite using different particle, this result is
consistent with the previous study for pion transfer in thesame sample system [1].

II. EXPERIMENTAL
The muon irradiation experiments were performed at the
MUSE D2 beam line of Materials and Life Science
Experimental Facility in Japan Proton Accelerator ResearchComplex (J-PARC). We selected the following samples formeasurement; C6H6 + CCl4 (33%) mixture, C6H6 + CCl4 (3%)
mixture, C6H12 + CCl4 (33%) mixture, C6H12 + CCl4 (3%)
mixture, pure C6H6, pure C6H12, and pure CCl4. Muonic Xrays, which are emitted after formation of muonic atoms,
were measured by Ge detectors.

Fig. 1. Muonic chlorine X-ray structure. Cl (n–n′) means muonic Cl X-ray
emitted with muon deexcitation from principal quantum number n to n′.
[1]－ 229 －

A. Shinohara et al., Hyperfine Interact. 106, 301 (1997).

24-NCP-06

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Research for Fusion Reaction Mechanisms with Deformed Nuclei
S. Ueno1, K. Toda1, A. Asano1, N. Takahashi2, Y. Kasamatsu2, T. Yokokita2, A. Yokoyama3,
1

Graduate School of Natural Science and Technology, Kanazawa Univ.
2
Graduate School of Science, Osaka Univ.
3
Institute of Science and Engineering, Kanazawa Univ.

Abstract – In order to better understand the reaction on the fusion
reaction, we have focused on the deformation of the nuclei. We
have researched for the fusion reactions of 169Tm+16O [1],169
Tm+20Ne, and 165Ho+20Ne [2]. The cross sections for fusion
were compared between systems of different entrance channels.
The results are consistent with the idea that the degree of
deformation makes an effect on the rising edge of excitation
functions near the Coulomb barrier.
Keywords – Fusion reaction/ Excitation function/ Deformed
nucleusI.

INTRODUCTION

Heavy ion fusion reaction is often used in the synthesisof heavy elements recently. For the synthesis of transactinides, evaporation residues cross section is very small
compared to fission. Briefly, it is important to understandthe reaction mechanism and to know the conditions for
efficient synthesis.
We have focused on the deformation of nuclei. In thisstudy, in order to study the effect of the degree of nuclear
deformation on the fusion reaction, we have researched forthe fusion reactions of 169Tm+16O [1], 169Tm+20Ne, and165
Ho+20Ne [2]. Figure 1 shows deformed nuclei in a
spheroid model and Table 1 shows the degree of nuclear
deformation of 20Ne, 16O, 169Tm and 165Ho based on themodel. In 169Tm+20Ne and 165Ho+20Ne systems, the target
nucleus 165Ho is more deformed than 169Tm. In 169Tm+16O
and 169Tm+20Ne systems, the projectile nucleus 16O isspherical, while 20Ne is deformed. Both systems of169
Tm+16O and 159Ho+20Ne form the same compound
nucleus, 185Ir*.
aab

Osaka University. The targets were prepared byelectrodeposition with standard solution on an Al foil of 2.7
mg/cm2 thickness. For instance, the 169Tm content was 4.55.1 mg/cm2 in thickness. In order to achieve experiments ofwide energy range in a single irradiation, energy
degradation technique was used. In the present experimentusing two stacks with four targets each, each target wasirradiated at a different energy below 155 MeV in
169
Tm+20Ne system. Typical beam intensity was 1 particle�A. The activities produced in each target were assayedusing a high resolution HPGe detector. Excitation function
was made from the measured activities.
III. RESULTS AND DISCUSSION
The evaporation residues detected, for instance, in
Tm+20Ne system were 185Pt, 183�185Ir, 181,182Os and 181Re.
Figure 2 shows the excitation function for fusion reactionof 169Tm+20Ne, 169Tm+16O [1] and 165Ho+20Ne [2]compared with the theoretical calculations using code
HIVAP taking into consideration degree of deformation of
nucleus. In order to compare the systems between different
entrance channels, let the value obtained by subtracting the
Coulomb barrier [3] from the incident energy, (Ecm�Bc),
be the horizontal axis in the figure. Comparing 169Tm+16O,
169
Tm+20Ne and 159Ho+20N systems, more deformed systemof 159Ho+20Ne induced fusion reaction from lower incident
energy. Comparing 169Tm+20Ne and 165Ho+20Ne systems,
starting points for fusion reaction were nearly the same.
The trends were reproduced by HIVAP calculation.
169b

Figure1 Deformation of nucleus
Table1 Degree of deformation of relevant nuclei
20

a/b

Ne

16

169

0.75

1.00

0.95

O

Tm

165

Figure2 Excitation function of 169Tm+20Ne (�), 169Tm+16O (�) [1]and 165Ho+20Ne (�) [2] compared to theoretical values of each system

Ho

1.16

[1]
[2]
[3]

II. EXPERIMENTAL
The bombardment for synthesis was carried out using
O and 20Ne beam supplied from the AVF cyclotron
facility at Research Center for Nuclear Physics (RCNP),
16－ 230 －

A. Asano, master thesis of Kanazawa Univ. (2010)
K. Toda, master thesis of Kanazawa Univ. (2013)
R. Bass, Nuclear Reactions with Heavy Ions, Springer-Verlag, NewYork (1980)

24-NCP-07

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Extraction behavior of Nb and Ta in HF solutions with tributyl phosphate
M. Murakami1,2, S. Tsuto1, K. Ooe1, H. Haba2, J. Kanaya2, S. Goto1, and H. Kudo1
Department of Chemistry, Faculty of Science, Niigata University, Niigata 950-2181, Japan
2
Nishina Center for Accelerator-Based Science, RIKEN, Saitama 351-0198, Japan

Abstract – Extrtaction behavior of carrier-free Nb and Ta withtributyl phosphate (TBP) from HF solutions was studied by abatch method. Tantalum is extracted well to an organic phase,
while Nb is left in an aqueous phase at 0.053�1.0 M HF
concentrations. The similar extraction trends of Nb and Ta areshown in the solid phase extraction using a TBP resin. The
extraction equilibria in the solid phase extraction are attained
within �10 s.
Keywords – niobium, tantalum, extraction, tributyl phosphateI.

INTRODUCTION

In the synthesis experiment of an element 115,
chemically separated 27-h spontaneously fissioning nuclide
was assigned to 268Db which is the descendant of 288115[1,2]. To clarify this 27-h nuclide is actually Db, further
chemical investigations are needed for both of known
nuclides of dubnium, 262Db (T1/2 = 34 s), and 27-h
spontaneously fissioning nuclide.
Tributyl phosphate (TBP) is one of the most effective
extractants used for industrial separation of Nb and Ta [3].
In this work, solvent extraction behavior of Nb and Ta with
TBP was first studied by a batch method. Solid phaseextraction with a TBP resin was also performed to examine
the feasibility of this resin to an automated rapid reversedphase chromatography apparatus for 262Db.

III. RESULTS AND DISCUSSION
Figure 1 shows the dependence of the D values of Nb
and Ta on the initial HF concentration ([HF]ini) with 1.8 M
TBP — 1,2-dichloroethane solution as an organic phase.
Tantalum was extracted well at the [HF]ini of 0.053 to 1.0
M, while Nb was left in an aqueous phase.
The number of TBP molecules combined with the Nb
and Ta compounds was examined by varying the TBP
concentration at the constant [HF]ini. The number of
combined TBP molecules was found to be 3 for Ta at[HF]ini � 2.7 M. This agrees with the results in Refs. [3,4].
Although the number of TBP molecules combined with the
Nb compound is reported as 3 [3], our results show that the
number is 2 independently of [HF]ini. This results show that
Nb and Ta are extracted with different chemical forms.
Using the 48 wt-% TBP resin, the dependence of the
distribution coefficients of Ta on [HF]ini was similar to thatof the D values in the liquid-liquid solvent extraction.
Niobium was not extracted at � 10 M. The time required
for the extraction equilibrium was less than 12 s for both of
Nb and Ta. This indicates that the present extraction system
could be applicable to an on-line experiment with the shortlived 262Db.
103

II. EXPERIMENTAL
95g

102
179

The radiotracers Nb (T1/2 = 34.991 d) and Ta (T1/2 =1.82 y) were produced in the bombardments of 14-MeV
proton beam supplied by the RIKEN AVF cyclotron onnat
Zr and natHf target foils, respectively.
In the experiment of the solvent extraction, 1 mL of HF
solution containing 95gNb and 179Ta tracers were shaken
with 1 mL of TBP—1,2-dichloroethane solution for 180 min
at 25�C. After centrifugation, 700 �L of each phase wastransferred to an polypropylene tube separately, and thensubjected to �- and X-ray measurements with a Ge detector.
The distribution ratios (D) of Nb and Ta were deduced
from the observed radioactivities.
The solid phase extraction was performed withfollowing procedures. TBP resin was prepared byadsorbing TBP on a support material (MCI GELCHP20/P30, Mitsubishi Chemical Co.) [4]. A portion of 20
to 30 mg of the TBP resin was shaken with 400 �L of HF
solution containing 95gNb and 179Ta tracers for 6 s to 60 min.
After filtration, 200 �L aliquot was transferred to apolypropylene tube. The distribution coefficients of Nb andTa were calculated with the observed radioactivities and theweight of the used resin.

Distribution ratio

1

101
100
10-1
10-2
10-3 -3
10

10-2

10-1

100

[HF] inFig. 1. Distribution ratios of Nb and Ta.
[1]
[2]
[3]
[4]
[5]

－ 231 －

S. N. Dmitriev et al., Mendeleev Commun. 15, 1 (2005).
N. J. Stoyer et al., Nucl. Phys. A 787, 388c (2007).
Z. Zhu and C. Y. Cheng, Hydrometallurgy 107, 1 (2011).
H.Haba et al., Radiochim. Acta 95, 1 (2007).
S. Nishimura et al., Trans. JIM 5, 79 (1964).

24-NCP-08

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013�������������������������������������-32P] LABELLEDADENOSIN TRIPHOSPHATE
Wira Y Rahman1*, Endang Sarmini1, Herlina1, Triyanto1, Rien Ritawidya1, Abdul
Mutalib1 and Santi Nurbaiti2
1

Center for Radioisotope and Radiopharmaceuticals (PRR) - BATAN)
Biochemistry Research Division, faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl.
Ganesha 10 Bandung, Indonesia, 40132*Tel/fax : (6221)7563141, email: wira@batan.go.id2

ABSTRACT
Adenosine triphosphate-��������� ����� �-32�� ��-32P]-ATP) has been widely used in the biotechnology
research, usually as a tracer to study aspects of physiological and pathological processes. In order tosupport biotechnology research in Indonesia, a process for producti��������-32P]-ATP in accordancewith a more simple glycolysis enzymatic reaction utilizing glyceraldehid 3-phosphate dehydrogenase,3-phosphoglyceryc phosphokinase and lactate dehydrogenase has been conducted. DLglyceraldehydde 3-phosphate, Adenosine Diphosphate (ADP) and H332PO4 was used as precursors
for this reaction. Purification of ��-32P]-ATP was performed by using DEAE-Sephadex column
chromatography. The results showed that �������������� ������� ��� ��-32P]-ATP was 99,49% withradioactivity was 1,175 mCi for 20 minutes enzymatic reaction. The result suggested that thismodification method can be used for producing ��-32P]-ATP to support the provision of radiolabeled
nucleotide for biotechnology research in Indonesia.
Key words : labeled nucleotide ��-32P]-ATP, synthesis, enzymatic reaction, DEAE-Sephadex column
chromatography－ 232 －

24-NCP-09

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Production of 88Nb and 170Ta for chemical studies of element 105 Db using the
GARIS gas-jet system
M. Huang,1 M. Asai,2 H. Haba,1 D. Kaji,1 J. Kanaya,1 Y. Kasamatsu,3 H. Kikunaga,4 Y. Kikutani,3 Y.
Komori,3 H. Kudo,5 Y. Kudou,1 K. Morimoto,1 K. Morita,1 M. Murakami,5 K. Nakamura,3 K. Ozeki,1
R. Sakai,1 A. Shinohara,3 T. Sumita,1 K. Tanaka,1 A. Toyoshima,2 K. Tsukada,2 Y. Wakabayashi1 andA. Yoneda2
1

Nishina Center for Accelerator-Based Science, RIKEN
2Advanced Science Research Center, JAEA
3
Graduate School of Science, Osaka University
4
Research Center for Electron Photon Science, Tohoku University
5
Department of Chemistry, Niigata University

Keywords – superheavy element chemistry, Nb, Ta, Db, GARIS,
gas-jet method, recoil transfer chamber

We plan to study chemical properties of element 105,
Db, produced in the 248Cm(19F,5n)262Db reaction using thegas-jet transport system coupled to the RIKEN gas-filled
recoil ion separator, GARIS1). It is important to perform Db
chemistry together with Ta and Nb under identicalconditions to find different chemical behavior among thehomologues. In this work, we tried to produce isotopes of170
Ta (T1/2 = 6.76 min) and 88Nb (T1/2 = 14.55 min) in thenat
Gd(19F, xn)170Ta and natGe(19F, xn)88Nb reactions,
respectively, using the GARIS gas-jet system.
A 106.4-MeV 19F9+ beam was extracted from the
RIKEN linear accelerator. A natGe target of 0.29 mg/cm2
thickness was prepared by vacuum evaporation onto a 0.89
mg/cm2 Ti backing foil, while a natGd2O3 target of 0.34
mg/cm2 was prepared by electro-deposition on a 0.87
mg/cm2 Ti foil. The two arc-shaped Ge targets and two
Gd2O3 were mounted together with four 0.95 mg/cm2 Ti
blank foils on a rotating wheel of 100-mm diameter, which
was rotated at 1000 rpm. The beam energy was 103 MeV in
the middle of the target and the typical intensity was�������������� �� ��������� �� �����. The working He
pressure of GARIS was 33 Pa. At the focal plane of GARIS,a recoil transfer chamber (RTC) of 100-mm inner diameterand 0~100-mm adjustable depth was installed. Evaporation
residues separated with GARIS were passed through a 0.5��� ������ ������� thermalized in RTC, and weretransported by the He/KCl-aerosol-gas-jet system to achemistry laboratory. The He flow rate was 2.0 L/min, andthe inner pressure of RTC was 47 kPa. After collection of
the aerosols on a glass filter (ADVANTEC GB-100R) for 1
and 3 min for 170Ta and 88Nb, respectively, the filters were
subjec���� ��� �-ray spectrometry using a Ge detector. The
magnetic setting of GARIS was varied in the magnetic
rigidity (B����������������–1.80 Tm for 170Ta and 0.850–

0.979 Tm for 88Nb. In the GARIS separation of 88Nb at low
B�� �������� ���� ����� ���������� ����� ��wer charge statesbroke the thin Mylar foil of RTC. Thus, we installed a
retractable Al shutter of 2-mm thickness and 30×100-mm2
size at the focal plane to protect the Mylar foil from theundesired beam particles. The gas-jet efficiencies are very
sensitive to the depth of RTC and recoil ranges of theevaporation residues in RTC. To effectively collect 88Nb
atoms in RTC, a 3-���Al degrader foil was used to reduce
their recoil ranges before entering the RTC.
The 221.2-keV and 671.2-���� �-rays are useful forchemical studies of 170Ta and 88Nb, respectively. Yield
distributions of 170Ta and 88Nb related to B�� ���� ����������
in Fig. 1. The optimal B�� �� 1.64±0.01 and 0.936±0.001
Tm were determined for 170Ta and 88Nb, respectively.
Under the optimal B� and with the 100-mm depth RTC, theproduction yields of 170Ta and 88Nb in the chemistrylaboratory were evaluated to be 8.65±0.56 and 0.61±0.02k������� ������ �-min and 3-min aerosol collection,
respectively. The gas-jet efficiency of 88Nb was 41±2%,while that of 170Ta was 77±3%.
104

Yield (arb. unit)

Abstract – We developed a production technology forradioisotopes of Ta and Nb for chemical studies of element 105,
Db, using the RIKEN gas-filled recoil ion separator � GARIS.
Isotopes of 170Ta and 88Nb produced via the natGd(19F, xn)170Ta
and natGe(19F, xn)88Nb reactions, respectively, were successfully
extracted by the gas-jet method to a chemistry laboratory after
physical separation by GARIS.

103
170

Ta
Nb

88

102
0.8

0.9

1.0

1.5

1.6

B� (Tm)

1.7

1.8

1.9

Fig.1. Yields of 170Ta and 88Nb as a function of ��.

[1]－ 233 －

H. Haba et al.: Chem. Lett. 38, 426 (2009).

24-NCP-10

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Half-life measurement of 7Be in several materials
T. Ohtsuki

Research Center for Electron Photon Science, Tohoku University
1-2-1, Mikamine, Taihaku, Sendai, 982-0826, Japan
Abstract – The formation of atom-doped C60 and C70 etc. has
been investigated by using several types of radionuclides
produced by nuclear reactions. From the trace of theradioactivities after high performance liquid chromatography(HPLC), it was found that formation of endohedral fullerenes of
Be atom is possible by a recoil process following the nuclear
reaction. The decay rate of 7Be electron capture (EC) was
measured in C� 0 and Be metal with a reference method. The
half-lives of 7Be endohedral C70 and 7Be in Be metal (Bemetal(7Be)) were found to be 52.45±0.04 and 53.25±0.04 days,
respectively. This amounts to a 1.5% difference in the EC-decay
half-life between 7Be@C70 and Be metal(7Be). The results are areflection of the different electron wave-functions in nuclear site
for 7Be inside C70 compared to when 7Be is in a Be metal. The
further theoretical interpretation is needed for these experimental
results.
Keywords – Electron Capture Decay, Beryllium-7, Half-life

I.

INTRODUCTION

A long-standing challenge has been to establish thedegree to which manipulation of the environmental factors
can in practice change nuclear decay rates in experiments
to determine the decay rate of 7Be compounds. In addition,
there have been several observations of variations in thehalf-life with host metals, chemical forms, and pressure.
From the early data, the half-life of 7Be as a function ofdifferent chemical forms and/or host materials have been
limited almost to within 0.2%. In recent studies, however,large variations have been observed as a function ofdifferent chemical forms and pressures. Therefore, aprecise measurement is still needed to obtain the absolutedecay rate in different circumstances.
After the discovery of C60 and the subsequent successful
production of several kinds of fullerenes, endohedral
fullerenes which have one or more atoms inside the C60, C70,

cages etc. currently have attracted great interest. If theirmass production becomes possible, they would have many
interesting applications such as stable molecular devices in
nano-meter scales and/or as functionalized materials inmany fields. We have examined the formation ofendohedral fullerenes by a nuclear recoil implantation ofseveral foreign atoms following nuclear reactions[1,2]. We
found that the 7Be atom can be endohedrally doped tocreate the 7Be endohedral fullerenes.
Because of the unique chemical form of fullerenes and/or
several factors contributing to give rise to this environment;
many �-electrons of C60(C70), and special dynamic motions
inside C60(C70) etc., the electron contact density on the 7Be
nuclei can be affected significantly by the electron
environment of C60(C70). Therefore, it is intriguing to�
measure the half-life of the 7Be inside C60(C70); “how does
the EC decay rate in 7Be change inside the C60(C70) cage
relative to other situations?”
So far, we compared the half-life of 7Be when it isencapsulated in a C60 cage to that of 7Be in Be metal as areference. We found a surprisingly shorter half-life of 7Be
inside C60[3,4]. This fact implied that the 7Be atoms arelocated in a unique environment inside C60 cage.
Furthermore, in order to see the size effect of fullerenes, wedemonstrate the change of decay rete of 7Be in 7Be@C70
and in Be metal [Be metal(7Be)]. The decay rate of 7Be
electron capture (EC) was measured in C�0 and Be metal
with a reference method. The half-lives of 7Be endohedral
C70 and 7Be in Be metal (Be metal(7Be)) were found to be
52.45±0.04 and 53.25±0.04 days, respectively.
[1] T. Ohtsuki et al., Physical Review Letters 77 (1996) 3522.
[2] T. Ohtsuki et al., Physical Review Letters, 81 (1998) 967-970.
[3] T. Ohtsuki et al., Physical Review Letters 93 (2004) 112501.
[4] T. Ohtsuki et al., Physical Review Letters 98 (2007) 252501－ 234 －

24-ENP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Verification of anticlockwise gyre in the semi-closed water area of Lake Nakaumi,
southwest Japan, by using 224Ra/228Ra activity ratios
Ritsuo Nomura1,* Mutsuo Inoue2, Hisaki Kofuji3 and Shota Ikeda1

1

Foraminiferal Laboratory, Faculty of Education, Shimane University, Matsue 690-8504 Japan
Institute of Nature and Environmental Technology, Kanazawa University, Wake, Nomi, Ishikawa 923-1224 Japan3
Mutsu Marine Laboratory, Japan Marine Science Foundation, Minato, Mutsu, Aomori, 035-0064 Japan
2

Abstract –The Honjyo area in Lake Nakaumi is a semi-closed brackish waterarea where some mixing of up-flowing marine water and downflowing lake water take place. A large-scale gyre that caused by theresidual circulation was once indicated by a temporal algal
blooming that spread over the semi-closed Honjyo area in brackish
Lake Nakaumi. In order to verify this type of water circulation, we
examined 224Ra (t1/2=3.66 d)/228Ra (t1/2=5.75 y) activity ratios ofboth upper and lower waters that differentiated by a well-developed
halocline. The 224Ra/228Ra ratios in the upper water were lowest in
the central area, suggesting the formation of anticlockwise gyre. The
ratios in the lower water were rather uniform, but a basin-wide
anticlockwise flow of water is also indicated. The 224Ra/228Ra ratio
is clearly effective to trace the water flow for both the deep andsurface waters.
Keywords – 224Ra/228Ra ratio, Water flow, Lake Nakaumi

I.

INTRODUCTION

Estuarine biota has been critically influenced by anincreased eutrophication in Japan. The environmental andbiological interaction is complicate, but the water charactersand the dynamic water movement are major factor tounderstand the total environment of estuarine water.
The Honjyo area, occupying ~20 % of Lake Nakaumi, wasclosed for 28 years. This closed area is now partly opened
and permitted the exchange of marine water and lake water
through the opened slit [1]. After the closed area opened, theoriginal massive low salinity water changed to form a density
stratification of bottom and surface waters. In order to clarify
the deep and surface water dynamics, we analyzed
224
Ra/228Ra ratio of both deep and surface waters tounderstand the water residence time and the circulation ofwater.

keV), respectively. �����������-ray counting time for 224Ra and228
Ra was 18,000 seconds and the second counting time was
85,000 seconds. Owing to the short half-life of 224Ra, first �ray counting for 224Ra was conducted between 3-5 days after
the sampling.
II. RESULTS AND DISCUSSION
Both the upper and lower waters in the Honjyo area show
lower 224Ra/228Ra ratio, compared to that in the Sakai Channel.
The ratios of the upper water show the range between 0.020.15, and those of the lower water are 0.08-0.20. These ratios
are similar to the ratio of the Nakaumi water. It is noted thatthe 224Ra/228Ra ratio of the upper water shows regional
difference, which is higher in western and northern sides,
while the central and eastern sides are lower. The 224Ra/228Ra
ratios of lower water are characterized by similar ratios,
excepting the place near the Ohmisaki slit.
In 2010, algae blooming spread over the surface of the
Honjyo area, showed a large-scaled anticlockwise gyre in thearea. Our reconstructed surface water flow, using 224Ra/228Ra
ratios, is similar to the large-scale anticlockwise gyre shownby the algae powder. The 224Ra/228Ra ratios in the lower water
are rather uniformly distributed, but the lower water may
form a large-scale anticlockwise flow over the basin.
133°8´

133°10´

133°9´

133°11´

133°12´

133°13´

35°32´

0.12
0.15
M.S.

35°31´

0.02
0.11

0.21

0.05

Honjyo area

0.08

35°30´

A. Methods of study

0.09

Ten sampling locations were set in and out of the Honjyo
area (Fig. 1). We used Mn-fiber to collect Ra from lake water(40-60 L) prefiltered with a polypropylene filter cartridge (~1L/min; 0.5 �m median pore size). Mn-fiber was dried andthen ashed within 24 hours. Ash powder was completely
sealed in the styrene bottle.
�-Spectrometry was performed using a coaxial-type Gedetector. The 224Ra and 228Ra activities were evaluated fromthe �-ray peaks of 212Pb (235 keV) and 228Ac (338 and 911

35°29´

0.13

Lake Nakaumi

O.S.

0.10

Water flow

M.S. Moriyama Slit
O.S. Ohmisaki Slit

Figure 1. Distribution of 224Ra/228Ra ratios in the Honjyo area and the
supposed flow of upper water.
[1]－ 235 －

Nomura, R. et al., 2013. Opening of the closed water area andconsequent changes of 228Ra/ 226Ra activity ratios in coastal lagoon
Lake Nakaumi, Southwest Japan. Applied Radiation and Isotopes. DOI:
10.1016/j.apradiso.2013.03.069

24-ENP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effect of hydroxylated fullerene on U(VI) Adsorption onto oxidized multi-walledcarbon nanotubes
Jing WANG1, Zhan LI2, Peng LIU1, Wei QI1, Juanjuan BI1, Wangsuo WU1*

1 Radiochemistry Laboratory, School of Nuclear Science and Technology, Lanzhou University, Lanzhou 73000, China
2 Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 73000, China
Abstract –Herein, hydroxylated fullerene (C60(OH)n) was chosen as
the third phase to investigate its impact on U(VI) adsorption onto
carbon nanotubes. The results showed that the drastic effect of
C60(OH)n on U(VI) adsorption of oMWCNTs was not significant at
low concentration of C60(OH)n, whereas a negative effect wasobserved at higher concentration. The adsorption of U(VI) onto
oMWCNTs was enhanced with increasing pH values at pH < 6, but
decreased after pH reached 6. The main mechanism may be theadsorbed Cu(II) on oMWCNTs is "squeezed" down to the solution
by the adsorption of C60(OH)n onto oMWCNTs. The double sorption
site model was applied to simulate the adsorption isotherms of
U(VI) in the presence of C60(OH)n and fitted the experimental datawell. This provides reference for studying the interactions between
carbon nanomaterials and radionuclide in various conditions of
natural environment. Meanwhile, it also brings theoretical basis forstudying the biological safety problems caused by multi-component
environment pollution.
Keywords –Effect, Hydroxylated fullerene, U(VI) adsorption,
Oxidized multi-walled carbon nanotubes

I.

� ��

�% = �� + � × � ������� ���m/V����-1)
1
0.5
0.25
0.1

�� ���
267.26-4148.21-10.97-7.72

DSSM modelk�b� ��-165.72-773.414246.26
12867.49
104.89127.13185.38
55.43
�� �

R2
0.94850.97390.97570.9457INTRODUCTION

Carbon nanotubes has potential application in the disposal of
nuclear fuel reprocessing, due to the large specific surface
area, the surface is easy to be modified, resistant to heat andradiation. As far as we known, the study concerning themechanism for radionuclide selective adsorption on a varietyof carbon nanomaterials in the ternary system was sparse.
However, it is difficult to achieve the adsorption contributionof each carbon nanomaterial when they are all chosen as
adsorbent in the experiment. Two different water-soluble
carbon nanomaterial must be selected as the adsorbent toresolve this problem.
�oMWCNTs and the nature and species of U(VI); k represents
the rate constant.
Table 1 Parameters of double adsorption site model*

Fig. 1 Effect of C60(OH)n on U(VI) adsorption onto
oMWCNTs as a function of pH, m/V =0.5 g/L, T = 25±1 ºC,
I=0.01 mol/L NaNO3, C[UO22+]initial =1.12×10-4 mol/L.

(1)

Where Co (mg/L) is the initial concentration of U(VI)before adsorption; Cs (mg/g) for the equilibrium
concentration of U(VI) in the solid phase after adsorption;
Ce (mg/L) is the equilibrium concentration of U(VI) in theliquid phase; Cf (mg/L) is definited as the initialconcentration of C60(OH)n; b is the parameter forcharacterization the adsorption of C60(OH)n, it depends on
the species and surface character of C60(OH)n and thenature of oMWCNTs; C1 and C2 are the performanceparameters for the sorption characterization of oMWCNTs,
these parameters depend on the surface character ofFig. 2 Effect of oMWCNTs dosage on U(VI) adsorption onto
oMWCNTs as a function of C60(OH)n initial concentrations,
pH=7.00±0.10, I=0.01 mol/L NaNO3, T = 25±1 ºC,C[UO22+]initial =1.12×10-4 mol/L.
�

Corresponding author: Wangsuo Wu,
Tel & Fax:+8609318913594,
E-mail:wuws@lzu.edu.cn(W.Wu).

－ 236 －

24-ENP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Corrosion of Copper in Water and Colloid Formation under Intense Radiation Field
Kotaro Bessho1, Yuichi Oki2, Naoya Akimune3, Hiroshi Matsumura1, Kazuyoshi Masumoto1,
Shun Sekimoto2, Naoyuki Osada4, Norikazu Kinoshita5, Hideaki Monjushiro1, Seiichi Shibata2
1

Radiation Science Center, High Energy Accelerator Research Organization (KEK),
Research Reactor Institute, Kyoto University (KURRI), 3 Graduate School of Engineering, Kyoto University,
4
Graduate School of Engineering, Tohoku University, 5 Institute of Technology, Shimizu Corporation

III. RESULTS AND DISCUSSION
Figure 1 shows soluble and size-separated colloidal
concentrations of Cu in water without irradiation or after the

0.4
0.0

1.2
0.8

1.2
0.8
0.4
0.0

1.2

1.2

0.8

Irrad.: 2.0 h0.8

Irrad.: 2.0 h 0.8

0.4

0.4

0.4

0.0

0.0

0.0

0 3 7 16 200

0 3 7 16 200

0 3 7 16 200

12 h

0.8

Irrad.: 12 h 0.8

Irrad.: 12 h0.8

0.4

0.4

0.4

Particle size (nm)
1.2

0.4
0.0

Co-60 �-ray irrad. fac.
2.9 kGy/h
21 kGy/hCu (ppm)

2.0 h

1.2

0.0

0 3 7 16 200

Particle size (nm)
1.2

70 h

Particle size (nm)
1.2

0.0

0 3 7 16 200

Particle size (nm)
1.2

0.8

Irrad.: 70 h 0.8

0.4

0.4

0.0

0 3 7 16 200

Particle size (nm)Particle size (nm)
1.2

0.0

0 3 7 16 200

Particle size (nm)Cu (ppm)

0.8

Without
irradiation

Cu (ppm)

1.2

Cu (ppm)

Irradiation experiments were carried out at the 60Co �-ray
irradiation facility or the electron linear accelerator (eLINAC) at the Research Reactor Institute, Kyoto University(KURRI). Cu vessels (Inside:19� x 75 mm) filled with purewater (26 ml) were irradiated by �-rays from 60Co source, orbremsstrahlung and neutrons generated by a 30 MeV electron
beam striking a Ta target assembly. At the 60Co �-ray
irradiation facility, samples were irradiated by �-ray with thedose rates of 2.9 kGy/h or 21 kGy/h for 2 to 240 h. At the eLINAC facility, irradiation experiments were carried out withseveral beam-current conditions, and the irradiation times
were varied between 2 to 24 h.
After the irradiations, water samples in the Cu containers
were collected and filtrated with four kinds of ultrafiltration(UF) units for particle size separation. Estimated pore sizes of
the UF units were 200 nm, 16 nm, 7 nm, and 3 nm. Elemental
concentrations of Cu in each UF filtrate and original samples
before UF were determined by ICP-AES analyses.

Cu (ppm)

II. EXPERIMENTS

Cu (ppm)

At high-energy accelerator facilities, colloid formation incooling water is an important subject for radiation
management at high-energy accelerator facilities, because thepresence of colloidal species complicates the behavior ofradionuclides in the cooling water systems [1]. It’s possiblethat intense radiation field inside accelerator facilities affects
the corrosion of metal components and formation of metalrelated colloid in the cooling water. Effects of radiation on
corrosion of copper and formation of copper-related colloid
in water were studied.

Cu (ppm)

INTRODUCTION

Cu (ppm)I.

Cu (ppm)

Keywords – Radiation effect, Corrosion, Colloid

irradiation at the �-ray irradiation facility or the e-LINAC
facility. The results for the LINAC experiments wereobtained at the downstream (0-deg) sample position, where
flux of neutrons can be neglected compared to flux ofbremsstrahlung. The results demonstrate that irradiation ofhigh-energy photons (�-ray or bremsstrahlung) clearly affects
the elution of Cu into water and formation of Cu-related
colloid / particle in water phase.
Concentration of soluble Cu species increased with photon
intensity. Formation of colloidal species was also noticeable
at intense photon environment. Furthermore, qualitativeevaluations using water-quality test kits clarified that H2O2
and O3 were generated in water by irradiating �-ray orbremsstrahlung. These results imply that high-energy photons
produce active species, such as H2O2, O3 and OH radicals, inwater. These active species may affect various processes,
such as corrosion of Cu materials, transfer of Cu species into
water as a soluble species or colloidal species, and growth ofcolloidal species in water phase.
Time dependence of size-profiles for Cu species formed atconstant dose rates imply that dissolution of Cu materials inwater and formation of Cu-related colloid occurring in
intense radiation environments progress in the time scale ofseveral hours to hundreds hours.

Cu (ppm)

Abstract – Radiation effects on corrosion of copper in water andcolloid formation were investigated. Irradiation experiments using
60
Co �-ray irradiation facility and electron LINAC demonstrated
that high-energy photons promote corrosion and elution of copper
into water and formation of copper-related colloids / particles inwater phase.

Cu (ppm)

2

0.0

0 3 7 16 200

Particle size (nm)1.4

Irrad.: 72 h

e-LINAC
10 �A (0-deg)
Irrad.: 2.0 h

0 3 7 16 200

Particle size (nm)2.0

Irrad.: 12 h

0 3 7 16 200

Particle size (nm)4.6

0 3 7 16 200

Particle size (nm)Figure 1 Soluble (0-3 nm) and colloidal concentrations (3-7, 7-16, 16-200nm) of Cu in water without irradiation, after the irradiation at Co-60 �-ray
irradiation facility, and after the irradiation at electron LINAC. Irradiation
time : 2.0 h, 12 h
[1]

－ 237 －

K. Bessho et al., Eleventh Meeting of the Task-Force on Shielding
Aspects of Accelerators, Targets and Irradiation Facilities (2012)

24-ENP-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Study on Unattached Fraction of Radon Progeny and its Environmental Influence
Factors
1

Lu GUO1, Lei ZHANG2, Qiuju GUO1

State Key Laboratory of Nuclear Physics and Technology, Peking University, Beijing 100871,China
2
Solid Dosimetric Detector and Method Laboratory, Beijing 102205, China

Abstract – The exposure of radon and its progeny contributes
more than half of the natural radiation exposure received by the
public. The unattached fraction of radon progeny is an importantparameter in radiation dose estimation through dosimetric
process; however, not so much data has been reported. For abetter understanding on temporal variation and its environmental
influence factors of the unattached fraction of radon progeny, aseries of field measurements were performed periodically by
adopting a new developed integrating monitor for measuring
unattached fraction of radon progeny, and an instrument formeasuring aerosol concentration in both indoor and outdoor
environments.
It was shown by the measurement results that the ranges ofunattached fraction of radon progeny in indoor and outdoor
environments all over the year were 8.4%�16.5% and9.4%�28.2%, respectively. Seasonal and diurnal variations of theunattached fraction of radon progeny were also analyzed. It
comes to the conclusion that during the winter season theunattached fraction of radon progeny is stable in indoor
environment because of the little change on aerosol concentration�
temperature and humidity indoor in Beijing area, while on theother hand, it changes a lot in outdoor environment due to thegreat undulation of atmospheric factors, and the average of theunattached fraction of radon progeny is higher in outdoor
environments than that of indoors. While in summer, theunattached fraction of radon progeny in indoor environment wasclose to the values of outdoor environment, and both of them hadlower average than that in winter.
Keywords – radon;
conversation factor

unattachedfraction;aerosol;dose－ 238 －

24-ENP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Preliminary Study on Measuring Radon Progeny Concentration Using Alpha/Beta
Spectroscopic Method

1

Abdumomin Kadir1, Lei Zhang2, Qiuju Guo1, and Juncheng Liang3

State Key Laboratory of Nuclear Physics and Technology, School of Physics, Peking University, Beijing, 100871, China
2
Solid Dosimetric Detector and Method Laboratory, Beijing, 102205, China
3
Ionizing Radiation and Medical Science, National Institute of Metrology, Beijing, 100013, China

Abstract – The accurate measurement of radon progeny
concentration is essential for dose evaluation of radon exposure.
Alpha/beta spectroscopic methods have great advantage comparing
with traditional total counting methods as well as alpha-spectrum
methods. This work introduces a radon progeny measurement
method using alpha/beta spectroscopy. Sample 10 min with unit flowrate (1 L/min), 1 min delay and then record the alpha/beta
spectroscopy at 3 min internals for 30 min, the uncertainty of thismethod is 9.3% in a typical indoor environment (CRn=40 Bq/m3,
F=0.4). Experiment comparison results confirm that this method
could greatly improve the measurement precision of radon progeny
concentration.
Keywords – radon progeny; spectroscopic method; least-squarecalculation; accurate measurement;－ 239 －

24-ENP-06

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The Measurement Comparability of 134Cs and 137Cs in Foodstuff Samples in Japan- Result of Inter-Laboratory Experiment for Certification of Certified Reference
Material
Tsutomu Miura1, Yoshitaka Minai2, Shoji Hirai3, Hiroshi Iwamoto4, Chushiro Yonezawa5, Yoshinobu
Uematsu6, Akira Okada7�Masami Shibukawa8�Koichi Chiba1�Kiyoshi Kitamura9�Takahiro
Yamada10�Kazutoshi Kakita11�Isao Kojima11
1

National Metrology Institute of Japan, AIST, 2 Musashi University, 3Tokyo City University, 4Environmental Technology
Service Co, Ltd., 5Japan Institute of International Affairs, 6Japan Accreditation Board, 7TERM, 8Saitama University, 9Japan
Chemical Analysis Center, 10Japan Radioisotope Association, 11The Japan Society for Analytical Chemistry

Abstract – The measurement comparability of 134Cs and 137Cs infoodstuff samples in Japan was evaluated based on the interlaboratory experiment for certification of certified referencematerial (CRM) for environmental radioactivity analysis.
Keywords – measurement comparability, certified referencematerial, Environmental radioactivity, 134Cs, 137Cs, interlaboratory experiment method, Uncertainty

I.

INTRODUCTION

Following the mega earthquake, tsunami, and theaccident at the Fukushima No.1 nuclear power plant on
March 11, 2011, a massive amount of radioisotopes werereleased in the environment. This situation required urgent
measurements of radioactive isotopes in foodstuff samples
for human health. The CRM is essential to accurate andprecise measurement of radioisotopes in the samples. The
Japan Society of Analytical Chemistry was developed thecertified reference material of brown rice (JSAC0731 andJSAC0732) and bovine muscle flakes (JSAC0751 andJSAC0752) for measuring radioactive isotopes of 134Cs and137
Cs support by Grant-in-aid Japan Science andTechnology Agency. The certification of the 134Cs, 137Cs
and 40K in candidate CRM of brown rice and bovine
muscle for environmental radioactivity analysis was
performed by the inter-laboratory experiment method.
Twelve laboratories, including the research institutes, JCSS
(Japan Calibration Service System) accredited calibration
labs, universities, and industrial testing labs in Japan
participated in the inter-laboratory experiment forcertification. The certified values and associated expanded
uncertainties (k=2) of 134Cs, 137Cs, and 40K in brown rice
CRM were 141 Bq kg-1 ± 9 Bq kg-1, 210 Bq kg-1 ± 13 Bq
kg-1�and 75 Bq kg-1 ± 7 Bq kg-1, respectively [1]. And also,
the certified values and associated expanded uncertainties(k=2) of 134Cs, 137Cs, and 40K in bovine muscle CRM were174 Bq kg-1 ± 12 Bq kg-1, 297 Bq kg-1 ±20 Bq kg-1�and
276 Bq kg-1 ± 46 Bq kg-1, respectively [2].
In this paper, we present a measurement comparability of134
Cs and 137Cs in foodstuff samples in Japan resulting fromthat of the inter-laboratory experiments.

Instruments and methods
All participants of the inter-laboratory experiments
measured 134Cs, 137Cs, and 40K in the candidate CRM using
the Ge semiconductor detector.
Results and discussions
The example of the results of inter-laboratory experiments
is shown in Fig.1. In that case, the z-score of the allreported values ranged from -3 to 3, the all data were used
for calculation of the certified value.

Fig.1 The result of inter-laboratory experiment of 134Cs in JSAC
0731 brown rice CRM.

Acknowledgement
Our deepest appreciation goes to participants the interlaboratory experiment for certification of CRMs.
APSORC’13 HEADING (WITHOUT NUMBER)[1][2]－ 240 －

Certificate of JSAC 0731, 0732 Brown rice certified referencematerialforenvironmental
radioactivity,
www.jsac.or.jp/srm/CRMJSAC0731.
Certificate of JSAC 0751, 0752 Bovine muscle flakes certified
referencematerialforenvironmental
radioactivity
www.jsac.or.jp/srm/CRMJSAC0751.

24-ENP-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Synthesis and Characterization of Volatile Technetium Compound
Bradley C. Childs1, Frederic Poineau2, Ken R. Czerwinski2
1

University of Nevada Las Vegas, Las Vegas, Nevada 89154, USA

Abstract – Technetium-99 is an important fission (T1/2= 2.13.105 y)
product of the nuclear industry. Technetium in its highest oxidation
state (VII) is highly mobile and can represent a threat to theenvironment [1]. There are over 55 million gallons of high level
mixed waste located at the Hanford site. Waste tanks at the Hanfordsite contain Tc that could potentially leak, and in the context ofmanagement of technetium, a glass waste form was proposed tocounteract the issue [2]. In the process of synthesizing melt glass
between the temperatures of 600 °C and 1100 °C, volatiletechnetium compounds were observed in the reaction tube. These
compounds displayed characteristic colors based upon the reaction
environments of either breathing air or nitrogen gas. A breathing
air atmosphere produces a red compound that adheres to the wallsof the reaction tube. An atmosphere of nitrogen gas produces awhite compound that was observed on the walls of the reaction tube.

B. Additional Synthetic Routes
One way to determine the exact species being volatilized
is to observe the technetium compound being used in thebatch synthesis material. NaTcO4 will also be observed
without adding it to the batch material to see if volatile
species are still produced in the same manner. Other
pertechnetate salts will be observed as well with and without
the batch material.

Keywords – Technetium, Red, Volatile,I.

INTRODUCTION

A study of how technetium behaves as a waste-form andthe speciation that correlates with the waste-form has
garnered much attention. One of the proposed methods tocreate a waste-form was vitrification. The main issue withvitrication is dealing with volatile products that form in theprocess of manufacturing the glass from vitrification. The
temperatures that are reached allow for radioactive
compounds to become airborne and can present a problem
when trying to retain all of the radioactive material. As it
pertains to technetium, Tc2O7 boils at 311 °C and TcO2 boils
at temperatures above 900 °C which is problematic because
melting temperatures exceed the boiling points of thosecompounds very easily [3]. Most speciation studies go into
how the glass is formed, but the focus of the study at hand is
to look at the volatilized species.

Fig.1: Volatile Red CompoundFig.2: Volatile White Compound

REFERENCES

A. Vitrification Process
The process that was used to produce volatile species
involves making glass material. Melt glass formers based on
the LAWE4H batch composition were used while loading 1%
technetium by mass to this mixture by way of sodium
pertechnetate (NaTcO4) [4]. A temperature range between
600 °C and 1100 °C will be used to produce the material.
Two different environments will be created while producing
volatile species. The first of which will be breathing air.
Under these conditions we expect to see a red volatile species(Fig.1). The second environment will be nitrogen gas. It is
expected that a white volatile species will be observed fromthis synthesis (Fig.2).

[1]
[2]
[3]
[4]

－ 241 －

Y. Liu, J. Terry and S. Jurisson, Radiochim. Acta, 2007, 95, 717–725
W.W. Lukens et al., Dissimilar behavior of technetium and rhenium inborosilicate waste glass as determined by X-ray absorption
spectroscopy. Chem. Mater. 19, (2007) 55-56.
J.G. Darab and P.A. Smith Chem. Mater. 1996, 8, 1004-1021.
DM-100 Melter Testing to Support LAW Glass Formulation
Correlation Development,” K. Abel and J. Westsik, WTP Test
Specification, 24590-WTP-TSP RT-04-0004, Rev. 0, 1/12/05.

24-ENP-08
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Time Variation of Concentrations of Radioactive Cesium-134, 137 and Iodine-129 in
the Ohori River, Chiba Prefecture, Japan
Nao Shibayama1, Keisuke Sueki2, Kimikazu Sasa 2,3, Yukihiko Satou1, Tsutomu Takahashi3,
Masumi Matsumura3, Hiroyuki Matsuzaki4, Michio Murakami5, Rey Yamashita6, Mahua Saha6,
Hideshige Takada6, Yukio Koibuchi7, Soulichan Lamxay7, Taikan Oki8
1

Graduate School of Pure and Applied Sciences, Univ. of Tsukuba
2Faculty of Pure and Applied Sciences, Univ. of Tsukuba
3
Research Facility Center for Science and Technology, Univ. of Tsukuba
4
MALT, The Univ. of Tokyo
5“Wisdom of Water”(Suntory), The Univ. of Tokyo
6
Tokyo Univ. of Agri. & Tech.
7
Graduate School of Frontier Sciences, The Univ. of Tokyo
8
Insitute of Industrial Science, The Univ. of Tokyo

Abstract
Radioactive nuclides emitted from the Fukushima Dai-ichi
nuclear power plant were observed for the long term in Ohori River,
Chiba Prefecture, Japan. In this presentation, we report time
variation of concentrations of 134Cs, 137Cs and 129I in the suspended
soils (SS) and dissolved matter (DM) from the flow of the river were
measured. The concentrations of radioactive cesium 134 and 137 in
SS were gradually decreasing in long term observation and risingon the rainy day. The DM/SS ratios of 137Cs were almost constantover time. In the DM, the 129I data showed strong correlation withcesium data.
Keywords
Cesium-134, 137 ; Iodine-129 ; time variation ; river waterI.

INTRODUCTIONRadioactive cesium and iodine emitted from the
Fukushima Dai-ichi nuclear power plant were detected fromenvironmental water, reflecting an aspect of dynamics ofthese radioactive nuclides in the environment. In themetropolitan area, comparatively high concentration ofradioactive cesium isotopes were detected from sediment of
Ohori River in Chiba Prefecture[1]. In this work, the long-term
variations of the concentrations of the radioactive cesium andiodine in the suspended soils (SS) and dissolved matter (DM)were measured for Ohori River, and the trend of nuclides was
discussed.
II.

III.

RESULTS AND DISCUSSION

Time variations of concentration of radioactive cesium in
the SS of Ohori River are shown in Fig.1. The average
concentrations of radioactive cesium were gradually
decreasing in long term observation. The concentration ofradioactive nuclides in the SS sampled by Auto-Sampler wastreated as average for a certain period. The momentary
concentrations of radionuclides in the SS were obtained fromthe river water sampled every two or three weeks. In mostpoints, the momentary concentration was lower than the
average concentration, but a few points which corrected inrainy differed from the tendency due to rain fall. The DM/SS
ratios of 137Cs were almost constant, which may consideredas the equilibrium constant of cesium between SS and DM. In
the DM, the 129I data showed strong correlation with cesium
data. The iodine data, however, is insufficient.

METHODSThe SS samples of two or three weeks are collected by the
SS Auto-Sampler[2] which installed at the middle of river near
the Showa-bridge, and the river water samples are collected
every two or three weeks in the same place from May, 2012
at Ohori River. The river water was filtrated. The SS was
defined as residue of 0.7 �m filter and the DM was defined as
the component passing through the 0.2 �m filter. The
concentrations of 134Cs and 137Cs were determined from the �ray spectrum obtained by HPGe detectors. 129I in the river
was investigated about the same samples by AMS at MALT,The Univ. of Tokyo[3].

Fig.1. Time variation of concentration of radioactive cesium in SS of Ohori
River. Solid line and dashed line show the average concentration of 137Cs
and 134Cs, respectively. Square points and triangular points show momentary
concentrations of 137Cs and 134Cs, respectively.

REFERENCES
[1]
[2]
[3]

－ 242 －

Ministry of Environment, 2011,
http://www.env.go.jp/jishin/monitoring/result_pw111222-1.pdf
Phillips et al. (2000) Hydrol. Process. 14, 2589-2602.
H. Matsuzaki et al., Nucl. Instr. and Meth. B, 259, 2007, 721–726.

24-ENP-09

Ra isotopes in Na-Cl type groundwater in Japan
1

Junpei Tomita1,a, Takahiro Takada1, Seiya Nagao1, Masayoshi Yamamoto1

Low Level Radioactivity Laboratory, Institute of Nature and Environmental Technology, Kanazawa University, Wake, Nomi,
Ishikawa 923-1224, Japana
Department of Radiation Protection, Nuclear Science Research Institute, Japan Atomic Energy Agency, Tokai-mura, Ibaraki
319-1195, Japan.

Abstract – Radium isotopes (226Ra and 228Ra) were measured for
Na-Cl type groundwater samples collected from Hokkaido, Aomori,
Akita and Yamagata Prefectures in Japan. The 226Ra contents variedin the wide range from 9 - 5000 mBq kg-1 and their values wereroughly correlated to the total dissolved solid (TDS). Activity ratiosof 228Ra/226Ra in groundwater ranged from 0.3 – 4.2 and most ofthem clustered around those of 232Th/238U of common rocks in Japan.
These observations agreed well with the previous results from
Ishikawa, Toyama and Niigata Prefectures, and overall indicatedthat Ra was mainly transported into the groundwater by �-recoil
process and its concentration in groundwater was constrained byadsorption-desorption reaction depending on salinity.
Keywords – Ra isotopes, Na-Cl type groundwater, �-recoil,adsorption-desorption reaction

I.

INTRODUCTION

Radium isotopes (226Ra (T1/2=1600 y) and 228Ra (T1/2=
5.75 y)) in groundwater have been investigated worldwide
from the various viewpoints such as geochemical interest andradiation protection. Activities of Ra isotopes in groundwater
vary widely, and anomalously high 226Ra contents over
several tens of Bq kg-1 have been found in saline waters andbrines.
In Japan, Ra isotopes in groundwater have been
investigated mainly in relation to the radioactive hot spring,and groundwaters with high 226Ra concentration over 1 Bq
kg-1 have been found at hot springs such as Arima and
Masutomi. Since these hot springs are commonly originatedfrom granite areas where have relatively high U contents, it
was considered that such higher 226Ra in water was attributed
to the U in granite. Recently, Na-Cl type groundwaters withintermediate salinity (ca.1-36‰) have been obtained from thedeep wells with the development of more sophisticateddrilling techniques. We have studied the distribution of Ra
isotope concentrations in these Na-Cl type groundwatersfrom coastal area and sedimentary basin in Ishikawa, Toyama
and Niigata Prefectures facing to the Japan Sea of Central
Japan, and found that some of them contained relatively high226
Ra over 1 Bq kg-1 even in coastal areas and sedimentarybasin.
Authors are interested in clarifying the geochemicalmechanism of such high 226Ra occurrence, and expanded
research to groundwater at Hokkaido and Tohoku Districts(Aomori, Akita and Yamagata Prefectures). In this study, we
report the Ra contents in Na-Cl type groundwaters from theseareas. Constraining factors which Ra content becomes higher
in groundwater will be mainly discussed, including the results
obtained previously from other areas such as Ishikawa,Toyama and Niigata Prefectures.
II. MATERIAL AND METHODSNa-Cl type groundwater samples were collected from thecoastal area and sedimentary basin in Hokkaido, Aomori,
Akita and Yamagata Prefectures in Japan. Radium isotopes
were co-precipitated with BaSO4, and their activities were
determined by �-ray spectrometry.
III. RESULTS AND DISCUSSION
Activities of 226Ra in groundwater from Hokkaido, Aomori,
Akita and Yamagata Prefectures were observed in the wide
range from 9 - 5000 mBq kg-1. These 226Ra activities ingroundwater samples showed an increasing tendency withincreasing total dissolved solid (TDS) (Fig. 1). Activity ratiosof 228Ra/226Ra of them varied from 0.3 – 4.2, and most ofthem clustered around 0.5 - 2. These ratios were nearly
similar to those of 232Th/238U of common rocks in Japan.
These observations agreed well with the previous results from
Ishikawa, Toyama and Niigata Prefectures.
Ra isotopes are supplied into groundwater by someprocesses: 1) decay of dissolved parent nuclides (Th isconsidered as insoluble element); 2) weathering and/or
dissolution of aquifer rock; 3) �-recoil at water-rockinterface; and 4) desorption reaction at water-rock interface.
Results both relationships between 226Ra and TDS andactivity ratios of 228Ra/226Ra in groundwater samples obtained
here indicated that Ra was mainly ejected into thegroundwater by �-recoil process and its Ra was constrainedby adsorption-desorption reaction depending on salinity.

－ 243 －

Fig. 1 Relationship between 226Ra-TDS in groundwater

24-ENP-10

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

A new method to estimate 210Po/210Pb activity ratio in atmospheric aerosol byalpha spectrometry
1

2

N. Momoshima1, S. Nishio2, K. Hibino2, S. Sugihara1

Radioisotope Center, Kyushu University, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Graduate School of Science and Technology, Kumamoto University, Kurokami, Kumamoto 860-8555, Japan

Keywords – aerosol, 210Po 210Pb activity ratio, alpha spectrometry
Various kinds of radionuclides are observed in
the atmosphere, among them radon and its daughter
nuclides attached to aerosol are most abandon andthe daughter nuclides finally decay to 210 Pb within a
few hours. The formed 210 Pb (22.3 y) decays to 210 Bi(5 d) followed by 210 Po (138 d). The half life of210
Po is rather long compared to the removal processfunctioning to atmospheric aerosols; therefore
210
Po/ 210 Pb activity ratio as well as 210 Bi/ 210 Pb
activity ratio is usable to estimate residence time ofaerosol in the atmosphere.
The growth curves of 210 Po from 210 Pb in aerosol
are shown in Fig.1 as a function of initial210
Po/ 210 Pb activity ratios. The growth patterndiffers depending upon the initial 210 Po/ 210 Pb
activity ratio. The initial activity ratio varies in theenvironment due to additional input of 210 Po toatmosphere from such as volcanic release, fireburning of vegetation etc. Atmospheric migration ofsoil dusts increases the initial activity ratio because
of secular radioactive equilibrium in soil. Under thegeneralenvironmental
circumstances
major
radionuclide in aerosol would be 210 Pb and then,210
Po is considered to be the main alpha particle
emitted from aerosol. If we measure a growth of210

Po activity with time and compared with growth
pattern shown in Fig. 1, we can estimate the210
Po/ 210 Pb activity ratio of the aerosol samples.
The theoretical calculation of 210 Pb- 210 Bi- 210 Po
equilibrium suggests that 210 Po/ 210 Pb slightly
depends on initial 210 Bi/ 210 Pb activity ratio. The
measurement time of a few days would be necessary
for alpha spectrometry to obtain statistically
acceptable counts. Then, the 210 Po growth patterndependent on the initial 210 Bi/ 210 Pb activity ratio
would be obscure. However, the proposed method is
simple and no chemical separation is necessary.
The growth of 210 Po activity in the aerosol
collected on a membrane filter and measured several
times with a silicon surface barrier detector of analpha spectrometer is shown in Fig. 2 as an example.
The growth pattern is analyzed under theassumption that the initial 210 Bi/ 210 Pb activity ratio
is 0.6, which would be the representative value inthe general environment [1]. The least square fitting
was carried out to obtain the initial 210 Pb and 210 Po
counts. The measurements were done at theidentical geometrical configuration between thedetector and the sample, and in a series ofmeasurements the same detector of the same alpha
spectrometer system was used.
[1] Rangarajan, C., J. Environ. Radioactivity, 15, 193-206(1992�

Fig. 1 Theoretical change in 210Po/210Pb activity ratiowith time at different initial 210Po/210Pb activity ratio.

Fig. 2 Counts of 210Po measured with the alpha
spectrometer for the aerosol collected on a membranefilter and the theoretical counts obtained by least square
fitting.

－ 244 －

24-ENP-11
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Sedimentary environment inferred from sedimentation rates by

and their inventories in Mutsu Bay, Japan210

Pb and 137Cs

Kazuhito Hamataka1, Seiya Nagao1, Michio Kato2, Isao Kudo3, Masayoshi Yamamoto1
1

Low Level Radioactivity Laboratory, KINET, Kanazawa University, Ishikawa 923-1224, Japan
2
Graduate School of Science, Kanazawa University, Kanazawa, Ishikawa 920-1192, Japan
3
Graduate School of Fisheries Sciences, Hokkaido University, Sapporo 060-0808, Japan

Abstract –Fourteen sediment cores were collected from Mutsu Bay,
Aomori in Japan, and excess 210Pb and 137Cs were measured
�-spectrometrically. The spatial distributions of sedimentation rates
by 210Pbex and 137Cs and their inventories were studied in order toclarify whole pictures about the sedimentary environment of Mutsu
Bay. Excessively post-depositional mixing (up to a depth of 10-15cm) of surface sediments by bioturbation was observed on the210
Pbex depth profiles in cores from the offshore areas. The
sedimentation rates calculated varied in the wide range from 0.04 to
0.2 g/cm2/y. The sedimentation rates using 137Cs method could not
be applied. Apart from the 210Pbex inventories from the nearshorearea, the responding inventories (17-30 kBq/m2) from the offshore
area were higher than the reported value of ca.15 kBq/m2 in thesurrounding soils, indicating that the sediment focusing due to theinner current etc., to the deeper area from the surroundingnearshore area, affects the sediment accumulation in the offshorearea.
Keywords –Mutsu Bay, Aomori, sedimentation rate, inventory, 210Pb,
Cs, sedimentary environment

137

I.

Measurements of 210Pb and 137Cs: The samples were then sieved
through a 2-mm mesh to remove pebbles and fragments of shell, andpulverized in an agate mortar to obtain homogeneous samples.
An aliquot of 5-10 g of sample was packed into a plastic vessel andstored for more than 3 weeks. The 210Pb, 226Ra (from daughter
nuclide 214Pb) and 137Cs were measured by a low–background �-ray
spectrometer with a high pure Ge detector (planar or well type).
The
spectrometerwascalibrated
withstandards
preparedbytheNew
Brunswick Laboratory (NBL)
reference materials No. 42-1
(4.04%
uranium),andanalytical
grade
KCl.
Unsupported 210Pb activity(210Pbex) was calculated fromthe difference between the total
210
Pb and the 226Ra (from 214Bi)
contents.
Fig. 1 Sampling sites in Mutsu Bay
III. RESULTS AND DISCUSSIONINTRODUCTION

Semi-enclosed bay is sensitive to human activity and change ofnatural environment, and these directly and strongly impact in its
sedimentary environment.
Mutsu Bay (surface area of 1580 km2, average depth of 34 m, andmaximum depth of 75 m), which is located in the north of Honshu inJapan, is indirectly connected with the open sea by a narrow channel
through which seawater flows in and out the bay. The east floor of
Mutsu Bay is relatively flat and shallow (40 m deep on average).
The coastal areas are excessively populated and extensive scallop
farming has been popularly practiced since 1970s. The present–day,
death of scallop due to overcrowded cultivation and generation of
red tides by declining water quality are going on, and muds aremarkedly accumulating in the offshore areas (Minoura et al. (1992)).
We have been interested in clarifying whole pictures about such
sedimentary environment of Mutsu Bay, investigating the sediment
rates by using radioactive 210Pb and 137Cs and their inventories in
sediments.
II. MATERIAL AND METHODSCore sampling: The core sediment samples were collected duringcruises in May and August 2011, and June and September 2012. A
small gravity corer (3.5 or 8.0 cm in diameter) was used to collectsurface sediments (20-40 cm long) at 14 locations (Fig. 1). The
obtained cores were immediately cut every 1 cm from top along thecore, and after taking them to laboratory the samples were freezedried.

To date, activity measurements of 210Pb and 137Cs were finishedfor cores from St.1 to St.10. Overall, the sediments (Sts. Sts. 2-4 and6-8) from the offshore area were mostly mud, while sand andcoarser sediments, with their low mud contents, are restricted to thenearshore area. Surface mixed layers (up to a depth of 10-15 cm)
were observed on the 210Pbex depth profiles from the offshore area,
evidencing the excessively post-depositional mixing of surface
sediments by bioturbation and so on. For other sites, 210Pbex
concentrations declined more or less exponentially with depth.
Sedimentation rates calculated for these cores varied in the wide
range from 0.04 to 0.2 g/cm2/y. Sedimentation rates using 137Cs
method could not be applied. A generally increasing trend in
sedimentation rate after the late 1970s, when correspond to the rapid
increase of scallop-production activity, was clearly observed at St.10.
Excess 210Pb and 137Cs inventories were calculated as the sum of210
Pbex and 137Cs through a sediment core, respectively. The 210Pbex
inventories ranged from 7-30 kBq/m2. Apart from the values (7-9kBq/m2) from the nearshore areas, the responding inventories (1730 kBq/m2) for cores (Sts. 2-4 and 6-8) from the offshore areas were
somewhat higher than the reported value of ca.15 kBq/m2 estimatedfor the surrounding soils, indicating that the sediment focusing due
to the inner current etc., to the deeper area from the surroundingnearshore area, affects the sediment accumulation in the offshore
area. The 137Cs inventories (0.08-0.14 kBq/m2) were clearly lower
than its inventories (around 3 kBq/m2) in the surrounding soils.
Further works are going on organic contents and grain-size of
sediments.
K. Minoura et al. (1992), Marine Geology, 103, 487-502.

－ 245 －

24-ENP-12

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Distribution of radiocarbon in Japanese agricultural soils
Nobuyoshi Ishii, Keiko Tagami, Shigeo Uchida

Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences
Abstract – Distributions of C-14 in solid, liquid, and gas phases
were determined by batch sorption tests using 142 Japanese
agricultural soil samples. The agricultural soils used wereclassified into “paddy” and “upland” soils. Each of the soil
samples was suspended in deionized water containing [1, 2-C-14]
sodium acetate and shake-incubated for 7 days. After the
incubation, the distributions of C-14 in solid, liquid and gas
phases were approximately 35%, 5% and 60% of the spiked C-14,
respectively. These results suggested that if the C-14 of acetate
migrated from a TRU repository site to agricultural soils, most of
the C-14 would be released into the air and the rest would be
distributed in the soil solid phase. The distribution of C-14 in gas
phase was lower for upland soils than for paddy soils..
Keywords – TRU waste, Radiocarbon, Distribution, Agricultural
soils

I.

INTRODUCTION

Transuranic (TRU) waste is generated during theoperation and dismantling of reprocessing facilities andmixed oxide (MOX) fuel fabrication facilities, and thewaste contains radionuclides that have long half-lives. The
dominant nuclides contributing to the dose from TRU
waste are C-14 and I-129 [1]. These radionuclides,
therefore, are very important in safety assessments forgeological repositories of TRU waste.
C-14 could be released from a geological repository
over a timescale of several thousand years. Because there
is little information regarding reliable migration andrealistic transport models, the possible migration of C-14
from a TRU repository site to the biosphere throughgroundwater presents some concern. It is, therefore,
required to clarify the behavior of C-14 in the environment
due to the reduction of exposure to C-14.
In general the environmental behavior of chemicals is
influenced by various factors such as land use, soil type,temperature, pH, oxidative conditions and so on. The
behavior of C-14 may differ between paddy and uplandsoils. In this study, distribution of C-14 for both Japanese
paddy and uplands was determined and compared. The
relationships among the distribution of C-14 and selectedsoil properties were discussed.

For batch culture experiments, 0.5-g of air-dried soil
sample was soaked with a 5-mL of the radioactive solution.
The culture was shake-incubated at 25���������������������
dark. After the incubation, the C-14 activities of the culture
were determined to estimate the distribution of C-14 insolid, liquid and gas phases by measuring C-14 in solid,
liquid phase with a liquid scintillation counter.
III. RESULTS AND DISCUSSION
Distribution of C-14 in solid, liquid and gas phases were
determined on day 7 of incubation. The mean values of
those distributions were 59.1 ± 8.6% in as phase, 35.4 ±
7.7% in solid phase, and 5.5 ± 5.4% in liquid phase. For
each phase, a positive excess kurtosis was found (2.7 forsolid, 7.1 for liquid and 4.2 for gas), and the interquartile
range, which is the difference between the third and firstquartiles, was less than 10%. Results of these statisticalanalyses mean that the distribution of C-14 in each phase
had small variation ranges for Japanese agricultural soils.
It should, however, note that there were big differences
between the two extreme values for each phase. These
values were far from the average and thus must be paid
attention in safety assessments for geological repositories
of TRU waste.
Distribution in liquid phase was correlated positively
with pH of the culture solution. Similar results were foundin our previous study [3].
Significant differences in the distribution of C-14
between paddy and upland soils were found for all phases.
Distributions in solid and liquid phases were higher for the
upland soils than for paddy soils, but, on the other hand,
distribution in gas phase was lower for upland soils than forpaddy soils. The difference in distribution in liquid phase
may be explained by pH of the solution because pH of theupland samples was significantly higher than that of the
paddy samples.
This work was supported by the Agency for Natural
Resources and Energy, the Ministry of Economy, Tradeand Industry (METI), Japan.
REFERENCES

II. MATERIALS AND METHODS
A total of 142 agricultural soils (63 paddy soils and 79
upland soils) were collected throughout Japan. The soil
samples were dried at room temperature, and then passed
through a 2 mm mesh sieve to obtain fine particles.
[1,2-C-14] sodium acetate was used as the chemical
form of C-14. This solution was diluted with deionizedwater to a specific activity of 1.8 kBq mL-1 and was filtersterilized to remove microorganisms [2]. The specificactivity corresponded to 4.2 x 10-1 nmol mL-1.

[1]

[2]
[3]

－ 246 －

JAEA, FEPC, Second progress report on research and development
for TRU waste disposal in Japan –Repository design, safetyassessment and means of implementation in the generic phase-,
JAEA-Review 2007-010, FEPC TRU-TR2-2007-01(2007).
N. Ishii, S. Uchida, “Bacteria contributing to behaviour ofradiocarbon in sodium acetate,” Radiat. Prot. Dosimetry. 146, 151154 (2011).
N. Ishii, H. Koiso, H. Takeda, S. Uchida, “Partitioning of 14C into
solid, liquid and gas phases for various paddy soils in Japan,” J. Nucl.
Sci. Technol., 47, 238-243 (2010).

24-ENP-13
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Lateral distributions of 228Th/228Ra and 228Ra/226Ra ratios
in surface waters of the Sea of Japan and their physical implications
Y. Furusawa1, M. Inoue1, S. Nagao1, M. Yamamoto1, Y. Hamajima1, H. Kofuji1, K. Yoshida1
Y. Nakano1, K. Fujimoto2, A. Morimoto3, T. Takikawa4, Y. Isoda5
1

2

Low Level Radioactivity Laboratory, Kanazawa University
Fisheries Research Agency, National Research Institute of Fisheries Science3
Hydrospheric Atmospheric Research Center, Nagoya University
4
National Fisheries University
5
Graduate School of Fisheries Sciences, Hokkaido University

Abstract –We examined 228Th/228Ra and 228Ra/226Ra ratios in surface watersfrom the Sea of Japan by low background �-spectrometry. Theselateral distributions clarified the aspects of physical movement ofgeochemical species on surface.
Keywords –228
Th/228Ra ratio, 228Ra/226Ra ratio, Sea of JapanI.

INTRODUCTIONof the Kuroshio water in the Honshu Island side. On the other
hand, 228Th/228Ra ratio of waters on the transect A exhibited
gradual decrease (<0.01 to 0.12) from south to north,dominantly reflecting a higher flux of biogenic particles in
shelf water [5]. In this study, we examined the lateral
distributions of 228Th/228Ra ratio as well as 228Ra/226Ra ratioon surface of the Sea of Japan and clarify the circulation
patterns of particles and water masses. This is an operationthat we are currently engaged in, by obtaining additionalsurface water samples.

Many researchers have studied the flow pattern of the
Tsushima Warm Current (TWC), a major feature of the flow
patterns in the Sea of Japan, using various techniques [1].
However, the origin and characteristics of the circulation
pattern of the TWC have not yet been well clarified becauseof the markedly complicated seasonal variation in thecirculation. The seasonal variation in the 228Ra/226Ra ratio
recorded for the surface waters of the Sea of Japan isconsidered to be mainly controlled by the remarkable changes
in the mixing ratio of the 228Ra-poor Kuroshio (228Ra/226Ra =0.2) and the 228Ra-rich continental shelf waters (228Ra/226Ra =3.5) within the East China Sea (ECS) [2]. Activity of particlereactive 228Th (half-life, 1.91 y) in seawater is governed bybiogenic particle behavior, and therefore the combination of
228
Th and 228Ra activities (228Th/228Ra ratio) in seawater
samples is useful for the study of scavenging processes in the
Sea of Japan.
II. METHOD AND SAMPLING SITE
We collected 165 surface water samples (20 L) during
the research expeditions of T/V Oshoro Maru, R/Vs Mizuho
Maru, Tansei Maru, Soyo Maru, and Tenyo Maru (Fig. 1).
Low-background �-spectrometry was performed on thesamples using Ge-detectors at the Ogoya Underground
Laboratory in Japan [3, 4].
III. RESULTS AND DISCUSSION
Along the Tsushima Strait, the 228Ra/226Ra ratio ofsamples on the transect A gradually increased from south tonorth (from 0.8 to 2.3). On the transect B, the 228Ra/226Ra
ratio of coastal-side waters (0.6-0.8) was lower than that ofoffshore-side waters (1.2). This reflects a higher mixing ratio

Fig. 1. Sample locations for seawater

References[1] Hase et al. (1999) J. Oceanogr. 55, 217-234[2] Nozaki et al. (1989) Geophys. Res. Lett. 16, 1297-1300[3] Y. Nakano et al. (2008) J. Oceanogr. 64, 713-717[4] Y. Hamajima & K. Komura (2004) Appl. Radiat. Isot. 61, 179-183[5] M. Inoue et al. (2012) Geochem. J. 46, 311-320－ 247 －

24-ENP-14

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Vertical profiles of 228Ra and 226Ra activities in the Sea of Japan and theirimplications for water circulation
1

M. Inoue1, M. Minakawa2,*, K. Yoshida1, Y. Nakano1, H. Kofuji1,
S. Nagao1, M. Yamamoto1, Y. Hamajima1

Low Level Radioactivity Laboratory, Kanazawa University
Fisheries Research Agency, National Research Institute of Fisheries Science*present address; National Research Institute of Aquaculture

2

II. SAMPLES and EXPERIMENTAL

AbstractBy employing low-background �-spectrometry combined

We analyzed a total of seawater samples collectedwith minimal radiochemical processing, we examined verticalin water columns in the Sea of Japan for 226Ra and 228Ra.

profiles of 226Ra (t1/2 = 1600 y) and 228Ra (5.75 y) activities in

Low-background �-spectrometry was performed using

water columns in the Sea of Japan. The results indicate

well-type Ge-detectors, which are located at the Ogoya

continuous delivery of 228Ra to the Deep Proper Water (DPW),

Underground Laboratory, Japan [2]. Detailed explanations

and clarify aspects of the transport of 226Ra and 228Ra by waterof these experimental procedures were presented elsewherecirculation.

[3]. �-Peaks for 228Ra measurement (228Ac; 338 and 911keV) on a blank sample, which was performed our

Keywords- 226Ra, 228Ra, Deep Proper Water, residence time, low-

experimental procedures on 50 L of distilled water, were“not detected” level. Therefore, we corrected only least Ra-

background �-spectrometrycontaminated Ba-reagent blank, which accounted for <1%
228

Ra for our water samples.

I. INTRODUCTION
The Sea of Japan is surrounded by the EurasianIII. RESULTS and DISCUSSION

continent and the Japanese Archipelago, and is connectedto the Pacific and other marginal seas by the very shallow

In the Japan Basin, the 226Ra activity of the water

Tsushima, Tsugaru, and Soya Straits (<~150 m of depth).

samples gradually increased from surface to the DPW (1.5-

Therefore, the deep water, so-called the Proper Water of

2.3 mBq/L). The 228Ra activity of the water exhibited steep

the Sea of Japan, has no influx from a surrounding sea,

gradients with depth from the surface to the Upper Proper

indicating unique vertical water circulation [1]. 226Ra and

Water

228

Ra of seawater have been used as powerful tracer forcontinuously delivered to the DPW by the active water

studying the migration of water masses. However, standard

circulation before it radioactively decays. The results(1.8-0.2

mBq/L),

andshort-lived

228

Ra

is

Ra of deep seawater

indicate continuous delivery of 228Ra to the DPW, andusually required very large volumes (hundreds to thousands

clarify aspects of the transport of 226Ra and 228Ra by waterof liters) because of its low activity and previously reported

circulation. The residence time of the DPW is calculated todata are not sufficient to allow investigating the details of

be about 100 y.

�-spectrometry for measuring

228

the vertical distribution of 228Ra in oceans. In the present
study, we analyzed seawater samples from the Japan Basin,Acknowledgements
We thank the researchers, captain, and crew of R/V

Yamato Basin, and Tsushima Basin within the Sea of Japan,
for 226Ra and 228Ra.

Soyo Maru for their assistance during sampling.
References[1] Gamo, T. and Horibe, Y. (1983) J. Oceanogr. Soc. Jpn 39, 220-230:[2] Hamajima, Y. and Komura, K. (2004) Appl. Radiat. Isot. 61, 179-183:[3] Nakano, Y. et al. (2008) J. Oceanogr. 64, 713-717.

－ 248 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

24-ENP-15

Induced radioactivity in air and water at medical accelerators
K. Masumoto1, K. Takahashi1, H. Nakamura1, A. Toyoda1, K. Iijima1, K. Kosako2, K. Oishi2, F.
Nobuhara3
1

High Energy Accelerator Research Organization (KEK)2
Shimizu Co.
3
Tokyo Nuclear Service Co

Abstract – Activation of air and water has been evaluated at the
10 and 15 MeV linear electron accelerator facilities. At 15 MeV
irradiation, the activity of 10-min-half-life 13N was observed in thecase of the air in the glove box. Air and water samples were also
bombarded by 250 MeV protons and 400 MeV/u carbon, and theirradiation dose was 10 Gy at the isocenter. Upon the ionchamber monitoring of the air sampled from the glove box, 15O,
13
N, and 11C activities were mainly observed. At the end of protonand carbon irradiation, the activity of the water was found to be������ ��� ������-3 ���� �������� ������-3, respectively. From thedecay analysis of the induced activity in water, 15O, 13N, and 11C
were detected.
Keywords – Activation, Air, Water, Medical accelerator

I.

INTRODUCTION

Accelerators have been widely used in medical
applications, especially in cancer treatment. Electron linear
accelerators have been used in hospitals for the X-ray
irradiation of diseased organs. Particle accelerators havealso been used in recent times as a powerful tool for cancer
therapy. In this work, we investigated the activation of air
and water in treatment rooms in hospitals for radiation
safety management. In the case of photonuclear reaction,
several positron emitting radioisotopes such as 15O and 13N
can be produced by the bremsstrahlung at higher than 15
MeV in air. In case of hadron irradiation, many
radioisotopes might be produced by high-energy particles.
In this work, we measured the induced activity in air andwater caused by the electron and hadron accelerators
employed for medical use, in order to determine whether
the concentration of radioactivity was below regulated
levels.

(1) Air: The air in a glove box of 250L was irradiated andsampled with a vacuum ionization chamber formeasurement. An aerosol was also collected on a HEPA
filter by an air sampler.
(2) Water: After irradiation, dose rate of water surface wasmonitored using a NaI(Tl) survey meter and the gammaray spectrum was measured using a LaBr3(Ce)scintillation spectrometer.
III. RESULTS AND DISCUSSION
At the 15 MeV irradiation of bremsstrahlung, theactivity of 13N was 0.87 Bq•cm-3 at the end of theirradiation. As the activity of 13N was also detected on thefilter paper, NOx fomation was presumed. Activity of water
could not be detected.
In case of 250 MeV proton irradiation, activities of 15O,
13
N, and 11C were found to be 1.9, 0.6, and 0.6 Bq•cm-3 at
the end of irradiation in air sampled from the glove box.
The activity of 13N was also detected on the filter paper. By
the decay curve analysis of water activity obtained from thesurface dose rate of the polyethylene tank, activities of 14O,
15
O, 13N, and 11C were found to be 91000, 12000, 1100, and
190 Bq•cm-3 at the end of irradiation, respectively.
In case of carbon irradiation, we performed irradiationof air for two times and fitted the decay curve for 14O, 15O,
13
N, 11C, and 41Ar. Average activities of 14O, 15O, 13N, 11C,
and 41Ar were 0.8, 1.1, 0.08, 0.09, and 0.006 Bq•cm-3 at theend of irradiation. By the decay curve analysis of water
activity obtained from the surface dose rate of thepolyethylene tank, activities of 14O, 15O, 13N, and 11C were
found to be 2100, 2000, 100 and 180 Bq•cm-3 at the end of
irradiation, respectively.

II. EXPERIMENTAL

IV. CONCLUSION

A. Activation of air and water(1) Electron accelerator:10 and 15MeV irradiations for 10
min were performed by Varian Clinac 2100C and Clinac
iX, respectively. Doses were 40 and 60 Gy at theisocenter, respectively.
(2) Proton accelerator: 200 MeV proton beam wasirradiated for 3.25 min on an area of 0.15 m × 0.15 m,
and 10 Gy at the isocenter.
(3) Heavy ion accelerator: Carbon beams of 400
MeV/nucleon was irradiated for 2 min on an area of 0.15
m × 0.15 m, and 10 Gy at the isocenter.
B. Activity measurement

In case of 10 MeV irradiation, we could not detect theresidual activity in air and water. In the case of 15 MeV
irradiation, we observed 13N in the air sampled from theglove box irradiated in front of the beam exit window andon the filter collected by the air samplers in the irradiation
room and the maze. In the case of 250 MeV proton
activation and 400 MeV/u carbon irradiation, activation of
air was not excessively high and the induced activity wascomparable to that induced by 15 MeV irradiation for theelectron accelerator. But induced activity of water was
extremely high. The main radionuclides detected were 13N
and 11C, 10 min after irradiation with protons and 11C, 20
min after irradiation with carbon－ 249 －

24-ENP-16

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Radioactivity determination of 14C and 3H in solid waste samples by liquid
scintillation counter
Jong-Myoung Lim1*, Mun-Ja Kang1, Kun-Ho Chung1, Chang-Jong Kim1, Geun-Sik Choi1
1

Environmental Radioactivity Assessment Team, Korea Atomic Energy Research Institute989-111 Deadeok-daero, Yuseong-gu, Daejeon, 305-353, Korea

Abstract –This study reports the comprehensive efforts made toevaluate the analytical procedure for 3H and 14C in solid sample.
The sludge samples from National Physical Laboratory (NPL)
proficiency program (Environmental Radioactivity Proficiency
Test Exercise 2012) were combusted by high temperature furnace
and analyzed in LSC. The various performance tests of analyticalmethod were conducted with standard solutions. The detection
limit and uncertainty of the method were also evaluated in detail.
Major factors of standard uncertainty were grouped into counting
error, sample homogeneity, and efficiency calibration. Finally,
sensitivity tests of these major factors were performed.
Keywords – tritium, 14C, radioactivity, combusting, sludge,

As an attempt to reduce social costs and apprehension
arising from the radioactivity in environments, an accurate
and rapid assessment of radioactivity is highly desirable.
Nuclear wastes (e.g., sludge, activated carbon, oils, resins,etc.) have been consistently generated by actions to preventthe emission of radioactive pollutants from nuclear sites.
To decide a proper disposal option of these nuclear wastes,
we need an analytical method that can determine theradioactivity of 3H and 14C which exists in very low levels.
The 3H in the water (tritiated water; HTO) is major
chemical form in the environment. Through the natural orindustrial process with organic compounds, tritium is easily
converted into organic bound tritium (OBT). The HTO
form is easily lost at a temperature around 120°C, whereas
the strongly-bounded tritium with the form of non-HTO
requires high temperature of a few hundred degrees incentigrade for complete extraction. The 14C decays into 14N
through beta decay(Emax=156 kev). The main
anthropogenic origin of 14C is thermal neutron activation of
14
N in the nuclear reactor by a neutron capture reaction
14
N(n,p)14C. For extraction of 14C which exist in lattice
structure, it requires also high temperature to oxidize 14CO2
gas.
Radioactivity of 3H and 14C in waste water sludge has
been determined by the following combustion method. The
sludge samples were combusted in a purpose-designed
tubular high temperature furnace (Raddec Pyrolyser
TrioTM) which consist of six quartz tubes with the length of
1.5 m and the diameter of 1.5 cm. The combusting
temperature was controlled stepwise up to 800°C. The 3H
and 14C were trapped in 0.1 M HNO3 and carbon absorbersolution (Carbo-Sorb® E, Perkin Elmer), respectively. The
measuring of the radioactivity was carried out in LSC(Walac 1220 Quantulus, Perkin Elmer).
This study reports the comprehensive efforts made toevaluate the analytical procedure for 3H and 14C in solid

sample. The sludge samples from National PhysicalLaboratory (NPL) proficiency program (Environmental
Radioactivity Proficiency Test Exercise 2012) were
combusted by high temperature furnace and analyzed in
LSC. The various performance tests of analytical method
were conducted with standard solutions. In order toevaluate dynamic range of the method, real samples withspiking 3H and 14C standard solution were analyzed.
Duplicated samples (n=6) were analyzed to see therepeatability of this method. The results showed that
relative standard deviations for 3H and 14C are about 11%
and 2.9%, respectively. The activity concentrations werecompared statistically with the assigned values. The
deviation between the two values for 3H and 14C are about
14.5% and 5.7%, respectively. The detection limit anduncertainty of the method were also evaluated in detail.
Major factors of standard uncertainty were grouped into
counting error, sample homogeneity, and efficiency
calibration. Finally, sensitivity tests of these major factors
were performed.
Table 1. Uncertainty budget of the analytical procedure for solid sample
Uncertainty factor

3

H

14

Counting error
Sample homogeneity
Lab control standard
Efficiency calibration
Overall process

0.53
5.3
2.0
5.0
3.0

2.15
1.1
2.0
5.0
3.0

Combined uncertainty

8.1

6.6

Measured values

66.7

2.0

Uncertainty(k=1)

5.3

0.1

Standard
uncertainty

[1]
[2]

Unit

%

Bq/g

Kim, H.R., Kang, M.J., Choi, G.S. An experiment on theradioactivity characteristics of the tritium contaminated metal sample,
Annals of Nuclear Energy, 2011. 1074- 1077.
Hou, X., Roos, P. Critical comparison of radiometric and mass
spectrometric methods for the determination of radionuclides inenvironmental, biological and nuclear waste samples. Analytica
chimica Acta , 2008. 105-139.

*Corresponding author. E-mail: jmlim@kaeri.re.kr－ 250 －

H

24-ENP-17

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
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��"������ ��;� �����������!���"�����/01－ 251 －

24-NPP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Mössbauer Study of Iron Carbide Nanoparticles Produced by Sonochemical
Synthesis
1

Department of Chemistry, Tokyo University of Science
Department of Engineering Science, The University of Electro-Communications, 3RIKEN

Abstract – Iron carbide nanoparticles were synthesized byultrasonic irradiation of iron pentacarbonyl or ferrocene indiphenylmethane. Mössbauer spectra of the as-prepared particles
measured at room-temperature and 6 K indicated only one doublet.
The particles were annealed at 600 °C under argon for 2 h, and the
Mössbauer spectrum measured at room-temperature consisted of
Fe3C, �-Fe, and a paramagnetic component.
Keywords – Sonochemistry, Iron carbide, Iron pentacarbonyl,
Ferrocene, Nanoparticles

I. INTRODUCTION
Iron carbide nanoparticles of various compositions havebeen studied extensively due to their magnetic properties.
Recently, Fe/Fe3C nanoparticles were synthesized bysonicating iron pentacarbonyl Fe(CO)5 in diphenylmethaneand subsequent annealing [1]. But the mechanism of thesonochemical reaction and the effect of annealing are yet to
be investigated. In this study, we performed sonolysis of
Fe(CO)5 in diphenylmethane and both the as-preparednanoparticles and the particles after annealing were measured.
The similar experiments were performed using ferrocene
FeCp2 in order to investigate the difference of the products
depended on precursors.
II.

EXPERIMENT

0.1mol of Fe(CO)5 in diphenylmethane was irradiatedusing a high intensity ultrasonic horn (Ti-horn, 20 kHz) underargon flow for 1 h. 15 mmol of FeCp2 in diphenylmethane
was also sonicated under argon flow for 6 h. After thesonication, the products were centrifuged, washed withhexane and dried in vacuum. The product was annealed underargon flow for 2 h. The product was investigated by
Mössbauer spectroscopy, X-ray diffraction (XRD), andtransmission electron microscope (TEM).
III. RESULTS AND DISCUSSION
Nanoparticles were produced by sonolysis of Fe(CO)5 in
diphenylmethane. Mössbauer spectra were measured at 293 K
and 7 K, and there observed only one doublet; � = 0.35 mm/s,
�Eq = 0.94 mm/s at 293 K and � = 0.48 mm/s, �Eq = 0.94mm/s at 7 K. Thus, the product was a paramagnetic
compound. The XRD patterns with broad peaks and the TEM
images showed that the nanoparticles were amorphous. Then,the sample were annealed at 300 °C, also the Mössbauer

spectrum exhibited a doublet (� = 0.35 mm/s, �Eq = 0.88mm/s) at 293 K. However, Mössbauer spectrum measured at
6 K of the sample consisted of two sextets (� = 0.45 mm/s, H= 491 kOe and � = 0.42 mm/s, H = 428 kOe) and a doublet (�= 0.41 mm/s, �Eq = 1.12 mm/s). The some of the XRD
patterns of the sample corresponded to those of Fe3O4. It waspresumed that the particles after annealing consisted of
Fe/O/C. Room-temperature Mössbauer spectrum of thesample annealed at 700 °C showed only one sextet (� = 0.35mm/s, H = 511 kOe) which was assigned to �-Fe2O3.
Next, nanoparticles were produced by sonolysis of FeCp2
in diphenylmethane in order to eliminate the effects ofoxygen in the sample. Mössbauer spectra measured at room
temperature showed a doublet (� = 0.36 mm/s, �Eq = 0.94mm/s) (Fig.1a) while the spectrum measured at 6 K also
showed one doublet (� = 0.44 mm/s, �Eq = 0.98 mm/s).
However, Mössbauer spectrum of the sample after annealing
at 600 °C showed two sextets and a doublet (Fig.1b). The
sextets were assigned to cementite Fe3C (� = 0.20 mm/s, H =211 kOe) and �-Fe (� = 0.02 mm/s, H = 333 kOe). Iron
oxides were not found in the sample produced from FeCp2.
IV. CONCLUSION
Nanoparticles produced by ultrasonic irradiation ofFe(CO)5 in diphenylmethane consisted of Fe/O/C, whereas
the nanoparticles produced by sonolysis of FeCp2 in
diphenylmethane did not contain oxygen. As-preparedparticles were paramagnetic amorphous, and the particles
with magnetic nature were produced after annealing. FeCp2 is
an adequate starting material to produce iron carbide particles.
100.0

Fig.1 Room-temperaturemössbauer spectra of (a)as-prepared nanoparticles
produced by sonolysis of
FeCp2 in diphenylmethaneand (b) the sample after
annealing at 600 °C underargon flow for 2 h.

99.5

99.0

Relative velocity (%)

2

R. Miyatani1, Y. Yamada1, Y. Kobayashi2,3

98.5

100.0
99.5
99.0
98.5
98.0
97.5
-10

-5

0

5

10

Velocity (mm/s)[1]－ 252 －

S. I. Nikitenko, Yu. Koltypin, I. Felner, I. Yeshurun, A. I. Shames, J. Z.
Jiang, V. Markovich, G. Gorodetsky, and A. Gedanken, J.Phys. Chem.
B. 108, 7620-7626 (2004)

24-NPP-02

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

MÖSSBAUER STUDY OF IRON FLUORIDE FILMS PRODUCED BY PULSEDLASER DEPOSITION
1

K. Shiga1, Y. Yamada1, Y. Kobayashi2,3Department of Chemistry, Tokyo University of Science
Department of Engineering Science, The University of Electro-Communications, 3RIKEN

2I.

INTRODUCTION

Pulsed laser deposition PLD in an ambient gas is a very
useful method to produce compound films controlling thecompositions [1-4]. In this study, we performed PLD of Fe
metal in SF6 atmosphere to produce iron fluoride films
deposited onto Al substrates, and their structures andcompositions were investigated. While SF6 is known as aninert gas, it decomposes to produce F atoms in a plasma
plume produced by the laser ablation followed by a
production of iron fluorides.
II. EXPERIMENTAL
A block of Fe metal in a vessel filled with pure SF6 gas
was irradiated using Nd: YAG laser (523 nm, 85 mJ/pulse,
10 Hz) for 110000 pulses, and the laser-evaporated Fe
atoms were deposited onto an Al substrate. The SF6
atmosphere was maintained at a desired pressure between 1
and 5 Pa, and the Al substrate was kept at desired
temperature between 298 and 873 K using a heater. The
synthesized iron fluoride films were investigated by
Mössbauer spectroscopy, powder X-ray diffraction (XRD),
and scanning electron microscopy (SEM).
III. RESULTS AND DISCUSSION
PLD of Fe onto Al substrate at 298 K was performed in a
SF6 ambient gas of 5 Pa to produce an iron fluoride film.
The Mössbauer spectrum of the film was measured at 298
K (Fig. 1a) and only one doublet ( = 0.49 mm/s, Eq =0.58 mm/s) was observed. When the same sample wasmeasured at 6 K (Fig. 1b), Mössbauer spectrum changed toshow a sextet ( = 0.59 mm/s,  = 561 kOe) which was
assigned to FeF3. It was considered that the crystalline sizeof FeF3 in the film was very small showing thesuperparamagnetic nature at a high temperature. The XRD
pattern of the sample showed broad lines, and it was also
confirmed that the film consisted of small crystalline. Next,
PLD of Fe in SF6 of 5 Pa onto the Al substrate at 873 K
was performed. The Mössbauer spectrum of the film

IV. CONCLUSION
PLD of Fe in SF6 gas produced FeF3 or FeF2 films. The
crystalline size in the film was controlled by the substratetemperature while deposition. Composition of films wascontrolled by the pressure of ambient gas.
100.0

Relative Intensity (%)

Keywords – Iron fluoride, Film, Pulsed laser deposition,
Mössbauer spectroscopy

measured at 298 K (Fig. 2a) showed a sextet ( = 0.49mm/s,  = 395 kOe) of FeF3 as well as an unassigned
doublet ( = 0.46 mm/s, Eq = 1.71 mm/s). The crystal
growth on the substrate surface was enhanced by increasing
the substrate temperature while deposition to show the
sextet at 298 K. SEM images of the films revealed that thefilm produced at 873 K had rugged surface because of thecrystal growth, whereas the film produced at 293 K had asmooth surface. Similar experiment was performed at a low
pressure 1 Pa of SF6, and the Mössbauer spectra measured
at room temperature (Fig. 2b) showed a doublet ( = 1.39mm/s, Eq = 2.76 mm/s) of FeF2. The assignments of thefilms were also confirmed by the XRD patterns. The
composition of the films clearly depended on the ambientSF6 pressures.

Relative Intensiy (%)

Abstract – Iron fluoride thin films were produced by a reaction oflaser-evaporated iron atoms with sulfur hexafluoride gas. The
composition of thin films changed varying a pressure of ambient
SF6 gas: FeF3 was obtained at a high pressure while FeF2 was
obtained at a low pressure. It was also demonstrated that the
crystalline size of FeF3 in the film was controlled by the substratetemperature while PLD.

(a)

98.0

100.0

-10 -5

0

5

5 Pa

99.5
100.0

1 Pa

97.0

(b)

99.0

100.0

10

Velocity (mm/s)

Fig.1 Mössbauer spectra of an iron
fluoride film produced by PLD onto
an Al substrate at 298 K in 5 Pa of
SF6 ambient gas. The film wasmeasured at (a) 298 K and (b) 6 K.

-10 -50

5Fig.2 Room-temperature
Mössbauer spectra of iron fluoride
thin films produced by PLD onto
an Al substrate at 873 K.
The pressures of SF6 are indicatedin the figure.

[1] D. Yokoyama, K. Namiki, H. Fukasawa, J. Miyazaki, K. Nomura, Y.
Yamada, J. Radioanal. Nucl. Chem., 272, (2007) 631[2] Y. Yamada, H. Yoshida, K. Kouno, J. Phys.: Conf. Ser. 217, 012096(2010)[3] Y. Yamada, H. Yoshida, Y. Kobayashi, Hyper. Int. 198, (2010) 55[4] R. Usui, Y. Yamada, Y. Kobayashi, Hyper. Int. 205 (2012) 13－ 253 －

10

Velocity (mm/s)

24-NPP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Iron sulfide particles synthesized in liquid phase
R. Shimizu1, Y. Yamada1, Y. Kobayashi2,3Department of Chemistry, Tokyo University of Science2
Department of Engineering Science, The University of Electro-Communications, 3RIKEN
1

Abstract – Iron sulfide particles were prepared by a polyol method
using ferrocene as a precursor. The composition of the particles
changed varying a mixture ratio of 1,2-hexadecanediol and 1octadecanethiol. Iron (III) sulfide (Fe2S3) which has not been
available in normal conditions was obtained.
Keywords – Iron (III) sulfide, Particles, Mössbauer spectroscopy,
polyol method

I. INTRODUCTION
Generally, iron sulfide is stable having divalent iron Fe(II),and few Fe(III) sulfides have been reported. As the iron (III)sulfide have been appeared in an amorphous form, and thus,
the existence has been the subject of discussion. Mössbauer
spectra of Fe(III) sulfide (Fe2S3) was reported in a literature[1], but the crystal structure was not clear. An unstable phase
could be stabilized in a form of small particles. In this study,
we synthesized iron sulfide particles using a polyol method,
and their Mössbauer spectra were measured.
II.

the samples produced under the conditions with HD (Fig. 2bd). Mössbauer parameters of the doublets had the similarvalues of iron (III) sulfide (Fe2S3) reported in the literature[1].
XRD patterns of the samples were shown in Fig. 3, and theyields of FeS, Fe1-xS and �-Fe were in good agreement withthe results obtained by the Mössbauer spectra. Besides thesewell assigned XRD patterns, unassigned XRD patterns wereobserved. The peaks marked ‘X’ in Fig. 3 may correspond to
Fe2S3 with a long-range periodic structure which wereobserved for the first time.
IV.

Iron sulfide particles were prepared by the polyol method.
Iron(III) sulfide (Fe2S3) particles having a long-range periodic
structure were found. The Mössbauer spectra of Fe2S3
showed that it was paramagnetic.

EXPERIMENTAL

A mixture of ferrocene (2 mmol), oleylamine (30 mL), 1,2hexadecanediol (HD), and 1-octadecanethiol (OT) (varying
the mixture ratio of HD / OT = 0 mmol / 8 mmol, 8 mmol / 2mmol, 8 mmol / 4 mmol, 8 mmol / 8 mmol) was heated toreflux for 2 h at 320 °C under a flow of argon. Particles were
washed three times with ethanol and hexane after air cooling.
The synthesized iron sulfide particles were investigated by
Mössbauer spectroscopy, powder X-ray diffraction (XRD),
and scanning electron microscopy (SEM).
III.

CONCLUSION

Fig. 1. SEM images of the iron sulfide
particles synthesized with the molar ratio of
HD / OT (a) 0/ 8 and (b) 8 / 4.

RESULTS AND DISCUSSION

Fig. 1 shows SEM images of iron sulfide particles. Particle
size changed dramatically by a presence of polyol: theparticles produced without HD were ~ 1 �m (Fig. 1a),whereas the particle produced with HD were 100 ~ 200 nm(Fig. 1b).
Fig. 2 shows the Mössbauer spectra measured at room
temperature of iron sulfide particles obtained in various
mixture ratio of HD / OT. The particles produced without HD
were assigned to Fe1-xS (pyrrotite) (Fig. 2a). When the small
amount of OT (2 mmol) was added, two sets of sextet wereobserved, which were assigned to FeS (troilite) and �-Fe (Fig.
2d). Two sets of doublet (� = 0.38 mm/s, �Eq = 0.73 mm/s
and � = 0.44 mm/s, �Eq = 0.47 mm/s) were observed in all

Fig. 2. Room-temperature
Mössbauer spectra of the ironsulfide particles synthesized in a
mixture of HD / OT = (a) 0 / 8,(b) 8 / 8, (c) 8 / 4, and (d) 8 / 2.
[1]

－ 254 －

Fig. 3. XRD patterns of the ironsulfide particles synthesized in a
mixture of HD / OT (a) 0 / 8, (b) 8/ 8, (c) 8 / 4, and (d) 8 / 2.
(�) FeS or Fe1-xS, (�) �-Fe, (×)
unidentified peaks

A. H. Stiller, B. Jack MaCormick, P. Russell, P. A. Montano, J. Am.
Chem. Soc. 100, 2553-2554 (1978)

24-NPP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Mössbauer and XRD studies of NiCuZn ferrites By Sol-Gel auto-combustion
1

Chenglong Lei1, Qing Lin1,2*, Haifu Huang3, Hui Zhang1, Yun He1

College of Physics and Technology, Guangxi Normal University, Guilin 541004, China
Department of Information Technology, Hainan Medical College, Haikou 571101, China
3
Nanjing National Laboratory of Microstructures and Jiangsu Provincial Laboratory for NanoTechnology,,Department of
Physics, Nanjing University, Nanjing 210093, Chinae-mail:hy@gxnu.edu.cn
2

Abstract:
The Ni0.6Cu0.2Zn0.2CexFe2-xO4 ferrites�0�x���85� have been
prepared by Sol-Gel auto-combustion method and we haveinvestigated the effect of impurity CeO2 phase to the microstructureand hyperfine magnetic field in spinel ferrite. The results of XRD
patterns confirm the average crystallite size of samples decreases
with Ce3+ substitution increasing and the lattice parameters vary as afunction of x content. 57Fe Mössbuaer spectra at room temperature
for all samples confirm the [Fe3+- O2--Fe3+] super exchangeinteraction decrease due to cerium substitution. For low temperatureauto-combustion samples it reveals one normal sextet line and one
doublet line x�����������������������-resolved ferromagnetic order.
Lattice defects are determined and Mössbuaer spectrums vary frommagnetic sextet to relaxation doublet at x�����������������������
CeO2 phase. In contrast, the Mössbuaer spectra for the samples
sintered at 800�/3h detect the secondary phase� -Fe2O3 where thecation distribution occurs and it collapses to paramagnetic
doublet(x����������3+ substitution has its maximum limit values ofsuper exchange interaction and high sintering temperature will affectthis interaction.
Keywords: NiCuZn ferrite, Rare earth, Cerium substitution,
Mössbuaer, XRD

I.

Fig.4 and Fig.5 show the Mössbauer spectra (RT) of
Ni0.6Cu0.2Zn0.2CexFe2-xO4 nanocrystalline ferrites measured atroom temperatures , respectively.

RESULTS AND DISCUSSION

We have successfully prepared ferrite system Ce3+ doped
Ni0.6Cu0.2Zn0.2Fe2O4 by Sol-Gel auto-combustion method.
The XRD patterns of ferrite as-brunt and sintered at 800�/3h
powders are shown in Fig.1-3, respectively.

The lattice parameter changes as a function of the cerium
substitution. The Mössbauer spectra (RT) results illustratethat only after low temperature auto-combustion the samples
exhibit ferromagnetism and a super para-magnetism.
[1]

[2]
[3]

－ 255 －

Aphesteguy, J.C., et al., Characterization of nanosized spinel ferrite
powders synthesized by coprecipitation and autocombustion method.
Journal of Alloys and Compounds, 2010. 495(2): p. 509-512.
Nedkov, I., R.E. Vandenberghe, and A. Zaleski, Surface magnetic
disorder in nanostructured Ni0.5Zn0.5Fe2O4 particles. Journal ofMagnetism and Magnetic Materials, 2010. 322(18): p. 2732-2736.
S.I.Moussa, R.R.Sheha, E.A.Saad, N.A.Tadros, Synthesis andcharacterization of magnetic nano-material for removal of Eu3+ ionsfrom aqueous solutions, Journal of Radioanalytical and Nuclear
Chemistry, 2013. 295: 929–935.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

24-NPP-05

Thermal Stability of Locally-Associated Al and In Impurities in Zinc Oxide
1

S. Komatsuda1, W. Sato1,2, and Y. Ohkubo3

Graduate School of Natural Science and Technology, Kanazawa University
2
Institute of Science and Engineering, Kanazawa University
3
Research Reactor Institute, Kyoto University

Abstract – Local structures in 100 ppm Al-doped ZnO were
investigated by means of the time-differential perturbed angularcorrelation method. From distinct perturbation patterns obtained
for the samples annealed in different conditions, we found that the111
In, which is strongly associated with Al ions in ZnO, gradually
breaks the interaction and occupies the defect-free substitutional
Zn site in high-temperature vacuum.
Keywords – Al-doped ZnO, electric field gradient, In-111,
perturbed angular correlationI.

INTRODUCTION

Zinc Oxide (ZnO) doped with group 13 elements (Al,Ga, In) as impurity donors is expected to be applied tofunctional devices as n-type semiconductors. For apractical use of ZnO as a conduction-controlling device, it
is of great importance to study the physical and chemical
states of the dilute impurity ions in ZnO. The timedifferential perturbed angular correlation method (TDPAC)
is very suited for that purpose because it can directly
provide atomic-level information of impurity atoms. In ourprevious TDPAC studies, we found that Al ions and 111In
probe doped in ZnO can form local associations even at
extremely dilute concentrations[1]. In this work, we haveinvestigated the stability of the interaction between Al and
In impurities in various conditions.

perturbed by the outer surrounding field. This spectrum
shows that 100 ppm Al and 100 ppt 111In are locallyassociated in ZnO matrix, suggesting that there is a strong
attractive force between Al and In in ZnO[1]. Figure 1(b)and 1(c) show TDPAC spectra obtained for the samples
annealed in vacuum at 1023 K and 1173 K respectively, for
24 h after the probe was doped. For the spectrum in Fig.
1(b), two different components appearing in the spectra for
the Fig. 1(a) and undoped ZnO[2] were observed. The
component appearing in the spectrum for undoped ZnO has
become more visible in Fig.1 (c). These observations
imply that in high-temperature vacuum, the probe resides
solely at the substitutional Zn site being independent of the
field produced by Al ions. Showing TDPAC spectra of thesamples annealed in various conditions, we discuss thestability of locally-associated Al and In impurities doped in
ZnO.
-0.2
-0.15

(a)

-0.1
-0.05
0
0.05
-0.15

R (t)

II. EXPERIMENTS
For the synthesis of 100 ppm Al-doped ZnO,
stoichiometric amounts of Al(NO3)3 � 9H2O and ZnO
powder were mixed in ethanol. The suspension was heatedto evaporate the ethanol until dryness. The powders werepressed into disks and sintered in air at 1273 K for 3 h. For
TDPAC measurements, commercially available 111In
solution was added in droplets onto each of the sintereddisks at the concentration of 100 ppt. The disks again
underwent heat treatment in air at 1373 K for 2 h. Then thedisk samples were ground into powder, and sealed in aquartz tube in vacuum respectively.
The samples
underwent further heat treatment in vacuum at 1023 K and
1173 K for 24 h. The TDPAC measurements were carriedout for the 171-245 keV cascade � rays of 111Cd(�111In)
probe with the intermediate state of I = 5/2 having a halflife of 85.0 ns.

(b)

-0.1

-0.05
0
0.05

-0.15

(c)

-0.1
-0.05
0
0.05
0

50

100

150

200

Time (ns)

250

300

Fig.1 Room temperature TDPAC spectra ofCd(�111In) embedded in 100 ppm Al-doped
ZnO annealed (a) in air at 1373K, (b) in vacuum at1023 K, and (c) in vacuum at 1173K.

111

III. RESULTS[1]

Figure 1(a) shows a TDPAC spectrum obtained for the
sample heat-treated in air. The directional anisotropy, R(t),is plotted as a function of the time interval between the
cascade �-ray emissions, t, during which the probe is[2]－ 256 －

S. Komatsuda, W. Sato, S. Kawata, and Y. Ohkubo, J. Phys. Soc.
Jpn. 80, (2011) 095001.
W. Sato, Y. Itsuki, S. Morimoto, H. Susuki, S. Nasu, A. Shinohara,
and Y. Ohkubo, Phys. Rev. B 78 (2008) 045319.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

24-NPP-06

Structure and Antimony-121 Mössbauer Spectra of Hypervalent Antimony
Compounds with an Antimony–Gold Bond in Equatorial Position
Masashi Takahashi, Asumi Sato, Shiro Matsukawa
Department of Chemistry, Toho University
Funabashi, Chiba 274-8510 Japan

Abstract – Hypervalent antimony compounds having Sb–Au bondin equatorial position are studied. [Rf2SbAu(PPh3)2] (Rf =C6H4C(CF3)2O–) has a short Sb–Au bond (2.6813 Å). 121Sb
Mössbauer spectrum of [Rf2SbAu(SMe2)] indicates a large
electron density along the Sb–Au bond. These results suggests a
dative interaction of the gold fragments to hypervalent antimony
atom.
Keywords –Mössbauer Spectroscopy, Hypervalent Compound,
Dative Bond, Antimony, GoldI.

three coordinated gold atom. The antimony atom adopts
trigonal bipyramidal geometry as expected. The Sb–Au
length (2.6813 Å) is shorter than that of (1) (2.7086 Å).
The Sb–O and Sb–C lengths are slightly longer than thoseof 2. The O–Sb–O and C–Sb–C angle is almost the same tothose of 2. These results suggest the high electron density
along the equatorial Sb–Au bond due to the strong electron
donation from gold atom. Two phosphine ligands at gold
atom should afford the electron density to Sb atom
effectively and might stabilize the Sb–Au bond.

INTRODUCTION

Since the first report on the ruthenaboratrane, in which
the boron atom at the pivot position of a tripodal ligand
acts as the Lewis acid [1] , unconventional metal to ligand
donation (M��) attracts keen interests. Although theinvestigations are mostly carried out using the electron
deficient borane ligands such as RnB(C6H4PR’2)3–n, theheavier main group elements such as phosphorus, antimony,silicon and tin can be used as the Lewis acidic point
because these elements accept the electron pair to form
hypervalent compounds. Indeed quite recently Wade andGabbai have demonstrated such M�� interactions using[(C6H4PPh2)3 SbAuI] (1) [2]. On the other hand we havealready suggested that the existence of electron flow fromorganometallic fragment to antimony atom in thehypervalent antimony compounds Rf2SbMCpLn [M = Fe,
Ru, Cr, Mo, W; L = CO, PPh3 etc; Rf = C6H4C(CF3)2O–](2) using 121Sb Mössbauer spectroscopy. [3] These results
inspired us to extend our investigation to the Au fragments.
II. EXPERIMENTAL
material: Rf2SbAuL (L = SMe2, PPh3) were prepared by
the reaction of [Rf2Sb]– with AuLCl using a modified
method for [Rf2SbFeCpLn]. The compounds werecharacterized using 1H, 19F and 31P NMR.
Structural determination: X-ray diffraction data werecollected on a SMART APEX (Bruker) at 150 K. Data
were processed as routine.
121
Sb Mössbauer spectrum: Mössbauer spectrum wasmeasured at 20 K using a Ca121SnO3 source on a
Mössbauer measurement system from Wissel (MDU-1200,
DFG-1200, MVC-450, CMCA-550). The spectrum wasanalyzed using a MossWin software. The value of theisomer shift was given relative to InSb.

Figure 1 Crystal Structure of [Rf2Sb–Au(PPh3)2] Sb–O = 2.1095, 2.1237;
Sb–C = 2.123, 2.123 Å; O–Sb–O = 161.75; C–Sb–O = 107.10°.

Fig. 2 shows the Mössbauer spectra of [Rf2SbAu(SMe2)](3). As expected 3 has a large negative quadrupole coupling
constant (–23.91 mm s–1) and a large asymmetry parameter(0.67). The isomer shift value (2.63 mm s–1) is anintermediate value between typical Sb(V) and Sb(III)complexes.
The Mössbauer
parametersindicateconsiderable electron density is present along the Sb–Au
bond, suggesting a strong electron donation of gold atom.

Figure 2 121Sb Mössbauer spectrum of [Rf2SbAu(SMe2)] at 20 K.

III. RESULTS AND DISCUSSION
The reaction product with AuCl(PPh3)2 was confirmed
to be [Rf2SbAu(PPh3)2] (Fig. 1), which has unexpectedly a

[1]
[2]
[3]

－ 257 －

Hill, A. F. et al. Angew. Chem. Int. Ed. 1999, 38, 2759.
Wade, C. R.; Gabbai, F. P. Angew. Chem. Int. Ed. 2011, 50, 7369.
Takahashi, M. et al. Z. Naturforsch. 2001, 57a, 631.

24-NPP-07
APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013��������������� �������������������������������������������
Jun Miyazaki1, Takashi Nagatomo2, Yoshio Kobayashi3, 4, Michael K. Kubo5, Yasuhiro Yamada6,
Mototsugu Mihara7, Wataru Sato8, Kazuya Mae5, Shinji Sato9, Atsushi Kitagawa9
1

College of Industrial Technology, Nihon University
J-PARC Center, High Energy Accelerator Research Organization
3
Department of Engineering Science, The University of Electro-Communications
4
RIKEN Nishina Center for Accelerator-Based Science, RIKEN
5The Division of Arts and Sciences, International Christian University
6
Department of Chemistry, Tokyo University of Science7
Department of Physics, Osaka University
8
Institute of Science and Engineering, Kanazawa University
9
Department of Accelerator and Medical Physics, National Institute of Radiological Sciences
2

Keywords Ð In-beam Mšssbauer Spectroscopy, �-decay of
Lithium hydride, DFT Calculations

I.

Mn,

57

INTRODUCTION

In-beam Mšssbauer spectroscopy is a powerful technique
to obtain the direct information on exotic chemical or
physical state of the nuclear probe that was implanted into thesample such as metal or inorganic solid. Lithium hydride(LiH) is an ionic solid having the rock salt type crystal
structure in which one Li+ cation is surrounded by six Hanions. In our previous study1, we reported the in-beam
Mšssbauer spectra of 57Mn implanted into LiH from room
temperature to over 800 K. In this study, we report the
spectra under room temperature and discus the local structureof 57Mn/57Fe implanted into LiH.
II. EXPERIMENTAL
The measurements were performed using Heavy Ion
Medical Accelerator in Chiba (HIMAC) at National Instituteof Radiological Science (NIRS) in Chiba, Japan. 57Mn beam
(E =~ 260A MeV) was produced from the projectile fragmentprocess of nuclear collisions between 58Fe ions (500A MeV,
� 1 � 106 particles per beam) and 9Be nuclei in a 27 mm thickproduction target. The beam pulse was generated every 3.3 swith a ~300 ms duration and with 1 � 106 particles/pulse.
The energy of the 57Mn nuclei was adjusted using energy
degraders to stop the ions at an appropriated depth in thesample. The polycrystalline LiH (Wako Pure Chemical) was
mounted on a cold finger or BN heater in a vacuum chamberin order to control the sample temperature from 11 K to over800 K. A parallel-plate avalanche counter (PPAC) was
employed as a detector. The anti-coincidence method thatuses a plastic scintillation detector to detect and rejectextraneous �-rays was employed to obtain high-quality inbeam Mšssbauer spectra with improved S/N ratios.
III. RESULTS AND DISCUSSION
In-beam Mšssbauer spectra of 57Mn/57Fe implanted into
LiH at 11, 274, 294 K were shown in Fig. 1. Obtained
spectra were fitted with some single lines and doublet lines.
In the spectra at 3 temperatures, the single line peaks of S (IS= -0.54 mm/s) and SÕ (IS = 0.07 mm/s) were observed. As
compared with the result from DFT calculations, S is
assigned to be in 57Fe at the substitutional Li site and SÕ is
assigned to be in 57Fe at the stubstitutional H site in LiH
crystal. Symmetrical doublet peaks of D1 (IS = -0.59 mm/s,
�EQ = 0.57 mm/s) and DÕ (IS = -0.03 mm/s, �EQ = 0.58mm/s) were also observed, and new doublet peak of D2 (IS =-0.60 mm/s, �EQ = 2.34 mm/s) was observed at 11K (Fig.1c).
In the result from DFT calculations, doublet peaks are
assigned to be in 57Fe at the substitutional Li or H site with aneighboring atom deficiency. The temperature dependenceof the relative intensities in this study suggests that the latticedefects recover with an increase temperature.

��������������������

Abstract Ð We report the in-beam Mšssbauer Spectra of 57Mn
implanted into polycrystalline LiH at under room temperature. As
compared with the result of DFT calculations, 57Fe atoms were
implanted into Li or H substitutional site in LiH crystal. With anincrease the sample temperature, we could observe the decrease oflattice defects.

S
D1

�
�
�
�
�
�
�
�
�
�
�
�
�

SÕ

��������
DÕ

D2

��

��

��������

���������������������������

�

Fig.1 In-beam Mšssbauer spectra of 57Mn implanted into LiH[1]－ 258 －

T. Nagatomo et al., Hyperfine Interact, ���, 125-128 (2012)

24-NPP-08

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Evaluation of Vacancy-Type Defects in ZnO
by the Positron Annihilation Lifetime Spectroscopy
1

R. Ono1, T. Togimitsu1, and W. Sato1,2

Graduate School of Natural Science and Technology, Kanazawa University
2
Institute of Science and Engineering, Kanazawa University

Abstract – Annealing-temperature dependence of the formation ofvacancy-type defects in ZnO has been studied by means of thepositron annihilation lifetime spectroscopy. It was found that the
lifetime does not drastically change for ZnO samples annealed at
the temperature range below 600 � , whereas annealingtemperature dependence of the lifetime was observed above 600�,showing the minimum value at 1000�.
Keywords – positron annihilation lifetime spectroscopy, ZnO,
annealing effect, vacancy, grain boundaryI.

INTRODUCTION

Zinc oxide (ZnO) is an intrinsic n-type semiconductor
having optoelectronic properties. Because vacancy-type
defects brought about in the formation process of ZnO is
known to affect the intrinsic properties, for futureapplications, it is important to understand various behaviors
of defects in ZnO such as generation, recovery,
agglomeration and diffusion. For the evaluation of theirvacancy-type defects, positron annihilation lifetime
spectroscopy (PALS) is one of the most powerful methods
and we have applied this spectroscopy to part of our studies
on local structures of ZnO. In the present study, we
examined annealing-temperature dependence of positron
lifetime to evaluate the concentration and size of vacancytype defects formed in ZnO.

originate from self absorption in the source materials, andComponent 3 corresponds to positron annihilations in the
ZnO samples. The lifetime of Component 3 is the averageof those in the bulk and defects in ZnO samples. It is
obvious from the slopes of the decay curves of Component
3 that the lifetime of positrons in ZnO annealed at 1000�
is shorter than that for 600�. The short lifetime can be
explained as a result of the recovery of vacancy-type
defects. Particle growth arising from the heat treatment
may be another cause of the lifetime shortening because theamount of vacancy-like defects present in grain boundaries
is considered to become less by the phenomenon. The
positron lifetime, to the contrary, increases in ZnO samples
annealed at temperatures above 1000�. The reason for theincrease has not been understood yet. For the total
understanding of the defect formation process, further dataacquisition at other sample-preparation conditions is now
underway.

II. EXPERIMENTS
Polycrystalline ZnO powders (purity 99.99%) werepressed into pellets at 75 MPa. They were annealed in air atdifferent temperatures ranging from 200 to 1200� for 2h.
A 22Na (as in NaCl) positron source covered with Kapton
film was sandwiched with the sample disks. Positronannihilation lifetime was measured with a conventional
circuit at room temperature. BaF2 scintillators were used forthe detection of 1275- and 511-keV � rays.
III. RESULTS
It was found from the PALS measurements that the
lifetime does not drastically change for ZnO samples
annealed at the temperature range between 200 to 600�.
However, obvious temperature dependence was seen for
those annealed at higher temperatures. In Fig.1 is shown
the PALS spectra obtained for the ZnO samples annealed(a) at 600� and (b) at 1000�. The spectra reproduced by
the lines named A are made up of three different decay
components as numbered 1-3. Components 1 and 2－ 259 －

Fig.1 PALS spectra for ZnO pellets annealed (a) at 600� and (b) at
1000�.

24-AAP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of ultratrace-levels of 99Tc using ICP-QMS in the low level radioactive
waste samples
Te-Yen Su, Tsuey-Lin Tsai, Hsin-Chieh Wu, Lee-Chung Men

Chemistry Division, Institute of Nuclear Energy Research, Longtan, Taoyuan 32546, Taiwan, R.O.C.
Abstract –A rapid, accurate and less labor intensive approach wasdeveloped to determine 99Tc in the low level radioactive wastes(LLW). Only 0.1 g of solid radwastes was firstly dissolved using
microwave digestion and then the specific TEVA resin was used forchemical separation to remove most of the matrices piror toinductively coupled plasma- quadrupole mass spectrometry (ICPQMS) measurement. The minimum detectable activity (MDA) of
ICP-QMS for the determination of 99Tc in LLW samples was 8.5
mBq g-1 (13.6 pg g-1), which was comparable to that of doublefocusing magnetic sector field inductively coupled plasma mass
spectrometry (ICP-SFMS), 5.3 mBq g-1. The sensitivity of the ICPQMS method for the determination of 99Tc was much superior tothat of the alternative radiochemical methods (e.g., liquid
scintillation analyzer; LSA) when accounting for the dataacquisition time for identical, low-concentration samples.
Approximately 88 % of the chemical recovery was achieved and thisdeveloped technique was successfully applied to LLW samples for99
Tc measurement within 5 minutes.
Keywords –99Tc; inductively coupled plasma-quadrupole mass
spectrometry (ICP-QMS); low level radioactive wastes (LLW)－ 260 －

24-AAP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Development of an Automatic Prompt Gamma-ray Activation Analysis System
1

Takahito OSAWA1

Neutron Imaging and Quantum Beam Analysis Group, Quantum Beam Science Directorate,
Japan Atomic Energy Agency (JAEA),

Abstract – An automatic prompt gamma-ray activation analysis
system was developed and installed at the Japan Research Reactor
No. 3 Modified (JRR-3M). The main control software, referred to as
AutoPGA, was developed using LabVIEW 2011 and the hand-madeprogram can control all functions of the analytical system. The coreof the new system is an automatic sample exchanger andmeasurement system with several additional automatic control
functions integrated into the system. Up to fourteen samples can be
automatically measured by the system.
Keywords – Prompt gamma-ray analysis; Automatic analysis;
Revolute robot; LabVIEW

Prompt gamma-ray analysis (PGA) using a neutron beam
generated by a nuclear reactor is a convenient andnondestructive elemental analytical technique. PGA can be
widely used in various science and technology fields [e.g. 1],
because the analytical methods have high sensitivity forcertain specific light elements.
The PGA system at the JRR-3M at the Japan Atomic
Energy Agency (JAEA) was constructed in 1992 [2].
Although the system using cold and thermal neutron beams
achieved a very low gamma-ray background level, it was
outdated because no improvements had been made since its
construction. In this study, an automatic system for PGA wasdeveloped in order to update the old analytical system andimprove its measurement efficiency.
The new automatic PGA system is mainly composed of
two computers (PC1 and PC2), four programs, a six-axis
vertical revolute joint robot (Mitsubishi RV-3SD, Fig.1), anddata acquisition devices. Although the inside of the shielding
body is not changed most of the devices and systems on theoutside of the shielding body are completely improved in thiswork. The core of the new system is an automatic sample
exchanging and measurement system, and several automatic
control functions: such as helium flow control, neutron flux
recording, internet functions, and machine vision, have been
integrated into the system.
In the system, fourteen samples hung on the center ofTeflon frames with Teflon strings that can be placed onto asample stand. Each sample frame is selected and introduced
into a Teflon sample box using a revolute joint robot.
Opening and closing of the loading hatch is enabled withcompressed air and air bulbs that are controlled using a
digital output module. A physical interlock on the loading
hatch that synchronizes with the neutron beam shutter isoperated by a single-pole single-throw relay, and the relay
can also control the opening and closing of the neutron beam
shutter.

Fig.1 A revolute joint robot of the automatic PGA system

A robot sequence program written in MELFA BASIC V
was designed by the author. The AutoPGA program isinstalled in PC1 and controls the entire series of automatic
analytical operations. When the user clicks the start button
AutoPGA starts the servomechanism of the robot and initiates
the sequence program. It then closes the neutron beam shutter,releases the interlock, and opens the loading hatch. When themachine vision system judges that the lid is not placed in thecorrect position, the sequence program stops working. The
robot begins operating, and the Teflon lid on the Teflon
sample box is removed and placed on a lid stand. The robot
selects the sample frame and introduces it into the sample box
and then places the lid on the sample box. The loading hatch
is closed, the neutron shutter is opened, and the measurement
is begun. An existing measurement program (SEIKO EG&G
Spectrum Navigator) is installed in PC2 and is used for themeasurements. In the automatic analysis, a batch processing
mode is utilized that calls a communication program (PGATalk created by the author) after each measurement. PGATalk sends a signal to PC1 via TCP, and AutoPGA
recognizes the completion of the gamma-ray recording andbegins to exchange the sample. When the sample exchange iscomplete, AutoPGA sends a signal to PC2 and PGA-Talk is
automatically shut down. Spectrum Navigator then begins themeasurement of the next sample.
[1][2]－ 261 －

T. Osawa, Y. Hatsukawa, P. W. U. Appel, H. Matsue, Nucl. Instrum.
Meth. Phys. Res. B 269 (2011), pp. 717-720.
C. Yonezawa, A.K.H. Wood, M. Hoshi, Y. Ito and E. Tachikawa, Nucl.
Instr. and Meth. A 329 (1993), pp. 207-216.

24-AAP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Concentration of Heavy Metal Elements in Chinese Medicine by INAA
S. Ishihara1, E. Furuta2, N. Iwasaki1, Y. Yoshihara3, R.Okumura4, Y.Iinuma4
1

Ochanomizu University, Facility of Sciences
Ochanomizu University, Graduate School of Humanities and Sciences3
Ochanomizu University, Facility of Human Life and Environmental Sciences
4
Kyoto University, Research Reactor Institute2

Abstract – An instrumental neutron activation analysis of Chinese

medicines and medicinal herbs was performed, in which they havepossibilities to contain toxic elements. By the preliminary
experiments, there were some medicines that arsenic and mercury
were included by observing gamma-ray spectroscopy with neutron
irradiation. The Chinese medicine can be purchased through theInternet easily; however, it is considered that some regulations may
be necessary.
Keywords – Chinese medicine, Arsenic, Mercury, INAAI.

INTRODUCTION

III. RESULTS
Table shows the results of 4 elements in the samples fromroute-1. Among 12 kinds of Chinese medicines, 6 kinds ofthem included As, and 5 kinds of them included Hg. On theother hand, these 4 elements were not included in 2 of them.
Other elements detected were sodium, potassium, calcium,
scandium, iron, manganese, lanthanum, and selenium andthese elements were included a few ten ppm except for
calcium of a few thousand ppm.
Table

Chinese medicine is used all over the world because of its
safer image than Western pharmaceutical products. It is
possible to purchase everywhere through the Internet.
However, a few reports mentioned some of them included
some kinds of toxic elements like arsenic (As), lead (Pb),mercury (Hg) and cadmium (Cd) [1]. Chinese medicines andmedicinal herbs may be taken in continuously for a long term.
So, if they include some toxic elements, it develops a healthproblem. Therefore, many kinds of Chinese medicines andmedicinal herbs which can be purchased in an Asian area
were analyzed by neutron activation at the KUR for the
purpose of clarifying the actual situation. The preliminary
experimental results were shown in the presentation.

Sample�����
Niuhuang Jiedu Pian���
Fluit, Lonicera�����Shiquan Dabu Wan�����
Tenma Shouwu Pian���
Cannabis sativa
��� (Musk)
Liu Shen Wan
����
Weiqitong Pian�����
Hou –Hashi
�����
Muxiang Shunqi Wan
�����
Rehmannia glutinosa

II. EXPERIMANTAL
Many kinds of Chinese medicine and medicinal herbs
were purchased from 5 routes to analyze the heavy metalelements; 1. 12 kinds of Chinese medicines were sold with aprescription by a hospital doctor in China; they were not soldto public in a market, 2. 8 kinds of Chinese medicines werebought through the Internet from China, 3. 11 kinds ofChinese medicines were bought at a market of Korea, 4. 47
kinds of medicinal herbs were bought at a market of Vietnam,
and 5. 25 kinds of Chinese medicines were bought at a
medical corner of a super market in Japan; they were
produced in Japan. Each of them was enclosed almost 100
mg in a double polyethylene bag. The standard samples usedwere JA-2 and JR-2 of rock standard. The samples were put
in capsules with standards and irradiated 5MW × 10 min or
1MW × 30 min at KUR. After cooling among 5 days, thecapsules were opened to take out samples, each sample was
enclosed in a new polyethylene bag, and then started
measurement of medium and long half-life radionuclides.

Four elements concentrations in 10 Chinese
medicines (ppm)

IV.

51

Cr

60

Co

76

As

203

Hg

7.1%
8.0

1.1

3.3

1.6
1.8

1.7
1.9
47

76

1.8

6.7%

6.7%

14

3.8

2.8
1.4

4.9
1.6

CONCLUSION

Some of Chinese medicines included high concentrationof toxic elements such as As and Hg. It is considered that aregulation how to sell or a limitation of the purchase method
is necessary.
[1]－ 262 －

Agilent Technologies; www.agilent.com/chem/jp

24-AAP-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Application of instrumental neutron activation analysis to assess dietary intake ofselenium in Korean adults from meat and eggs
Jong-Hwa Moon1, Sun-Ha Kim1, Yong-Sam Chung1, Ok-Hee Lee2

1

Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon, 305-353, Korea
Dept of Food Science and Nutrition, Yongin University, 470, Samga-dong, Cheoin-Gu, Yongin, 449-714, Korea

2

Abstract – Selenium is a key constituent of enzyme in glutathione
peroxidase, which is effective in decreasing various types ofoxidative stress, Thus, the adequacy of selenium intake is very
important in decreasing the risks of various degenerating diseases
such as cardiovascular disease, or certain cancers. Lately, theintake of animal foods is increasing among Koreans owing to a
dietary transition toward a western style. This study was
conducted to measure the selenium content in meat and eggs, andthen assessed the selenium intake from these foods. Forty
frequently eaten items among meat and eggs were analyzed using
an Instrumental Neutron Activation Analysis. The selenium
content in 100g of raw meat and eggs ranged from 8.1ug to
50.9ug. In particular, 100g of beef contained 12.4ug to 50.9ug ofselenium; pork, 11.2ug to 22.6ug chicken, 10.2ug to 13.7ug andeggs, 28.6ug to 43.0ug. Thus, beef viscera and chicken eggs
contain the highest amounts of selenium among these groups.
100g of Pork belly, the most frequently eaten meat type among
Koreans, contains 14.6ug of selenium. An evaluation of dietary
selenium intake shows that the total selenium supply from meats
and eggs was 28.4ug/day and 27.5 ug/day in adult men andwomen, respectively. These are over one-half of the Korean
RNI(Recommended Daily Intake) of 55ug/day.
Keywords–Instrumental Neutron Activation Analysis, Selenium,
Meat and Eggs, Dietary Intake

I.

INTRODUCTION

As the biological activity of food selenium in humans isdependent, sometimes to a very large degree, on the source
and chemical form of the selenium consumed, an increased
intake of animal food can facilitate meats and eggs asimportant sources for selenium intake in Koreans.
Considering these points, an evaluation of selenium intake
in Koreans from animal foods is very important. This study
was conducted to analyze the selenium contents in meats
and eggs, and to assess the consumption pattern ofselenium in Koreans from these animal foods.

III. RESULTS
The selenium contents in the different parts of beef wereranged from 12.4ug to 50.9ug in 100g of the edible portions,where the highest value was shown with beef liver. The
selenium contents in raw Korean pork ranged from 11.2ug
to 22.6ug in 100g of food, showing a difference according
to the pork region. Pork belly, the most frequently eatenmeat among Koreans, contained selenium at an amount of
14.6ug at 100g. The raw chicken contained selenium with arange of 10.2ug to 13.7ug in 100g, showing only a small
difference by the chicken part. The selenium contents in thefrequently eaten eggs were in the range of 28.6ug 43.0ug
for 100g. Eggs were distinct in that they contained thehighest amount of selenium among the meats with a rangeof 38.9ug to 43.0ug for chicken eggs, and of 28.6ug for thequail egg per 100g of eggs. The processed pork products
contained selenium in a range of 8.8 - 14.9 ug for 100g,
which is lower than the raw unprepared pork meat. Amongthe pork products, Pyeonuk and pork hocks, cooked pork
products, showed selenium contents of 19.4 and 21.1ug for
100g, respectively. The prepared chicken, mostly from fast
food eateries, contained selenium in a range of 7.4 to
11.5ug for 100g. An evaluation of dietary selenium intake
shows that the total selenium supply from meat and eggs
was 28.4ug/day and 27.5ug/day in adult men and women,
respectively. These are over one-half of the Korean RNI(Recommended Daily Intake) of 55ug/day.
ACKNOWLEDGEMENT
This work was carried out under the Nuclear Researchand Development Program of the Korean Ministry of
Education, Science, and Technology.
REFERENCES

II. EXPERIMENTAL
The number of meat items used in the selenium analysis
was 13 items for raw beef, 8 items for raw pork, 3 items for
raw chicken, 4 items for raw eggs, and 12 items for theprocessed meat products, respectively. Most of the foods
were bought between September 2009 and February 2010.
All domestically produced and imported meats and eggs ina raw or processed state were purchased from markets witha nationwide network around Seoul and Keunggido. The
meat sample was ground using a blender with a titanium
blade, and freeze-dried in a lyophilizer at various times of
24 - 96 hours. The analysis of selenium was performed byinstrumental neutron activation analysis using the
HANARO research reactor.

[1]
[2]

－ 263 －J Rotruck JT, Pope AL, Ganther HE, Swanson AB, Hafeman DG,
Hoekstra WG. Selenium: biochemical role as a component ofglutathione peroxidase. Science 1973, 179:588-90.
The Korean Nutrition Society, Dietary Reference Intake for Koreans,
Seoul, 2010, p 481-97.

24-AAP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Evaluation of Hypoxia at Dredged Trenches in Tokyo Bay by Determination ofRedox Sensitive Elements in the Sediments
T. Yamagata1, K. Shozugawa1, R. Okumura2, K. Takamiya2, M. Matsuo1
1

Graduate School of Arts and Sciences, The Univ. of Tokyo
2
Research Reactor Institute, Kyoto Univ.

Abstract – Sediment samples were collected from Tokyo Bay, andthe concentrations of some elements were determined byinstrumental neutron activation analysis (INAA).Though hypoxia
has been observed in dredged trenches, it is suggested that upper
layers of the sediments are more oxidative than lower layers.
Keywords – Hypoxia, Sediment in Tokyo Bay, Instrumental neutron
activation analysis (INAA)I.

out depending on half-lives of elements. For analysis of U,
samples were irradiated for 20 min at 1 MW or 4 min at 5
MW, and then gamma-ray was measured for 1200 seconds(live time) by Ge detector after 3 days cooling. Regarding Th
and Ce, samples were irradiated for 20 min at 1 MW or 4 min
at 5 MW, and the measurement time of gamma-ray was for
9000 seconds (live time) after 3 weeks cooling.
III. RESULTS AND DISCUSSIONINTRODUCTION

Hypoxia is water mass contained little dissolved oxygen(DO) (< 2 ml of O2 / liter) [1], which is known as dead zone
in coastal sea. At the seabed in Tokyo Bay, large-scale
dredging operations had been done in 1970s. In particular, thedredged trenches off Makuhari have the maximum area anddepth. In dredged trenches severe hypoxia has been observedin annual summer seasons, and the hypoxia has disappearedin winter. But the influence of dredged trenches on hypoxia is
not revealed yet. Therefore, it is important to estimate theinterannual variations of hypoxia by analyzing sediments.
To evaluate the sedimentary environment such as redox
conditions, the method using the Th/U-Ce/U plot based on
the data obtained by INAA was reported by Honda et al [2].
It is very useful because the correlation coefficient between
the Th/U and Ce/U ratios is high, but it hasn’t been used forevaluating the sedimentary environment at dredged trenches,
where the conditions are unique. In this study, sediment cores
were collected from the Makuhari dredged trenches in Tokyo
Bay. Concentrations of U, Th, and Ce in the sediments wereanalyzed by INAA. And then the sedimentary environment is
discussed in connection with the depth profiles of theelements and the Th/U-Ce/U plot.

The DO in the seawater at dredged trenches and referencesite (non-dredged area) indicated the similar vertical
distribution at each station. From the depth of 8 m, the DO
decreased suddenly. And below the depth of 10 m, the water
became anoxic in dredged trenches. It turned out that strong
hypoxia has developed at the dredged trenches.
From the depth profiles in dredged trenches, the Th/U andCe/U ratios are higher in the upper layers than in the lower
layers. It is said that the concentrations of Th and Ce in
sediments increase when condition of seawater is oxidative.
On the other hand, the concentration of U increases whencondition is reductive. It is considered that the sedimentary
environment of the upper layers is more oxidative than thelower layers.
Figure shows the Th/U-Ce/U plots of the sediments. The
correlation coefficient between the Th/U and Ce/U ratios ishigh enough. Therefore, this method is also useful forevaluating the hypoxia at dredged trenches, in which theenvironment changes drastically on each summer and winterseason.

II. EXPERIMENTAL
The sediment samples were collected at dredged trenches(water depth 25.5 m and 18.9 m) and reference site (nondredged seabed, water depth 10.7 m) off Makuhari in Tokyo
Bay on August 2012. Sediments were collected by a coresampler at each point. Water quality data were also obtainedby a multichannel water quality meter and an oxidationreduction potentiometer. All cores were cut in the verticaldirection at 0.6 – 3.0 cm intervals after freezing.
Approximately 30 mg of freeze-dried sediments were
packed in double polyethylene film bags. All samples were
irradiated at the pneumatic tube, Kyoto University Reactor(KUR). Two types of gamma-ray measurement were carried

Fig. Th/U-Ce/U plots of the sediments collected from Tokyo Bay[1][2]－ 264 －

R. J. Diaz and R. Rosenberg, Science, 321, 926-929 (2008).
T. Honda and K. Kimura, Bull. Soc. Sea Water Sci., Japan, 57, 166-180(2003) (in Japanese).

24-AAP-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of ultra trace amounts of Mn in iron meteorites by preconcentration
neutron activation analysis
1

Y. Tanaka1, Y. Arai1, T. Imamura1, Y. Oura1

Department of Chemistry, Tokyo Metropolitan University

I.

INTRODUCTION

Meteorites contain cosmogenic nuclides produced by anuclear reaction with cosmic rays. Cosmogenic nuclides areuseful for determination of exposure and terrestrial ages. In
general, only radionuclides and noble gas stable-isotopes canbe detected as cosmogenic nuclides. Although it is difficult to
detect cosmogenic stable nuclides in stony meteorites, somecosmogenic stable nuclides could be detected in ironmeteorites, which consist of mainly an iron–nickel alloy,
since iron meteorites have little geochemical lithophileelements. Among such stable nuclides we focus on Mn.
Natural Mn is a monoisotopic (55Mn) element. But ironmeteorites have also a cosmogenic radioisotope, 53Mn, which
has longest half life among detectable cosmogenic
radionuclides. One of practical methods for determination of53
Mn is a preconcentration neutron activation analysis(preNAA) using 53Mn(n, �)54Mn reaction. We suggested that55
Mn content should be required for determination of ultra
trace 53Mn in iron meteorites by preNAA because ofcorrection of 55Mn(n, 2n)54Mn. But accurate concentration iniron meteorites is rarely reported. Almost 53Mn in ironmeteorites is extrapolated to be comsogenic by 45Sc contents[1]. If accurate 55Mn concentration can be determined, 55Mn53
Mn system for exposure age will be also established. And
estimation of original 55Mn concentration is interesting forconsidering a differentiation of planets. Determination of55
Mn in iron meteorites by NAA is well known to beinterfered by 56Fe(n, p)56Mn reaction. Therefore, the removalof iron prior to irradiation or irradiation at a channel withhigh Cd ratio is required. Thus we tried to determine 55Mn
concentration in iron meteorites by preNAA using wellthermalized neutrons.
II. EXPERIMENTAL
Using radiotracers, a chemical procedure using an ionexchange method was developed for separation of Mn fromiron meteorites based on one by Fujimoto and Shimura [2].
After dissolution of a sample in 2 M HF, the HF solution was
loaded on a cation exchange resin. Adsorbed Mn was eluted
by 8M HCl, and then Mn in HCl - 2-propanol solution was
purified by an anion exchange method. This procedure wasapplied to Japan steel standard samples and Gibeon ironmeteorites followed by irradiation of separated Mn fraction
for 4 hours at the thermal column pneumatic transport system(Tc-Pn) and for 1 hour at Pn-2 in Kyoto University Research
Reactor (KUR). In addition, sensitivity of 55Mn(n, �)56Mn andcontribution of 56Fe(n, p)56Mn at Tc-Pn in KUR and at PN-3
in the Japan Research Reactor-3 (JRR-3), Japan Atomic
Energy Agency were evaluated by using Mn standard and Ti
plate, respectively.
III. RESULT AND DISCUSSIONIn Mn fraction irradiated for 1 h at Pn-2, no 59Fe and 60Co
was observed. Our chemical procedure removed > 99.99% of
Fe and Co and > 99.5% of Ni, Ir and Cr, and overall
procedure blank of Mn was about 30 ng. Determined Mnconcentration in steel standards (JSS003-5 and JSS001-5) and
Gibeon meteorites are shown in Table 1. Low determination
values in Run-1 were guessed to be caused by low chemicalyield. In Run-2 a chemical yield was estimated to be 91% anddetermined concentrations on Mn in steel standards wereconsistent with certified values. It is concluded that down to
30 ppb of Mn can be determined by our method.
Sensitivities of Mn were 930 cps/�g and 2400 cps/�g for 4
h irradiation at Tc-Pn and 20 min irradiation at Pn-3,
respectively. And contributions of (n, p) reaction werecorresponding 16 ngMn/gFe and 97 ngMn/gFe for Tc-Pn and
PN-3, respectively. Since Fe was sufficiently removed,
contribution of 56Fe(n, p) reaction was more than 150 times
smaller than the present procedure blank. A detection limit of
Mn by preNAA was 30 ppb, assuming that a half of induced56
Mn is resulted by a blank. Even INAA using Tc-Pn candetermine such concentration of Mn. Reducing a procedureblank is highly required for lower detection limit.
TABLE 1: Result of Mn content
Sample

Unit

INAA*

JSS003-5
JSS001-5
Gibeon

ppm
ppb
ppb

24.9 ± 0.2
36.1 ± 2.2

preNAA
run1
run2
19.8 ± 0.4 26.0 ± 0.3
27.5 ± 2.2
273 ± 9415 ± 7

CertifiedValue
27 ± 130 ± 10*Corrected for (n, p) reaction.
[1][2]－ 265 －Oura et al., Proc. Radiochim. Acta 1.383 (2011).
K. Fujimoto and M. Shimura, Bunseki Kagaku 50, 175 (2001).

24-AAP-07

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Instrumental photon activation analysis of geological and cosmochemical samples
Naoki Shirai1, Shun Sekimoto2, Mitsuru Ebihara1
1

Tokyo Metropolitan University
Kyoto University Research Reactor Institute

2

I.

INTRODUCTION

Bulk chemical compositions for terrestrial andcosmochemical materials are significantly important toelucidate the formation, evolution processes andmagmatism of planetary bodies. Compared to geologicalsamples, cosmochemical samples pose several severe
requirements to their analytical methods for chemicalcompositions. High sensitivity and accuracy for as many aselements as possible are required for analytical methods
applied to such samples because of the limitation of sample
amounts usable for analysis. Non-destructive analysis formany elements is equally favorable. Nuclear analyticalmethods represented by prompt gamma-ray analysis (PGA),
instrumental neutron activation analysis (INAA) andinstrumental photon activation analysis (IPAA) meetalmost all these requirements. Among these nuclear
analytical methods, INAA has been commonly used as ananalytical tool in comomochemistry for a long time, while
PGA and IPAA have not been very often applied tocosmochemical samples.
In PAA, (�,n) reaction is used for determination ofelemental abundances which is an opposite reaction ((n,��)reaction) used in INAA. Thus, IPAA could determine
elemental abundances which cannot or hardly be
determined by INAA. Ebihara et al. [1] examined thesuitability of PAA by analyzing cosmochemical samples(chondrites) and concluded that PAA is as effective as
NAA for analyzing chondritic meteorites. Usually samples
are irradiated by using 30 MeV electrons in IPAA.
However, corrections of interferences caused by secondary
nuclear reactions such as (�,p) and (�,pn) are necessary.
Although the sensitivity obtained by activation with 20
MeV electrons are suppressed compared to the activation
with 30 MeV electrons, activation with 20 MeV electrons
reduces the degree of such interferences. In this study, we
performed IPAA by using a linear electron accelerator at
Kyoto University Research Reactor Institute (KURRI) andcompared the results obtained the activation with 20 MeV
with those for activation with 30 MeV.
II. EXPERIMENTAL
In this study, four Geological Survey Japan standards
materials (JA-2, JB-3, JR-1 and JG-1) were analyzed. In
addition to these terrestrial geological samples, the Allendemeteorite was analyzed as a cosmochemical samples. Eachsamples was taken into a sample container (9 mm�) madeof highly Al foil (Al: 99.5 %, Niraco Co., Ltd). In addition
to rock samples, chemical reagents were irradiated tocorrect the spectral interferences. Five to ten samples werestacked, among which thin foil disks (9 mm�) of Au wereplaced for as monitoring the intensity of photon. Samples ina block were put in a quartz tube. Irradiations were
performed by using a linear electron accelerator at KURRI.
Electrons were accelerated by the linear accelerator toabout 20 and 30 MeV. After irradiation (about 30 hrs),
samples were taken into new Al foil and measured for
gamma rays several times with different cooling intervals at
KURRI and the Laboratory of Radioisotopes, Tokyo
Metropolitan University. Elemental abundances were
determined by comparison method by using JB-1.
III. RESULTS AND DISCUSSION
Table 1 shows the interfering reactions and theircontributions to nuclides produced by corresponding
reactions for activation with 20 MeV and 30 MeV electrons.
As shown in Table 1, significant contributions frominterfering reactions were found in activation with 30 MeV
electrons. Thus, determinations of Cr, Co and Mn
abundances need the correction of corresponding
interferences. As expected, contributions from interfering
reactions with 20 MeV electrons were lower than those inactivation with 30 MeV electrons.
A total of 17 elements (Ca, Sc, Ti, Cr, Mn, Fe, Co, Ni, Zn,
As, Rb, Y, Zr, Nb, Cs, Ba and Ce) were determined ingeological reference standard materials and the Allendemeteorite. Our Cr and Mn values obtained from activation
with 30 MeV electrons were different from literature values.
Improper corrections of the interfering reactions were
responsible for these differences. In contrast, our Cr andMn values obtained from activation with 20 MeV electrons
were in good agreement with literature values. For otherelements, there were no differences between the two sets ofour values obtained from the activations with 20 and 30
MeV electrons, which were consistent with literature values.
Table 1. Interfering reaction and correction rate for interference.
Element
Reaction used forInterfering
Correction rateinterfereddetermination
reaction
30 MeV
20 MeV52
56
Cr
0.036 mgCr/gFe
Cr(�,n)51Cr
Fe(�,�n)51Cr
59
60
Co
3.7 mgCo/gNi
0.88 mgCo/gNi
Co(�,n)58Co
Ni(�,pn)58Co
55
56
Mn
6.2 mgMn/gFe
0.1 mgMn/gFe
Mn(�,n)54Mn
Fe(�,pn)54Mn

Reference: [1] Ebihara M. et al. (2000) J. Radioanal. Nucl.
Chem., 244 (3), 491-496.

－ 266 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

24-AAP-08

Monte Carlo Calculation of Chloride Diffusion in Concrete

1

A. A. Naqvi1, Khateeb-ur-Rehman1, M. Maslehuddin2, O.S.B. Al-Amoudi3 and M. Raashid1

Department of Physics, 2Center for Engineering Research, and 3Department of Civil and Environmental Engineering
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia

Abstract – Coefficient of chloride diffusion is calculated byapplying the Fick’s second law of diffusion to a chloride
concentration profile. Then from the signal strength for various
chlorine gamma-ray energies was then calculated at the detector.
of the portable D-D neutron generator based PGNAA setup.

An excellent agreement was noted between the reported results ofthe calculations for the 252Cf neutron source-based portable
PGNAA setup and the D-D portable neutron generator based
PGNAA setup developed by the authors.

Keywords –Coefficient of chloride diffusion ; Fick’s second lawof diffusion; DD based Portable neutron generator based PGNAA
setup; detector chloride signal strength calculationI.

INTRODUCTION

Corrosion of reinforcing steel is mainly caused due to thechloride ions. These ions either diffuse to the steel surface
from the service environment or they are contributed by the
mixture ingredients. The penetration of chloride ions fromthe service environment is a diffusion controlled process[1]. Consequently, the coefficient of chloride diffusion is
calculated by applying the Fick’s second law of diffusion toa chloride concentration profile. A prompt gamma-ray
neutron activation (PGNAA) setup has been designed
utilizing a portable neutron generator by the authors [2].
The setup, which mainly consists of a D-D portable neutron
source along with its moderator placed side by side with ashielded gamma-ray detector, allows the determination ofchloride concentration in a concrete structure from one side.
The D-D portable PGNAA setup has been modeled for thedetermination of chlorine concentration at various depths
using a MCNP simulation code following the proceduredescribed elsewhere [1] for a 252Cf neutron source based
PGNAA setup.

In the reported study, the chloride diffusion profile wasmodeled for several values of diffusion coefficients as afunction of time. These chloride concentrations are thenutilized as an input to the MCNP based model [1]. The
signal strength for various chlorine gamma-ray energies
was then calculated at the detector. An excellent agreement
was noted between the reported results of the calculations
for the 252Cf neutron source-based portable PGNAA setup[1] and the D-D portable neutron generator based PGNAA
setup developed by the authors[1]
Livingston, R.A., Al-Sheikhly, M., Mohamed, A.B.
“Numerical simulation of the PGNA signal from chlorine diffusion
gradients in concrete,” Applied Radiation and Isotopes, Vol. 68 (2010), pp.
679–682.
[2]
Naqvi, A. A., Kalakada, Z., Al-Matouq, F.A., Maslehuddin, M.
and Al-Amoudi, O.S.B., “Chlorine detection in fly ash concrete using a
Portable Neutron Generator,” Applied Radiation and Isotopes, Vol.
70(2012), pp.1671-4.

.

－ 267 －

24-APP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Catalysis Induced by Radiation in Fatty Acids Adsorbed on Clay Minerals
1

A. Negron-Mendoza1*, S. Ramos-Bernal1, M. Colin-Garcia2 and F.G. Mosqueira3

Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, UNAM. A.P. 70-543, México, D.F. 04510,
México.
Instituto de Geología, Universidad Nacional Autonoma de Mexico, México, D.F. 04510, México
3
Dirección General de Divulgación de la Ciencia, Universidad Nacional Autonoma de Mexico, D.F. 04510, México

Abstract – We have studied the behavior of small fatty anddicarboxylic acids adsorbed in sodium-montmorillonite and exposed
to gamma radiation. It is observed that the radiation-induced
decomposition of the clay-acid system goes along a definitive path(oxidation) rather than following several modes of simultaneous
decomposition, as in the case of the radiolysis without the clay. Thispreferential synthesis promotes the formation of a hydrocarbon
compound with one carbon atom less than the parent compound
Keywords –Decarboxylation reaction, carboxylic acids, gamma
radiation, montmorillonite, 14CO2I.

INTRODUCTION

The adsorption of certain organic compounds by clays
gives rise to the transformation of the adsorbate by the actionof clays. These kinds of reactions play an important role inmany natural and industrial processes. In the context of oil
and gas exploration, for example, the source and trap of
petroleum hydrocarbons frequently are clay-rich rocks. Claywater based muds are also seen as environmental friendly
alternatives to toxic oil-based fluids [1].
In this perspective, several investigators [2, 3] havestudied the thermal decomposition of fatty acids in thepresence of clay minerals. The differences found by several
workers for the distribution patterns of hydrocarbons may becaused largely by thermal alteration. In addition, radioactive
bombardment alters these sediments. It is an important
subject that has not been extensively studied.
The modification by ionizing radiation of the activity ofheterogeneous catalysis is a relatively new problem inradiation chemistry. The sensitization of radiation-chemical
reactions by solid surfaces may increase the catalytic activityof the clay. The aim of this paper is to study the radiationinduced decomposition of carboxylic acids adsorbed in a clay
mineral as an example of heterogeneous radiation catalysis
that can be correlated to natural and industrial processes.
II.

the clay were prepared. The addition of the clay into thesolution was in an oxygen-free bag, with continues agitation.
(3) For gas analysis, 0.1 g of the clay was evacuated for one
hour and 1 mL of the solution was added, in an oxygen-freebag. The samples were in special glass tubes with a stopcockthat was connected to a Toepler pump. We used blanks tocorrect the yield of gas samples. Some runs were made with
14-carbon label acetic acid (CH314COOH) to show that theCO2 obtained was from the target acid. 14CO2 was measured
by a scintillation technique. The irradiations were carried out
in a high intensity gamma source of 60Co (Gammabeam 651
PT). The radiation doses were from 46. kGy to 300 kGy
III.

RESULTS AND REMARKSThe irradiation of aqueous carboxylic acid produced many
compounds, for example for acetic acid, the total yield of
polycarboxylic acids was 22% and for succinic acid wasabout 35%. The principal feature of these series of radiolysis
experiments was the production of the dimer of the acid, as
the principal way of decomposition of the target compound,but many other acids were formed. For example, in theradiolysis of acetic acid (CH3CO2H), the main product was
succinic acid (CH2CO2H)2, the dimeric product. The
formation of CO2 from the decarboxylation reaction was only
7%. The decomposition of the target compound increased asa function of the dose.
The radiolysis performed in presence of clay decreased
considerably the number of formed products. For example, in
acetic acid, the production of polycarboxylic acids was 4.8 %and the formation of carbon dioxide increased to 81 %.
The main result obtained shows that the radiolysis of thesystem clay-acid goes along a defined path rather thanshowing various pathways of decomposition. The main
pathway was the decarboxylation of the target compound
rather than condensation/dimerization reactions.
ACKNOLEDGEMENTS

MATERIALS AND METHODSThe experimental part is divided in two stages: (1)Radiolysis of aqueous solutions of the carboxylic acids, (2)Study of heterogeneous radiolysis of the water-carboxylic
acid-clay system(1) Aqueous solutions of carboxylic acids (0.1 mol L-1),
oxygen free, prepared in a glass syringe (acetic, succinic,aconitic); (2) Aqueous solutions of acids containing 0.3 g ofThis work was supported by PAPIIT Grant No. IN110513 and the
CONACyT Grant No. 168579/11.

[1]
[2]
[3]

－ 268 －REFERENCES

Skipper, N. Hannon, A., and Buchanan, P. ISIS Experimental Report,
Rutherford Appleton Laboratory, RB 1205 (2001).
Eisma, E. and Jurg, W.J. in G. Eglinton and M.J. Murphy (Editors)
Organic Geochemistry, Springer Verlag, New York, (1969).
Simoyama, A. and Johns, W.D., Nature, 232, 14 (1971).

24-APP-02
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�－ 269 －

24-APP-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Radiation synthesis and cesium removal of cellulose microspherebased hybrid adsorbent
Long Zhao1*, Yanliang Chen1, Yuezhou wei1

School of Nuclear Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China*Corresponding author: Fax: (+86) 213420-7654; E-mail address: ryuuchou@sjtu.edu.cn
1

Abstract –A novel cellulose-based hybrid adsorbent was
successfully prepared by radiation-induced grafting of glycidyl
methacrylate (GMA) onto the surface of cellulose microspheres,
followed by epoxy ring-opening reaction to introduce ammonium
12-molybdo phosphate (AMP). The characterization of theobtained adsorbent was investigated in detail. To evaluate theadsorption performance of the novel adsorbent, batch and column
mode adsorption experiment against cesium (Cs) was conducted.
Keywords –radiation grafting; ammonium12-molybdophosphate;
cellulose microsphere; cesium; adsorption

I.

INTRODUCTION

It is well known that the leakage and spread of 137Cs
generated from the accident of atomic power plant such as
Fukushima nuclear disaster can affect human health, andlead to severe environmental problem [1-2]. Several
techniques have been employed for treating Cs containing
aqueous solutions, which include adsorption, reverse
osmosis, extraction and precipitation. Among thesemethods, adsorption has the advantages on high efficiency,
easy handling, availability of different adsorbents and costeffectiveness.
Ammonium 12-molybdophosphate (AMP), which showshigh selectivity toward Cs ion, can act as one of the mostpromising adsorbent materials for this purpose. [3]. However,
AMP is still not employed on a large scale because of its
fine powder form which hinders simple column operation.
To overcome this disadvantage, in this study, we proposeda novel hybrid adsorbent which could be easily prepared byradiation grafting. In current work, AMP can be introduced
onto glycidyl methacrylate (GMA) grafted cellulose
microsphere surface through epoxy ring-opening reaction.
The whole preparation procedures are rather simple.
To evaluate the adsorption performance of the novel
adsorbent, batch and column mode adsorption experiments
by using a nonradioactive Cs solution will be conducted.
In this report, the synthesis conditions and adsorption
properties of the novel adsorbent prepared by radiation
grafting are introduced in detail.

eligible solvent and then grafted polymers were dried in
vacuum. Thereafter, the grafted cellulose microsphere with
GMA having epoxy groups was reacted with AMP in aturbid liquid state at 80oC for 18h. The resulting adsorbent
was washed with water and dried in vacuum and kept for
further use. The structure of the resulting adsorbent was
confirmed by micro-FTIR spectra, TG and XPS analysis.
The batch adsorption of Cs has been investigated as afunction of contact time, pH, Cs and NaCl concentration. A
column-mode adsorption test was carried out using 15mlvolume column at a flow rate of space velocity 10h-1 forinitial Cs of 5 mg L-1 at pH5.4. The concentration of Cs
was measured by atomic absorption spectrophotometer(AAS) and Inductively Coupled Plasma Mass Spectrometer(ICP-MS).
It was found that adsorption equilibrium could beachieved within 30 min for initial Cs of 5 mg L-1. It isbelieved that the functional groups concentrated in surface
result in such quick adsorption. Cs uptake of adsorbent
depends on solution pH, with a maximum Cs uptake at pH
5.4. The adsorption kinetics was well described by thepseudo-second order model equation, and the adsorption
isotherm was better fitted by the Langmuir mode. Fig.1.
showed the breakthrough curves of column adsorption
experiment. The breakthrough curve indicated that the Cs
adsorption amount at the breakthrough point was 0.75gCs/L-adsorbent, and the Cs can be completely removed till
the flux reached roughly 150 bed volumes.

Fig.1. Breakthrough curves of adsorbent.

II. EXPERIMENTAL AND RESULTS
Adsorbent was prepared by pre-irradiation grafting
polymerization. Initially, trunk polymer was sealed inpolyethylene bags purged with nitrogen gas. The sample
bags were irradiated by EB generated from an accelerator,
at a voltage of 750 keV and a dose rate of 10 kGy per passunder the cooling of dry-ice. After getting rid of oxygen bynitrogen flow, monomer solution was injected into thesample bags. The grafting reaction was then performed in awater bath at desired temperature and reaction time. The
homopolymer and unreacted monomer were removed by

Lastly, it was found that 80% adsorption capacity canbe kept even though the adsorbent was exposed to
1000kGy �-irradiation. These results suggested thatobtained adsorbent could be used to removal Cs fromwastewater.
REFERENCES
[1]
[2]
[3]

－ 270 －

IAEA Technical Report Series, No. 356 (1993).
K. Takeshita and T. Ogata, J. Ion Exchange.23,1 (2012).
W. Faubel and S. A. Ali, Radiochim. Acta, 40, 49 (1986).

24-APP-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Study about separation mechanism of endohedral metallofullerenes with
Lewis acid

K. Chiba1, T. Hamano1, E. Takeuchi1, K. Akiyama1, S. Kubuki1, and H. Shinohara2
1

Department of Chemistry, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
2

Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
separated by PTFE membrane filter (pore diameter is

Keywords – Metallofullerene, Lewis acid, Separation

INTRODUCTION

0.2 �m, Millex, Merck Millipore). The EMFs

Recently, a method for the separation andremaining on the filter were washed by water andpurification of endohedral metallofullerenes (EMFs)

acetone. After that, DCB was passed through thewith Lewis acid was reported[1]. It is found that EMFs

filter to recover the EMFs. The gamma-ray emitted

in fullerene crude extract are selectively oxidized

from 141Ce in the samples was measured for thewith Lewis acid and separated with especially highdetermination of separation efficiency by germanium

yield (>99 %) by the liquid Lewis acid such as TiCl4

semiconductor detector (GMX25, SEIKO EG&G).

I.

and SnCl4. On the other hand, the method using solid

AlCl3/CB was also added to purified La@C82

Lewis acids like AlCl3 needs long time for the

DCB solutions and their vis-NIR absorption spectra

separation compared to liquid Lewis acid and thewere measured (UV-3600, SHIMADZU) in order toseparation efficiency is decreased to around 40 % forinvestigate the electronic states of the EMF.
III. RESULTS AND DISCUSSION

the same reaction time. Based on the previous study,
it is presumed that homogeneous diffusion of Lewis

In comparison of the radioactivity of 141Ce atacid in crude extract solution lead to the efficient

before / after separation, the efficiency with AlCl3/CBinteraction between EMFs and Lewis acid.

was determined as about 40 %. This is corresponding

In this session, we will report the effect ofto that with solid AlCl3. It suggests that the separation

diffusion of AlCl3 to the separation and the detail ofefficiency is not much affected by homogeneous

separation mechanism of EMFs.

diffusion of Lewis acid.

II.

In the vis-NIR spectra of the mixed solution of

EXPERIMENTAL

Soot containing La EMFs were produced by arc

La@C82 and AlCl3/CB, two characteristic absorption

rods

bands at 1000, 1400 nm of La@C82 were disappeared(La:C=1:130). The produced soot were dissolved to

but new band was raised at 1300 nm after 5 min of

1,2,4,-trichlorobenzene (TCB), and then refluxed foradding AlCl3/CB. This result indicate that neutral

12 hours. The TCB solution including crude extracts

La@C82 is immediately oxidized by the addition ofof fullerenes was filtered and evaporated to dryness.

Lewis acid and cationic species of La@C82 isAfter that, the crude extracts were re-dissolved to

produced within 5 minute.

discharge

methodwith

La/Co-dichlorobenzene (DCB). EMFs ofcomposite

141

Detail of the mechanism of separation will beCe, which are

known to behave as with La EMFs, were added to

discussed in the session.

these solutions as a radioactive tracer. Chlorobenzene
solution of AlCl3 (AlCl3/CB) was added to the crude[1]

extract. These mixed solutions were stirred and then

－ 271 －

K. Akiyama et al., J. Am. Chem. Soc., 134, 9762-9767,(2012).

24-APP-05

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

CRYSTAL STRUCTURE AND SPIN STATE OF MIXED-CRYSTALS OF
Fe(NCS)x(NCBH3)2-x(bpp)2 (bpp = 1,3-BIS(4-PYRIDYL)PROPANE)
Haruka Dote1, Hiroki Yasuhara1, Satoru Nakashima2
1

2

Graduate School of Science, Hiroshima University
Natural Science Center for Basic Research and Development (N-BARD), Hiroshima University

Abstract

New mixed crystals, Fe(NCS)x(NCBH3)(2-x)(bpp)2 weresynthesized. 57Fe Mössbauer spectroscopy showed that theratio of low-spin state in the Fe(NCBH3)2 unit changed
with the change of x. The results revealed that the highspin site of Fe(NCS)2 unit affects the spin state ofFe(NCBH3)2 unit.
Keywords

Mössbauer spectroscopy, mixed crystals, spin-crossover,assembled complexes
I.

INTRODUCTION

Self-assembled coordination polymers containing
transition metal ions and organic bridging ligands haveattracted intensive interests because of their potential
abilities for selective inclusion and transformation of ionsand molecules.1) It is possible to construct various
structures for porous assembled iron complexes bridged bybis(4–pyridyl) type ligand. We have studied iron complexes
bridged by 1,3–bis(4–pyridyl)propane (bpp), which has
three methylenes, by using single crystal X–ray diffraction
analysis,
Mössbauer
spectroscopy,
and
SQUID
measurements. Fe(NCX)2(bpp)2 (X = S, Se, and BH3) had a
2D interpenetrated structure and the NCBH3 complex
showed a spin–crossover phenomenon.2) We alsosynthesized Fe(NCX)2(bpp)2· 2(benzene) (X = S, Se, and
BH3). They had a 1D structure and were in temperatureindependent Fe� high-spin state. Both 2D interpenetrated
and 1D structures were converted to each other bydesorption and adsorption of benzene molecules.3) Recently,
we discussed the spin state of the mixed crystals with zincor cobalt ion both in the 2D interpenetrated and 1D
structures for the assembled complexes bridged by bpp.4) In
the present study, we discussed the structure of the mixed
crystals of iron with NCS and NCBH3 for the assembled
complexes bridged by bpp, and then we discussed the spinstate of the mixed crystals.
�. Results and Discussions

We carried out single crystal X-ray diffraction analysis of
By
comparing
Fe(NCS)1.8(NCBH3)0.2(bpp)2.
Fe(NCS)1.8(NCBH3)0.2(bpp)2 with Fe(NCS)2(bpp)2, andFe(NCBH3)2bpp2, we found that the structure is similar toFe(NCS)2(bpp)2 but has shorter b-axis and longer c-axis.
The result is consistent with the result of powder X-ray
diffraction.
We measured Mössbauer spectra of the present mixed
crystals. All the spectra consist of Fe(NCS)2 unit andFe(NCBH3)2 unit. Fig. 1 shows that ratio of NCBH3 andfraction of low spin in mixed anion crystal. The result
reveals that the ratio of low-spin state in the Fe(NCBH3)2
unit changed with the change of x and revealed the highspin site of Fe(NCS)2 unit affects the spin state ofFe(NCBH3)2 unit. The results suggest the chemical pressure
effect, in which Fe(NCS)2 unit next to Fe(NCBH3)2 unit
makes Fe(NCBH3)2 unit to become high spin from low spin
at low temperature.
�. ConclusionWesynthesized
new
mixed
anion
crystals,
Fe(NCS)x(NCBH3)(2-x)(bpp)2. 57Fe Mössbauer spectroscopy
showed that the high-spin site of Fe(NCS)2 unit affects thespin state of Fe(NCBH3)2 unit.

Fig 1. Ratio of NCBH3 and fraction of low spin in mixed anion crystal

Elemental analysis of Fe(NCS)X(NCBH3)2-X(bpp)2 showedthat x is 0.25, 0.65, 0.95, 1.15, 1.1, 1.25, 1.4, 1.7, 1.8, and1.9, when the preparation ratio of x is 0.2, 0.4, 0.6, 0.8, 1,
1.1, 1.2, 1.4, 1.6,and 1.8, respectively. This reveals that theobtained crystals show a trend that the ratio of NCS
increases compared with the preparation ratio. All themixed crystals showed the similar powder X-ray diffraction
patterns, and the (002) diffractions of the mixed crystals are
not the superposition of those from Fe(NCS)2(bpp)2 andFe(NCBH3)2(bpp)2. The (002) diffractions are shifted tohigher degree by increasing ratio of NCS.

[1]
[2]
[3]
[4]

－ 272 －

B. Moulton, M. J. Zaworotko, Chem Rev., 101 (2001) 1629
M. Atsuchi, H. Higashikawa, Y. Yoshida, S. Nakashima, and K.
Inoue, Chem. Lett., 36 (2007) 1064.
M. Atsuchi, K. Inoue, and S. Nakashima, Inorg. Chim. Acta, 370(2011) 82
S. Nakashima, T. Dote, M. Atsuchi, and K. Inoue, J. Phys., C217,
01035 (2010).

24-APP-06

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Analysis of Fragments of a Roman Mask using Mössbauer spectroscopy
Paulo de Souza1,2, G. Klingelhöfer3, P Gütlich3, M. Egg4
1

2

University of Tasmania, Hobart TAS 7001 Australia
Commonwealth Scientific and Industrial Research Organisation, Hobart TAS 7001 Australia
3
Johannes Gutenberg-Universität Mainz D-55128 Germany
4
Römisch-Germanisches Zentralmuseum, Mainz D-55116 Germany

Abstract – A fragmented roman mask was found in excavations

at ”Villa von Allmend”, Saarland, Germany. The mask is made ofiron, covered externally by bronze. Such objects were used in war
games during the height Roman times. During the excavations
around the mask other metallic objects were also found. Someclearly belong to the mask, such as the left ear (Figure 1, top left),among other fragments that cannot be associated with the mask
without further investigation. Some of these fragments were
investigated using backscattering Mössbauer spectroscopy. The
objective was to determine whether the fragment was a piece ofthe roman mask or was part of another object laying in the
excavated area, and shed additional light on the manufacturing
process of the mask itself.

The current communication discusses the results of the analysis offragments from this roman mask using the miniaturised
Mössbauer spectrometer (MIMOS II). This instrument wasdeveloped by Dr. Klingelhöfer’s research group in Mainz forspace exploration [1] and was successfully used onboard NASA’s
Mars Exploration Rovers [2]. Thanks to MIMOS II portability,
robustness, low-power consumption and relative good radiation
shielding, in situ characterization became possible. Theseadvantages of MIMOS II were explored in a number of outdoor
applications [3, and references therein]. In archaeology the
instrument has been applied in the analysis of rock paintings [3]and on a greek Vase [4].
On this roman mask, the results yield the understanding of theprovenance of fragments and were used to guide the process of its
restoration. The Mössbauer spectra on pieces that clearly belong
to the mas show the presence of many iron oxides including
wüstite (FeO1-x). Wüstite has been interpreted as the indication of
production of ‘brand patina’ on the surface of the object. This
oxide phase could be produced by fast cooling under reducing
atmosphere (e.g., putting the hot metal in a bath of animal fat).
Patina was a surface treatment used by romans to improve
resistance to corrosion and for aesthetics purposes. Therefore, theabsence of wüstite would imply in a possible mismatch with theoriginal mask.

Fig. 1. Room temperature Mössbauer spectra of some of the studied
metallic fragments. On the top, the left ear of the mask; on the bottom, anunidentified fragment (probably from the metallic box where it wasplaced), and on the left, the final appearance of the reconstructed mask.

REFERENCES
[1]

[2]

[3]

Keywords – Mössbauer spectroscopy, archaeology.
[4]－ 273 －

G. Klingelhöfer, R. V. Morris, B. Bernhardt, D. Rodionov, P. A. de
Souza, S. W. Squyres, J. Foh, E. Kankeleit, R. Gellert, C. Schröder,S. Linkin, E. Evlanov, B. Zubkov, O. Prilutski (2003) The Athena
MIMOS II Mössbauer Spectrometer Investigation. Journal ofGeophysical Research, v. 108, No. E12, 8067. doi:
10.1029/2003JE002138.
G. Klingelhöfer, R. V. Morris, B. Bernhardt, C. Schröder, D.
Rodionov, P. A. de Souza, A. Yen, R. Gellert, E. N. Evlanov, B.
Zubkov, J. Foh, U. Bonnes, E. Kankeleit, P. Gutlich, D. W. Ming, F.
Renz, T. Wdowiak, S. W. Squyres, R. E. Arvidson (2004) Jarosite
and Hematite at Meridiani Planum from Opportunity's Mössbauer
Spectrometer.
Science,
306,1740-1745.
doi:
10.1126/science.1104653.
C. Schröder, G. Klingelhöfer, R. V. Morris, B. Bernhardt, M.
Blumers, I. Fleischer, D. S. Rodionov, J. Gironés López, P. A. de
Souza (2010) Field-portable Mössbauer Spectroscopy on Earth, theMoon, Mars, and Beyond, Geochemistry: Exploration,
Environment, Analysis, 11 (2011) 2, 129-143. doi: 10.1144/14677873/09-IAGS-018.
P. A. de Souza, B. Bernhardt, G. Klingelhöfer, P. Gütlich (2003)
Surface Analysis in Archaeology Using the Miniaturized Mössbauer
Spectrometer MIMOS II. Hyperfine Interactions, v. 151, 125-130.
doi: 10.1023/A:1025444209059.

24-APP-07

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Synthesis of 14C labeled C60 with higher specific activity
1

T. Tadai1, K. Akiyama1, H. Aoshima2, R. Ibuki2, S. Kubuki1
Department of Chemistry, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
2
Vitamin C60 BioResearch Corporation, Chuo-ku, Tokyo 103-0028, Japan

Keywords Keywords – 14C-labeled C60

I.
INTRODUCTION
Recently, Fullerenes and their derivatives have been
attracted to the medical and cosmetics fields. However,there are some problems for the application of fullerenes,
such as nano toxicity. To overcome these problems, further
study about drug disposition is required. As one of the mostuseful technique, the radioactive tracer method using 14Clabeled C60 is applicable for this purpose. Synthesis of 14Clabeled C60 has been reported so far [1, 2]. However,synthesis of 14C-labeled C60 with higher specificradioactivity is desired for the detail study. In this session,
we will report the development of synthesis and theproperties of produced 14C-labeled C60 such as specificradioactivity.
II. EXPERIMENTAL
Ba14CO3 (0.2 mmol, 57 mCi/mmol) was mixed with PbCl2
and AgCl and then put into the electric furnace for heating
at 450 oC to produce labeled CO2 under He gas flow. The
produced CO2 gas was stored in the plastic bag, and thenintroduced to the Et2O solution of 2-lithiofuran to produce
the furoic acid. The produced furoic acid was reduced with
LiAlH4 in THF solution to obtain the labeled furfuryl
alcohol. This alcohol was condensed by the evaporator, andthen dissolved into o-dichlorobenzene (o-DCB). For thepolymerization of this alcohol, p-toluenesulfonic acid wasadded into this o-DCB solution. The polymer solution wasadsorbed on a porous carbon rod (PC5060G, Tokai Carbon

Inc.) and dried at 200 oC under He gas stream for 1 hour.
After that, carbon rod was set into fullerene generator andsintered by the electric resistance heating method. The
resulting 14C-impregnated graphite electrode was thenemployed as an anode for the arc discharge for the fullerene
production. The soot containing 14C-labeled C60 wererecovered from the generator as a CS2 solution and thenfiltered to remove the insoluble substances. The 14C-labeled
C60 was purified from these filtered crude fullerenes by
HPLC (Buckyprep, Nakarai tesque Inc.). Their total weightand specific radioactivity were determined by UV/vis
absorption and liquid scintillation counter (LSC).
III. RESULTS AND DISCUSSION
The yield of 14C was estimated from the radioactivity in
Ba14CO3 and in obtained C60, and found to be 0.73 %. Thisis about 3 times larger than that of previously reported
value [1]. As the results of UV/vis absorption measurement,
the total weight of purified C60 is found to be about 3 mg.
The specific radioactivity of these C60 estimated from theradioactivity determined by the results of LSC
measurement and total weight of C60, were found to be 18.4
mCi/mmol. Enrichment of 14C for this sample was about
14
C: 12C = 1: 200. This value is the highest among that ofprevious reports and indicate that the most enriched 14Clabeled C60 is produced by our method.
[1] W. A. Scrivens, et al., J.Am.Chem.Soc.,116, 4517-4518, 1994.
[2] S. R. Wilson, et al., Fullerene Sci. & Technol., 4, 43-48, 1996.

－ 274 －

24-APP-08

��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Adsorption Behavior of Zr and Hf to TTA-resin in Microcolumn for Determining
the Forming Ability of Rf Monofluoride Complex
Y. Kitayama1, Y. Shigeyoshi1, A. Yokoyama2, A. Toyoshima3, K. Tsukada3, K. Ooe4, E. Maeda1,
H. Kimura1, H. Kikunaga5, Y. Kudou6, J. Kanaya6, M. Huang6, and H. Haba6*1 Graduate School of Natural Science and Technology, Kanazawa University*2 Institute of Science and Engineering, Kanazawa University*3 Japan Atomic Energy Research Institute*4 Institute of Science and Technology, Niigata University*5 Research Center for Electron Photon Science, Tohoku University*6 Nishina Center for Accelerator-Based Sience, RIKEN

Abstract � We study aqueous chemistry of Rf to determine theforming ability of monofluolide complex of Rf. Reversed-phase
chromato-graphic behaviors of non-carrier tracers of Zr and Hf
with TTA-resin were observed for simulation of the Rf experiment.
Although we obtained good adsorption behavior and shortequilibrium time for the batch experiment, the chemical system in
microcolumn does not appear to come to equilibrium and needs
further improvement.
Keywords � Reversed-phase chromatography, Zirconium(Zr),
Hafnium(Hf), Rutherfordium(Rf)

I.

INTRODUCTION

Rutherfordium (Rf) has attracted a lot of attention in
research on the chemical properties of a super heavy element.
For the purpose of its speciation in aqueous solution, we aim
to observe the chemical behavior of Rf by means of reversedphase chromatography with a chelate extractant of 2-thenoyltrifluoroacetone (TTA) as the stationary phase. It extracts
quadrivalent metal ions preferentially, and, that is, it will
make possible determination of a specific complex formation
constant of Rf. [1]In this work, we observed chemical equilibrium times anddistribution coefficients of non-carrier tracers of Zr and Hf
with TTA-resin in the acid solutions of HF/HNO3 forsimulation of the Rf experiment. Then, on-line reversedphase chromatography of Zr was performed with AutomatedRapid Chemistry Apparatus (ARCA), which was also used
for an on-line chemical system for the Rf experiment.

The solutions eluted through TTA-resin were collected andsubjected to �-ray spectrometry by using a Ge detector.
�.

RESULTS AND DISCUSSION

The batch experiment demonstrated that the best performance in adsorption was obtained for TTA (octanol) resin on
Kel-F resin and TTA (octanol) on CHP20/P20 resin. The
equilibration was attained in less than 1 min for the cases.
Besides, it was found that the results of experimental with
TTA resin agree with those of solvent extraction behavior forZr and Hf at the lower acid concentrations.
In the on-line experiment, an example of the obtained
elution curves is shown in Fig. 1 for TTA on CHP20/P20
resin with a 89mZr tracer. It shows the tracer atoms areadsorbed on the resin. However, the equilibration times in theon-line experiment appears to be not as short as we had
expected from the batch experiment; Kd value from the online experiment was observed lower than that for the batch
experiment. Therefore, we should find better conditions for
shorter equilibration time for the experimental with Rf.
In conclusion, reversed-phase chromatography with TTA
resin has the potential for speciation of a Rf chemical species
although the resin preparation needs further improvement to
optimize the experimental condition for Rf. Thus far we havesucceeded in introducing 261Rf into ARCA system and its
measurement by �-ray spectrometry.

�� EXPERIMENTAL
In the batch experiments with 88Zr and 175Hf tracers, weobserved equilibrium times and distribution coefficients on
TTA-resin in the solution of 9.5×10�5 � 10�1 M HF / 10�1 M
HNO3 , 1×10�4 M HF / 10�2 �10�1 M HNO3. and 1.0×10�4 M
HF / 10�2 �10�1 M HNO3 by assaying in �-ray spectrometry
with a Ge detector.
In the on-line experiment, an reversed-phase chromatography was performed with the 89mZr atoms produced in the89
Y (p, n) reaction at the RIKEN K70 AVF cyclotron. They
were transported with KCl/He gas jet and collected in ARCA.
They were dissolved in acid solutions of HF/HNO3, and thesolutions were introduced in the microcolumns (1.6mm��
7mm) filled up with TTA-resin at flow rate of 0.1-1 mL/min.

Fig. 1. An example of elution curve of Zr on the TTA resin.
The conditions were 1.0×10-4 M in [HF], 0.01M in [HNO3] for the 1st eluteand 1.0×10-4 M in [HF], 0.01M in [HNO3] for the 2nd elute at 0.1 mL/min inflow rate
Reference:[1] M. Araki, T. Nanri., Y. Takeda, M. Nishio, M. Nishikawa, Y. Kasamatsu, Y. Ezaki,
Y. Kudou, H. Haba, and A. Yokoyama: RIKEN Accel. Prog. Rep. 43, 271 (2010).

－ 275 －

Poster Session 3
Wednesday, 25 September 2013
18:50 ~ 20:00

Scientific Topics (Abbrev.)

1. Fukushima issues (FK)
2. Education in nuclear and radiochemistry (ED)
3. Nuclear forensics (NF)
4. Nuclear energy chemistry (NE)
5. Nuclear chemistry (NC)

6. Actinide chemistry (AC)
7. Environmental radiochemistry (EN)
8. Radiopharmaceutical chemistry and Nuclear medicine (RP)
9. Nuclear probes for materials science (NP)
10. Activation analysis (AA)

11. Application of nuclear and radiochemical techniques (AP)－ 277 －

25-FKP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013235

U/238U Isotopic Ratio in Environmental Samples at the Fukushima Area

Y. Shibahara1, T. Fujii1, S. Fukutani1, T. Kubota1, R. Okumura1, T. Ohta2, K. Takamiya1, N. Sato1,
M. Tanigaki1, Y. Kobayashi1, H. Yoshinaga1, H. Yoshino1, A. Uehara1,
S. Mizuno3, T. Takahashi1, and H. Yamana1
1

Research Reactor Institute, Kyoto University
Faculty of Engineering, Hokkaido University
3
Nuclear Power Safety Division, Fukushima Prefectural Government2

Abstract – 235U/238U isotopic ratio of environmental samples inFukushima prefecture was analyzed by thermal ionization mass
spectrometry and inductively coupled plasma mass spectrometry. A
possibility of atmospheric release of uranium during the accident ofFukushima Daiichi nuclear power plant was discussed.
Keywords– uranium isotope ratio, thermal ionization mass
spectrometry, inductivity coupled plasma mass spectrometry

Uranium has three major isotopes (234U, 235U, and 238U)
and is widely distributed in the environment. The relative
isotopic abundances are 0.0054% (234U), 0.7200% (235U), and99.2745% (238U), respectively [1]. The range of naturalvariations of uranium isotopes [1] are shown in Table 1.
Fukushima Daiichi nuclear power plant used UO2 and mixed
oxide (MOX) fuels, in which the averaged 235U
concentrations are 3.4-3.7 wt% and 1.2 wt%, respectively.
Table 1. Isotopic composition of uranium[1]Isotope
Range of natural variations [%]234
U0.0050-0.0059
235
U
0.7918-0.7207
238
U
99.2739-99.2752

On the accident of Fukushima Daiichi nuclear power plant,huge amount of fission products were widely released. Since
uranium is a heavy element, if it was released, the fallout may
have been distributed at the near site of nuclear power plant.
The purpose of the present study is, from the viewpoint ofsafety assessment, to check that the 235U/238U ratio inenvironmental samples at the Fukushima area falls within therange of natural variations. The spent nuclear fuel includes
236
U generated via the neutron capture of 235U. The 236U/238U
ratio in the river and ocean close to the Fukushima area has
been investigated with accelerator mass spectrometer [2]. In
the present study, we analyzed 235U/238U in environmental
samples (soils, plants, and so on) at the Fukushima area withthermal ionization mass spectrometer (TIMS) and inductively
coupled plasma mass spectrometer (ICP-MS).
Samples were immersed in concentrated HNO3 and heatedat 413 K. After evaporation of HNO3, diluted HNO3 wasadded, and then, uranium was recovered from the samples byion-exchange chromatography with ion-exchange resin andextraction chromatography with UTEVA-resin. The
concentration of uranium recovered was analyzed withquadrupole ICP mass spectrometer (ICP-QMS) or ICP atomic
emission spectrometer (ICP-AES).
Uranium isotopic ratios were analyzed with a TIMS
(Triton-T1, Thermo Fisher Scientific) with a rhenium double
filament system and/or an ICP-MS (Element 2, Thermo
Fishier Scientific). As the reference material of mass
spectrometry, standard material CRMU010, in which theatomic percent of 235U is certified to be 1.0037±0.0010% [3],was used.
The sample solution of 1 ppm uranium in 1 M HNO3 was
prepared for TIMS. Each solution of 1 �L (1 ng of U) was
loaded onto a rhenium evaporation filament. The mass
spectrum was obtained with a secondary electron multiplierdetector. The sample solution of 10 ppb uranium in 0.1%
HNO3 was also prepared for ICP-MS. Our analytical result of
CRMU010 agreed with the certified value within ��
analytical error. Based on the validity of isotopic analysis, the235
U/238U ratio in the environmental samples inside the 3 km
range from the Fukushima Daiichi nuclear power plant was
analyzed. A possibility of atmospheric release of nuclear fuelmatrix during the accident of Fukushima Daiichi nuclear
power plant is discussed.
[1] J. K. Böhlke et al., J. Phys. Chem. Ref. Data, 34, 57 (2005).
[2] A. Sakaguchi et al., Geochemical. J., 46, 355 (2012).
[3] E. L. Garner et al., Nat. Bur. Stand. (U.S.), Spec. Publ. 267-27 (1971).

－ 278 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-FKP-02

Particulates of Ag and Pu radioisotopes released from
Fukushima Daiichi nuclear power plants
H. Kimura1, M. Uesugi2, A. Muneda2, R. Watanabe1, A. Yokoyama3,
T. Nakanishi4
1

Grad. School Nat. Sci. Tech., Kanazawa Univ., 2Col. Sci. Eng., Kanazawa Univ., 3Inst. Sci. Eng., Kanazawa Univ.,
4Adv. Sci. Res. Cent., Kanazawa Univ.

Abstract –Due to Fukushima Daiichi nuclear power plants
accident, a large amount of radionuclides were released into
environment. The radioactivities of 134Cs, 137Cs, 110mAg, 238Pu, and239+240
Pu in a soil sample collected in Futaba, Fukushima were
determined by � spectrometry or � spectrometry. We searched forthe dispersion of these radioactivities in a soil sample, whichsuggests the existence of hot particles for Pu contamination.
Keywords –238Pu,, 110mAg ,137Cs, hot particle,

I.

INTRODUCTION

Massive radionuclides were released into environment
due to the Fukushima Daiichi nuclear power plant(FDNPP) accident. The volatile fission products, such as
137
Cs, 134Cs were considered to be deposited as several
chemical forms through dry deposition and wet deposition.
On the other hand, the deposition procedures of nonvolatile nuclides such as Pu isotopes and 110mAg were notclear, and it is predicted that these radionuclides were
deposited as hot particles. The existence of hot particles
may cause their radioactivity concentrations to vary over awide range even if soil samples are collected in a place. In
this work, we researched for the dispersion ofradioactivities in a homogenized soil sample collected in
Futaba, Fukushima.

III. RESULTS
Figure 1 shows correlation between 238Pu and 137Cs for
six aliquots. The radioactivity of 238Pu in one aliquot isclearly higher than the others, and the ratio of 238Pu/239,240Pu
of the former is also higher. This result suggests theexistence of hot particle of Pu in that aliquot. Figure 2
shows the good correlation between 137Cs and 110mAg.
Therefore it was suggested that hot particles of 110mAg did
not exist in the soil sample. These results suggest thedifference of the release processes of 110mAg and 238Pu
although both of them are non-volatile nuclides.
high ratio of
238
Pu/239,240Pu

Fig.1 Correlation between 238Pu and 137Cs

II. EXPELIMENTS
Sample collection

A soil sample was collected in Futaba located at 4km
north-west of Fukushima DNPP.

Preparation

Firstly, the sample was agitated by hand hundred times,
and it was dried at 105� overnight. Secondly, it was
crushed in a mortar, and sieved through at 2mm sieve.
Finally, it was heated at 450� for 4 hours to decompose
organics.
1 Measurement of Pu
After addition of a tracer of 242Pu, six aliquots of 10g
soil were leached with 10 M HNO3-0.01M HF. And then,after isolation of Pu atoms through an ion exchange
procedure the atoms were electrodeposited on a steel
plate and subjected to ��������������.
2 Measurement of 110mAg
Some aliquots of 1.0g soil sample were prepared, andthey were subjected to � spectrometry.
－ 279 －

Fig.2 Correlation between 110mAg and 137Cs

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-FKP-03

The measurement of 14C/12C ratios in Japanese plant samples
affected by anthropogenic sources
Risa Hashimoto 1, Aki Inoue 1, Yasuyuki Muramatsu 1, Hiroyuki Matsuzaki 2
1

Depertment of Chemistry, Gakushuin University
School of Engineering, the University of Tokyo2

In relation to anthropogenic influences of 14C in the atmosphere,
we have carried out the following two different studies;(1) secular variation of 14C/12C ratio in rice harvested in Japan,(2) influence of the Fukushima nuclear accident on 14C/12C ratio
in plant leaves in the region.
Analytical results by AMS for rice collected from 1951 to 2012
showed that 14C/12C ratios decreased exponentially after thePartial Test Ban Treaty in 1963. The residence time of 14C in theatmosphere is estimated to be about 10 years.
Plant leaves collected about 9km from the reactor showed aweak increase of 14C/12C ratios. This suggests that 14C wasreleased by the accident and influenced the 14C/12C ratios in plantleaves collected near the reactor.
Keywords – 14C; anthropogenic sources; plant samples; secularvariation; Fukushima; AMS

I.

at the University of Tokyo and Japan Atomic Energy
Agency.
In order to examine the possible influences of 14C for
plants, we have collected leaves of Japanese cedar in
Okuma, 9km far from FDNPP, in September, 2011. Since
cedars are evergreen, leaves were contaminated at the timeof the accident. We analyzed old leaves, which were grown
before the accident, and new leaves, which were grownafter the accident. Cedar leaves were washed with purewater in order to remove particulate matters deposited on
the plant surface. For comparison with background samples
collected far from FDNPP, we analyzed pine needles in
Chiba prefecture and rice samples collected in Niigata
prefecture. The samples were also homogenized in a
blender, and prepared graphite targets for AMS.
III. RESULTS

INTRODUCTION

14

C is produced in nature by cosmic ray reactions in theupper atmosphere, and its production changes by the flux ofcosmic rays. The produced 14C immediately reacts with an
oxygen molecule, resulted in the production of 14CO2 and it
is absorbed by plants through photosynthesis. Therefore
plants are reflected atmospheric 14C/12C ratios at that time.
14
C is also released into the atmosphere by anthropogenic
sources such as nuclear weapons tests and nuclear accidents.
In this study, we focus on 14C released from anthropogenic
sources and carried out the following two studies using
AMS. We determined 14C/12C ratios in rice harvested inJapan to study recent influence of the past nuclear weapons
tests. We also studied whether there were influences on
12 14
C/ C ratios in the plants due to the accident at the
Fukushima Daiichi Nuclear Power Plant (FDNPP) occurredin March, 2011. Although there are many papers reporting
the release of several nuclides, there are almost no data for
14
C. In the last year, we have determined 14C/12C ratios inJapanese cedars and pine needles collected in Fukushima
prefecture. Some enhancements of 14C levels wereobserved. However, we still have lack of 14C data.
Therefore, we analyzed additional samples collected near
the FDNPP and studied whether the 14C/12C ratios in theplants were affected by the accident.

Results obtained for rice showed that 14C/12C ratios
decreased exponentially with time after the Partial Test Ban
Treaty in 1963. The residence time of 14C in the atmosphereis estimated to be about 10 years.
For the cedar samples collected in Okuma, 14C/12C ratios
in the old leaves (grown before the FDNPP accident) were
found to be higher than the new leaves (see Fig.1). Since
14 12
C/ C ratios in new leaves were almost the same as theratios in the other samples collected from outside of
Fukushima. From the above-mentioned results, 14C in theold leaves was increased because of the influence of 14C
released by the FDNPP accident. 14C/12C ratios did notchange so much, even the samples were washed. Therefore,
we assume that most of 14C were taken as gaseous forms
and associated with plant tissues in the leaves. Contributionof 14C associated with particulate matters deposited on theleaves seems to be small.

II. EXPERIMENT
Rice samples harvested from 1951 to 2012 were used forthe analysis. They were homogenized in a blender andoxidized to produce CO2. Then, the CO2 was purified in a
vacuum line and reduced to prepare graphite target for
AMS. 14C/12C ratio in the graphite was measured by AMS

Fig 1. 14C/12C ratios in Japanese cedar leaves collectedfrom Fukushima and those in other samples frombackground areas－ 280 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-FKP-04

Radiocesium and stable cesium in edible wild plants (Sansai) collected from forests
in Fukushima Prefecture
SUGIYAMA, M.1, MURAMATSU, Y.1, OHNO, T.1, SATO, M.2
1

2

Gakushuin University
Fukushima Agricultural Technology Center

Abstract –Keywords – radiocesium, stable cesium, edible wild plants,
transfer to plants

I.

INTRODUCTION

An accident occurred at the Fukushima Dai-ichi Nuclear
Power Plant in March 2011, consequently large quantities
of radioactive materials were released into the environment.
Farmlands and forests in Fukushima Prefecture were
widely contaminated and their products were affected by
the released radionuclides. The most importantradionuclides related to vegetation are Cs-134 (half-life:2y) and Cs-137 (half-life: 30y), which have relatively long
half-lives. Concentrations of radiocesium in vegetables andrice decreased with time. However, radiocesium
concentrations in edible wild plants and mushrooms often
exceeded the guideline (100 Bq/kg) for foods stuffs.
Therefore, it is important to identify plants whichaccumulate cesium and to clarify the transfer mechanism ofradiocesium. In this study, we analyzed both radiocesium
and stable cesium and considered the mechanism of highradiocesium transfer into the plants. We also compared thetransfer of stable cesium with other stable elements to
examine the availability of cesium to plants.

III. RESULTS AND DISCUSSIONRadiocesium concentrations differed by the plant
species. We first expected that the concentrations ofradiocesium should be similar within a same group(Araliaceae) collected from the same area. However, leavesof Acanthopanax sciadophylloides showed very highconcentrations up to about 20,000 Bq/kg. Therefore,transfer mechanism of cesium for Acanthopanax
sciadophylloides seems to be different from the other two
species of Araliaceae. For stable cesium, we also found thehighest concentration in this species. This suggests that thetransfer through roots should be a dominant pathway to
explain high radiocesium concentrations in Acanthopanax
sciadophylloides. The high uptake of stable cesium in thisspecies suggests that the contribution of translocation
pathways from barks and leaves might be low, because
stable cesium exists mainly in soils and not in barks of thetrees. In addition, we also compared stable Cs with K and
Rb which are also one of the alkali elements. The Cs/Rb
ratios and the Cs/K ratios in leaves of Acanthopanax
sciadophylloides were higher than those in the other speciesof Araliaceae and bamboo shoots. These findings indicatethat Acanthopanax sciadophylloides absorbs cesium
selectively than the other alkaline elements. In forests,
radiocesium is accumulated in surface soil layers (including
litter layer) in which contents of organic matters are high.
Since radiocesium is more mobile in organic layers
compared to mineral soil, it was more readily taken up by
the plant.
2.5
Radiocesium (×10� Bq kg�¹)

High concentrations of radiocesium were observed in edible wild
plants and bamboo shoots collected from forests in Fukushima
Prefecture following the nuclear accident. We have analyzed
radiocesium and stable cesium in a variety of plant samples. The
highest concentrations of radiocesium and stable cesium were
found in leaves of Acanthopanax sciadophylloides. The Cs/Rb
ratios and the Cs/K ratios were also high in this species. These
results suggest that leaves of Acanthopanax sciadophylloides
absorb Cs selectively from surface forest soil.

II. MATERIALS AND METHODS
Four different edible wild plants, Acanthopanax
sciadophylloides (Koshiabura), Kalopanax septemlobus(Harigiri), Aralia elata (Taranoki), bamboo shoots(Takenoko), were collected from forests in Iitate-mura,
Fukushima, and they were measured with a Ge-detector.
Then the samples were freeze-dried and milled with amixer. Powdered samples (0.1 g) were digested in teflon
vessels with an acid mixture (HNO3, HF and HClO4) on a
hot plate. After digestion, the samples were evaporated todryness. Then, the residues were dissolved in 2% HNO3.
Concentrations of stable elements (Li, Na, Mg, K, Ca, Mn,
Co, Cu, Zn, Rb, Sr, Cs and Ba) were determined by ICPMS. To have a better precision in the analysis, triplicate
samples were prepared and determined for these elements.

2

R² = 0.94

1.5
Koshiabura
1

Harigiri
Taranoki

0.5
0

0

0.2

0.4
0.6
Cs-133 (ppm)

0.8

1

Fig. 1. Relationship between radiocesium and stable cesium in plantleaves of Araliaceae collected from Iitate-mura, Fukushima.

－ 281 －

25-FKP-05

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Annual Variation of Radioactivity in Marine Biota in the Pacific off Fukushima
after TEPCO's Fukushima Daiichi Nuclear Power Station Accident
TatsuoAono 1, Satoshi Yoshida1, Tadahiro Saotome 2,Takuji Mizuno 2,
Yukari Ito3, Jota Kanda3, Takashi Ishimaru 3
1

National Institute of Radiological Sciences
Fukushima prefecture fisheries experimental station
3
Tokyo University of Marine Science and Technology
2

Abstract – Many kinds of marine biota could be observed in the
coastal area around off Fukushima after this accident, and it issuggested that the changes of activity are caused by the feeding
and sediment effects in biota.
Keywords – Marine organisms, 134Cs, 137Cs, 110mAg

I. Introduction
The pollution in marine environment spread byradioactive substances widely after the accident of
TEPCO's Fukushima Daiichi Nuclear Power Station(F1NPP) with the 2011 Great East Japan Earthquake andTsunami. It’s been 2.5 years since this accident. The
activities of Cs-134 and Cs-137 decreased exponentially inseawater. When the activities of radionuclides had
decreased in seawater, it was thought that these gradually
decreased in marine biota and sediment before this accident.
However, the high activities of radio casesium have beenmonitored in fish in the coast area around off Fukushima.
Little notice of the benthos was taken, because there are notedible as foodstuff. Marine biota were collected around off
Fukushima due to investigate the activities of radionuclides.
The aims of the present study were to examine thetemporal changes in radioactivity and to clarify thevariation factor in marine biota.

II. Method
Marine biota samples were collected with plankton net,dredge sampler, and trawl during the cruise of T/S Umitaka,
T/S Shinyo, and some research and fishing vessels. Afterbeing classified into species (Polychaete, Sea Urchin,
Starfish, Sea Slug and Crab etc.) and packed into a plastic
container. The radioactivity was determined by gamma ray
spectrometry using a HPGe detector (Canberra, GX-2019).
The activities of radionuclides of biota in the sampling datewere calculated with the correction of the decay and thecoincidence - summing of 134Cs. Detection limits of 134Cs,
137
Cs, and 110mAg were estimated within 1 and 0.5 Bq/kg(wet wt), respectively.

III. Results and Discussion
The radioactivities of 137Cs and 110mAg in marine biota
were from 1 to 400 Bq/kg (wet wt) and from less than 1 to55 Bq/kg (wet wt), respectively. The high correlation
between the activities in biota and densities in dry samples
were observed in the benthos. It is suggested that it iscaused by the feeding and sediments effects in biota.

－ 282 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-FKP-06

Migration behavior of 134Cs and 137Cs in the Niida River water in Fukushima
Prefecture, Japan during 2011-2012
Seiya Nagao1, Masaki Kanamori2, Shinya Ochiai1, Masayoshi Yamamoto1
1

2

Low Level Radioactivity Laboratory, Kanazawa University
Graduate School of Natural Science and Technology, Kanazawa University

Abstract – The radioactivity of 134Cs and 137Cs in the water
samples from the Niida River, which flows through highcontaminated area, was measured with gamma-spectrometry
using ammonium molybdophosphate (AMP)/Cs compound method.
Total radioactivity of 134Cs and 137Cs ranged from 0.254 to 4.18
Bq/L during May 2011-August 2012 and decreases withincreasing time except for the rain events. The radioactivity was
1.20 Bq/L for 134Cs and 1.83 Bq/L for 137Cs after the rain eventdue to the typhoon No.4 in June 2012. The particulate phase of134
Cs and 137Cs was 47-93% in normal flow condition and 86-91%
in high flow condition by rain events. These results indicate thatsuspended solids are major carrier of 134Cs and 137Cs in the Niida
River.
Keywords – radiocesium, radioactivity, heavy rain, suspended
solidsI.

INTRODUCTION

A nuclear accident at the Fukushima Daiichi Nuclear
Power Plant (NPP) occurred after the 2011 Tohoku
earthquake and tsunami. About 15 PBq of both 134Cs and137
Cs was released from the NPP as a result of venting
operations and hydrogen explosions. Surface deposition of134
Cs and 137Cs reveals considerable external radioactivity
above 3000k Bq/m2 in a zone extending northwest from the
NPP. Therefore, it is important to elucidate the short-term
to long-term impacts of the Fukushima Daiichi NPP
accident on ecosystems of river watershed environments.
This study investigated the transport of 134Cs and 137Cs in asmall river, Niida River running through IIdate, inFukushima Prefecture, Japan at normal and high flow
conditions during 2011-2012.

size of 7 µm) filters and a pore size of 0.45 µm membranefilters. Filtration was conducted using No. 5A filters andthen filtered with membrane filters.
The 134Cs and 137Cs were measured using gamma-ray
spectrometry with a low background Ge detector at the Low
Level Radioactivity Laboratory and the Ogoya
Underground Laboratory of Kanazawa University.
III. RESULTS AND DISCUSSIONRadioactivity of 134Cs and 137Cs in the river waters
ranged from 0.15 Bq/l to 3.83 Bq/l, and from 0.19 Bq/l to
4.18 Bq/L, respectively during May 2011-August 2012 (Fig.
1). Highest value was found in May 2011. The radiocesium
concentration indicates decreasing trend with increasingtime after the Fukushima Daiichi NPP accident. However,
the higher radioactivity was observed in March and June2012 after rain events.
Percentage of 134Cs and 137Cs associated with riverine
suspended solids was 47-48% at normal flow condition in
July and September 2011, but after December 2011 ranged
from 75 to 93% at normal flow condition and 86-91% athigh flow condition due to rain events. It appears to bedifferences in the radioactivity and existence forms between
early period of July-September and after December 2011.
These results indicate that the transport processes of134
Cs and 137Cs from watershed to river vary with riverwatershed condition and water discharge condition.
Figure 1. Radioactivity and percentage of particulate phase of 137Cs inwaters from the Niida River.

II. MATERIALS AND METHODS
Niida River is located in Fukushima Prefecture, Japanand flows through IIdate with higher contaminated area ofradiocesium and Minami-Souma with medium to low
accumulation area. It has a watershed area of 585 km2 and
78 km in length.
Field experiments were conducted at a fixed station in
the lower Niida River during the period of May 2011November 2012. The 20 L of surface river water samples
were collected at the station using buckets. In normal flow
condition, dissolved and particulate phase of radiocesium
was separated using cartridge filters with pore sizes of 10µm, 1 µm, and 0.45 µm. The radioactivity of 134Cs and137
Cs in the river waters before and after the filtration wasmeasured with gamma-ray spectrometry using ammonium
molybdophosphate (AMP)/Cs compound method. In heavy
rain events with typhoon, particles were separated using
centrifugation and filtration with No. 5A (approximate pore
－ 283 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-FKP-07

Migration Behavior of Radiocesium Released from Fukushima Daiichi Nuclear
Power Plant Accident
Toshihiko Ohnuki1, Naofumi Kozai1, Fuminori Sakamoto
1

Japan Atomic Energy Agency, Tokai, Ibaraki, 319-1195 Japan

Abstract – The migration behavior of radiocesium in plants
and soil collected in Fukushima, Japan have been studied
by the analyses of contaminated plants and soil using
autoradiography, sequential desorption, size fractionation,
XRD, and SEM analysis. Autoradiography analysis of tree
samples collected after 2 and 8 months after the accident
showed that radiocesium was mainly distributed as likespots on the branches and leaves of the trees emerged
before the accident, and was little detected in new branch
and leaves emerged after the accident. On the contrary,radiocesium was detected at the outermost tip of branches
in the trees collected after 20 months of the accident. Morethan 65% of radiocesium were remained in the residual
fraction of the soil samples after the sequential desorption.
Approximately 70% of radiocesium in the residual fraction
were associated with the size fractions larger than theelutriated one, even though mica like minerals were
contained in the elutriated one. Therefore, plants and soil
act as retardation barrier in the migration of radiocesium.
Keywords – Radiocesium, migration, autoradiography, desorpionI.

INTRODUCTION

The nuclear accident at the Fukushima Daiichi Nuclear
Power Plant (FDNPP) occurred as a consequence of themassive earthquake and associated tsunami that struck the
Tohoku and north Kanto regions of Japan on 11 March
2011. A series of hydrogen explosion was occurred from 13
March to 15 March at the units 1, 2, and 3. The release rateof 137Cs on 15 March is estimated between 1012 and 1015
Bq/h. This fallout radioactive Cs were dispersed from
FDNPP to ocean and land. Some of the released radioactive
Cs was deposited on the ground of the area located northwest direction from FDNPP. Many scientists have studied
migration of radiocesium to estimate dose rate and to
estimate the fate in the terrestrial environment. However,
the migration behavior of radiocesium is not fully
understood.
In the present study, migration behavior of radiocesium
has studied by the analyses of contaminated plants and soil
using autoradiography, sequential desorption, size
fractionation, XRD, and SEM analysis.
II. EXPERIMENTAL

the accident. For the analyses of soil spatial distribution
was measured by autoradiography, and mobility was
examined by sequential desorption using appropriate
desorption reagent solutions. Size distribution of residual
radiocesium after the sequential desorption was analyzed
by size fractionation using sieve and the elutriation. The
mineralogical components of soil were analyzed by XRD
and SEM-EDS analyses.
III. RESULTS AND DISCUSSION
The autoradiography analyses of Cryptomeria japonica,
Torreya nucifera, and Thujopsis dolabrata var. hondae
collected on approximately 2 and 8 months after theaccident showed that radiocesium was mainly distributed as
like spots on the branches and leaves of the trees emerged
before the accident, and was little detected in new branch
and leaves emerged after the accident. On the contrary,radiocesium was detected at the outermost tip of branches
in the trees collected after 20 months of the accident.
Morus alba collected after 22 months contained
radiocesium in and outside of the stem, even though noradiocesium was detected in the root, strongly suggestingthat some radioacesium was translocated from the outsidestem to inside. These results indicate that distribution ofradiocesium deposited on/in the trees has been graduallychanged with time in the scale of the year.
Autoradiography analysis of the thin section of soil
showed that radiocesium in soil was distributed as likespots on the soil particles. More than 65% of radiocesium
were remained in the residual fraction of the soil samples
after treatment of a 1 mole L-1 NH4Cl solution and a 1 mole
L-1 CH3COOH solution. Approximately 70% and 10% ofradiocesium in the residual fraction were associated withthe size fractions larger than the elutriated one and withelutriated one, respectively. XRD and SEM-EDS analyses
showed that a variety of minerals were present in the soil
involving mica like minerals. XRD spectrum of elutriatedsoil fraction showed the presence of mica like minerals.
These results strongly suggest that radiocesium wasirreversibly associated with soil components other thanmica like minerals in the contaminated soil.
Therefore, plants and soil function as barrier to retard
the migration of radiocesium deposited by the accident of
FDNPP.

The samples of plants were collected on the places
located between 4 and 55 km from FDNPP at
approximately 2, 8, 20, and 22 months after the accident.
The spatial distribution of radiocesium on the plants wasanalyzed by autoradiography analyses.
Soil was sampled in Iitate, Fukushima on 1 month after－ 284 －

25-FKP-08

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Research on Atmospheric Radionuclides from the Fukushima Nuclear Accident at
the MRI, Japan
Yasuhito Igarashi1, Koji Adachi 1, Taichu Tanaka1, Mizuo Kajino1, Tsuyoshi Sekiyama1,
Takashi Maki1, Yuji Zaizen1, Masao Mikami1
1

Meteorological Research Institute, Japan

Abstract – By the Fukushima nuclear accident, atmosphericenvironments over Japan, especially the eastern part, wereseriously polluted by a massive amount of the anthropogenic
radionuclides. The Meteorological Research Institute, Japan(MRI) has devoted into the clarification of these earlier
environmental impact not only by the observations but also bymodel simulation endeavors. Major research activities at the MRI
are briefly introduced in this presentation.

the degree of the pollution by the radio-Sr can confirm
trivial compared with Cs over the metropolitan region.
As further trials an imaging plate (IP) analysis, which
visualizes the radioactivity distributions in air filter samples,and particle analysis using a scanning electron microscope(SEM) with energy-dispersive X-ray spectrometer (EDS),
have been carried out. The purpose of these analyses is to
identify the host particles which carry the radionuclides.

Keywords – Fukushima nuclear accident, radio-Sr, radio-Cs,
Radioactive aerosol, Numerical transport and deposition
modeling

III. SIMULATION ENDEVOURSI.

INTRODUCTION

The Meteorological Research Institute, Tsukuba, Japan(MRI) has carried out observations on the atmosphericradionuclides for more than 50 years. In order to clarify the
impacts of the Fukushima nuclear accident in theatmospheric environment and its control factors, theobservations have continued after the disaster in March
2011. Also, the model simulations were conducted toreconstruct radioactive plume transport and depositions of
the radioactive contaminants over the regional as well as
the global environment.
II. OBSERVATION ENDEVOURSThe MRI locates ca.170 km southwest of the accidental
site. The monthly total deposition of 137Cs at the MRI was
23±0.9 kBq/m2 in March, 2011. This amount is 6-7 digits
higher than the level prior to the disaster. The total 137Cs
deposition was 25.5 kBq/m2 for the year 2011. Simple sumof the monthly 137Cs deposition flux due to the global
weapon tests since 1954 gives about 7 kBq/m2. Considering
the physical decay for the global fallout 137Cs, theFukushima 137Cs contamination could be about 20 times
larger than the global fallout. Almost the same extent of134
Cs deposited, thus the surface radio-Cs contamination
extended about 50 kBq/m2. This value almost corresponds
to that around Tsukuba obtained by the air-borne survey
conducted by the Ministry of Education, Culture, Sports,
Science and Technology, Japan (MEXT).
On the contrary, the monthly 90Sr deposition at the MRI
was 4.4±0.1 Bq/m2 in March, 2011, which was about
1/5000 of that of 137Cs during the same month. Referring to
the level before the disaster, this deposition exhibits 2-3
digits of enhancement; the environmental and healthimpacts were not as enormous as radio-Cs. The total 90Sr
deposition was about 11 Bq/m2 for the year 2011 and it was
about 1/2500 of 137Cs. Until the middle of 2012, the90
Sr/137Cs activity ratio varied about 400~5000 and after all

In order to improve our understanding of the temporaland spatial distributions of transport and depositions of theradionuclides due to the Fukushima accident, both global
and regional atmospheric transport models have been
employed. For the global transport MASINGAR (Model of
Aerosol Species IN the Global AtmospheRe), withhorizontal model grid of about 0.56o and 40 vertical layers(from surface to 0.4hPa), was used. The horizontal windcomponents were nudged by global analysis of Japan
Meteorological Agency (GANAL) dataset. The model
deals with 137Cs, 133Xe, and 131I. Emission flux estimates by
Chino et al. (2011) and Stohl et al. (2011) were used for137
Cs and 131I, and 133Xe, respectively. The model simulated
advective transport, eddy diffusion, convective transport,
dry and wet depositions, and radioactive decay.
More detailed distribution and processes for the
Fukushima radioactivity, a regional transport model MRIPM/r (Passive-tracers Model for Radioactivity) has beendeveloped. This model classifies the aerosol particles into 6
categories, and considers condensation, evaporation,cohesion, activation of cloud condensation nuclei and ice
nuclei,dissolution,
collision(washout),
cloud
microphysical processes (conversion processes amongrainout, cloud water, ice clouds, raindrops, snow, hail) anddry deposition. The model also incorporated physical andchemical processes of radionuclides and the interaction
with the environment aerosol.
In addition to these, emission analysis from the accident
by inverse modeling approach, and advanced approach ofensemble simulation of atmospheric dispersion ofradionuclides during the accident have been performed.
The overview of the current status and challenges ofthese observations as well as simulation studies are given.
[1]
[2]
[3]
[4]
[5]
[6]

－ 285 －

Igarashi et al., 2013EGU
Adachi et al., 2013EGU
Maki et al., 2013EGU
Sekiyama et al., 2013EGU
Tanaka et al., 2013AMS
Kajino et al., 2011JMSJ Fall Meeting25-FKP-09

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Presuming techniques of radioactive cesium concentration in muscle for beef cattle
T. Ohtsuki1, F. Koga2, M. Uchida2, Y. Ishikawa2, T. Takase3, K. Kawatsu3, M. Mogi4 S. Murayama4,
Y. Izumi4, H. Kikunaga1, T. Tachiya5, Y. Shiraishi2, K. Endo2
1

Research Center for Electron Photon Science, Tohoku University
Fukushima Agricultural Technology Center Livestock Industry Research Center, Fukushima Prefecture
3
Faculty of Symbiotic System Science, Fukushima University
4
Japan Environment Research Co., LTD,
5
Comtec Eng. Co., LTD, Fukushima

2

Abstract – The contamination of livestock products by theradioactive cesium (Cs134 and Cs137) is a serious problem in
Tohoku area after the accident of the Fukushima No.1 nuclear
power plant. The presuming techniques of the radioactive cesium
concentration in muscle and blood for these beef cattle weredeveloped in this study. We found that the measurements of theradioactive cesium from outside of body are really possible byusing several inches(“) NaI scintillation detectors.
Keywords – radioactive cesium, beef cattle, measurement fromoutside of body, NaI scintillation detector

I.

INTRODUCTION

The contamination to the livestock products, byradioactive cesium is becoming a serious problem in
Tohoku area after the accident of the No.1 nuclear power
plant of Fukushima. Especially, beef cattle which fed
excessively contaminated stock food should be still
continuously monitored. Since Ge-detectors are restricted
and if we use them, so much time is needed for presumingof the cesium contamination by taking blood sample[1],then, another technique for the concentration check insidebody(muscle) for the living cattle should be considered.
Here we demonstrate the monitoring system by using NaI
scintillation detectors from outside of cattle body.

MCA(digiBASE)
collimator5” NaI

Fig. 1(a) 5” NaI detector and its collimator: setting inside
the collimator, (b)Measurement system of cattle fromoutside of the body (special frame for keeping the cattlebody).
III. RESULTS
Results of the measurements are shown in Fig. 2. From
the figure it is clearly seen the cesium peaks, namely, thecesium contaminated cattle has much higher count rates of
Cs134 and Cs137 than those of the contamination-freecattle even though the similar count rates of K40 between
them. Small peaks of Cs134 and Cs137 for contaminationfree cattle are due to the back ground from atmosphere.
Detail of the results will be shown and discussed in theconference.

II. MONITORING SYSTEM AND MEASURENENTS
The monitoring system is consist of 2”, 2.5” and 5” NaI
scintillation detectors for measuring the Cs134 and Cs137
concentrations in the cattle body, collimators (Pb material),
phantoms (plastic tank: the specific liquid like insidematerials are contaminated by several concentrations of
Cs134 and Cs137), special frame for keeping the cattle
body on the inside and its radiation shielding materials
consist of several sheets of Pb curtains. We use a portable
MCA system for data acquisition. The 5” NaI detector andits collimator are shown in Fig. 1(a) and the special framefor keeping the cattle body and the portable MCA system
are also shown in Fig. 1(b). Firstly, we took calibration
curves between the Ge and NaI detectors by using
phantoms by which the cesium concentration is known.
The practical measurements were performed by comparisonof contamination-free cattle and contaminated them. The
measurement time and position were set to 600 sec at thethigh and haunches (further shorter time like 300 sec. isneeded for the measurements). The data are analyzed by thecode Fukushima by provided Niki Grass Co. Ltd. for doing
better deconvolution.

Fig. 2 Two spectra with 5” NaI scintillation detector are
shown, the results of contaminated cattle fed by thecontaminated stock food (higher count rate) and thecontamination-free cattle (lower count rate).
[1] T. Takase et. al., Radioisotopes 62 (2013), in press.

－ 286 －

25-FKP-10

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Spatio-temporal distribution of atmospheric radiocesium at monitoring stationsfor Suspended Particulate Matter in Fukushima area released from the TEPCO
Fukushima Daiichi Nuclear Power Plant accident
Haruo Tsuruta1, Yasuji Oura2, Mitsuru Ebihara2, Mitsunori Ishimoto3, Yosuke Katsumura3,
Toshimasa Ohara4, Teruyuki Nakajima1
1

Atmosphere and Ocean Research Institute, The University of Tokyo, Japan2
Department of Chemistry, Tokyo Metropolitan University, Japan
3
Center for Regional Environmental Research, National Institute for Environmental Studies
4
Nuclear Professional School, The University of Tokyo, Japan

Keywords Spatio-temporal distribution,
Fukushima, filter tapes of SPM monitor

I.

atmospheric

137

Cs,

INTRODUCTION

No data has been found of continuous monitoring ofradioactive materials in the atmosphere in Fukushima area
after the Fukushima Daiichi Nuclear Power Plant(FD1NPP) accident on March 11, 2011, although it greatly
contributes to accurate evaluation of the internal exposure
dose, to reconstruction of emission time series of released
radionuclides, and to validation of numerical simulations
by atmospheric transport models. Then, we havechallenged to retrieve the radioactivity in atmosphericaerosols collected every hour on a filter tape which was
installed in Suspended Particulate Matter (SPM) monitor
with beta-ray attenuation method used at air pollution
monitoring networks in Japan. In the previous paper [1],the concentration of 134Cs and 137Cs collected on the filter
tapes has been successfully measured by a Ge detector, andtime series of hourly atmospheric concentrations of 134Cs
and 137Cs was also made at many monitoring stations for
SPM in Fukushima prefecture and the adjasent areas. The
purpose of this paper is that, by using these data, spatiotemporal distribution of 137Cs will be shown in Fukushima
area, and the transport of radioactive materials from the
FD1NPP will be discussed by analyzing meteorological
data and radiation dose rate.

Nakadori

FD1NPP

Abukuma
Highlands

prefecture (Fig. 1) during March 15-16 and 20-23, 2011,
was used for a detailed analysis. Meteorological data of
AMeDAS stations, GPV (Grid Point Value) and RadarAMeDAS precipitation by Japan Meteorological Agency
was also used. Regional deposition rate for 137Cs on theearth’s surface with airborne measurements by MEXT wasused in comparison with spatial distribution of the polluted
air masses.
III.

RESULTS AND DISCUSSIONHigh concentrations of 137Cs (>10 Bq m-3) were measured
in Nakadori twice, the first period from 9:00 (JST) Mar. 15
to 3:00 Mar. 16, and the second period from 13:00 Mar. 20
to 06:00 Mar. 21. In the first period, the polluted air masses
transported from the FD1NPP over Abukuma Highlands,
were found in the afternoon of Mar. 15. The time of the
maximum concentration changed from the early afternoon
in the south to the night in the north, and the maximum
concentration was much higher in the south than in thenorth. According to the deposition rate of 137Cs on the soil
surface in regional scale measured by MEXT [2], higher
deposition rate was measured in the northern part than in
the southern part, possibly due to more precipitation in thenorthern part. In the second period, however, higher 137Csconcentrations began to be measured in the northern part in
the early afternoon of Mar. 20. In the night, the time of the
maximum 137Cs was found early in the north and late in thesouth. During the second period, radiation dose rate in
Nakadori did not show any increase due to no precipitation.
Thus, the radiocesium dataset by measuring filter tapes
installed in the SPM monitor is very useful to retrieve thespatio-temporal distribution of 137Cs in an area which has
no continual data of radionuclides in the atmosphere.
[1] Oura, Y. et al.: a paper in this Symposium, 2013[2] MEXT: Intensive field study on the measurements of radionuclides
deposited on the soil surface in east Fukushima, HP of MEXT, 2011.

Fig. 1 SPM monitoring stations in Fukushima prefecture

II. DATA FOR ANALYSIS
Hourly atmospheric concentrations of 134Cs and 137Cs inseveral monitoring stations in Nakadori of Fukushima－ 287 －

25-EDP-01

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Education of Nuclear and Radiochemistry in Hallym University, Korea
Y. H. Chung

Department of Chemistry, Hallym University, 1 Hallymdaehak-gil, Chuncheon 200-702, Korea
yhchung@hallym.ac.kr
Nuclear and radiochemistry course has been provided by
Department of Chemistry in Hallym University (HU) for
more than ten years. It is designed mainly forundergraduates who want to pursue their career in thepertinent fields such as chemistry of spent fuel of nuclear
reactors,
radiopharmaceuticalchemistry,
radiation
chemistry and nuclear chemistry. There are twenty-two
reactors currently operating in Korea and a few researchfacilities are treating cancer patients using an accelerator. A
heavy-ion accelerator, RAON, will be commissioned in2017 and provide various rare isotopes produced by IF (inflight fragment) and ISOL (Isotope Separation On-Line)methods [1]. RAON’s superconducting linear accelerator
will accelerate uranium beam up to 200 MeV/u with 400
kW beam power. In addition to RAON, a KHIMA (Korea
Heavy Ion Medical Accelerator) project for cancer therapy
was initiated in 2010 by KIRAMS (the Korea Institute ofRadiological & Medical Sciences) and will include asuperconducting cyclotron to be completed at the end of2016 [2]. The cyclotron will provide heavy ions whose
maximum energy and beam intensity are 430 MeV/u and1.7x1010 pps, respectively. Nuclear and radiochemistry
program in Hallym University is going to embrace theongoing progress in Korea.
[1] S. K. Kim, RAON: Heavy Ion Accelerator for Rare Isotope Science in
Korea, The 16th Inter. Conf. on Accelerators and Beam Utilizations,November 8-9, 2012, Gyeongju, Korea.
[2] G. B. Kim, Current Status of KHIMA Project, The 16th Inter. Conf. on
Accelerators and Beam Utilizations, November 8-9, 2012, Gyeongju,
Korea.

－ 288 －

25-EDP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Use of Small 68Ge/68Ga Generators in Experiments for the Education ofRadioisotope-related Fields as well as of Natural and Social Sciences in General
Tadashi Nozaki,1 Koji Ogawa2
1

School of Sciences, Kitasato University
School of Allied Health Sciences, Kitasato University

2

Experiments undertaken in schools usually give more
vivid and unforgettable impression to the students than
lectures. Several characteristics of radioisotopes can be usedefficiently in the education of radioisotope-related fields aswell as of natural and social sciences in general. Many
radioisotopes useful for education are given from isotope
generators, of which 68Ge/68Ga generator has proved to be of
the widest use, as understood from the decay properties ofboth nuclides shown here and from chemical properties of thedaughter, 68Ga.
68

Ge: 271 d, EC, no���---- Black matter for many detections
Ga: 67.7 m; ���, 90 % 1.9 MeV; EC, 10 %����������eV 1.0 %, etc.

68

Although large scale 68Ge/68Ga generators for PET use
are commercially available, we were unable to find any stablesupply of small types. For full use of this generator, thus weshould become able to make it by ourselves. First we
examined the method of preparing the adsorbent for parentdaughter separation, and have proved the following procedure
to be highly useful: (1) prepare gelatinous precipitate of
hydrated SnO2 from SnCl4 and NaOH solutions and wash itby repeated centrifugation and re-suspension in water; (2)collect and warm gently the centrifuged mass with occasional
turn-over with a non-metallic spatula to give moist particles;�������������������������������������������������������������
to crash them into smaller sizes, and leave them overpotassium acetate (CH3CO2K) at room temperature fordrying; (4) after 1 week, treat the particles just as in Step 3
but with a sieve ��� ������ ���� ��� ����� ������ �5) collect bysieving particles of about 50 to ������ size, and keep themover CH3CO2K; (6) after more than 2 weeks, dip the particles
in refluxing 0.1 M HNO3 for 3 hours, and (7) after being left
to cool, replace the HNO3 with 1 M HCl. After 2 days, theparticles, hydrated SnO2, is ready for use.
Usually 1 mL disposable plastic syringe is used for thegenerator column, to which the adsorbent (apparent volumeof 0.3�0.4 mL) suspended in HCl is added. Then 1 M HCl
solution of 68Ge (1 to 100 kBq) with daughter 68Ga is added
to the column. The column is further washed with 100 mL of
1 M HCl flowing slowly through it for wash away some finesuspensions . In Japan, the generator with 68Ge activity under
100 kBq can be used free from law regulation.

The 68Ga is eluted into 1/3 mL of 1 M HCl in about 30 sec
with 65-70 % yield. Since quantitative separation is possiblefor 68Ge and 68Ga in 1 M HCl, some hot-atom effect isthought to make 68Ga formed in the column partly nonelutable. Under frequent milking, the breakthrough of 68Ge isa few tens ppm. No change was observed in thesecharacteristics in 9 months, the half-life of 68Ge.
Self-making of the generator is thought to be a common
experimental theme, and can be guessed to give joy andsatisfaction to the participants in handling samples preparedby their self-made devices, even when ready-made adsorbent
was supplied them in the generator making. Comparison of
the growth curve of 68Ga observed after milking with thecurve obtained by calculation from the differential equation is
expected to be highly effective in the study of how to treat
some observed phenomena by mathematical means. The
eluted 68Ga is highly suitable for the following chemical
experiments: adsorption on cellulose under various pH;
solvent extraction and ion exchange separation; and isotopic
exchange between Ga3+ and Ga-EDTA complex.
We have almost completed a guide book for theexperiments given above, and now are working further for thefollowing themes: (1) utilizing the generator as the source ofannihilation radiation, �-ray absorption by various substances,and coincidence measurement for localization and for low
background counting; and (2) utilizing 68Ga as tracer, studies
on contamination and decontamination, leak hunting,synthesis of radiopharmaceuticals, and measurement of
uptake by plants.
Since a vast variety exists in the principal aim,
experiences and scientific levels of possible candidates to theexperimental study, at least three courses should be prepared.
Also, the guide book should be so made as the teachers andinstructors are able to select adequately the themes for eachcourse. As for usual high school curriculums, only a few toseveral days are allotted to the education related with nuclear
phenomena. Hence, it is of prime importance, we believe, to
set up a rental system, in which generators, radiation
detectors, etc., are sent to individual high schools fromregional centers according to predetermined schedules,
preferably together with instructor(s).

－ 289 －

25-NFP-01

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Application of alpha spectrometry to the measurement of a single plutonium
particle for nuclear safeguards
Kenichiro Yasuda, Daisuke Suzuki, Fumitaka Esaka and Masaaki Magara
Research group for analytical chemistry, Japan Atomic Energy Agancy

Abstract – For rough estimation of isotopic composition in asingle plutonium particle before precise measurement by thermal
ionization mass spectrometry (TIMS), alpha spectrometry wasdemonstrated using 10 particles in a standard reference material
NBS947. The particles with diameters of around one micrometer
were picked up and put onto TIMS filaments by amicromanipulator attached to a scanning electron microscope(SEM). The particle on the filament was transferred to an alpha
spectrometer chamber. And then, the activity ratio of(238Pu+241Am)/(239Pu+240Pu) was measured for each particle.
Finally, precise Pu isotope ratios of 240Pu/239Pu and 241Pu/239Pu
were determined with TIMS. The measured activity ratios andisotope ratios were in good agreement with the reference data
within the measurement uncertainty.
Keywords – alpha spectrometry, plutonium particle, nuclear
safeguards

I.

INTRODUCTION

The International atomic energy agency (IAEA) has
adopted environmental sampling as a new method for thestrengthened safeguards system [1-2]. The objectives ofthis method are to detect undeclared nuclear materials andactivities. One of the analytical methods for environmental
sampling is particle analysis, which is a powerful tool for
nuclear safeguards to detect undeclared nuclear activities.

In this method, isotope ratios of nuclear materials inindividual particles were measured by secondary ion mass
spectrometry (SIMS) [3-5] or thermal ionization mass
spectrometry (TIMS) [6-8]. Prior to the analysis with TIMS,
the particle containing nuclear materials should be put onto
a filament. However, there is no conclusive proof that
nuclear materials exist in the particle on the filament. The
purpose of this study is to check if the particle on thefilament contains nuclear materials before measuring theisotope ratios by TIMS, and to compare the activity ratios
and the isotope ratios of the particle.

[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

－ 290 －

D.L. Donohue, J. Alloys Compd., 11, 271-273 (1998).
D.L. Donohue, Anal. Chem., 74, 28A-35A (2002).
G. Tamborini, M. Betti, V. Forcina, T. Hiernaut, B. Giovannone, L.
Koch, Spectrochim. Acta B53, 1289-1302 (1998).
M. Betti, G. Tamborini, L. Koch, Anal. Chem., 71, 2616-2622(1999).
F. Esaka, K.T. Esaka, C.G. Lee, M. Magara, S. Sakurai, S. Usuda, K.
Watanabe, Talanta, 71, 1011-1015 (2007).
C.G. Lee, L. Iguchi, F. Esaka, M. Magara, S. Sakurai, K. Watanabe,
S. Usuda, Jpn. J. Appl. Phys., 45, L294-L296 (2006).
C.G. Lee, D. Suzuki, F. Esaka, M. Magara, N. Shinohara, S. Usuda,
J. Nucl. Sci. Technol., 46, 809-813 (2009).
O. Stetzer, M. Betti, J. van Geel, N. Erdmann, J.V. Kratz, R.
Schenkei, N. Trautmann, Nucl. Instrum. Meth. Phys. Res. A525,
582-292 (2004).

25-NEP-01

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

High LET Radiolytic Degradation Studies of Separation Processes for Spent
Nuclear Fuel
Jeremy Pearson and Mikael Nilsson

University of California – Irvine, USA
Department of Chemical Engineering and Materials Science,916 Engineering Tower, Irvine, CA, 92697
E-mail: nilssonm@uci.edu
Treatment of used nuclear fuel through solvent extraction
separation processes is hindered by radiolytic damage fromradioactive isotopes present in used fuel. The nature of thedamage caused by the radiation may depend on theradiation type, whether it be low linear energy transfer(LET) such as gamma radiation or high LET such as alpharadiation. Used nuclear fuel contains beta/gamma emitting
isotopes but also a significant amount of transuranics which
are generally alpha emitters. The effects of gamma
radiation on solvent extraction ligands have been more
extensively studied than the effects of alpha radiation. Thisis due to the inherent difficulty in producing a sufficientand confluent dose of alpha particles within a sample
without leaving the sample contaminated with long lived
radioactive isotopes. Helium ion beam and radioactive
isotope sources have been studied in the literature. We havedeveloped a method for studying the effects of high LET
radiation in situ via 10B activation and the high LET
particles that result from the 10������7Li reaction which
follows. This method has been applied to organic solutionsof TBP and CMPO, two ligands common in TRU solvent
extraction treatment processes. Rates of degradation of
TBP and CMPO and their respective degradation productsin the presence of high LET radiation are presented anddiscussed. These results are also compared to gamma
studies performed in our lab and other gamma and alphastudies found in the literature. The possible application ofthis method to a variety of other solvent extraction ligands
to study the effects of high LET radiation is also considered.

－ 291 －

25-NEP-02

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effects of helium retention and lithium depletion on tritium behaviors in Li2TiO3
1

Makoto Kobayashi1, Hiromichi Uchimura1, Kensuke Toda1, Misaki Sato1,
Katsuyoshi Tatunuma2, Yasuhisa Oya1 and Kenji Okuno1

Radioscience Research Laboratory, Faculty of Science, Shizuoka University, Shizuoka, Japan
2
Kaken Co. Ltd., 1044, Hori, Mito-city, Ibaraki, 310-0903, Japan

Abstract – The effects of helium retention on tritium behaviors inlithium-titanate (Li2TiO3) were investigated. The synergetic effectof helium retention and lithium-depletion was also examined withusing lithium-depleted Li1.8TiO2.9. Deuterium introduced into
Li2TiO3 by ion implantation was desorbed as three peaks at 400,
490 and 620 K. Deuterium retention at 400 K for Li1.8TiO2.9 waslarger than that for Li2TiO3 due to the existence of larger amountof lithium vacancies. Deuterium retention by lithium vacancies
was decreased by He implantation because of the occupation ofvacancies by He.
Keywords – Tritium, Li2TiO3, Helium, TDS

I. INTRODUCTION

For the establishment of D-T fusion reactors, acomprehensive model of tritium migration processes insolid tritium breeder materials must be developed.
Tritium migration behavior in lithium-titanate (Li2TiO3),
which is one of candidates for tritium breeder materials,
has been studied by out-of-pile annealing experiments.
However, the effects of helium generated by Li(n,�)Treaction on tritium migration in Li2TiO3 have not been
focused in detail. It is generally known that helium canretain in the materials by forming bubbles, which will
exist in Li2TiO3 after long-term operation, and affect on
tritium migration process by acting as diffusion passes
and/or trapping sites. These predictions motivated us toinvestigate the contributions of helium retention on
trapping and release of hydrogen isotopes in Li2TiO3.
The pre-irradiation of He+ was performed into sintered
Li2TiO3 pellet. Thereafter, D2+ irradiation was carriedout. Thermal desorption spectroscopy (TDS)
measurements were adopted for the elucidation of
deuterium retention and release behaviors. The same
experimental procedure was also done for lithiumdepleted Li2TiO3 (Li1.8TiO2.9) to understand the effectsof helium retention with lithium burn-up, which are
simultaneously occurred in actual environment.

desorption behaviors were examined by TDS using ahigh resolution mass spectrometer to separate He+ andD2+ from room temperature to 1173 K with the heating
rate of 5 K min-1..
III. RESULTS AND DISCUSSION
D-TDS spectra for Li2TiO3 and Li1.8TiO2.9 are shownin the figure. D-TDS spectrum for only D2+ irradiated
Li2TiO3 showed that D release was distributed in thetemperature of 350- 750 K. The D release spectrum wasconsisted of three release peaks at around 400, 490 and
620 K. The TDS spectrum for the D2+-irradiatedLi1.8TiO2.9 also showed the same D release peaks.
However, the deuterium retention in the peak at 400 K
was increased compared to that for Li2TiO3. This factindicates that deuterium released at 400 K was weakly
trapped by lithium vacancies. He+ pre-irradiated Li2TiO3showed the decrease of deuterium retention in therelease peaks at 400 and 490 K. The deuterium trappingsites for the release peaks at 490 K and 620 K would be
the irradiation defects such as oxygen vacancies and thedangling oxygen atoms, respectively. Therefore, helium
retention would only reduce the deuterium retention in
irradiation defects. These results suggest that helium
would disturb deuterium to retain at irradiation defects
by substituting them, however, hardly affects forchemical binding due to the little chemical affinity ofhelium.

II. EXPERIMENTAL
The powders of Li2TiO3 and Li1.8TiO2.9 were pressed
into a disc shape with the size of 10 mm� × 0.5 mmt, andsintered at 1173 K for 3 h. These samples were installed
into a vacuum system and heated at 1173 K for 3 h toremove impurities. The He+ implantations were donewith the implantation energy of 3 keV He+, ion flux of
1.0 × 1018 He+ m-2 s-1 and ion fluence of 1.0 × 1022 He+m-2. Thereafter, 3.0 keV D2+ implantations were carriedout with the ion flux and ion fluence of 2.0 × 1018 D+ m2 -1
s and 2.0 × 1022 D+ m-2, respectively. The deuterium－ 292 －

Fig. D-TDS spectra for Li2TiO3 and Li1.8TiO2.9
with D2+ and He+ implantations

25-NEP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Adsorptivity of Various Metal Ions
onto Benzo-18-crown-6 and Dibenzo-18-crown-6 Resins
Masanobu Nogami1, Tomohiro Haratani1, Yu Tachibana2, Toshitaka Kaneshiki3,
Masao Nomura3, Tatsuya Suzuki2
1

2

Department of Electric and Electronic Engineering, Kinki University
Department of Nuclear System Safety Engineering, Nagaoka University of Technology
3
Research Laboratories for Nuclear Reactors, Tokyo Institute of Technology

Abstract – Adsorptivity of various metal ions onto silica-supported
resins consisting of benzo-18-crown-6 (B18C6) and dibenzo-18crown-6 (DB18C6), repectively, was investigated in hydrochloric
acid and nitric acid media. Pd(II) and Ag(I) for HNO3 and Fe(III)and Ba(II) for HCl were found to be adsorbed by both resins,
respectively. It was also found that Sr(II) for HCl and Ca(II) for
HNO3 were adsorbed by B18C6 and DB18C6 resins, respectively.
These facts indicate that the two resins which have almost the samering size adsorbed metal ions with smaller cationic diameters except
Ba(II) with different selectivity.
Keywords – benzo-18-crown-6, dibenzo-18-crown-6, resin, nuclide
separationI.

INTRODUCTION

It is well known that macrocyclic compounds such as
crown ethers selectively form complexes with metal ions, andtheir applications to the treatment of radioactive liquid wastes
by liquid-liquid extraction have widely been investigated.
Recently we have synthesized silica-supported resins wherecrown ethers are chemically bonded to the polymer
network[1,2]. The chemical structure of dibenzo-18-crown-6(DB18C6) resin, for example, is shown Figure 1. So far the
resins have mainly been studied for the purpose of isotope
separation, e.g. zinc and calcium, and little information on
adsorptivity of various metal ions by these resins is available.
In the present study, adsorptivity of various metal ions onto
benzo-18-crown-6 (B18C6) and DB18C6 resins wasinvestigated in hydrochloric acid and nitric acid media.

II. EXPERIMENTAL
B18C6 and DB18C6 resins were synthesized by following
the earlier paper[2]. Adsorptivity of metal ions by the resins
to at equilibrium was examined by a batch method at 25oC
using solutions of HNO3 or HCl up to 9 mol/dm-3 (= M)containing each metal ion (1mM).
III.

RESULTS AND DISCUSSION

Pd(II) and Ag(I) for HNO3 and Fe(III) and Ba(II) for HCl
were found to be adsorbed by both resins, respectively. It wasalso found that Sr(II) for HCl and Ca(II) for HNO3 wereadsorbed by B18C6 and DB18C6 resins, respectively. In
general, the distribution ratios increased with increasing
concentrations of HCl. On the other hand, dependence of
HNO3 concentrations on the distribution ratios was foundmuch smaller for HNO3 system. No or very little adsorptions
were observed for the other examined metal ions. These facts
indicate that the two resins which have almost the same ring
size adsorbed metal ions with smaller cationic diameters
except Ba(II) with different selectivity. Extraction
experiments using DB18C6 and dichloromethane as thediluent showed different selectivity, i.e., Zn(II) and Zr(IV)were extracted from HNO3 of higher concentrations andFe(III) was extracted from HCl of higher concentrations,
respectively. No or very little extractions were observed forthe other examined metal ions. Such a difference may result
from the structure except the part of DB18C6, e.g. oxygen
atoms of the hydroxyl group. Investigation of detailed
adsorption mechanisms is the task in the future.
ACKNOWLEDGMENT
This work was partially supported by the Grant-in-Aid for
Scientific Research (B) (KAKENHI No. 23360423).
[1]

Figure 1 Chemical structure of DB18C6 resin[2]－ 293 －

Ding X, Suzuki T, Nomura M, Kim HJ, Sugiyama Y, Fujii Y (2007) J
Radioanal Nucl Chem 273:79-84
Hayasaka K, Kaneshiki T, Nomura M, Suzuki T, Fujii Y (2008) Prog
Nucl Energy 50:510-513

25-NEP-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Cesium adsorption ability and stability of metal hexacyanoferrate irradiated withgamma-rays
Makoto Arisaka1, Masayuki Watanabe1, Manabu Ishizaki2, Masato Kurihara2, Rongzhi Chen3, Hisashi
Tanaka3
1

Research Group for Radiochemistry, Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency
2
Department of Material and Biological Chemistry, Faculty of Science, Yamagata University
3
Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology

Keywords – cesium, metal hexacyanoferrate, gamma-irradiation,
adsorption ability, stability

I.

INTRODUCTION

Metal hexacyanoferrate, MHCF, is known as anadsorbent for selective adsorption of cesium (Cs) ion insolutions. In nuclear industry, an application of MHCF (M= Fe, Cu or Ni) to recovery of Cs from high level
radioactive waste has been studied. Recently, we reported
an electrochemical application of MHCF for Cs recovery [1,2].
It has been commonly accepted that the selectivity of
MHCF to Cs ions are caused by regular lattice spaces
surrounded by cyanide-bridged metals. However, theintrinsic mechanism of Cs ion adsorption still has not been
made clear. So far, we have revealed that synthesized
FeHCF, obtained as a charge-compensated salt
(FeIII4[FeII(CN)6]3), has much higher Cs adsorption ability
than that of commercially purchased FeHCF, i.e., prussian
blue having ideal perfect lattice. The higher ability is
attributed to the presence of lattice defect sites [3].
In this study, the influence of irradiation with gammarays to MHCF having lattice defect sites on Cs adsorption
ability and stability in HNO3 solutions was investigated for
application of MHCF to practical Cs separation process.
II. EXPERIMENTAL
Irradiated sample is a mixture of MHCF and HNO3
solution. MHCF used in this study is as follows;
FeIII4[FeII(CN)6]3 (FeHCF), CuII3[FeIII(CN)6]2 (CuHCF),
NiII3[FeIII(CN)6]2 (NiHCF).

Irradiation with gamma-rays was done at the Co-60
gamma ray irradiation facilities in Takasaki Advanced
Radiation Research Institute of Japan Atomic Energy
Agency. Samples in glass tubes were intermittently
irradiated with gamma-rays from 1.0 × 1016 Bq 60Co source
at an absorbed dose rate of 10 kGy h-1 in air at room
temperature for a maximum of 27 hours. A dose absorbed
by each sample was corrected for an electron density.
Absorbed doses were calibrated by a cellulose triacetate
film dosimeter.
III. RESULTS AND DISCUSSION
After gamma-ray irradiation, the HNO3 solutions wereseparated from the sample by filtration. To evaluate theradiolytic degradation of MHCF, the amount of M (= Fe,
Cu or Ni) in HNO3 solution was determined by ICP-AES.
The result for CuHCF was shown in Fig.1 as an example.
It was found that the amounts of Fe and Cu increasedslightly with an increase of the total adsorbed dose. The
increase was attributed to radiolytic decomposition of
CuHCF. Under the adsorbed dose conditions (50 - 300kGy), the weight percent of Fe and Cu in the solutions toinitial weight of CuHCF was less than 0.05%. From theviewpoint of usage for a long period, it suggests that the
CuHCF is fully stable. Moreover, the composition ofcarbon, nitrogen and hydrogen in CuHCF is independent of
the total adsorbed dose.
The Cs adsorption experiment was performed using theirradiated MHCF as adsorbent.
The distribution
coefficients of Cs into MHCF were independent of the total
adsorbed dose. This indicates that the Cs adsorption ability
was maintained under gamma-ray irradiation.
0.06
0.04
%

Abstract – The influence of irradiation with gamma-rays to metal
hexacyanoferrate (MHCF: M = Fe, Cu or Ni), which is known as
an adsorbent for selective adsorption of cesium (Cs) ion insolution, on Cs adsorption ability and stability was investigated in
HNO3 solutions. Under the adsorbed dose conditions (50 - 300kGy), it was found that the MHCF is fully stable although theradiolytic decomposition of MHCF was slightly observed with anincrease of the total adsorbed dose, which was confirmed by anincrement of Fe, Cu or Ni concentration in HNO3 solution after
the irradiation. The weight percent of the metal in the solution toinitial weight of MHCF was less than unity. Moreover, no change
in composition of carbon, hydrogen and nitrogen in MHCF wasobserved. On the other hand, the distribution coefficients of Cs to
the irradiated MHCF were independent of the total adsorbed dose.
This indicates that the Cs adsorption ability was maintained
under gamma-ray irradiation.

0.02
0

0

100 200 300 400
kGy

Fig.1 Weight percent of Fe (�) and Cu (�) to initial weight of CuHCF
in HNO3 solutions after the irradiation.
[1]
[2]
[3]

－ 294 －

R. Chen et al., Electrochem. Commun., 25, 23-25 (2012).
R. Chen et al., Electrochim. Acta, 87, 119-125 (2013).
M. Ishizaki et al., Phys. Chem. Chem. Phys., submitted.

25-NEP-05

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Residual Actinides Separation from the DIAMEX/SANEX Secondary Waste andDecontamination of the Spent DIAMEX Solvent from the “Difficult-to-Strip”
Elements
Jan John, Ferdinand Šebesta, Kamil V. Mareš, František Klimek, Martin Vlk

Czech Technical University in Prague, Department of Nuclear Chemistry, Brehova 7, 115 19 Prague, Czech Republic
Abstract

One of the contemporary issues connected with thespent nuclear fuel is its reprocessing. The presence oflong-lived radionuclides in the spent nuclear fuel is
responsible for its long-term radiotoxicity. A decrease of
the long-term radiotoxicity may be achieved by partitioningof minor actinoids with their subsequent transmutation. The
main goals of the Partitioning and Transmutation are
decreasing the time and the volume needed to store highradioactive waste, and a reduction of the hazard associatedwith the spent fuel and radioactive waste.
Among the processes under development for thePartitioning, the families of DIAMEX and SANEX
processes studied by the broad international collaborations
in Europe should be mentioned. This paper summarizes theresults of the studies of two process-relevant issues of theseprocesses – development of materials and processes for the
residual actinides separation from the secondary waste, anddecontamination of the spent organic solvent from the“difficult-to-strip” elements.
During the study of materials and processes for residual
actinides separation, the behaviour of TODGA–PAN solid
extractant in applications involving processing of large
volumes of solutions was tested. In an experiment with
5.10–5M Eu(NO3)3 sorption from 3M HNO3, it was
confirmed that no significant washing of TODGA from thesolid extractant occurs even during the processing of morethan 300 BV of the simulated waste. In another experiment,
it was shown that the repeated sorption / elution cycles do
not significantly influence the practical sorption capacity ofthe solid extractant.
For the mutual separation of An and Ln, preconcentrated from the secondary waste streams, two novel
solid extractants (SEXs) – the E5-C5BTBP[nitrobenzene]
and E5-CyMe4BTBP(cyclohexanone) – were proposed anddeveloped. With the E5-C5BTBP[nitrobenzene] SEX, very
good separation of americium and europium was achieved.
From a loaded column, 98.6 % of europium was washed in
8.7 BV of the eluant; the europium fraction contained only
0.3 % of the total amount of americium sorbed on thecolumn. Then, americium was efficiently eluted with 0.5M
glycolic acid with pH ~ 4. In the total volume of the eluant
used (3.1 BV), 99.7 % of americium was recovered; theamericium fraction contained 1.4 % of the amount ofeuropium originally sorbed on the column.
The E5-CyMe4BTBP(cyclohexanone) SEX was tested
for the selective separation of An from Ln and othercomponents of the simulant of a model secondary waste
stream – PUREX raffinate without both the major andminor actinides. In batch experiments, the Am Dg was
found to display a pronounced maximum at 1M HNO3. As

expected on the basis of the liquid-liquid extraction
experiments, the kinetic studies revealed that the uptake of
Am by the new SEX is much faster than for the similarmaterials with 1-octanol or nitrobenzene diluents.
Two dynamic experiments were performed with acolumnloadedbythenew
E5-CyMe4BTBP(cyclohexanone) SEX. The experiments
revealed that the maximum achievable flow-rate for anegligible Am break-through is ~ 5 BV/hr for the given
experimental set-up. An almost quantitative uptake of Am
from a mixed carrier free Am – Eu solution in 1M HNO3
was achieved during the treatment of all the ~ 60 BV of thefeed; Am could be easily eluted from the column by
0.5M HGlyc at pH = 4. The cumulative data for theexperiment were: americium: recovery > 98 %, < 1 % of
Eu in Am fraction; europium fraction: recovery > 99 %,contaminated by < 2 % of Am.
A serious obstacle in industrialization of the DIAMEX
process is accumulation of “difficult-to-strip” elements (e.g.
Ru, Y, Mo, Pd, Zr, Sr etc.) in the spent solvents. The aim of
the study performed was to verify the possibility to
decontaminate such spent solvents by solid sorbents. A
problem in the pre-selection of potentially suitable sorbents
turned out to be the fact that for the case of spent solventsand the metals like Ru or Pd, their speciation in organic
phase is hardly predictable and may well be of non-ionicnature (colloids or pseudo-colloids containing reduced
species etc.).
For the experimental part of this work, the DIAMEX
solvent based on TODGA in kerosene / 1-octanol (5 vol.%)
mixture was used as a reference system. An attempt tocharacterize speciation of the elements of interest in thesimulant of the spent solvent was done by FTIR, ESI-MS,
APCI-MS, and thin layer chromatography.
More than 50 solid sorbents of various nature, identified
as potentially prospective, were obtained and theirefficiency for the removal of Ru and Y from the simulated
spent solvent was screened in batch contact experiments.
The results obtained revealed that relatively high weight
distribution ratios Dg, sufficient for the design of a process
for quantitative separation of the contaminants from thesolvent, can be achieved for some of the solid sorbents, e.g.
Amberlyst A26 or Fe-EDA-SAMMS. For the prospective
materials, sorption kinetics and sorption isotherms were
determined. The materials with the highest sorption
capacity were tested in dynamic column experiments. The
results obtained in these tests will be presented in detail.

－ 295 －

25-NEP-06

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Thorium based Molten Salt Fuel Cycle
Qing-nuan Li*, Lan Zhang, Wen-xin Li�Guo-zhong Wu
Shanghai Institute of applied physics, Chinese Academy of Sciences, Shanghai, China*Corresponding author. Tel: +86 21 39194059. Email: liqingnuan@sinap.ac.cn

Abstract –In 2011, Chinese Academy of Sciences (CAS), after
discontinuing the research and development activity in nuclear
energy for decades, started to implement Strategic Priority
Research Program "Future Advanced Fission Nuclear Energy(FANE)". To perform this program, two sub-bases, the north andthe south, were deployed in CAS. Shanghai Institute of applied
physics (SINAP), as the south sub-base, is taking in charge of
research and development of "Thorium-based Molten Salt
Reactor Nuclear Energy System (TMSR)". According to thisresearch plan, two kinds of molten salt nuclear reactors, i.e.
2MW uranium-thorium fluoride molten salt reactor (TMSRLF1)and 2MW pebble bed fluoride salt-cooled high temperature
reactor (TMSR-SF1), will be designed and developed. Three fuelcycle models will also be implemented orderly, one-through fuelcycle on TMSR-SF, modified open fuel cycle on TMSR-SF and
TMSR-LF, and closed fuel cycle on TMSR-LF.
Pyrochemical processing methods are judged to be the only

technologies for the fuel of MSRs with integrated reprocessing
technologies. Because the liquid fuel for MSR is a mixture ofmolten fluorides, the fuel processing and reprocessing
technologies planned are pyrochemical or pyrometallurgical
techniques, which are based on separation of 233U and fission
products in molten fluoride salt. Considering the special
advantages of fluoride volatility and electrometallurgical
techniques, a preliminary protocol based on closed fuel cycle has
been proposed for the treatment of fuel from TMSR. The
recycling techniques of fuels proposed in this protocol include
fluoride volatilization, distillation of molten salt carriers,
electrochemical deposition. The simple experimental devices forabove techniques have been established, and the feasibility
studies are ongoing in SINAP.
Keywords –TMSR;
techniques－ 296 －

fuel cycle; reprocessing; pyrochemical

25-NEP-07

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Study on electrochemical behaviors of rare earth elements in FLINAK eutectic salt
Li-fang Tian, Wei Huang, Feng Jiang, Chang-feng She, Hai-yang Zheng, De-wu Long*, Qing-nuan Li
Shanghai Institute of applied physics, Chinese Academy of Sciences, Shanghai, China*Corresponding author. Tel: +86 21 39194677. Email: longdewu@sinap.ac.cn

Abstract –The reliable data on the electrochemical behaviors of
key elements, such as lanthanides and actinides, is thefoundation to assess the feasibility of application of theelectrometallurgical method in recovery of the valuable actinides
from fission products. For this purpose, the electrochemical
behaviors of some rare earth elements (REs) in FLINAK eutectic
� weresalt (46.5 LiF - 11.5 NaF - 42.0 KF, mol %) at 550
studied, including samarium (Sm3+), europium (Eu3+), yttrium(Y3+), neodymium (Nd3+), and gadolinium (Gd3+) ions. The redox
potentials, the number of exchanged electrons and the diffusion
coefficients were determined by electrochemical transienttechniques, such as cyclic voltammetry, square wave

voltammetry and chronopotentiometry. For Y3+, Gd3+ and Nd3+,
the results showed a three-electron reduction from the trivalentions to metals near the potential of -1.95 V (or more negative) vs
Ni/NiF2 reference electrode. However, no metallic Sm and Eu
could be formed because only the reduction of their trivalent ionsto divalent ions occurred in the electrochemical window of
FLINAK eutectic salt. Further work on the electrochemical
extraction of REs from FLINAK is ongoing.
Keywords –FLINAK eutectic salt; Electrochemical behavior;
Rare earth elements; Sm3+, Eu3+, Y3+, Nd3+ and Gd3+

－ 297 －

25-NCP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Measurement of cosmogenic nuclides in meteorites by well-type Ge detector in Ogoya
Underground Laboratory- Correction of coincidence sum effect for Al-26, Co-56, Na-22, and Co-60 Yasunori Hamajima
Kanazawa Univ. LLRL.

Abstract – Two carbonaceous chondrite samples of about
3 ~ 5g, which have fallen in California on April 22, 2012,were measured by well-type Ge detector in Ogoya
Underground Laboratory from May 21, 2012 for 30 days.
Cosmogenic Co57, Cr51, Be7, Co58, Mn54, Co56, Co60,
Na22, and Al26 were detected within the error of 20% or less,(That of Al26 is about 33%). The correction of coincidence
sum effect would require for Al26, Co56, Na22 and Co60.
The correction factors of these nuclides have been estimatedfrom total efficiency as a function of gamma-ray energy.
Keywords – chondrite cosmogenic nuclides, well-type Ge

detector, sum coincidence effect, total efficiency
I.

INTRODUCTION

Measurement of cosmogenic nuclides in meteorite, usually
several tens of g, has been carried out by using a coaxial Ge
detector. In case of small samples, a well-type Ge detector
will be advantageously, because of high counting efficiency.
And also, the efficiency does not depend much on the sample
shape and its height up to about 40 mm in the well. On theother hand, coincidence sum effect is not negligible small, forannihilation and cascade gamma-ray.
In this experiment, two carbonaceous chondrites were
measured by a well-type Ge detector in Ogoya Underground
Laboratory. The correction of coincidence sum effect would
require for Al26, Co56, Na22 and Co60. The correction
factors of these nuclides have not been estimated from peak
to total ratio, but from total efficiency as a function of
gamma-ray energy. In this paper, I will discuss the method of
the correction that will be required for all Ge detectors.

III. RESULTS AND DISCUSSION
Cosmogenic Co57, Cr51, Be7, Co58, Mn54, Co56, Co60,
Na22, and Al26 were detected within the error of 20% or less,(That of Al26 is about 33%). The corrections of coincidence
sum effect with annihilation gamma-ray for Na22 and Al26,
and with cascade gamma-ray for Co56 and Co60 have beenrequired. Those of Na22 and Co60 are corrected by standard.
Total efficiency as a function of energy was estimated asfollowing equation;(1)����������������
here, ����, ���and T2 are apparent peak and single peak, andtotal efficiency, respectively. Figure 1 shows the results ofefficiency. The lower cross marks are apparent efficiencies,
triangles and diamonds are single peak efficiencies, andupper line shows the total efficiency. The total efficiency
curve as a function of energy leads to correction ofcoincidence sum effect of all of nuclides including those withextremely complicate decay scheme, such as Co56.

II. EXPERIMENTAL
Two carbonaceous chondrite samples of about 3.15 g and5.16 g, which have fallen in Sutter’s Mill, California on April
22, 2012, were measured by well-type Ge detector in Ogoya
Underground Laboratory from May 21, 2012 for 30 days.
Counting efficiency was determined by JRIA mixing
standard volume source (Cd109, Co57, Ce139, Cr51, Sr85,
Cs137, Mn54, Y88, and Co60), Na22 source and natural
Lu176.

Figure 1. Efficiency of well Ge detector

I have estimated the apparent efficiency of 1809 keV of
Al26 from the total efficiency of 511 keV of Na22. Thisestimated apparent efficiency (2.62%) was consistent with theresult of Al26 standard AMS source (2.69%).
Correction of coincidence sum effect by total efficiency ispractical.

－ 298 －

25-NCP-02

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Development of Multipurpose Neutron Irradiation Apparatus at KUR
K. Takamiya1, Y. Yoshida2, H. Tanaka1, T. Fujii1, S. Fukutani1, T. Sano1, H. Yoshino1, Y. Iinuma1,
R. Okumura1, S. Shibata1
1

Research Reactor Institute, Kyoto University
Graduate School of Engineering, Kyoto University

2

II. APPARATUS

1013

106

1012

105

1011

104

1010

103

109

102

108

101

107

100

106

The developed neutron irradiation apparatus transport
samples loaded on a carrier from an experimental room
adjacent to the reactor to nearby the reactor core through ahorizontal beam hole (B-2) of KUR. The sample carrier has
a capacity of about 6 cm × 6 cm × 30 cm and materials of
up to 10 kg can be loaded. The carrier can be connectedwith plastic tubes to monitors and instruments placed at theexperimental room at a distance of about 4 m from thereactor wall. Circulating liquid samples can be irradiatedusing pumps and the tube.

0

100

200

300

10-1

-1

Neutron irradiation experiments, such as neutron
activation analysis and isotope production, have been
performed using various apparatuses at research reactors.
One of the most general apparatus is a pneumatic system,
which transport small capsules enclosing samples from alaboratory to a neutron irradiation field near a reactor core.
However, sizes and weights of samples are limited by thetransporting capacity of capsules, and irradiating liquidsamples is difficult for reactor safety in the pneumatic
system. A new neutron irradiation apparatus has beendeveloped at Kyoto University Reactor (KUR, 5 MW
thermal power) to overcome such limitations.

Gamma-ray Dose Rate / mGy�s

INTRODUCTION-1I.

The neutron flux and gamma-ray dose rate at various
position of irradiation field of the apparatus have beenmeasured. The neutron flux was measured by activation
method using gold wires. The gamma-ray dose rate wasmeasured by thermo luminescence dosimeters. Bothmeasurements were performed at the positions of 100 to
300 cm at intervals of 50 cm, and only neutron flux
measurements were carried out additionally at 0 and 50 cm
from the reactor-side edge. The results of the measurements
are shown in Fig. 1. The wide range of neutron flux that isfrom 108 to 1012 n/cm2/s was observed, which realizes
various kinds of neutron irradiation experiments. The
neutron flux and gamma-ray dose rate decrease as the range
from the edge increases. The decreasing trend of neutron
flux changes around the range at 100 cm because thesectional shape of the beam hole changes here. The
uniformity of neutron flux was also measured by activation
method using PET films1) at every 100 cm from the reactorside edge, and it was found the neutron flux at a section is
uniform.

-2

Keywords – Neutron Irradiation, Neutron Activation Analysis,
Online Measurement

III. MEASUREMENT OF NEUTRON FLUX ANDGAMMA-RAY DOSE RATE

Neutron flux / n�cm �s

Abstract – A new apparatus for various neutron irradiation
experiments has been developed at Kyoto University Reactor. The
apparatus can transport a larger space gently to a neutron
irradiation field adjacent to the reactor core. Therefore, various
samples, for examples, large and liquid samples can be irradiatedwith neutrons. And also samples can be joined to experimental
instruments with tubes that realize online measurements andcyclic irradiation experiments. Since setting samples at different
range from the reactor core can change irradiated neutron flux,
various experiments by wide range neutron flux can be performed.
Neutron activation analysis for large samples and liquid samples
becomes enabled by these characteristics. In order to apply theapparatus effectively, the neutron flux and gamma-ray dose rate
has been measured at various irradiation position. And changing
spectrum of irradiating neutrons has been tried using
polyethylene blocks as a moderator. The characteristics of theapparatus and the future plan are reported in this paper.

Range from reactor core / cm
Fig. 1 Variation of neutron flux and gamma-ray dose rate at various
positions in the B-2 beam hole.
[1]－ 299 －

K. Takamiya, et al, Proc. Radiochim. Act 1 (2011) 63-66.

25-NCP-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Development of a new continuous dissolution apparatus with a hydrophobic
membrane for superheavy element chemistry
K. Ooe1,2, K. Tsukada2,M. Asai2, T. K. Sato2, A. Toyoshima2, S. Miyashita2, Y. Nagame2, M. Schädel2,
Y. Kaneya3, H. V. Lerum4, J. P. Omtvedt4, J. V. Kratz5, H. Haba6, A. Wada7, Y. Kitayama8
1

Institute of Science and Technology, Niigata University
2
Japan Atomic Energy Agency
3
Graduate School of Science and Engineering, Ibaraki University
4
Department of Chemistry, University of Oslo
5
Institut für Kernchemie, Universität Mainz
6
Nishina Center for Accelerator-Based Science, RIKEN
7
Department of Chemistry, Tokyo Metropolitan University
8
Graduate School of Natural Science and Technology, Kanazawa University

Abstract –A new continuous dissolution apparatus of gas-jet
transported products was developed for superheavy element
chemistry. The new apparatus has a hydrophobic membrane forseparation of aqueous solution from the gas. We investigated thedissolution efficiencies with the apparatus for short-lived nuclides.
In the conference, the dependence of the efficiencies on the
aqueous- and gas-flow rates will be reported.
Keywords – Molybdenum, Tungsten, Continuous dissolution,
Hydrophobic membraneI.

INTRODUCTION

For investigation of the redox potentials of element
106, seaborgium (Sg), we plan to combine a flow
electrolytic column (FEC) [1] with the rapid liquid-liquid
extraction apparatus SISAK [2]. There is a technicalproblem in connection with these two apparatuses; a typicalliquid flow rate for SISAK of ~24 mL/min is quite higher
than that for FEC of ~1 mL/min. To successfully work withthese two apparatuses, it is required to reduce the liquidflow rate of the SISAK system. However, the dissolution
efficiency with the SISAK centrifuging degasser, which
continuously dissolves gas-jet transported nuclear reaction
products into an aqueous solution, drops with decreasingliquid flow rate. In the present study, therefore, wefabricated a completely new continuous dissolution
apparatus which successfully works with a lower liquidflow rate.
II. NEW CONTINUOUS DISSOLUTION APPARATUS
WITH A HYDROPHOBIC MEMBRANE
Our new degasser utilizes a hydrophobic Teflon
membrane to separate aqueous solution from gas (hereafter
called membrane degasser, MDG). It continuously
dissolves transported products by a gas-jet as follows. The
mixture of gas and aqueous solution enters the MDG. Then,
only the gas is sucked through the membrane with avacuum pump. On the other hand, the aqueous solution
does not pass through the hydrophobic membrane andelutes from an outlet.

III.

PERFORMANCE TEST

Dissolution efficiencies of gas-jet transported products
were measured using the MDG. Short-lived isotopes,
91m
Mo (T1/2 = 65 s), 93mMo (T1/2 = 6.9 h), and 176W (T1/2 =2.5 h), which are lighter homologues of Sg, were produced
simultaneously in the 89Y(7Li, 5n)91mMo, 89Y(7Li, 3n)93mMo,
and 175Lu(7Li, 6n)176W reactions, respectively, at the JAEA
tandem accelerator. Reaction products recoiling out of thetargets were transported to the chemistry laboratory by a
He/KCl gas-jet. The pressure in the target chamber was
130–140 kPa. The transported products were mixed with 1
M HCl/10-4 M HF solution before entering the MDG. The
carrier gas was then sucked through the membrane in the
MDG, while the aqueous solution was eluted from the
MDG. The aqueous sample was collected in a plastic bottle
and was then measured with a Ge detector.
IV.

RESULTS AND DISCUSSION

The dissolution efficiencies for Mo and W at a He gas
flow rate of 1.5 L/min were investigated as a function of
aqueous flow rate. In the result, a dependence of the
dissolution efficiencies on the half-life was observed; theefficiency for 93mMo (T1/2 = 6.9 h) was higher than that for
91m
Mo (T1/2 = 65 s) at aqueous flow rate of 0.6–6 mL/min.
The dissolution efficiency for 176W (T1/2 = 2.5 h) was
almost the same as that for 93mMo. Nevertheless, adissolution efficiency of more than 80% was obtained forshort-lived 91mMo at aqueous flow rates of 6–24 mL/min. A
high yield of around 70% was also observed at flow rates
of 1.8–3 mL/min. These results show that the MDG works
with a lower aqueous flow rate than the previous SISAK
degasser.
In the conference, the dependence of dissolution
efficiency on the He gas flow rate will be also reported.
[1][2]－ 300 －

A. Toyoshima et al., Radiochim. Acta 96, 323-326 (2008).
J. P. Omtvedt et al., Eur. Phys. J. D 45, 91-97 (2007).

25-NCP-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Cross-section Measurements of High Energy Neutron-induced Reactions
for Cu and Nb
K. Ninomiya1, T. Omoto1, R. Nakagaki1, N. Takahashi1, Y. Kasamatsu1, A. Shinohara1, S. Sekimoto2,
H. Yashima2, S. Shibata2, T. Shima3, H. Matsumura4, M. Hagiwara4, Y. Iwamoto5, D. Satoh5,
M. W. Caffee6 and K. Nishiizumi7
1

Graduate School of Science, Osaka University
Research Reactor Institute, Kyoto University
3
Research Center of Nuclear Physics, Osaka University
4
Radiation Research Center, High Energy Accelerator Organization
5
Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency
6
Department of Physics, Purdue University
7
Space Sciences Laboratory, University of California
2

Keywords–
cross-section,monoenergetic neutron

neutron-induced

reaction,

The determination of cross-sections by neutron-induced
nuclear reaction is very important in the view point of
space and planetary sciences to investigate the history ofcosmic ray exposure. These data are also required for
estimation of residual radioactivities in accelerator facilities.
However, cross section measurements in the energy region> 100 MeV have scarcely been undertaken because of the
difficulty in obtaining high energy monoenergetic neutrons.
So neutron-induced cross-sections are estimated by aproton-induced cross-section with the same energy or
calculated using theoretical models.
Our group has developed a method for determination ofhigh energy monoenergetic neutron cross-sections at the
Research Center for Nuclear Physics (RCNP), Osaka
University [1]. This method is based on two neutron
irradiation experiments produced by 7Li (p, n) 7Be reaction
with two different angles for the axis of the primary proton
beam to correct the contribution of the low energy neutron
reaction [2]. In this study, we performed cross-section
measurements with 197, 287 and 386 MeV neutrons for Cu
and Nb.
All neutron irradiation experiments were performed at
N0 beam line in RCNP. We obtained quasi monoenergetic
neutron fluence with 197, 287 and 386 MeV from 200, 300
and 392 MeV incident proton beam, respectively. The
details of the experimental methods were written inelsewhere [1]. Produced short-lived radionuclides wereidentified by high-purity germanium detectors, and neutron
cross-sections were determined. We also performed proton
irradiation experiments at the same beam line to obtainproton cross sections with the same incident energies.

The excitation function of 60Co for Cu target by protonand neutron-induced reactions are shown in Figure 1 withthe related literature values [2-5]. We found the crosssections of neutron-rich nuclides such as 60Co by neutron
bombardment reactions have a tendency larger than theseby proton reactions, and proton-rich nuclides such as 58Co
have an opposite trend. In the presentation, we will report
the detail experimental cross-section data and discuss suchcross-section difference by projectile using empiricalmodels for nuclear spallation reactions.

102
cross section / mb

Abstract – High-energy monoenergetic neutron-induced reactions
above 100 MeV have been studied for Cu and Nb targets.
Excitation functions of short-lived radionuclides were determinedby gamma-ray spectrometry. We also measured cross-sections byproton-induced reactions with the same energy range andcompared with each other. The cross-sections of neutron-rich
nuclides by neutron-induced reaction were systematically larger
than these by proton-induced reactions.

60

Co

101
287, 386 MeV neutron(this work)
300,392 MeV proton(this work)
55.0-61.0 MeV neutron [3]110.8 MeV neutron [2]226-375 MeV proton [4]27.6-196.6 MeV proton [5]

100

10-1

0

100

200

300

40

projectile energy / MeV
Figure 1. Excitation function for natCu (n, x) 60Co and natCu (p, x) 60Co
reactions.
[1]
[2]
[3]
[4]
[5]

－ 301 －

K. Ninomiya et. al., Proc. Radiochim. Acta., 1, 123 (2011)
J. M. Sisterson et. al., Nucl. Instrum. Meth., B240, 617 (2005)
E. J. Kim et. al., Nucl. Sci. Technol., 36, 29 (1999)
Th. Shiekel et. al., Nucl. Instrum. Meth., B114, 91 (1996)
S. J. Mills et. al., Appl. Radiat. Isot., 43, 1019 (1992)

25-NCP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Development of a rapid solvent extraction technique with flow injection analysis forsuperheavy element chemistry
T. Koyama1, N. Goto1, M. Murakami1,2, K. Ooe1, H. Haba2, J. Kaneya2, S. Goto1, and H. Kudo1,
1

Department of Chemistry, Faculty of Science, Niigata University, Niigata 950-2181, Japan
2
Nishina Center for Accelerator-Based Science, RIKEN, Saitama 351-0198, Japan

Abstract –A rapid solvent extraction system with flow injection
analysis based on microchip chemistry was developed to study
chemical properties of superheavy elements. Using this system,
solvent extraction experiments of 95gNb were performed as modelexperiments of element 105, dubnium. The extraction equilibrium of
Nb was reached in approximately 2 s. For on-line liquid-liquid
phase separation, a phase separator was also developed by use of amembrane filter.
Keywords – microchip, flow injection analysis, liquid-liquid
extraction, niobium, phase separationI.

INTRODUCTION

For the chemical investigation of superheavy elements withatomic numbers ≥ 104, a rapid chemical separation apparatus
is needed because of their extremely short half-lives. As a
rapid chemistry apparatus, we developed a solvent extraction
system with flow injection analysis (FIA) based on microchip
chemistry. This FIA system consists of solvent extraction andphase separation parts. In the solvent extraction part, aqueousand organic phases are mixed in a tube with a very small
inner diameter of 100-200 μm. Because of a large specificinterfacial area and a short diffusion length in the tube,
chemical equilibrium is rapidly reached. In the phaseseparation part, on-line liquid-liquid phase separation isachieved with a hydrophobic Teflon membrane. In this work,
solvent extraction of 35-d 95gNb with this system wasinvestigated as a model experiment of element 105, dubnium.
The performance of the membrane phase separator was also
investigated separately.

In order to examine the time needed for the extraction
equilibrium, a flow rate and an extraction coil length wereindependently varied. After extraction, both solutions werecollected in a polypropylene tube and two phases wereseparated by centrifugation. The separated two phases werethen subjected to γ-ray spectrometry using a Ge detector. A
batch extraction experiment of 95gNb using the same solutions
was also performed to compare with these using FIA system.
Two phase separation experiment with the membrane phaseseparator was performed without radiotracers. The flow rate
was 0.5 mL/min, and the length of extraction coil was 1 m.
The phase separation was checked by weighing the separated
solutions varying backpressure coil length in the aqueous
outlet (0.17 mm i.d.). The length of outlet tube for organic
phase was 10 cm.
III. RESULTS AND DISCUSSION
In the batch experiment, shaking time of 40 min was needed
to attain the extraction equilibrium. On the other hand, theequilibrium was reached within the contact time of 2 s using
the FIA system.
In the two phase separation experiment, a clear phaseseparation was observed with back pressure coil length ofabout 5-15 cm. And the separator withstood 6 h continuous
operation without replaining a membrane.
Therefore, this FIA system can be used for the solvent
extraction experiments of superheavy elements with halflives of several tens of seconds.

II. EXPERIMENTAL
The 95gNb tracer was produced in the bombardment of a
Zr target foil with a 14-MeV proton beam supplied by the
RIKEN AVF cyclotron. The carrier-free 95gNb tracer was
prepared by the chemical separation from the target usinganion-exchange technique[1].
A schematic view of the FIA system is shown in Figure 1.
Aqueous and organic solutions introduced in each reservoir
coils were pumped with double-plunger pumps, and mixed in
T-connector. As aqueous and organic solutions, 5 M HCl
solution containing 95gNb tracer and 0.1 M Aliquat 336 in
1,2-dichloroethane solution were used, respectively. The
mixture was fed into the extraction coil ofpoly(tetrafluoroethylene) (PTFE) tube of 0.17 mm i.d..
natFigure 1. Schematic view of the FIA system[1]－ 302 －

Y.Kasamatsu et al, J. Nucl. Radiochem. Sci. 8, 69 (2007).

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-NCP-06

Solid-liquid extraction of Mo and W by Aliquat 336 from HF and HCl solutions
towards extraction chromatography experiments of Sg
Y. Komori1, T. Yokokita1, K. Toyomura1, K. Nakamura1, Y. Kasamatsu1, H. Haba2, J. Kanaya2,
M. Huang2, Y. Kudou2, A. Toyoshima3, N. Takahashi1, A. Shinohara1
1

Graduate School of Science, Osaka University
Nishina Center for Accelerator-Based Science, RIKEN
3Advanced Science Research Center, Japan Atomic Energy Agency
2

Abstract –We are aiming to investigate complex formation
properties of Sg with fluoride and chloride ions by extraction
chromatography from HF and HCl solutions. We have selected
Aliquat 336 as an extractant for anionic species in aqueous
solution. In this study, solid-liquid extraction behaviors of carrierfree radiotracers Mo and W on Aliquat 336-loaded resin from 1–
10 M HF and 0.1–10 M HCl solutions were investigated.
Keywords – Superheavy elements, Seaborgium (Sg), Molybdenum,
Tungsten, Solid-liquid extraction

Element 106, seaborgium (Sg) is a group-6 element andthe most stable oxidation state of Sg in aqueous solution is
expected to be 6+ as with its lighter homologues,
molybdenum (Mo) and tungsten (W). The pioneering
aqueous chemical studies on complex formation andhydrolysis of Sg were carried out by Schädel et al. withcation-exchange chromatography in 5 × 10-4 M HF/0.1 M
HNO3 [1] and in HNO3 [2] using a liquid chromatography
apparatus, ARCA [3]. However, there are no reports on
aqueous chemical studies of Sg following these works. It isextremely difficult to perform chemical experiments of Sg
due to its low production rates and short half-lives of theisotope 265Sga,b (T1/2 = 8.5 s/14.4 s [4]). To progress
chemical studies of Sg, it is important to search forexperimental systems and conditions applicable to the Sg
experiment.
We are aiming to investigate complex formation
properties of Sg with fluoride and chloride ions byextraction chromatography from HF and HCl solutions
using ARCA. We have selected Aliquat 336 as an
extractant for anionic species in aqueous solution. In thisstudy, we have investigated solid-liquid extraction
behaviors of carrier-free radiotracers Mo and W on Aliquat
336-loaded resin (Aliquat 336/CHP20Y resin) from 1–10
M HF and 0.1–10 M HCl solutions by a batch method.
Extraction reaction kinetics was investigated anddistribution coefficients (Kd) of Mo and W were obtained asfunctions of HF and HCl concentrations. Extraction
chromatography with ARCA was also performed in 2–8 M
HCl solutions.
The short-lived isotopes 90Mo (T1/2 = 5.7 h) and 173W
(T1/2 = 7.6 min) were produced using the RIKEN K70 AVF
cyclotron. The Kd values of 90Mo and 173W were obtained
as functions of HF and HCl concentrations by a batch
method. Reaction products transported by the He/KCl gasjet system were deposited on a Naflon sheet for 1 or 5 min.
The collected reaction products were dissolved in 24�� ���of 0.1–10 M HCl (or 1–10 M HF) solutions. A 10–20 mg of

51.9-wt.% Aliquat 336/CHP20Y re����� ���� ��� ��� ���� ����(or HF) solution containing 90Mo and 173��� ���� ��� ��� acertain concentration of HCl (or HF) solution were mixed
in a PP tube. These samples were shaken for 5 min at 25 ºC.
Standard samples of 90Mo and 173W which contained noresin were also prepared and were shaken together with theresin-containing samples. After centrifugation, the aqueous
phase was pipetted into another PP tube which was���������� ��� �-ray spectrometry using a Ge detector todetermine radioactivities of 90Mo and 173W. Reaction
kinetics was also investigated at 25 ºC by varying theshaking time to be 10 s, 5 min, and 10 min in each 4 M HF
and 2, 6, and 10 M HCl solution. These batch solid-liquid
extractions were also performed using the isotopes 93mMo(T1/2 = 6.9 h) and 181W (T1/2 = 121 d).
The on-line extraction chromatography of Mo and W
was performed with ARCA. The 51.9-wt.% Aliquat
336/CHP20Y resin was filled into the 1.0 mm i.d. × 3.5 mm
microcolumn of ARCA. The reaction products transportedby the gas-jet system were deposited on the collection siteof ARCA for 5 min. After the collection, the reaction
products attached to the KCl aerosols were dissolved with 2,
4, 6, and 8 M HCl solutions and were subsequently fed
onto the column at a flow rate of 1 mL/min for 30 s. The
effluents were collected in PP tubes for every 50 ���������
Then, the remaining 90Mo and 173W in the column were
eluted with 400–�����������������3/0.01 M HF solution
and were collected in another PP tube. These fractions of
the effluents were assayed by �-ray spectrometry with a Ge
detector.
It was found that extraction reaction kinetics in 4 M HF
and 6 and 10 M HCl solutions is fast enough to reach theequilibrium state within approximately 10 s. In theextraction chromatography of Mo and W in 2–8 M HCl
solutions with ARCA, the order of extractability was Mo >W, which is consistent with the of order of the Kd values
obtained in the batch experiment.
[1]
[2]
[3]
[4]

－ 303 －

M. Schädel et al., Radiochim. Acta 77, 149 (1997).
M. Schädel et al., Radiochim. Acta 83, 163 (1998).
M. Schädel et al., Radiochim. Acta 48, 171 (1989).
H. Haba et al., Phys. Rev. C 85, 024611 (2012).

25-NCP-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Off-line isothermal gas chromatography of Zr and Hf compounds
Y.Oshimi, S.Goto, T.Taguchi, T.Tomitsuka, K.Ooe, H.Kudo

Department of Chemistry, Faculty of Science, Niigata University, Niigata 950-2181, Japan
Abstract –We obtained isothermal chromatographic data of Zr and
Hf chlorides in a macro-scale (about 1018 molecules). The
adsorption enthalpies(ΔHa) of the Zr and Hf chlorides on a quartz
surface were determined to be about –78 kJ/mol and –73 kJ/mol,
respectively, with analyzing these retention curves. The present ΔHa
values are very different from the earlier work[1] in micro-scale,but agree with the volatility deduced from the vapor pressure in
macro-scale.
Keywords – isothermal gas chromatography, zirconium andhafnium, adsorption enthalpy

I.

INTRODUCTION

Gas-phase chemical separation is one of the most utilized
method to study chemical properties of superheavy elements.
Using this method, adsorption enthalpies (ΔHa) of volatilecompounds of these elements can be determined based on
their adsorption-desorption processes on a column surface.
To clarify chemical property of element 104, Rf, gas
chromatographic behavior of chlorides of Rf and its
homologs, Zr and Hf, has been studied in the single-atomscale[1]. The reported sequence of volatility was Zr ≳ Rf > Hf.
But this volatile relation between Zr and Hf chlorides differ
from volatile sequence requested from the macro-scale thesevapor pressure curves[2]. Appropriate explanation about thisdifference has not been given until now.
In this study, we investigated gas chromatographic behaviorof volatile compounds which were formed with thermal
decomposition of oxychlorides of Zr and Hf.

Hf through the column were collected in quartz wool plugged
in a quartz tube connected just behind the column. An
absorption photometry using arsenazo III was applied todetermine the quantity of collected Zr and Hf.
III. RESULT AND DISCUSSION
The passed-through yields for Zr and Hf were obtained as afunction of the temperature of the isothermal column.
Adsorption enthalpies were calculated using a simulation
which is generally used in gas phase chemistry[3] and taken
into account the fact that thermal decomposition reaction of
the oxychlorides takes time. Adsorption enthalpies(ΔHa) on
a quartz surface for the Zr and Hf chlorides were obtained
about –78 kJ/mol and –73 kJ/mol, respectively. The present
ΔHa values for Hf are very different from the previously
reported values. This result is consistent with the fact that
HfCl4 is more volatile than ZrCl4. Our results agree with thevolatility deduced from the vapor pressure. Hence, there issome possibility that the Hf compound observed in theprevious work was not pure tetrachloride.
In the symposium, the experiments and the results will bepresented in more detail.
quartz wool attached MOCl 2・8H 2O (M=Zr,Hf)
collection
pathHewater cooling

II. EXPERIMENTAL
In this work, stable isotopes of Zr and Hf were used toconfirm whether the experimental technique is suitable before
the experiments under tracer scale. Schematic view of theexperimental equipment is shown Fig. 1. Quartz wool was
impregnated with 80 μL of ZrOCl2 or HfOCl2 water solution
containing about 2240 μg of Zr or Hf, and dried at 200 °C.
After drying, the wool was mounted in the reaction partwhich is composed of a quartz tube. Because the deposited
oxychloride may be hydrate, the reaction part was heated at
210 °C to remove hydration water completely. Then, heating
the reaction part at above 400 °C, the oxychlorides
decomposed into nonvolatile dioxide and volatile
tetrachloride, for example,
2HfOCl2 → HfO2 + HfCl4.
The produced tetrachloride was fed into an isothermal
chromatographic quartz column with He gas (1.0 L/min,purity ≳ 99.999 %). The tetrachloride compounds of Zr andreaction part isothermalpartwaste pathliquid N 2 trap

Fig.1. schematic views of the experimental equipment

[1]
[2]
[3]

－ 304 －

B. Kadkhodayan et al., Radiochim. Acta 72, 169 (1996)
A. Türler et al., J. Alloys Comp 271, 287 (1998)
I. Zvara, Radiochim. Acta 38, 95 (1985).

VacuumPump

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-NCP-08

Chemical studies of Rf and Db in liquid-phases using automated rapid chemical
separation apparatuses at JAEA
K. Tsukada1, A. Toyoshima1, M. Asai1, Y. Kasamatsu2, Z. J. Li3, Y. Ishii1, H. Haba4,
T. K. Sato1, Y. Nagame1, M. Schädel1
1

Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
3
Institute of High Energy Physics, Chinese Academy of Science, China
4
Nishina Center for Accelerator Based Science, RIKEN, Wako, Saitama 351-0198, Japan
2

Abstract – We present chemical studies of element 104,
rutherfordium (Rf), and element 105, dubnium (Db), in liquidphases at JAEA. The experiments based on an atom-at-a-timescale have been performed using an automated rapid ionexchange separation apparatuses, AIDA and AIDA-II. We havefound interesting information for the complex formations of Rf
with chloride, nitrate, sulfate, and fluoride ions and Db withfluoride ions in aqueous solutions.
Keywords – Superheavy elements, Ratherfordium, Dubnium, Ionexchange separation, Complex formation with chloride, nitrate,sulfate and fluoride, Automated apparatus

I.

INTRODUCTION

Chemical studies of the superheavy elements are
extremely challenging subjects in the fields of nuclear andradiochemistry [1]. An interesting aspect is to clarify basic
chemical properties of these elements, such as ionic radii,
complex formation and so on, and to elucidate the influenceof relativistic effects on valence electrons of the superheavy
elements [2]. The superheavy elements produced in heavyion-induced nuclear reactions at accelerators with low
production rates. As the available isotopes are short-lived,
they are usually available in quantities of only a few atoms
at a time. Chemical characterization of the superheavy
elements in liquid-phase experiments is performed by apartition method with single atoms. In order to havestatistically significant results, it needs to repeat same
experimental procedures over several hundred times withina cyclic time of a life-time of objective nuclides. In JAEA
we have developed automated rapid chemical separation
apparatuses to study chemical properties of Rf and Db inliquid-phases.
II. EXPERIMENTAL
The nuclides 261Rf (T1/2 = 78 s) and 262Db (T1/2 = 34 s)
were produced in the reactions 248Cm(18O, 5n) and248
Cm(19F, 5n), respectively, at the JAEA tandem
accelerator. For characterization of Rf, we conducted cyclic
discontinuous column chromatographic separations ofshort-lived nuclides in aqueous solutions and automateddetection of �-particles within a typical cycle of 1 minusing the automated rapid ion-exchange separation
apparatus AIDA (Automated Ion-exchange separation
apparatus coupled with the Detection system for Alpha
spectroscopy) [3] that consists of a modified computercontrolled liquid chromatography system ARCA

(Automated Rapid Chemistry Apparatus) [4] and an
automated on-line �-particle detection system. The
experimental approach involves comparative studies on thechemical properties of the superheavy elements with thoseof respective lighter homologues and a pseudo-homologue.
Thus, the experiments should be conducted together withthe lighter homologues under identical conditions. To
shorten the time for the sample preparation, the newly
developed rapid ion-exchange apparatus AIDA-II was
introduced. The apparatus is based on continuous sample����������� ���� ������������ ��� ����������� ���� ����������� �particle measurement. The ion-exchange part is the same asthat of AIDA. The AIDA-II was successfully applied forthe chemical experiments with Db.
III. RESULTS
We have investigated the ion-exchange chromatographic
behaviors of Rf in HCl, HNO3, H2SO4/HNO3, HF/HNO3
and HF solutions [3,5-10]. It has been found that thechemical properties of Rf are quite similar to those of thegroup-4 homologues, Zr and Hf, in the formation ofchloride, nitrate, and sulfate complexes, although there aresome differences in complexation strength between Rf andthe lighter homologues [3,5,6]. In contrast, fluoride
complex formation of Rf was found to be remarkably
weaker than those of Zr and Hf studied over a wide rangeof fluoride ion concentrations [7,8]. The formation constantof [RfF6]2- was observed to be at least one order ofmagnitude smaller than those of [ZrF6]2- and [HfF6]2- [5].
This result on the fluoride complexation is in agreementwith theoretical calculations including relativistic effects.
Anionic fluoride complexation of Db has also beenstudied [9,10]. The result demonstrates that the fluoride
complex formation of Db is considerably different fromthat of the group-5 homologue Ta, while the behavior of
Db is similar to that of the lighter homologue Nb [10].
[1]M. Schädel (ed), The Chemistry of Superheavy Elements, Kluwer
Academic Publishers, Dordrecht (2003).
[2] Pyykkö P, Chem. Rev .88, 563 (1988).
[3] Y. Nagame et al., J. Nucl. Radiochem. Sci. 3, 85 (2002).
[4] M. Schädel et al., Radiochim. Acta 48, 171(1989).
[5] Y. Ishii et al., Chem. Lett. 37, 288-289 (2008).
[6] Z. J. Li et al., Radiochim. Acta 100, 157 (2012).
[7] H. Haba et al., J. Am. Chem. Soc. 126, 5219 (2004).
[8] A. Toyoshima et al., Radiochim. Acta 96, 125-134 (2008).
[9] K. Tsukada et al., Radiochim. Acta 97, 83 (2009).
[10] Y. Kasamatsu et al., Chem. Lett. 38, 1084 (2009)－ 305 －

25-NCP-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013����������������������������������������������������������������������������������
�����������������������������������������
S. Miyashita1, A. Toyoshima1, K. Ooe2, M. Asai1, T. K. Sato1, K. Tsukada1, Y. Nagame1, M. Schädel1, Y.
Kaneya3, H. Haba4, J. Kanaya4, M. Huang4, Y. Kitayama5, A. Yokoyama5, A. Wada6, Y. Oura6 J. V.
Kratz7, H. V. Lerum8 and J. P. Omtvedt8
1

Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
2
Institute of Science and Technology, Niigata University, Niigata 950-2181, Japan
3
Graduate School of Science and Engineering, Ibaraki University, Mito, Ibaraki 310-8512, Japan
4
Nishina Center for Accelerator-Based Science, RIKEN, Wako, Saitama 351-0198, Japan
5
College and Institute of Science and Engineering, Kanazawa University, Kanazawa 920-1192, Japan
6
Graduate School of Science and Engineering, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan
7
Institut für Kernchemie, Universität Mainz, 55128 Mainz, Germany
8
Department of Chemistry, University of Oslo, P.O. Box 1033 - Blindern, NO-0315, Oslo, Norway��������� –� �������� ����������� ��� ������ ���� ����� ������ ��������������������� ������������� ���� ���� �������������� �����������
������������������������������ ��������������������������������
���� ������� ��� ���� ������������� ������ ��� ��� ���� �� ���� ����� �������������������������������������������������������
��������� –� ����������� ���������� �������� ������������ ������������
���������������������������������I.

INTRODUCTION

For the determination of the reduction potentials of
Seaborgium (Sg), we plan to carry out reduction experiments
using a rapid and continuous system consisting of a flow
electrolytic column (FEC) [1] combined with the liquidliquid extraction apparatus SISAK [2]. The oxidation statesof Sg will be chemically characterized its extraction behavior,and thus, rapid extraction enabling separation of Sg withdifferent oxidation states is required. From our results ofextraction-kinetics studies of 181W as lighter homologue of Sg
into toluene containing several extractants from 0.1 M HCl,
we found that 4-isopropyltropolone (Hinokitiol, HT) has fast
kinetics enough to be used together with SISAK. In the work
presented here, we examined the extraction with HT of 93mMo(T1/2 = 6.9 h) and 176W (T1/2 = 2.5 h) from a mixed solution
1.0 M HCl and 1.0 M LiCl solution.

organic phase was mixed in a vial and shaken for 600 s using
a mechanical shaker. After shaking, two phases wereseparated by centrifugation for 30 s. 500 μL of each aqueousand organic phase was taken into the vials. Radioactivity ofboth phases, 263 keV -rays of 93mMo and 102 keV -rays of
176
W, was detected by a Ge-detector. The distribution ratio(�) was calculated by the ratio of radioactivity of 93mMo and176
W in the two phases.
III. RESULT AND DISCUSSION
Figure 1 show that the variation of the � value of Mo and W
with respect to the concentration of HT in the organic phase([HT]) when the concentration of hydrogen ion in the
aqueous phase was 0.1 M. The � value of Mo and W
increased by increasing of [HT]. The slopes of the � value ofMo and W vs. [HT] in logarithmic scale are 1.88 and 1.54,
respectively. Those results indicated that Mo is formed an
extractable complex with two HT molecules and W is one
and/or two molecules.

II. EXPERIMENTAL
93m

Mo and 176W were produced in the 89Y(7Li, 3n)93mMo andLu(7Li, 6n)176W reactions, respectively. 89Y metallic foil
and natLu2O3 on Be foil were irradiated by a 62 MeV 7Li
beam from a tandem accelerator in JAEA. Reaction products
recoiling out of the target foils were transported with a
He/KCl gas-jet to the chemistry laboratory. Transported
products were collected on a PTFE sheet, and dissolved by amixed solution of 1.0 M HCl and 1.0 M LiCl. Then, ahydrogen ion concentration of solution was adjusted todesired ones. An organic phase was toluene containing acertain concentration of HT. 700 μL of each aqueous and175

Figure 1. Variation of the distribution ratio of Mo and W vs. theconcentration of HT in the organic phase when aqueous phase was 0.1 M
HCl / 0.9 M LiCl. Closed cycles and squares represent Mo and W,
respectively.
[1]
[2]

－ 306
304 －

A. Toyoshima et al., ���������������������� ��, 323
J. P. Omtvedt et al., ���������������� ����, ��, 91

25-NCP-10

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Development of Surface Ionization Ion-source for Determination of the First
Ionization Potentials of Heavy Actinides
Y. Kaneya1,2, T. K. Sato2, M. Asai2, K. Tsukada2, A. Toyoshima2, S. Miyashita2,
Y. Nagame1,2, M. Schädel2, N. Sato3, K. Ooe4, A. Osa5, S. Ichikawa2,6, T. Stora7, J. V. Kratz8
1

Graduate School of Science and Engineering, Ibaraki University, Mito, Ibaraki 310-8512, Japan
Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
3
Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
4
Institute of Science and Technology, Niigata University, Niigata 950-2181, Japan
5
Department of Research Reactor and Tandem Accelerator, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
6
Nishina Center for Accelerator Based Science, RIKEN, Wako, Saitama 351-0198, Japan
7
ISOLDE, CERN, CH-1211 Geneva 23, Switzerland
8
Institut für Kernchemie, Universität Mainz, 55128 Mainz, Germany
2

Abstract – We have developed a surface ionization ion-source aspart of the JAEA-ISOL that is coupled to a He/CdI2 gas-jet
transport system to determine the first ionization potential (IP) of
heavy actinides. Separation efficiencies of various short-lived
lanthanide isotopes as homologs of actinides that were produced
in nuclear reactions were measured with the present system.
Obtained results demonstrate that the developed ion-source would
be applicable to a measurement of the IP of heavy actinides.
Keywords – ionization potential ; lanthanide ; surface ionization ;
ISOL

I.

the ion-source by a He/CdI2 gas-jet transport system. The
products were ionized in the ion-source, accelerated with
30 kV, mass-separated at mass-separator in ISOL, andcollected on the aluminized Mylar tape. The amounts ofions were determined by���ray measurement with a HPGe detector. To calculate separation efficiencies, nuclear
reaction products transported from a target recoilchamber were directly collected on a separate catcher
system.
III. RESULTS AND DISCUSSIONINTRODUCTION

The first ionization potential (IP) directly reflects anatomic valence state influenced by relativistic effects which
are significantly noticeable for heavy elements. Therefore
information on the IP of heavy elements give us a better
understanding of relativistic effects. IPs of the heavy
actinides, however, have not been measured because of
their short half-lives and low reaction cross-sections. In
order to measure the IP of the heavy actinides, we need anapparatus which has higher separation efficiency.
In our previous work, we utilized a surface ionization ionsource coupled to a gas-jet transport system to study
nuclear decay properties and spectroscopy of short-lived
lanthanides and actinides [1]. Then, have improved the ionsource to measure the IP of lawrencium (Lr, Z = 103) andother heavy actinides [2]. In this work, to evaluate aperformance of the developed ion-source, we measured
separation efficiencies of various short-lived lanthanide
isotopes as homologs of actinides.

Separation efficiencies of various short-lived lanthanide
isotopes were measured. We compared the efficiencies
obtained by the developed ion-source with those theprevious ion-source. It is clearly found that the yields ofall the isotopes with the developed ion-source are larger
than those with the previous one. The separation
efficiency of Sm, for example, was 12% with thedeveloped ion-source while that with the previous ionsource was 3%. Furthermore, separation efficiency of Lu
whose volatility would be similar to that of Lr was about
4.2%.
From this result, the present system has sufficient
separation efficiencies to apply to measurement of the IPof the heavy actinides.
[1][2]

II. EXPERIMENTAL
Short-lived lanthanide isotopes, 140mPm, 142mEu, 143Eu,
Sm, 148mTb, 154Ho, 157Er, and 165Yb, were produced in
the irradiation of a 67.9 MeV 11B4+ beam from the JAEA
tandem accelerator on 136Ce / 141Pr / 159Tb and 142Nd / 147Sm/ natEutargets. Short-lived 168Lu was also produced in thereaction of 162Dy with a 11B4+ beam. Nuclear reaction
products recoiling from the targets were transported to143m－ 307 －

S. Ichikawa, et al. Nucl. Instr. and Meth. A 374 (1996) 330.
T. K. Sato, et al. Rev. Sci. Instrum. 84 (2013) 023304

25-NCP-11

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Comparison of the decay constants of 51Cr with various valence states
H. Kikunaga1, K. Takamiya2, K. Hirose1*, and T. Otsuki1
1*Research Center for Electron Photon Science, Tohoku University
2
Research Reactor Institute, Kyoto University

Present address: Advanced Science Research Center, Japan Atomic Energy Agency

Abstract – We have precisely measured the decay constants of51
Cr with 0, +3, and +6 valence states to investigate the effects ofchemical states on the decay constants of 51Cr. The value of{�(Cr6+)-�(Cr0)}/�(Cr0) was determined to be (5.3±2.2)×10-4,
whereas the difference less than 1.4×10-4 was observed for{�(Cr3+)-�(Cr0)}/�(Cr0). The results are compared withtheoretical estimated values calculated with a simple model.
Keywords – half-life, decay constant, chemical effectI.

INTRODUCTION

The decay constants of more than ten nuclides from 7Be
to Um were changed with changing environmental factors
such as its chemical state [1]. Kakiuchi and Mukoyama
reported the change in the decay constant of an electron
capture decay nuclide 51Cr was observed between two
chemical forms of CrCl3 and Na2CrO4 [2]. They also
estimated the value for the relative change in the decay
constant among 0, +3, and +6 valence states with a simple
theoretical model. The estimation shows that the relativechange in the decay constant between 0 and +3 state is in
the same degree as that between +3 and +6 state. In thisstudy, the decay constants of 51Cr have been precisely
measured with 0, +3, and +6 valence states to investigate
the effects of chemical states on the decay constants of 51Cr.

aluminum cups separately and sealed with an epoxy resin
adhesive.
These samples were measured in pairs of Cr2O3-metal
and K2CrO4-metal to reduce the influence caused by thedifference of detectors. The sample pairs were set in an
automated sample changer [3] and alternately placed in
front of a high-purity Ge detector at intervals of 7200 s.
The procedures were repeated over at least 95 d. A 137Cs
source was attached to near the Ge detector as a reference
source to correct for influential factors for determination ofhalf-life such as pile-up effect.
III. RESULTS AND DISCUSSION

235

II. EXPERIMENTAL

The decay constant of 51Cr was determined based on areference source method [4]. The ratio R (t) is given by thefollowing equation:
00(1)
R(t) � C sample(t) C ref(t) ,00
where C sample(t) and C ref(t) are count rates of a sample

and a reference source at the beginning of each dataacquisition, respectively. The decay constant of theradionuclide in the sample �sample is described in thefollowing equation:
�sample � �ref � a slope ,(2)

where a slope is the slope of the graph of ln R (t) against

The decay constants of 51Cr were measured for threechemical forms: chromium metal (Cr0), chromium (III)oxide Cr2O3 (Cr3+), and potassium chromate K2CrO4 (Cr6+).
The isotopes 51Cr was produced in the natCr(�, xn)51Cr
reactions. Target materials were about 100 mg of Cr metal,
Cr2O3, and potassium dichromate K2Cr2O7. Each target
material was sealed in a quartz tube and irradiated withbremsstrahlung photons. The irradiation was carried out
with the electron linear accelerator at Tohoku University.
The accelerator was operated at an electron energy of 30
MeV with a mean current of around 0.12 mA during the 8 hirradiation.
After the irradiation, the metal target and the Cr2O3
target was maintained at 800°C for 5 h in argon andatmosphere, respectively, with an electric furnace. The
K2Cr2O7 target irradiated was mixed into 250 mg of a nonradioactive K2Cr2O7 reagent and then dissolved in 3 mL of
distillated water. The solution was heated on a hot-plate
and alkalified with potassium carbonate to produce CrO42-.
The solution was filtered and the filtrate was evaporated toless than 1 mL on a hot-plate. Finally, a K2CrO4 sample
was prepared by recrystallization from the solution. The
metal, Cr2O3, and K2CrO4 samples were placed intime. �ref is the decay constant of the reference source,
here that of 137Cs.
In the present work, the relative difference in the decay
constant of 51Cr, {�(Cr6+)-�(Cr0)}/�(Cr0) was determined tobe (5.3±2.2)×10-4. On the other hand, the difference lessthan 1.4×10-4 at a 68% confidence level was observed for{�(Cr3+)-�(Cr0)}/�(Cr0). Kakiuchi and Mukoyama reported
the value of (5.3±2.1)×10-4 for {�(Cr6+)-�(Cr3+)}/�(Cr3+)[2], which is in good agreement with the our value of{�(Cr6+)-�(Cr0)}/�(Cr0). In the presentation, we will
discuss the comparison between the results obtained andthe theoretical estimation with a simple model calculation
[2].
[1]
[2]
[3]
[4]

－ 308 －

G. T. Emery: Ann. Rev. Nucl. Sci. 22, 165 (1972)
S. Kakiuchi and T. Mukoyama: Bull. Inst. Chem. Res., Kyoto Univ.
59, 27 (1981)
T. Ohtsuki et al.: Phys. Rev. Lett. 93, 112501 (2004)
H. Kikunaga et al.: Proc. Radiochim. Acta 1, 113 (2011)

25-NCP-12

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Selective Separation of Strontium (II) from Nitric Acid Solution by a
Macroporous Silica-based DtBuCH18C6 Adsorbent Modified with
Surfactants
WU Yan, CHEN Zi, WEI Yuezhou*

School of Nuclear Science and Engineering, Shanghai Jiao Tong University, China�

Corresponding author. Tel.: +86-21-34207654. E-mail address:yzwei@sjtu.edu.cn.

Keywords – Sr(II); silica-based support; crown ether; dodecyl
benzenesulfonic acid; adsorption

4',4'(5")-di(tert-butylcyclohexano)-18-crown-6(DtBuCH18C6), a microcyclic crown ether, has the ability
to extract Sr(II) due to the effective complexation of Sr(II)with hydrophilic crown ether, and a good match between
the cavity of crown ether and ionic radius of Sr(II) ion. The
SiO2-P support is a kind of inorganic material, which isprepared by synthesizing the SDB-copolymer inside themacroporous SiO2 substrate. In this study, DtBuCH18C6
modified with dodecanol and dodecyl benzenesulfonic acid
(DBS) was impregnated onto SiO2-P ((DtBuCH18C6+
dodecanol + DBS)/SiO2-P). The equilibrium and kinetics of(DtBuCH18C6 + dodecanol + DBS)/SiO2-P for adsorptionof Sr(II) were investigated under the conditions: varying
the shaking times, HNO3 concentration, and initialconcentration of metal ions. The chemical stability ofabsorbent in HNO3 medium was examined by measuring
the leakage of total organic carbon(TOC) in liquid phase. In
order to confirm the effect of surfactant(DBS) on
adsorption of Sr(II), the (DtBuCH18C6+ dodecanol)/SiO2P are synthesized for comparison. Compared to(DtBuCH18C6 + dodecanol)/SiO2-P, much higher
distribution coefficient (Kd) for (DtBuCH18C6+ dodecanol+ DBS)/SiO2-P was obtained in the range of 0.5 to 4 M
nitric acid. The uptake rate of Sr(II) on (DtBuCH18C6+
dodecanol + DBS)/SiO2-P in the presence of 0.5 M HNO3
was attained equilibrium within 1 h, and the relatively large
Kd value around 4×102 cm3/g was obtained, which was
improved 428 times compared with (DtBuCH18C6+
dodecanol)/SiO2-P. The adsorbent had almost no uptake forother tested metals such as Cs(I), Na(I), K(I), Pd(II),
Ru(III), Y(III), La(III), Nd(III) and Gd(III). The uptake ofSr(II) for (DtBuCH18C6+ dodecanol + DBS)/SiO2-P was
explained by Langmuir adsorption equation and thesaturated amount of adsorption was estimated to be 0.24
mmol/g in 0.5 M HNO3. The leakage of TOC from the(DtBuCH18C6+ dodecanol + DBS)/SiO2-P into aqueous
phase were below 95 ppm even in 4 M HNO3. Thesefindings suggest that the (DtBuCH18C6+ dodecanol +DBS)/SiO2-P are stable in HNO3 solution and would be
effective for the selective separation of Sr(II) fromradioactive liquid waste.

－ 309 －

25-NCP-13

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013����������������������������������������������������������������������������
�������������
Erik Johnstone1, Frederic Poineau1, Paul M. Forster1, Phillippe Weck,2 Christos D. Malliakas3, Eunja
Kim4, Mercouri G. Kanatzidis3, Brian L. Scott5, Alfred P. Sattelberger6, and Kenneth R. Czerwinski1
1

Department of Chemistry, University of Nevada Las Vegas, Las Vegas, NV, USA.
2
Sandia National Laboratories, Albuquerque, NM, USA.
3
Department of Chemistry, Northwestern University, Evanston, IL, USA
4
Department of Physics and Astronomy, University of Nevada Las Vegas, Las Vegas, NV,USA
5
Materials Physics and Applications Division, Los Alamos National Laboratory, Los Alamos, NM, USA
6
Energy Engineering and Systems Analysis Directorate, Argonne National Laboratory, Lemont, IL, USA.

��������� –������������ ������������ ����������� ������� �����������
��������������

Technetium (Z = 43) is the lightest element on the
periodic table with no stable isotopes. The most common
isotope, 99Tc (t1/2 = 2.1 x 105 a), is produced in nuclear fuels
as a primary fission product in ~6% yield. In comparison
to the surrounding stable transition metals, the fundamental
chemistry of technetium has been poorly studied. An
example of this is the binary halide system, which prior to2008 consisted of 3 known compounds for technetium(TcF6, TcF5, and TcCl4), whereas for rhenium there havebeen 12 identified.[1] In this work low-valent binary
technetium chlorides and bromides were synthesized in thesolid state and analyzed using various physicochemical
characterization methods including single-crystal andpowder X-ray diffraction (XRD), IR spectroscopy, X-ray
absorption fine structure (XAFS), and elemental analysis.

�� ���������������������������
TcBr3 has been prepared via two different methods: thestoichiometric reaction of the elements in sealed Pyrex
tubes or by passing HBr(g) over Tc2(O2CCH3)4Cl2 atelevated temperatures. Both synthetic methods yield theinfinite-chain structure of distorted TcBr6 face-sharing
octahedra. Technetium tetrabromide was synthesized fromthe reaction of Tc metal with excess Br2(l).[6] It isisostructural to technetium tetrachloride, and similarly
decomposes to lower-valent technetium bromides. Whenperformed in Pyrex tubes the decomposition of thetetrabromide yields a novel trigonal prismatic Tc(II)bromide cluster, Na{[Tc6Br12]2Br}.[7]�� ����������������������������
Technetium dichloride was synthesized from thestoichiometric reaction of the elements as a novelcompound with a new structure-type containing a Tc-Tc
triple bond. The α-phase of technetium trichloride wasprepared from the reaction of Tc2(O2CCH3)4Cl2 with
passing HCl(g) at elevated temperatures.[3]It isisostructural to ReCl3 with a triangular Tc39+ core structure
containing Tc=Tc bonds. The β-phase of the trichloride
was synthesized from the stoichiometric reaction of Tc
metal with Cl2(g) and it exhibits structural characteristics
comparable to the trichlorides of ruthenium andmolybdenum.[4] Technetium tetrachloride was synthesizedfrom the metal and excess chlorine gas in sealed Pyrex
tubes and used as a starting material for decomposition to
TcCl2 and TcCl3.[5]
[1]
[2]
[3]
[4]

Schwochau, K. Technetium: Chemistry and Radiopharmaceutical
Applications; Wiley-VCH: Weinheim, Germany, 2000.
Poineau, F., et. al., �����������������, ����, ���, 15864-15865.
Poineau, F., et. al. �����������������, ����, ���, 8814-8817.
Poineau, F., et. al. ������������, ����, ��, 4915-4917.

Figure 1. Binary Tc chlorides synthesized from the stoichiometric reactionof Tc metal and elemental chlorine in sealed tubes at elevatedtemperatures.

The low-valent technetium chlorides and bromides
synthesized exhibit interesting chemical and physicalproperties, and may serve as potential synthetic inorganicand radiopharmaceutical precursors, as well as potential
waste form-type material in the nuclear fuel cycle.
[5]
[6]
[7]

－ 310 －

Johnstone, E. V., et. al. �����������. ����, ��, 8462-8467.
Poineau, F., et. al. ����������������������, ���, 910-911.
Johnstone, E. V., et. al., ������������, ����, ��������5660-5662.

25-ACP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Solvent Extraction of Americium(III) and Europium(III) Using Hydroxyoctanoic
Acid and N-heteroaromatic Compound
Moe Seike1, Mai Eguchi1, Atsushi Shinohara1, Takashi Yoshimura2
1

Graduate School of Science, Osaka University
Radioisotope Research Center, Osaka University

2

Abstract – Solvent extraction of Am(III) and Eu(III) was investigatedusing two hydroxyoctanoic acids including a new 2-hydroxy-2trifluoromethyl-octanoic acid (L1-CF3) and two bidentate Nheteroaromatic compounds as extractants. The new lanthanide(III)complexes with bidentate N-heteroaromatic ligands weresynthesized and the structures were characterized to eight- or ninecoordinate. Solvent extraction of Am(III) and Eu(III) in 1octanol/acetic acid buffer solution was performed. The separation
factor using L1-CF3 was about 2.
Keywords – lanthanides, actinides, extraction, complex(CF3SO3)3 (Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
Yb) with bidentate N-heteroaromatic ligands.
The solvent extraction experiment was performed in theacetic acid buffer solution or nitric acid solution as theaqueous phase and 1-octanol containing the extractant as theorganic phase. The tube containing the same volume of twophases were shaken for 24 h in a thermostatic bath at 20 �.
The distribution ratios (D) of 152Eu and 241Am were
determined by gamma-ray measurement of each phase bymeans of a germanium semi-conductor detector.

I. INTRODUCTION

III. RESULTS AND DISCUSSION

It is recognized that separation of trivalent lanthanides
and actinides is difficult because of their similar chemical
properties. To date, various methods such as chromatography,
extraction, and electrophoresis have been investigated. In thepresent study, we report on solvent extraction usinghydroxyoctanoic acids and bidentate N-heterocyclic
compounds that have � electron-accepting ability. We
synthesized four extractants: two hydroxyoctanoic acids andtwo bidentate N-heteroaromatic ligands. The crystal
structures of lanthanides(III) with bidentate N-heteroaromatic
ligands were determined. The solvent extraction of 152Eu and241
Am was performed using hydroxyoctanoic acids andN-heteroaromatic compounds in 1-octanol/acetic acid.

In the case of L2-pz, the three types of structures witheight- or nine-coordinate were obtained by changing thecentral lanthanide ions. The change of coordination number
from nine to eight occurred between Gd and Ho. The eightcoordinate complexes exhibited intramolecular hydrogenbonds between triflate and L2-pz. In the case of L2-py, theeight-coordinated dinuclear complexes (Ln = Tb – Yb) wereafforded.
The D value of 0.60 for Eu and that of 0.50 for Am wereobtained at pH 4.8, when L1-CH3 was used as the extractant.
The D values were about 200 times larger than the values
without extractant: D = 3.0×10-3 for Eu and D = 2.2×10-3
for Am. When L1-CH3 and L2-pz/L2-py were added to theorganic phase, the D values were not changed from the values
using L1-CH3 in the pH region of 4 - 5.5. This indicates thatsynergetic extraction of L2-pz and L2-py is not shown to beeffective in this condition. This may cause that 1-octanol
coordinates to Eu and Am to inhibit coordination of bidentate
N-heteroaromatic ligands. In the case using only L1-CF3, theD value of 2.83 for Eu and that of 1.29 for Am were obtainedat pH 5.0. The values are several times larger compared withthose using L1-CH3 under the similar condition. This would
be due to decrease of pKa of extractant by substituting fromCH3 to CF3 group. Namely, carboxylate proton in L1-CF3
easily dissociates by the existence of electron-withdrawing
CF3 group. The value of separation factor of Eu and Am wasabout 2. In the case using L1-CH3 or L1-CF3 as theextractant, the logD values were increased with increasing pH.
The slope values suggest that two L1-CH3/L1-CF3
coordinate to the metal ions.

II. EXPERIMENTAL
Figure 1 shows the new 2-hydroxy-2-trifluoromethyloctanoic acid (L1-CF3) and three known compounds, 2hydroxy-2-methyl-octanoic acid (L1-CH3), 3-(2-pyrazinyl)pyrazole (L2-pz), and 2-(1H-pyrazole-3-yl)-pyridine (L2py)[1][2]. L1-CF3 was synthesized by referring to the literature
to prepare a hydroxycarboxylic acid with a long alkyl
chain[3].

Figure 1.

Extractants in this study.

Nineteen new lanthanide(III) complexes with L2-pz or
L2-py were synthesized by the reactions of [Ln(H2O)9]

[1]
[2]
[3]

－ 311 －

T. Yabuuchi, et al., Chem. Pharm. Bull., 1999, 47, 684-686.
K. L. V. Mann, et al., Polyhedron, 1999, 18, 721-727.
Blay, et al., Tetrahedron, 2002, 58, 8565-8571.

25-ACP-02

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Stability of uranyl peroxo-carbonato complex ions in the presence of metal oxide
in carbonate media

1

Dong-Yong Chung1, Min-Sung Park1, Keun-Young Lee1, Han-Beom Yang1, Eil-Hee Lee1,
Kwang-Wook Kim1, Jei-Kwon Moon1

Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon, 305-353, Republic of Korea

Abstract – This work studied the stability of uranyl peroxo
carbonato complex ions in a carbonate solution with hydrogen
peroxide in the presence of various metal oxides using absorption
spectroscopy. The uranyl peroxo carbonato complex ions selfdecomposed into uranyl triscarbonato complex ion in thepresence of various metal oxides.

No metal oxide[H2O2]/[H2O2]o

1

Keywords – Uranyl peroxo-carbonato complex, Hydrogen
peroxide, Metal oxides, Absorption spectra

0.1

MoO2
ZrO2
Gd2O3
CeO2
SrO
Nd2O3
PdO
RuO2
La2O3
Sm2O3
PrO2

PdO

RuO2

I.

INTRODUCTION

0.01

0

1

MoO2

2

3

4

5

Time (hour)Fig. 1. Change of hydrogen peroxide concentration with time in thepresence of each metal oxide at [Na2CO3]=0.5M, [H2O2]=1.0M, amount ofmetal oxide = 0.5 g/L.

B. Stability of uranyl peroxo-carbonato complex ions in thepresence of the metal oxides
When the absorbance of the uranyl peroxo-carbonato
complex ion solutions were measured in the presence of Ru
oxide powder. The features of the absorption spectrum of
the uranyl peroxo-carbonato complex solution graduallydisappeared with time. The peaks of uranyl tris-carbonato
complex appeared at 435, 448, and 462 nm (Fig. 2).
2.0Time (hour)
0
2
4.3
7.7
24
32
100

1.5

Absorbance

Uranium is selectively dissolved to form uranyl peroxocarbonato complex ions, UO2(O2)x(CO3)y2������, with a highsolubility in carbonate solutions that contain hydrogen
peroxide, H2O2. Recently, several carbonate-based
processes have been studied and suggested to treat
uranium-bearing waste and scraps generated during
uranium fuel fabrication, uranium sludge and spent nuclear
fuel [1–2]. Hydrogen peroxide is easily decomposed into
water and oxygen in aqueous solutions. Additionally,
uranyl peroxo-carbonato complex solution can selfdecompose into uranyl tris-carbonato complex ions,
UO2(CO3)34�, which are stable in a carbonate solution.
When a carbonate-based uranium leaching process usinghydrogen peroxide is applied to treat uranium-bearing
compounds, the stability of the uranium peroxo-carbonato
complex ions must be known to ensure that theconcentration does not change during prolonged storage [3].
In this study, the decomposition of hydrogen peroxide andthe stability characteristics of a uranium peroxo-carbonato
complex in a carbonate solution were investigated in thepresence of various metal oxides using absorption
spectroscopy.

1.0

0.5

0.0

II. RESULTS AND DISCUSSION

400

500

600

Wavelength (nm)700

A. Decomposition of hydrogen peroxide in the presence ofthe metal oxides in a carbonate solution

Fig. 2. Variation of asorption spectra of uranium dissolved solution([U]=3.25x10-2 M) in the presence of Ru oxide powder in 0.5M Na2CO3
solution (0.02g powder/30ml Na2CO3 solution).

The decomposition of H2O2 in the presence of metaloxide follows first-order kinetics. The rate constants for
RuO2, PdO and MoO2 are 115.1, 15.97 and 0.561 hr-1,
respectively. Rate constants of other metal oxides are
similar to the value, 0.292 hr-1 of rate constant in a 0.5 M
carbonate solution (Fig. 1). The decomposition rate ofhydrogen peroxide in the presence of metal oxide powders
was almost not affected with metal oxides except RuO2,
PdO and MoO2.

ACKNOWLEDGMENT
This work was supported by the National Research
Foundation of Korea grant funded by the Korea
government (MSIP).
[1]
[2]
[3]

－ 312 －

Kim, K.W.; Chung, D.Y; Yang, H.B.; Lim, J.K; Lee, E.H.; Song,
K.C.; Song, K-S. Nucl. Technol., 2009, 166, 170����.
Chung, D.Y.; Seo, H.S.; Lee, J.W.; Yang, H.B.; Lee, E.H.; Kim,
K.W. J. Radioanal. Nucl. Chem., 2010, 284,123-129.
Kim, K.W.; Lee, K.Y.; Chung, D.Y.; Lee, E.H.; Moon, J.K.; Shin,
D.W. J. Hazardous materials, 2012, 233-234, 213-218.

25-ACP-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Raman Spectroscopic Study on Uranyl and Neptunyl Complexes in Highly
Concentrated Calcium Chloride
Toshiyuki Fujii1, Akihiro Uehara1, Yoshihiro Kitatsuji2, and Hajimu Yamana1
1

Division of Nuclear Engineering Science, Research Reactor Institute, Kyoto University
2
Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

Abstract – In order to understand the coordination circumstanceof actinyl ions in concentrated inorganic electrolytes, U and Np
species in concentrated CaCl2 were analyzed by Raman
spectrometry. The �1 symmetric vibrational frequency of actinyl
ions was found to decrease with the increase of [CaCl2]. This may
be attributable that hydration water molecules at the equatorial
plane of actynyl were substituted by Cl- ions.
Keywords – Raman spectrometry, uranyl, neptunyl, calcium
chloride, hydrate melt

Calcium chloride hexahydrate, CaCl2·6H2O, possesses a
low melting point, 303 K. The melt is identical with 6.9
mol dm-3 (M) CaCl2 aqueous solution. The chemical
properties of the hydrate melt are considered to beintermediate between aqueous solutions and anhydrous
molten salts. A structural study on UO22+ in 6.9 M CaCl2 by
X-ray absorption fine structure (EXAFS) analysis showedthat the possible structure is UO2Cl2(H2O)2 [1]. This isdistinctly different from the hydrated UO22+ in diluted
acidic solutions, that is, UO2(H2O)52+. The coordination andredox behavior of UO22+ in 6.9 M CaCl2 has been studied
by Raman spectrometry and by using electrochemical
methods [2]. A change in the vibrational frequency ofsymmetrical stretching (�1) of UO22+ suggested that thecomplexation between U(VI) and Cl- at the equatorial planeof UO22+ depresses the bonding strength of U=O.
In the present study, we investigated the �1 frequencies
of uranyl and neptunyl in highly concentrated calcium
chlorides by Raman spectrometry. The �1 frequency was
also estimated by using ab initio methods. The ligand
exchange reaction between hydrated water and Cl- at theequatorial plane is discussed.
Calcium chloride dihydrate, CaCl2·2H2O, of analyticalgrade (Wako Pure Chemical Industries, Ltd.) was usedwithout purification. Weighed amounts of CaCl2·2H2O andwater were mixed for preparing various concentrations of
CaCl2. As a starting material, U3O8 was dissolved in 6 M
HCl. A nitric acid solution containing Np was also used. A
portion of these solutions was once dried by heating andthen the CaCl2 solution prepared was added. The
concentration of U or Np was 0.01 M. The sample wastaken in a quartz cell and the cell was sealed. Electronic
absorption spectra of the samples were measured in the
wavelength range from 340 to 1350 nm at 0.5 nm intervals
by using an UV/Vis/NIR spectrophotometer (Shimadzu,
UV-3100PC).
Raman spectra were measured by using a Raman
spectrophotometer (NRS-3100, JASCO). A green laser
with the wavelength of 531.9 nm was used at the output
power of 57.6 mW. The measurement interval of a chargecoupled device (CCD) detector was set to be every 0.3 cm-1.

The operations of each 3-seconds measurement wereaccumulated by 25 times. The experimental temperature
was 298 K.
The �1 frequency of UO22+ in 6.8 M CaCl2 was found at~855 cm-1. This agreed with the literature value [2]. With
the decrease of water content in the CaCl2 system, the �1
frequency decreased to the extent of ~7 cm-1. This suggeststhat hydration water molecules at the equatorial plane of
uranyl were substituted by Cl- ions, which depressed thebonding strength of U=O.
The CaCl2 system containing Np showed a specific
Raman spectrum. Figure 1 shows the Raman spectrum of
0.01 M Np in 6.8 M CaCl2. From electronic absorption
spectrum obtained, it was suggested that Np(VI) and Np(V)
coexist in the system. The Raman peaks shown in Fig. 1 arehence attributable to �1 vibrational modes of NpO22+ andNpO2+ complexes. Similar to the case of U, the Raman
peak at ~835 cm-1 shifted by changing water content of thesystem. This may also suggest that the ligand exchange
between hydrated water and Cl- at the equatorial plane of
neptunyl occurrs.

Fig. 1. Raman spectrum of 0.01 M Np in 6.8 M CaCl2. The spectrum wasdecomposed into three Raman peaks by Gaussian/Lorentzian sum function.
[1][2]－ 313 －

A. Uehara et al., NEA/NSC/DOC (2009) 15.
A. Uehara et al., J. Appl. Electrochem., 42, 455 (2012).

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-ACP-05

Electrode Reaction of Actinide Ions in a Weak Acidic Solution
1

Yoshihiro Kitatsuji1, Haruyoshi Otobe1, Takaumi Kimura1

Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

Abstract –Electrode reactions of U(VI) in weak acid solution are
different from those in acid solution. Electrolysis of U(VI) can
produce UO2 fine crystal, not hydrolyzed U(IV). The formed UO2
is easily deposited on an electrode and is electrode active.
Keywords – actinide ions, redox, weak acidic solution, aggregate

I.

INTRODUCTION

Actinide (An) ions such as uranium, neptunium andplutonium exist as ionic species of trivalent to hexavalent
in an aqueous solution. Most of studies concerning redox ofactinide ions by electrochemical method have focused onacidic solution in which An ions are dissolving stably.
However, redox behaviors of actinide ions in weak acid or
neutral solution are expected to be different from that in anacid solution, because redox of AnO2+/An4+ is affected by
H+. Also hydrolysis has a great influence on the redox. In
this paper, the authors report unique electrode reaction ofactinide ions concerning an aggregation in a weak acidic
solution.

U(V) ion was prepared from U(VI) by bulk electrolysis
at �0.35 V. U(V) solution showed the peak of absorbanceat 260 nm on UV/VIS spectrum. U(V) in a solution of pH
2.9 was stable for about 30 min. Then the peak at 260 nm
became smaller, and the absorbance at all range ofmeasurement was increased gradually. These results
suggest the formation of aggregate. Only oxidation currentof U(V) to U(VI) at �0.2 V was observed (curve b) by CVmeasurement immediately after preparation of U(V), but
CV curve was changed after aggregation (curve c): large
oxidation current peak was observed at +0.15 V and +0.3 V
in a first cycle of CV measurement; oxidation current of
U(V) was negligible; reduction current of U(VI) is about
half amount of the initial solution (cf. curves a and c). The
aggregate was prepared by electrolysis at �0.35 V in asolution of pH 2.9, and fluorite structure of UO2 wasdetermined by XRD analysis.
The authors conclude that U(IV) produced via
disproportionation of U(V) aggregates to form UO2. This
fine UO2 is easily deposited on electrode surface and iselectrode active to oxidize.

II. EXPERIMENTAL

-9

4 10

Voltammetry was carried out by using a microelectrodeof Au of 25 �m in diameter. Controlled potential differenceelectrolysis was performed with an Au gauze electrode (80mesh, 60 × 20 mm) as working electrode to bulk
electrolysis. A Pt wire and a silver-silver chloride electrodewith 1 M LiCl was employed as a counter electrode and areference electrode, respectively.
Oxidation states of actinide ions in sample solutions
after electrolysis were identified based on UV/VIS
adsorption spectrometry. The aggregate produced in theelectrolysis sample solution was analyzed by X-ray
diffraction after filtration.

(b)-9current / A

2 10

-9

-2 10

-9

-4 10

(a)

-9

2 10

current / A

III. RESULTS AND DISCUSSION
Reduction of U(VI) ion in a solution of pH 2 to 5 wasinvestigated by cyclic voltammetry (CV) with an Au
microelectrode. Reduction currents of U(VI) to U(V) wereobserved at ca. �0.2 V clearly(see, Fig. 1, curve a). When
CV measurements were repeated, oxidation peak current
was observed at +0.2 V in a first cycle of CV for a solutionof pH 4. In order to investigate this oxidation current,
stripping voltammetry was applied. Clear adsorption
current for oxidation of species produced by preelectrolysis
at �0.3 V was observed. Similar adsorption behavior atcarbon electrode had been reported by Duber previously[1],and they concluded that oxidation current was attributable
to oxidation of U(V) adsorbed on the electrode.

0

(c)

0
-9

-2 10

-9

-4 10
-0.5

0
0.5
Potential / V vs SSE

1

Fig 1. Cyclic voltammograms of 1mM U in a weak acid solution.
(a) U(VI), (b) U(V) immediately after preparation, (c) U(V)solution after 60 min. broken line are background current.

REFERENCE[1]－ 314 －

R. E. Dueber, A. M. Bond, P. G. Dickens, J. Electrochem. Soc.,
141(1994)311.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-ACP-06

Biomineralization of uraninite and uranyl phosphate controlled by organic acids
Yoshinori Suzuki1, Naofumi Kozai2, Toshihiko Ohnuki2

Graduate School of Bionics, Tokyo University of Technology, 1404-1 Katakura-cho, Hachioji, Tokyo 192-0982, Japan
2
Advanced Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan

Abstract – Biomineralization of uraninite (UO2) and uranyl
phosphate minerals are both able to decrease the mobility ofuranium in the environment. We examined biomineralization of
UO2 and uranyl phosphate by Shewanella putrefaciens in thebasic medium containing lactate as an electron donor, �glycerolphosphate as a phosphorous source, and uranyl nitrate in
the absence and presence of weak or strong complexing organic
acids (WCOA or SCOA) under an anaerobic condition. In thebasic medium, only biomineralization of UO2 was observed
because of rapid reduction of U(VI). Biomineralization of UO2
and uranyl phosphate occurred in the media with WCOA,
however the no biomineralization was occurred in the presence of
SCOA. It is thought that formation of stable U(VI)-, and U(IV)organic complexes prevents the biomineralization. These finding
suggest that coexisting organic acids control thebiomineralization of UO2 and uranyl phosphate minerals by
microorganisms.
Keywords –biomineralization, U-organic complexes, Shewanella
putrefaciens, effects of organic acids

I.

INTRODUCTION

Uranium is a radionuclide found in high- and low-level
radioactive wastes. Its safe geological disposal requires anunderstanding of the migration behavior of uranium in theenvironment. Biomineralization of uranium is one of theimmobilization mechanisms. The formation of uraninite(UO2) through bioreduction of U(VI) and of uranyl
phosphate minerals by microbial phosphate release are wellknown biomineralization. These two mechanisms havebeen investigated individually. However, there is thepossibility that the two types of biomineralization competeeach other in the environment. In this study, we examined
the biomineralization of UO2 and uranyl phosphate by
Shewanella putrefaciens under the conditions they compete.
It has been reported that the presence of organic acids,
which form complexes with uranium, affects the reductive
mineralization of UO2 [1]. Therefore we focused on theeffects of weak and strong complexing organic acids(WCOA and SCOA) on the biomineralization of uranium.

withdrawn. The uranium concentrations and UV-vis spectraof the aqueous phases were measured. The new solid
phases formed in the media were analyzed by SEM-EDS.
III.

100
Oxalic acid
Tartaric acid
Citric acid
EDTA
Acetic acid
Adipic acidNo additionalorganic acid

80
60
40
20
0
0

II. EXPERIMENTAL
Shewanella putrefaciens, an iron-reducing bacterium, wasincubated in the basic medium (pH 7.0), which contained
50 mM sodium lactate as an electron donor, 1 mM uranyl
nitrate as an electron acceptor, and 0.44 mM �glycerolphosphate as a phosphorous source, and mineralsalts under an anaerobic condition at 30°C. To evaluate theeffects of organic acids, 100 mM WCOA (acetic, or adipicacid), or SCOA (oxalic, tartaric, citric acid or EDTA) wereadded to the basic media and the cells were incubated in thesame way. Aliquots of medium were periodically

RESULTS AND DISCUSSION

The time courses of the total aqueous uranium during the
incubation are shown in Fig. 1. In the basic medium,
uranium in the aqueous phases decreased rapidly and newsolid phases were observed. In the basic media with
WCOA, the decreasing rates of aqueous uranium wereslower than that in the basic medium with no WCOA. New
solid phases also formed in these media. No decrease of
uranium in solution was observed the media with SOCA.
The UV-Vis spectra of the medium with SOCA showedthat U(VI) was reduced to U(IV) and formed aqueous
complexes with SOCA. This indicates that the stablecomplex formation inhibits the precipitation of uranium.
SEM-EDS and UV-Vis analyses of the new solid phases
indicated the solid phases in the basic medium were mainly
UO2, and those in the media with WOCA were mixture of
UO2 and uranyl phosphate. It was though that the additionof WCOA decreased the reduction rate of U(VI), andallowed U(VI) to react with inorganic phosphate releasedby biodegradation of �-glycerolphosphate. Uranyl
phosphate was not formed in the absence of �glycerolphosphate. These findings suggest that thebiomineralization behavior of uranium is highly affected byorganic acids and their complexing abilities with uranium.

U in solution [%]1

50Time [h]100150Fig. 1. Time course of aqueous uranium in the media with variousorganic acids during incubation with S. putrefaciens.

REFERENCES[1]－ 315 －

Y. Suzuki, K. Tanaka, N. Kozai, T. Ohnuki, Geomicrobiol. J., 2008,27(3), 245-250.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-ACP-07

Comparison of the spectroscopic characteristics of uranium species when U(III) in
a LiCl-KCl molten salt is leached out with water and ionic liquid
Hee-Jung Im, Kyuseok Song

Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute,
150 Deokjin-dong, Yuseong-gu, Deajeon 305-353, Republic of Korea
Abstract – U(III) in a LiCl-KCl molten salt was first dissolved into
an appropriate ionic liquid and water, and identification anddetermination of the uranium (U) in the LiCl-KCl molten salt
were performed using spectroscopic methods. The U(III) in LiClKCl molten salt showed the tendency of stable status in ionicliquid and unstable status in water. Based on the experimental
data, a predictive theory of the factors involved in the process is
discussed.
Keywords – Uranium species, LiCl-KCl eutectic, Molten salt,
Ionic liquid, Spectroscopy

I.

INTRODUCTION

As a type of spent nuclear fuel treatment, thepyrochemical process is well known for its nonproliferation of nuclear fuel cycles, separation of long-term
radioactive nuclides during processing, the recovery of
uranium for re-use as a nuclear fuel, and a significant
volume-reduction of high-level wastes. After the complete
pyrochemical processing is finished, a remaining small
amount of salt waste, apart from the salt for recycling
purposes, will be stored for the long term and is composedof some actinides and lanthanide species (mainly existing
as 3+ ions) dissolved in molten salt. In this study, weinvestigate the behavior of U(III) dissolved in LiCl-KCl
molten salt, especially when U(III) is leached out with ionicliquid compared to water, to obtain better understandable
information for long-term waste salt storage. An ionicliquid system, which is similar to the environment of aslushy micelle system in a ground water migration, wasconsidered as a medium for a convenient bench-scale
experiment, and the results were compared to those fromthe water medium for U(III) behavior in different media.

U(VI) during procedures, a characteristic peak of U(VI)was observed at 411 nm, and the color of the solution waschanged from pale purple to yellow immediately after thesolid was dissolved in water. Although at the preparation ofsamples, the U(III) was solidified on the LiCl-KCl molten
salt from 450oC to room temperature, the solidified U(III)was oxidized immediately in the presence of water.
The excitation spectrum of UCl3 in a LiCl-KCl molten
salt is shown in an ionic liquid by emission at 641 nm, andthe spectrum was compared to an excitation spectrum of anionic liquid only. There were specific peaks at 515 nm and534 nm. The emission spectrum of UCl3 in a LiCl-KCl
molten salt in ionic liquid was also obtained at a 515 nm
excitation, which was one of the positions obtained in theabsorption spectra. Peaks were observed at 588 nm, 610 nm,
and 640 nm.
Many experiments were undertaken to confirm
luminescence peaks and to elucidate the exact phenomenon
and mechanism.
IV. CONCLUSION
U(III) is unstable (oxidized) in an alkali fluoride molten
salt or under general conditions, but is stable in LiCl-KCl
molten salt. Moreover, the ionic liquid (1-hexyl-3-methylimidazolium chloride) used in this research did not cause
an oxidation or reduction of U(III) as 1-ethyl-3-methylimidazolium chloride or water does. The behavior of U(III)in LiCl-KCl is dependent on the contact solvent (ionicliquid or water), and the results, including the actual
assignment of each peak of the spectroscopic spectra, wereconclusive.

II. EXPERIMENTAL
A U(III) in LiCl-KCl molten salt was prepared from thereaction of uranium metal with cadmium chloride in a
LiCl-KCl mixture (44 wt.% LiCl) at 450 oC in an Aratmosphere glove box.
III. RESULTS AND DISCUSSION
Absorption spectra of the LiCl-KCl molten salt in anionic liquid and UCl3 in the LiCl-KCl molten salt in theionic liquid are compared. The peaks at 460 nm and 553
nm are from U(III).
However, the absorption spectrum of UCl3 in the LiClKCl molten salt with water was very different to thespectrum of UCl3 in the LiCl-KCl molten salt in the ionicliquid. As it is well known that U(III) is easily oxidized into
－ 316 －

25-ACP-08

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa,Japan, 22-27September 2013

Distribution of Neptunium in PUREX streams
Neetika Rawat, Aishwarya Kar, M.A. Mahajan, N.B. Khedekar, R.M. Sawant,
B. S. Tomar and K. L. Ramakumar
Radioanalytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085
Abstract:237Np, is formed in abundance in nuclear reactors,
however, the separation of neptunium from spent uranium fuel isdifficult owing to the existence of its varied oxidation states in the
dissolver solution. With a view to identify the stage in the PUREX
plant, which can be used to tap neptunium, an exercise wasundertaken to determine the distribution of neptunium in the
different stages of the PUREX plant.
Keywords:237Np, PUREX Streams,

INTRODUCTION
Np, the long lived isotope of neptunium is the target
isotope for production of 238Pu by the neutron capture
reaction. It is formed in abundance in nuclear reactors[1].
However, the separation of neptunium from spent uranium
fuel is a difficult task owing to the existence of the element
in varied oxidation states in the dissolver solution. With aview to identify the stage in the PUREX plant, which canbe used to tap neptunium, an exercise was undertaken to
determine the distribution of neptunium in the different
stages of the PUREX plant.
237
Np is a pure alpha emitter with no gamma lines andhence its analysis requirescareful radiochemical separationfrom bulk uranium, plutonium and fission products before
its estimation by alpha spectrometry. The alpha energies of
plutonium isotopes are higher than that of 237Np and hence
traces of Pu in the separated neptunium fractions would
have contribution at the alpha peak of 237Np (Figure 1).
Therefore, it was decided to measure the distribution ratios
of Np in various streams of PUREX process using 239Np
������� ����� ��������� from irradiated uranium target. The
actual column conditions of different streams were
simulated performing solvent extraction in lab scale for the
distribution of Np.
237

50

237
Np

4.7 MeV

Intensity

40
30

238
Pu

20

5.2 MeV

10
0
4.0

4.5

5.0

5.5

Energy (MeV)
Figure 1. Alpha spectrum of sample CD1 after plutonium séparation

EXPERIMENTAL
The 239Np tracer was obtained by irradiating natural
Uranium (10 mg) in reactor. The irradiated U was dissolvedin conc HNO3 and then evaporated to dryness and made up
to 20 ml using 3 M HNO3. Aqueous feed solution was
prepared by adding 237Np, 239Np tracer and U so as tomaintain U and Np concentration 380 g/L and 10 mg/L

respectively (acidity 3 M HNO3). Distribution of Np (DNp)
in different streams was followed by counting the 278 keVgamma line in the gamma spectra using a HPGe detector. 4
ml of feed was equilibrated for 15 min with 19.6 ml of
30 % TBP in NPH (O/A = 4.9). Phases were separated bycentrifugation. Suitable aliquots from the aqueous (HAW)
and organic phase (HAP) were taken for assay of 239Np.
16.4 ml from HAP was equilibrated with 4 ml of U(IV)((28 g/l) in N2H4 (0.2 M) at 0.6 M acidity (O/A = 4.1).
After phase separation, the organic and aqueous phases,labeled as 1BXU and 1BXP, respectively, were assayed forthe activity of 239Np. Subsequently 14 ml from 1BXU was
equilibrated with 15.45 ml of 0.01 M HNO3 (O/A = 0.906),
and the aqueous and organic fractions, labeled as 1CP and
1CW, respectively, were counted. 14 ml of 1CP wasconcentrated to 2.5 ml termed as 1CPCON. To 2.0 ml of
1CPCON, U(IV) was added such that U(IV) concentrationin final solution is 4.8 g/l and N2H4 is 0.2 M at 1.0 M
acidity. 1CPCON was diluted to 3.58 mL, and was labeled
as 2DCD. 1 ml of 2DCD was equilibrated with 2.3 ml of
30 % TBP (O/A = 2.3). The aqueous phase was labeled as
2DW. All the fractions were assayed for the activity of239
Np.
RESULTS AND DISCUSSION
The complete experiment following the above procedure
was carried out twice (Cycle 1 and Cycle 2). The DNpvalues and percentage of Np in different steps, for both thecycle are given in table 1. DNp values obtained for solvent
extraction steps in both the cycles are in good agreement
except for the step corresponding to HA column. DNp in
first cycle was found to decrease from 0.205 to 0.043 in thesecond cycle, which could be due to slow kinetics ofchange in oxidation state of neptunium. The decrease in
DNp values of Np from dissolver solution into TBP with thepassage of time, indicates the reduction of Np(VI) to Np(V).
Table 1.D values and percentage of Np in different steps
Sample name
Cycle 1
Cycle 2Distribution% Np
Distribution % Np
Coefficient, D
Coefficient, D
CD1
100
100
HAW
0.205
53
0.043
91
HAP
54
19
1BXP
0.266
26
0.26
9
1BXU
28
10
1CP
0.05
27
0.053
9.6
1CW
1.25
.4
1CPCON
27
9.6
2DCD
27
9.6
2DW
0.219
18
0.184
6.4
2DP
9
3.2

Reference
1. G.A.Burney and R.M.Harbour, Radiochemistry of
neptunium, Nuclear Science Series NS-3060(1974).

－ 317 －APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-ACP-09

����������������������������������������������������������
Yumi Sugo1, Yuji Sasaki2, Mitsumasa Taguchi1, Noriko S. Ishioka1
1

Quantum Beam Science Directorate, Japan Atomic Energy Agency
Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

Keywords Ð Solvent Extraction, Minor Actinide, Radiolysis

I.

INTRODUCTION

A
tridentate
extractant,
N,N,NÕ,NÕ-tetraoctyldiglycolamide (TODGA) has high extractability for
actinides such as americium and curium from nitric acidinto n-dodecane. �-Radiolysis study of the organic
extractants using an actinide radionuclide has someexperimental difficulties. For example, a long-term
exposure to actinides is required, and the extractants arecontaminated with the radionuclide. In the previous study[1], these issues were solved by irradiation with helium
ions provided by an accelerator. It was also found that theradiation chemical yield for the degradation of TODGA in
n-dodecane by helium ions corresponding to the �-particles
was less than that by �-rays. In this study, radiation effecton the extraction of 241Am was investigated using thesolution of TODGA pre-irradiated with �-particles, incontrast to the irradiation using actinides as an �-particles
emitter.
���������

�

�

�

�

���������

�

III. RESULTS AND DISCUSSION
The aqueous solutions containing 241Am at radioactive
concentration of 1.3 kBq ml-1 were used for the extraction
using the organic solutions pre-irradiated with �-rays.
After extraction, 241Am concentration in the aqueous phase
was less than 1 Bq ml-1. This indicates that 241Am isextracted almost quantitatively from the aqueous phase into
the organic one. Figure 1 shows 241Am concentration in theorganic phase as a function of dose absorbed by the organic
solution. The concentration in the organic phase nearly
kept constant even after irradiation with �-rays. The
absorbed dose had been estimated to be approximately 5
kGy per cycle in the actual process [2]. Consequently, it issuggested that the extractability of TODGA for minor
actinides can be maintained after recycling on the order ofdozens of cycles in the process.
In addition, we examined the �-radiation effect on theextraction of 241Am using the organic solution containing
complexing 241Am as �-particles emitter at radioactive
concentration of 8.4 MBq ml-1. The result will be discussed
in this presentation.
��

Abstract Ð �-Radiation effect on the extraction of 241Am wasinvestigated
using
the
solution
of
N,N,N',N'tetraoctyldiglycolamide
pre-irradiated with �-particles, incontrast to the irradiation using actinides as an �-particles
emitter. 241Am was extracted almost quantitatively from theaqueous phase into the organic one. The concentration in theorganic phase nearly kept constant even after irradiation with �rays.

����������� ������������ ���� �� �

2���������

���������

������

�

�

�

�

���

���

���

���������

II. EXPERIMENTAL

Fig. 1 241Am Concentration in the organic phase as a function of dose,

The organic solution of 0.1 M TODGA in n-dodecane
pre-equilibrated with nitric acid was irradiated with helium
ions provided by a tandem accelerator according to theprevious report [1]. Incident energy of the ions was
adjusted to 5 MeV corresponding to the typical energies ofthe �-rays emitted from actinide radionuclides. The
absorbed dose rate was approximately 1-3 kGy min-1.
The pre-irradiated solution was taken in an extraction
tube with an equal volume of an aqueous 3.0 M nitric acidsolution spiked with the radioactive tracer of 241Am. The
extraction tube was shaken mechanically for 30 min at
25±0.1¡C. After centrifugation, the aliquots of both phases
were taken and their �-activities were measured by liquid
scintillation counter.

obtained in the extraction using the solution of 0.1 M TODGA in
n-dodecane pre-irradiated with �-particles.

REFERENCES[1][2]－ 318 －

Y. Sugo et al., Radiat. Phys. Chem. ��, 1140 (2009).
G. M. Gasparini et al., Solv. Extr. Ion Exch. �, 1233 (1986).

25-ENP-01

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Retardation and Release Study of U(VI) on Phlogopite at Conditions Relevant to
Uranium Contamination in Environment
1

2

Pan Duoqiang1,2, Wang Zheming2, Wu Wangsuo1

Radiochemistry Laboratory, Lanzhou University, Lanzhou 730000, China
Pacific Northwest National Laboratory, Richland, Washington 99352, United State

Hexavalent Uranium, which is fertile in mining tailings andwastewater from nuclear production activities, is aprominent radioactive contaminant and has dispersed into
both sediments and water around the related uranium
processing sites, posing a potential health andenvironmental risk to the biosphere [1]. The mobility of
U(VI) in natural medium is significantly controlled by thesorption/desorption behavior which is influenced by U(VI)speciation,
sorbent
properties
andcoexistedorganic/inorganic ligands [2,3]. Desorption of absorbed
U(VI) from solid phase is actually considered to bepotential secondary release sources to hydrosphere and theextent of desorption reversibility largely depends on themechanisms involved in the sorption process [4]. As thesorption mechanism can vary by due to changes in sorption
conditions, such as ligand complexation and change of pH
or temperature, the uranium retardation and release rate inenvironmental media can be perturbed. Understanding thesorption mechanism and sorption reversibility of U(VI) is
imperative to predict the future retention/migration
behavior of U(VI) and to remediate contaminated soils andsubsurface sediments. Many spectroscopic technologies
that are capable of providing molecular-level information(FTIR, XPS, EXAFS, TRLIFS) have been employed to
identify U(VI) species and local atomic structures of thesurface complexes. Time resolved laser induced
fluorescence (TRLIF) spectroscopy, particularly when
performed at cryogenic temperatures, is one technique thatoffers high sensitivity and spectral resolution for theidentification of U(VI) speciation in complex media at low
U(VI) concentrations [5,6].
Here we applied a combination of batch sorption
experiment and liquid helium temperature (LHeT) TRLIF
spectroscopy to investigate sorption/desorption of U(VI) to
phlogopite, which is a typical rock forming mineral in

granite terrains. Effects of pH, humic acid (HA),
background electrolyte and temperature were studied indetail by batch method. The sorption isotherms at different
temperatures were simulated and analyzed by using
Langmuir and Freundlich models. Roles of HA andtemperature on sorption reversibility were investigated bysorption-desorption isotherms. The speciation of adsorbed
U(VI) at low concentration were monitored and thesorption/desorption mechanism were explored with the aidof TRLIF spectroscopy. The results shows that the sorptionof U(VI) on phlogopite is influenced obviously by pH
while only slightly by ionic strength. Inner-sphere surface
complexation and/or precipitation rather than ion exchange
and outer-sphere complexation are the primary sorption
mechanisms. HA makes little difference at low pH, while
inhibits U(VI) sorption at high pH mainly because offormation of soluble binary complexes and repulsive
interaction between both negative charged HA and solid
surface. High temperature is advantageous for U(VI)sorption, Langmuir model fits the sorption data better thanFreundlich model. The presence of HA switches U(VI)sorption reversibility by forming HA-bridge ternarycomplex.
Keywords: Uranium, Sorption/Desorption, Phlogopite, TRLIFS[1] Chakraborty S., et al., Environ. Sci.Technol., 2010, 44(10): 3779-3785.
[2] Chang H.S., et al., Environ. Sci.Technol., 2006, 40(4): 1244-1249.
[3] Chisholm-Brause C.J., et al., J. Colloid Interf. Sci., 2001, 233(1): 3849.
[4] Um W., et al., Environ. Sci.Technol., 2009, 43(12): 4280-4286.
[5] Wang Z., et al., Geochim. Cosmochim. Acta, 2005, 69(6): 1391-1403.
[6] Wang Z., et al., Geochim. Cosmochim. Acta, 2011, 75(10): 2965-2979.

－ 319 －

25-ENP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Application of Simplified Desorption Method to Sorption Study: (2) Sorption of
Neptunium (V) on Montmorillonite-based Mixtures
1

Naofumi Kozai1, Toshihiko Ohnuki1

Japan Atomic Energy Agency, Tokai, Ibaraki, 319-1195 Japan

Abstract – To elucidate the sorption behaviors of radionuclides in
multi-mineral systems and the mutual effects of minerals on thesorption, this paper carried out the sorption and desorption
experiments of neptunium(V) on montmorillonite-based twomineral mixtures. The Np sorbed on montmorillonite at pH from 4
to 8 was desorbed with 1M KCl solutions, indicating that thesorption was cation exchange. The Np sorbed on apatite and calcite
was nondesorbable with 1M KCl solutions, which is in harmony
with the knowledge that Np forms strong complexes with thephosphate groups of apatite and the carbonate groups of calcite. This
study utilized these clear distinguishes of the desorption behaviors
for examining the two-mineral systems. In montmorillonite-apatite
mixtures, the sorption on the montmorillonite was decreased and Np
was accumulated on the apatite. In montmorillonite-calcite mixtures,the sorption on the montmorillonite was decreased due to theinterference by the calcium and carbonate ions dissolved from
calcite while no accumulation of Np to calcite was observed.
Keywords – Neptunium, sorption, desorption, pH, montmorillonite,apatite, calcite

I.

INTRODUCTION

Sorption is one of the key mechanisms to control thesubsurface environmental behavior of the radionuclides. In
most of the relevant experimental studies, the sorption
experiments of radionuclides have been performed in a single
mineral system, while most of the subsurface environment isa multi-component system. The knowledge on the mutual
influence of minerals to understand the sorption in multicomponent systems is limited. This paper investigated thesorption of neptunium(V) in two-mineral systems.
Montmorillonite clay used as a major component mineral isfound ubiquitously in the soil environment. As minor soil
component minerals, apatite (Ca5(PO4)3OH) and calcite(CaCO3) were used. This paper applies a simplified
desorption method to the sorption study and discuss the
distribution of Np between minerals.
II. EXPERIMENTAL
This study used the same Na-montmorillonite as the oneused in the former study [1]. The apatite used is fine powderof commercial calcium-phosphate having hydroxyapatite(Ca5(PO4)3OH) like structure (Wako Pure Chemical
Industries Co. Ltd.). Natural calcite (CaCO3) was used afterground to particle sizes below 74 µm. These minerals wereused singly or used as montmorillonite-based mixtures(montmorillonite 95-99 w%). A Np (V) nitrate stock solution

was diluted with 0.01 M NaClO4 to yield a working solution-7
having a Np concentration of about 6x10 M.
The sorption and the desorption experiments wereconducted in the same way as the method described
elsewhere [1] except that a part of the sorption experiments
were carried out for up to 60 d.
III. RESULTS AND DISCUSSION
When Na-montmorillonite was used alone, the fraction of
the sorbed Np was roughly constant in the equilibrium pH
range from 4 and 8. Most of the sorbed Np was desorbed bytwice treatment with 1M KCl solutions. These results indicatethat the sorption is electrostatic one between NpO2+ and theconstant negative surface charge of the montmorillonite [2].
On the apatite and the calcite, all of the Np was sorbed in
the examined equilibrium pH ranges that were limited fromneutral to weak alkaline due to their partial dissolution. The
Np sorbed on these two minerals was hardly desorbed bytwice treatment with 1M KCl solutions. These results are
consistent with the knowledge that Np forms strong
complexes with the phosphate groups of apatite andcarbonate groups of calcite [3, 4]. The subsequent
experiments for the montmorillonite-based mixtures utilized
these clear differences; that is, the Np desorbed with 1M KCl
solutions was regarded as the Np sorbed on themontmorillonite fraction and the Np not desorbed with 1M
KCl solutions was the one sorbed on the apatite and calcite.
The montmorillonite-apatite mixtures sorbed several times
greater amount of Np than Na-montmorillonite itself, whilethat on the montmorillonite fraction in the mixture decreased.
Above pH 7 almost all of the Np was sorbed on the mixture
within 10 d and most of the Np was sorbed on the apatite
fraction. Below pH 7 the sorption on the mixtures increased
with time and needed a longer time (20 d) to reachequilibrium. This slow kinetics of the sorption did not occur
when those minerals were used singly and suggests a possible
Np sorption involving the phosphate ligands once dissolved
at low pH. The sorption on the montmorillonite-calcite
mixtures was less than that on Na-montmorillonite itself andno evidence of accumulation of Np to calcite was observed,
suggesting that the calcium and carbonate ions dissolved
from the calcite interfered with the sorption.
[1]
[2]
[3]
[4]

－ 320 －

Kozai N and Ohnuki T., APSORC13 Abstract.
Kozai N et al., Radiochimica Acta, 75, 149-158 (1996).
Moor R. C., Radiochim. Acta, ().
Zavarin M. et al., Radiochim. Acta, 93, 9-102 (2005).

25-ENP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Continuous measurement of radon exhalation rate of soil in Beijing
Lei Zhang1�2, Ke Sun2, Qiuju Guo2

1

Solid Dosimetric Detector and Method Laboratory, Beijing, 102205, China
State Key Laboratory of Nuclear Physics and Technology, School of Physics, Peking University, Beijing 100871, China

2

Abstract – The continuous measurement of radon exhalation rate ofsoil is quite important for local radon level estimation. A continuous
measurement system was developed and was applied to themeasurement of the radon exhalation rate of soil in Beijing. The
measurement results show that the average value of soil radon
exhalation rate is 42.5 mBq•m-2•s-1 in spring with a variation of
13.1~110 mBq•m-2•s-1 and 20.8 mBq•m-2•s-1 in summer with avariation of 1.1~112 mBq•m-2•s-1, which is quite constant withformer surveys. The precipitation has an important influence onradon exhalation rate, normally the radon exhalation rate increases
after a small rainfall, but it decreases to nearly zero shortly after ahuge rainfall(with a precipitation rate of 238.5mm•h-1). In May, theradon exhalation rate of soil in Beijing shows a clear periodic
variation, higher around noon and lower around midnight.
Keywords – Radon; Soil;
Measurement; precipitation

Exhalation

Rate;

Continuous－ 321 －

25-ENP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Dosimetric Evaluation of Thoron Exposure in Three Typical Rural Indoor
Environments in China
1

Lei Zhang1, Qiuju Guo2, Shanqiang Wang1

Solid Dosimetric Detector and Method Laboratory, Beijing, 102205, China
State Key Laboratory of Nuclear Physics and Technology, School of Physics, Peking University, Beijing 100871, China

2

Abstract – The brick houses, the mud houses and the cave houses
are the three typical rural residential houses in China, usually withnaked surface from where thoron gas easily comes out. In order toevaluate the thoron exposure of those indoor environments, a seriesof field measurements was carried out by using portablemeasurement devices of both thoron progeny concentration and thesize distribution of them. The dose conversion factors and annual
effective doses of thoron exposure in those environments arecalculated using dosimetric methods. Comparing with the results inurban indoor environment, it shows that the thoron progeny size
distributions of rural indoor environments (AMAD: 76.5nm; GSD:
2.7) are much smaller than those of urban(AMAD: 115nm; GSD:2.0), which make the dose conversion factors of thoron in rural
environments(307.4nSv/(Bq•m-3•h-1)) are much higher than those inurban indoor environments(113.4 nSv/(Bq•m-3•h-1)). The annual
average effective dose of thoron is influenced by dose conversion
factor as well as thoron equilibrium equivalent concentration, and aquite high value of 10.12 mSv•a-1 in mud house in Yangjiang area iscalculated by our survey.
Keywords – Thoron Progeny, Size Distribution, Dose Conversion
Factor, Dose Evaluation－ 322 －

25-ENP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Binary Technetium Phosphide Synthesis at Low Temperature Conditions
Bradley C. Childs1, William M. Kerlin1, Ken R. Czerwinski1
1

University of Nevada Las Vegas, Las Vegas, Nevada 89154, USA

Abstract – Binary technetium phosphide exists through hightemperature reactions that exceed 900 °C [1]. Recent phosphidestudies have indicated that transition metal phosphide species suchas molybdenum, ruthenium, and rhenium can be synthesized attemperatures that do not exceed 300 °C, and will provide a morereasonable synthesis technique. This process could allow for atechnetium waste form application due to the high melting point andlow solubility’s that many transition metal phosphide species exhibit.
Experimental methods include bench-top reactions that begin with aprecursor produced from a transition metal chloride combined witheither sodium hypophosphite (NaH2PO2) or ammonium
hypophosphite (NH4H2PO2).The second experimental method
involves using hydrothermal and solvothermal experiments withphosphorus and various metal chloride species.

A 23 mL Teflon lined Parr 4749 autoclave was used tohouse reactions that involved reacting phosphorus with RuCl3,
ReCl3, and MoCl3 while using ethylenediamine as the solvent
to create a reducing environment. The area for concern in thisreaction involves over reducing the metal species before it
gets a chance to react with the phosphorus. Therefore, water
was also used as a solvent in separate experiments to avoid
too much reduction. Afterwards, TcCl4, TcCl3, and TcCl2 will
be considered for the same reaction depending on thephosphorus chlorine products produced in comparison to thebinary phosphide product.
Acknowledgement: Funding for this research was provided by a

Keywords – Technetium, Phosphide, Synthesis

I.

B. Phosphorus hydro-solvothermal synthesis

SISGR Grant from the U.S. Department of Energy, Office of Science,
Office of Basic Energy Sciences, under Contract No. 47824B

INTRODUCTION

Nearly 2 tons of 99Tc (T1/2 = 2.13x105 ��������- = 280 keV)are produced in the United States each year. As spent fuel isbeing reprocessed, some of the technetium is present in theintermetallic epsilon phase (Mo, Tc, Ru, Rh, Pd), but
majority of the technetium can be found in the high activity
waste of reprocessing plants as pertechnetate (TcO4-) [2].
This becomes problematic due to the fact that TcO4- has ahigh mobility in the environment combined with its long halflife. Waste-form consideration must be given to thosecompounds that exhibit low solubility’s that also allow for
the waste to be stored for long periods of time without
degrading. Technetium phosphide compounds that can besynthesized at low temperatures may provide a method andcompound that will allow such a goal to be achieved.

REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]

A. Synthesis with NaH2PO2 or NH4H2PO2
Hypophosphite (H2PO2-) is a reducing agent that can also
provide phosphorus when reacting with a metal chloride [3].
This compound is also thermodynamically unstable attemperatures above 200 °C. This provides the basis for areaction between RuCl3, ReCl3, and MoCl3 to react with thehypophosphite anion. A precursor will be made by dissolving
one of the metal chlorides with NaH2PO2 or NH4H2PO2 in
distilled water [9] [10]. This mixture will then be heated to 60– 80 °C. The resulting precursor would then be heated instatic argon conditions at temperatures ranging between
200 °C and 300 °C. Based on results from the previous
reactions, technetium chloride (TcCl4, TcCl3, and TcCl2) will
be used in place of other metal chlorides.

－ 323 －

K. Schwochau, Technetium: Chemistry and Radiopharmaceutical
Applications, Wiley-VCH: Weinheim, Germany, 2000.
M.C.A. Sandino and E. Östhols, eds., Chemical Thermodynamics ofTechnetium, Chemical Thermodynamics, 1999, 3
Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the
Elements (2nd ed.). Butterworth–Heinemann.
Q. Guan and W. Li, Journal of Catalysis, 271, (2010), 413-415.
Q. Guan et al., Catalysis Communications, 14, (2011) 114-117.
Y. Xie et al., Journal of Solid State Chemistry, 149, (2000), 88-91.

25-ENP-06

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Dissolution behavior of 137Cs absorbed on the green tea leaves
Yasuhisa Oya1, Hiromichi Uchimura1, Kensuke Toda1, Takashi Ikka2, Akio Morita2, Kenji Okuno1
1

Graduate School of Science, Shizuoka University
Graduate School of Agriculture, Shizuoka University

2

Keywords – 137Cs, dissolution behavior, green tea leaves

I.

INTRODUCTION

Shizuoka is the most common tea production region in
Japan and more than 40% of tea leaves are produced in
Shizuoka prefecture, Japan. In the accident of 2011
Fukushima Daiichi Nuclear Power Plant (FNPP),
radiocesium species was felled in Shizuoka prefecture,
Japan, which leads the shipping restriction of tea products.
Recently, some of studies related to the distribution of fallout radiocesium in Shizuoka were reported [1]. In addition,
the dynamics of radiocesium in tea plant is also studied. It
was reported that the higher radiocesium activity was foundalong Warashina area and southern slope of Udo Hills,
where the most tasteful tea plant is produced. This
distribution is controlled by the wind condition in theafternoon on March 15, 2011. Therefore, the weather is oneof key parameter for the determination of radiocesium
distribution profiles. But, tea plant is grown in the uniquearea for radiocesium deposition and it is quite difficult to
get rid of fall out of radiocesium, when the nuclear power
plant accident is happened. Most of tea leaves are not eatenwith raw condition and, are processed and dried to brew
green tea. So the extrability of radiocesium from tea leaves
harvested after FNPP accident has been reported [2].
However, more detailed elucidation of dissolution behaviorof radiocesium adsorbed on the green tea leaves underwell-controlled condition is the next step to elucidate thefundamental behavior of radiocesium. In this study, thedissolution behaviors of 137Cs to water from green tea
leaves were studied as a function of water temperature, pH
and cesium ion concentration in water.

III. RESULTS
It was found that the temperature dependence on 137Cs
dissolution rate was almost proportional to the watertemperature. Fig. 1 shows the brewing time dependence on
137
Cs dissolution rate. Large dissolution rate was derived
for the higher temperature sample. The dissolution behavior
was assumed to be governed by the Arrhenius correlationand the activation energy was estimated to be 0.045 eV,
indicating that most of 137Cs would exist as the adsorbed
state and no chemical interaction with tea leaves. To
elucidate the key parameters to control the dissolution
behavior, pH dependence on 137Cs dissolution rate was also
evaluated from the pH = 1 to 13 and showing that no large
contributions of hydrogen ion and hydroxyl ion
concentrations on 137Cs dissolution. In addition,
dependences for concentrations of K+ and Cs+ on 137Cs
dissolution were also evaluated. It was confirmed that the
dissolution rate of 137Cs in water was reduced almost halfby the addition of the 1000 ppm Cs+.

Dissolution ratio of 137Cs / -Abstract – The green tea leaves was dipped in the 137CsCl solution
to elucidate the dissolution behavior of 137Cs contaminated on thegreen tea leaves. It was found that the amount of 137Cs dissolved
into tea water was controlled by the temperature of water, and theactivation energy of 137Cs dissolution was estimated to be 0.045
eV, indicating that most of 137Cs would exist as the adsorbed state.
In addition, the dissolution behavior was controlled by theconcentration of stable Cs dissolved in water, although no large
correlation with pH was observed.

1.0
0.8
0.6

278 K
298 K
323 K

0.4
0.2
0.0
0

200

400
600
Time / s

800

1000

Fig. 1 Brewing time dependence on 137Cs dissolution rate

REFERENCES

II. EXPREMENTAL
The 6.0 g fresh green tea leaves were purchased anddipped in 39 ml of 137CsCl solution with the 137Csconcentration of 0.5 kBq/ml. These tea leaves were driedby infrared lamp for one night. Thereafter, the tea wasbrewed by 200 ml water. The activity of 137Cs dissolved
into water was measured by NaI (Tl) scintillation counterfor 60 minutes.

[1]
[2]

－ 324 －

T. Tsuboi, H. Wada, M. Yanaga, Radiat. Safety Manag. 11 (2012)11-18.
K. Tagami, S. Uchida, N. Ishii, J. Radioanal Nucl. Chem. 292 (2012)
243-247.

25-ENP-07

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Characterization on the Radioactive Aerosols Dispersed during Plasma Arc
Cutting of Radioactive Metal Piping
1

T. Shimada 1 and T. Tanaka 1

Nuclear Safety Research Center, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki 319-1195, Japan

Abstract

In order to plan and execute the decommissioning of
nuclear facilities safely and properly, it is necessary tounderstand the production and dispersion behaviors ofradioactive aerosols which are dispersed during the cuttingof components activated and/or contaminated. It will cause
not only internal exposures of workers but public exposure
resulting from discharge of those radioactive aerosols to theenvironment. It is also important for radiological safetyassessment to figure out their behaviors. Therefore plasmaarc cutting experiments were carried out to obtain particle
size distribution and radionuclides concentrations.
Neutron induced-activated piping and surface
contaminated piping were segmented along the outersurface by well-trained workers using air plasma arc cutting,of which current power was 100A, in the contamination
control enclosure (4m length, 4m width, 4m height). The
former was the stainless steel piping of primary reactor
cooling system situated around the reactor pressure vesselof Japan Power Demonstration Reactor. It was 0.5m long,
318mm outer diameter, 17mm thickness. Values of specificradioactivity of 60Co and 63Ni in the base material were64.4Bq/g to 170.9 Bq/g and 378.5Bq/g to 797.8Bq/g
respectively. The tendency depended on the distance fromthe reactor core. The inner surface of the piping was
grinded just in case even though its surface had been
decontaminated by a chemical method after dismantling.
The latter was the carbon steel piping of liquid waste
treatment system of the advanced thermal reactor, FUGEN.
It was 6.9m long, 60mm outer diameter, 5.5mm thickness.
There was a great variability among the values ofradioactive surface contamination density of inner surfaceof the piping, from 552.1Bq/cm2 to 55,336Bq/cm2 of 60Co.
Air including aerosols was exhausted from the enclosure
to the local ventilation system. Particle size distribution of
the aerosols was obtained by sampling air though thenozzle at the center of the ventilation piping using ELPI(Electrical Low Pressure Impactor, Dekati Inc.) which
could classify particles into 12 stages of 50% cutoff
aerodynamic diameter, D50% ranging from 0.007 to 9.9�m.
This instrument enables to measure particle size
distribution and concentration of the aerosols in real-timeby corona charger and electro-meters at each impactor
stage. The radioactive quantity of 60Co of aerosols collectedon the impactor stage was measured by Ge semiconductor
detector. That of 63Ni was measured by liquid scintillation
counter after dissolved by hydrochloric acid and separated
by ion-exchange column.
Figure 1 shows the particle size distribution of specificradioactivity of 60Co and 63Ni of aerosols during cutting ofactivated piping. Those values were calculated by dividing
the quantity of radionuclide at the each stage by the weightof aerosols collected at the stage. Specific radioactivity ofboth 60Co and 63Ni of 0.09�m indicated the highest value.
Those of both 60Co and 63Ni of 0.15�m and 0.26�m
indicated the similar values to those of base material of thepiping. That of 60Co larger than 0.26�m indicated the halfvalue of the base material.
Figure 2 shows the particle size distribution of 60Co
specific radioactivity of aerosols during cutting of surface
contaminated piping. Specific radioactivity of aerodynamic
diameter of 0.05�m indicated the maximum value ofapproximately 2.7E+4 Bq/g which was fifty times as muchas the average value of the aerosols. That of 9.9�m wasapproximately 100Bq/g which was the eighth part of theaverage value. Compared with the activated piping, thedifference of specific radioactivity between maximum andminimum values were larger in contaminated piping. It isconsidered that contaminants on the inner surface weredirectly melted and vaporized by plasma arc and thenconcentrated into smaller particles
Those results indicated that the management for
dispersion behavior of smaller particles is important for theradiation protection during dismantling activities.

Figure 1 size distribution of specific radioactivity of activated piping

Figure 2 size distribution of specific radioactivity of surface contaminatedpipingThis work is a part of study funded by Japan Nuclear
Energy Safety Organization.

－ 325 －

25-ENP-08

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

A passive collection method for whole size fractions of suspended river materials
Takeshi Matsunaga1, Takahiro Nakanishi1, Mariko Atarashi-Andoh1, Erina Takeuchi1, Katsunori
Tsuduki1, Syusaku Nishimura1, Jun Koarashi1, Shigeyoshi Otosaka1, Tsutomu Sato2, Seiya Nagao3
1

Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, Tokai-mura, Ibaraki 319-1195, Japan
Division of Sustainable Resources Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 0608628, Japan
3
Low Level Radioactivity Laboratory, Institute of Nature and Environmental Technology, Kanazawa University, Ishikawa
923-1224, Japan
2

Abstract – An innovative, yet simple method for the passive
collection of radioactive materials in river water has beendeveloped and validated. This method makes long-term,
unmanned monitoring possible. In addition to regularradioactivity analyses, this method provides an opportunity forthe characterization of suspended materials based on its ample
collection quantities (more than several tens of grams). Thismethod may also be applicable to sediment-bound chemicals.
Keywords – River, Radionuclides, Chemicals, Passive collection,
Long-term monitoring, Suspended materials, Dissolved materials

I.

INTRODUCTION

The migration behavior of atmospherically derived
radionuclides and chemicals onto river catchments has been
extensively studied thus far. Transport of these materials
through rivers can be the most influential export process todownstream regions. These investigations, however, haveoften encountered essential difficulties; one of which is insampling frequency. Rainfall events play an important rolein fluvial transport of contaminants. However, it is difficult
to carry out frequent manned observations for thesestochastic events. Another difficulty is the ability to collectenough suspended material for characterization purposessuch as chemical extractions and mineralogical analyses.
The aforementioned analyses generally require several
grams of suspended material. The concentration of suchmaterials in river water typically ranges from a few mg l-1
to about 100 mg l-1, meaning that ten to a thousand liters ofwater are required. Accordingly, handling such large
amounts of water can be distressing. Here, we report aninnovative, yet simple collection method for suspended anddissolved components in river water.
II. METHODS
A. Collection of suspended components
Two filter vessels (957 mm height, 350 mm width, 6SL2S, Advantec Toyo Kaisha, Ltd.) were used sequentiallywith different nominal pore-sized filters, 100��m and0.5��m. Each vessel contained six cartridge filters ofwound type polypropylene (750 mm length). River water
was led to the system naturally using a drop of the riverbed
by hose from upstream. After an appropriate number ofdays of operation, the filters and the mud deposits on thebottom of the vessels were recovered. In the laboratory, thesuspended material that was collected on the wound fibers

was washed out with water in a bucket. The wash-water
samples and the mud samples were concentrated via
centrifugation. A composite of the mud sample wasobtained and subjected to wet sieving, such thatcomponents of four sizes were obtained: 1) <2000��m, 2)
500-2000 �m, 3) 75-500 �m, and 4) <75 �m, in principle.
The first and second components were air-dried. The thirdand fourth components were freeze-dried to obtain final
samples of suspended material.
B. Collection of dissolved components
The dissolved component, radiocesium in this study, wascollected from part of the outlet water from the filter
vessels. Namely, the outlet water was put through a seriesof two PVC columns (4 cm inner diameter, 20cm length),which contain Cs-specific adsorbent material (Anfezh).
III. RESULTS AND DISCUSSION
The effectiveness of this method was validated over a
period of 15 months of field operation time since December
2011. The test site was a hilly, forested catchment of 0.62
km2 containing a stream, located in the Northern area ofCentral Japan (Ibaraki Prefecture). The site was affected by
fallout from the Fukushima nuclear accident. In thisvalidation study, the aim was to obtain samples forradiocesium analyses. During the test period, ten sets ofsuspended material samples were successfully recovered.
Intervals were changed from two to six weeks dependingon the hydrological situation. Approximately 50-350 g ofsuspended material was recovered per collection period;
variance depended on the length of the period andprecipitation conditions. Adsorbent columns for dissolved
radiocesium were added after November 2012. The
collection efficiency of dissolved radiocesium was as highas 95 %. A consistent working method for collection ofdissolved components and suspended components has
therefore been established.
IV. CONCLUSION
A passive, yet simple collection method for radioactive
materials in river water has been developed and validated.
The method is advantageous as it: i) allows efficient
recovery of whole size fractions of suspended material, ii)
can be used in remote locations without electricity, iii) is
suitable for unmanned operations over long periods of time.

－ 326 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-ENP-09

Study of factors controlling organic pollution in Lake Kiba
1

Yuriko Kawano1, Seiya Nagao1, Shinya Ochiai1, Masayoshi Yamamoto1

Low Level Radioactivity Laboratory, Kanazawa Univ., Wake, Nomi, Ishikawa 923-1224, Japan

Abstract –Lake Kiba is located in Ishikawa Prefecture and has been facing
to high COD value, a simple indicator of organic pollution, oflake water. This study analyzed organic matter content in asediment core with time scale and discussed factors controlling
COD value. Sedimentation rate estimated from depth profile of210
Pbex is divided into three periods such as present-1989, 19891959 and 1959-past. TOC flux at the present is five times higher
than that of 1959. The TOC/TN molar ratio decreased from 15.7
to 12.8. These results suggest that accumulation of total organic
matter increases but the contribution of terrestrial organic matterand phytoplankton relatively varies with time.
Keywords – 210Pb, TOC, �13C

I.

INTRODUCTION

Lake as closed water area is likely to deposit pollutant
because of its hydraulic characteristics. Therefore, it is noteasy to improve water quality deteriorated. Chemical
oxygen demand (COD) is used as a simple indicator oforganic pollution in lake. The organic pollution is related tothe direct load of organic matter from lake basin and theindirect load of organic matter produced by phytoplankton
in lake. In order to facilitate water quality conservation, we
evaluate concentration and characteristics of organic matterand its origin in lake.
This study was intended for Lake Kiba, because the lake
ranked in the worst two of COD in Japanese lakes in 1990
and remains still high concentration level of COD (ca. 6mg/l). The purpose of this study is to understand factors
controlling variations in COD concentration of lake waters.
We collected a sediment core sample and measured totalorganic carbon (TOC), total nitrogen (TN), carbon andnitrogen isotopic ratio (�13C and �15N) to investigate
variation of organic matter accumulation at the lake
sediments because sedimentary organic matter recordedlake water environment during the period of past to present.

samples. 13C/12C and 15N/14N ratios were measured usingmass spectrometer and expressed as �13C and �15N,
respectively.
III. RESULTS AND DISCUSSIONS
210

Pbex activity in the sediment core gradually decreased
from 0 to 8 cm depth in core, and was nearly constantfrom 8 to 14 cm, but rapidly decreased from 14 to 26.7
cm (Fig. 1a). The sedimentation rate is 0.15 g/cm2/y at 0-8
cm depth and 0.05 g/cm2/y at 14-26.7 cm depth. Thechanges of sedimentation rate occurred in 1959 and 1989.
The sedimentation rate in recent years has been threetimes faster than in the past. This indicates thatenvironmental change in the basin has occurred.
TOC flux ranges from 4.3 to 7.5 in the depth interval of
0-8 cm, 2.0 to 3.9 at 8-14 cm and 0.7 to 1.8 at 14-20 cm(Fig. 1b). This result shows increases in the accumulationof organic matter in the lake. The C/N molar ratio
decreased from 15.7 to 12.8 towards the current, and �13C
showed some variation (Fig. 1c). This result suggests
contribution of phytoplankton relatively increased rather
than terrestrial organic matter during 1959-present.
These results suggest that organic matter supply fromthe lake basin and primary production in the lake increased
from 1959. This may be related to the changes in lake basin
environment and the increases of COD value in Lake Kiba.

II. STUDY SITE AND MERHODS
Lake Kiba is located in Ishikawa Prefecture and has
surface area of 1.44 km2 with an average water depth of 2.2
m. Major inflow rivers are Hiyou River, Bou River andYamashiro River. There are a number of drainage channels
from paddy field. Outflow water from the lake is only Mae
River.
A sediment core was collected in June 2012 with a HRtype corer at the center of lake. The collected core sample
was cut into 1 cm interval at 0-10 cm depth in core and 2
cm interval below 10 cm depth. After the samples were
freeze-dried, 210Pbex was measured by gamma spectrometry.
Sedimentation rate was estimated using constant rate ofsupply (CRS) model for the 210Pbex profile. Total organiccarbon (TOC) and total nitrogen (TN) were measured with
an elemental analyzer after HCl treatment of sediment－ 327 －

Figure1 The depth profile of 210Pbex content (a), TOC flux (b) andC/N molar ratio and �13C (c).

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-ENP-10

Rapid monitoring particulate Radiocesium with nonwoven fabric cartridge filter
and application to field monitoring
Hideki TSUJI1, Yoshihiko KONDO2, Shoji KAWASHIMA2, Tetsuo YASUTAKA1National Institute of Advanced Industrial Science and Technology
2
Japan Vilene Company. Ltd.

Abstract
A method for rapid monitoring particulate radiocesium using a
nonwoven fabric cartridge filter was developed, which needs nofurther preprocessing before served to a detector. By aperformance test, more than 98% of suspended solid (SS) wascollected. This method showed the same radioactivity
measurement accuracy as filtration by membrane filter and more
rapidextraction capability of SS.
Keywords – radiocesium, nonwoven fabric filter, suspended solid

I.

INTRODUCTION

The monitoring of dissolved and particulate radiocesiumin environmental waters became important after theaccident of TEPCO Fukushima Daiichi Nuclear Power Plant.
Our research group has developed a monitoring method toinvestigate the radiocesium concentration in water by eachexistence form. Yasutaka et al. (2013) developed a method
to absorb 90% of dissolved 137Cs in 20 L water within 10
minutes using Prussian blue impregnated nonwoven fabric.
Minami et al. (2013) set monitoring device onto paddy
fields and more than 99% of dissolved 137Cs in 400 L water
was absorbed within 24 hours. In this study, a method formonitoring particulate radiocesium using nonwoven fabriccartridge filter was developed. The measurement accuracy
and pre-concentration time was compared with a traditional
method. Furthermore, environmental water in Fukushima
Prefecture was monitored by this method.

100 L was pumped through the SS-cartridge. The detected SS
concentrations and 137Cs concentrations in SS-cartridge werecompared with those filtrated with a 0.45 ������������������
in laboratory.
III. RESULTS
In the result of performance test, all SS in the water wascollected in the cartridge for all experiments. The geometricefficiency of the cartridge was 0.71 on average (the S.D. was0.07) and the recovery rates of 137Cs, determined by dividing
the detected 137Cs by the geometric efficiency was calculated
as Fig.1
This cartridge could hold 30 g SS under 0.2 MPa flowpressure. For the field performance test, concentrations of both
SS and 137Cs filtrated by two methods showed almost the same
results in the samples from all locations except point E (Fig.2).
In contrast to almost one day by the membrane filtration, only
10 min is needed for 20 L water filtration by this SS-cartridge
method.
This study was supported by the budget (the developmentof systems and technology for advanced measurement andanalysis) from Japan Science and Technology Agency.
1.5
Recovery rates of 137Cs

1

II. MATERIALS AND METHODS

0.5
0.0

SS conc. : 10 mg/L
Flow vol. : 100 L
pH :7

100 mg/L
100 L
7

100 mg/L 100 mg/L
20 L
20 L
3
10

Fig.1 Recovery rates of 137Cs. Error bars indicate counting error.

Concentrations of
137Cs (Bq/L)

The radiocesium on SS was collected by the plain
nonwoven fabric in the cartridge (SS-cartridge). This filter
was made of polypropylene fibers with a pore size of ������
The performance of the cartridges was examined using thesimulated river water, which contains 137Cs (4,340 Bq/kgSS). The SS in water was set at 10 and 100 mg/L. Water
samples were pumped through SS-cartridge at a rate of 2.5
L/min. The SS weight collected in the cartridge wascalculated by the weight gain of SS-cartridge. The
concentration of 137Cs in SS –cartridge was measured by a
Ge semiconductor detector. The geometric efficiency of SScartridge was calculated by dividing the detected 137Cs
radioactivity by the actual 137Cs radioactivity in the cartridge,
which is determined from the collected SS weight and theconcentration of particulate 137Cs. In addition, the maximum
amount of SS weight in the SS-cartridge was determined bypassing water with 1,000 mg/L of SS.
Next, this method was also applied to measure particulate
137
Cs concentration of environmental water in Fukushima
Prefecture for testing field applicability. The river water of 20-

1.0

Collected by SS-cartridge
��4
SS-C�2
0.1

Collected by membrane
��3
��1 filter

0.08
0.06
0.04
0.02

0
Sampling
location : A

B

C

D

E

F

G

Fig.2 The concentrations of 137Cs in Abukuma River water.
Error bars indicate counting error.
[1][2]－ 328 －

Yasutaka et al.(2013), Appl. Chem. (in Japanese), in press
Minami et al.(2013), Abstract of APSORC13

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-ENP-11

In-situ measurement of 134Cs and 137Cs in seabed by underwater �-spectrometry
systems and application for the survey to the Fukushima Dai-ichi NPP accident
Hisaki KOFUJI

Japan Marine Science Foundation, Minato-Machi, Mutsu, Aomori, 035-0064 Japan
Abstract –Underwater �–spectrometry systems (Mooring and Towing system)with NaI(Tl) detector were applied to in-situ measurement of radiocesium
in seabedderived from the Fukushima Dai-ichi Nuclear Power
Planr(FDNPP) accident. Radiocesium concentration was calculated

from towing system data with short integrated time (2–5 min) by
the separating method of the �–ray counts to 4 contributions(134Cs+137Cs, 40K, U series and Th series nuclides) using 4 x 4matrix. Concentration of 134Cs+137Cs in sediments located about
80 km north from the FDNPP was calculated to be 150–200 at
muddy site and 5-25 Bq/kg-dry at sandy site, respectively.
Keywords – In-situ �–ray measurement, Sea Sediment, 134Cs,
137
Cs, Fukushima Dai-ichi NPP accident

I.

INTRODUCTION

Large amount of radionuclide were released toenvironment by the FDNPP accident on March 11, 2011. In
contrary to the gradual decrease of radiocesium
concentrations in seawater after the FDNPP accident, highlevels of radiocesium have remained in sea sediments
around the FDNPP. We applied underwater �-spectrometry
systems to measurement of radiocesium in seabed derived
from the FDNPP accident.

III. RESULTS AND DISCUSSIONSRadiocesium derived from the FDNPP accident was
detected in sediment by both systems (Fig. 2) and theposture of towing system on seabed was stable during
towing. These underwater �–spectrometry systems wereconfirmed to be available to survey radiocesium
contamination in seabed.
Radiocesium concentration could be calculated fromshort integrated time data (2–5 min) with small �–ray
counts by using 4 x 4 matrix. Assuming homogeneous
distributions of 134Cs and 137Cs in 0–10 cm depth of
sediment, the 134Cs+137Cs concentrations in sediment were
calculated from data by towing system to be 150–200
Bq/kg-dry at muddy site (St. A) and 5–25 Bq/kg-dry at
sandy site (St. B), respectively.
This work was performed with grant-in-aid from Watanabe
Memorial Foundation for The Advancement of New Technology.

MarkerBoat

II. SYSTEM AND METHOD
Towing
SystemMooring
SystemVideo
CameraSeabedVideo
CameraCTD Sensor
Underwater NaI(Tl)
Detector

Fig. 1 Illustration of field operation of underwater gamma-ray
spectrometry systems (mooring and towing system).
101

St.A (Mud)

134Cs,137Cs

Count Rate (cps/10keV)

Two underwater��–spectrometry systems with 3”��spherical NaI(Tl) detector were applied to in-situ
measurement on seabed. Mooring system: log the temporalvariation of radiation on seabed. Towing system: monitor
the spatial distribution of radiation on seabed with
underwater movie, depth, temperature, salinity in real timefrom a boat. Both of the systems are small (15–20 kg), it
can be lifted and retrieved by human hand from a boat (Fig.
1).
These systems were operated at 2 sites in coastal area
(37–38 m depth) located about 80 km north from the
FDNPP on September 6–7, 2012. The sediments are muddy
at St. A and sandy at St. B, respectively. For mooring
system, it was taking down to the seabed and recover after
2 hours. For towing system, it was towed slowly (1 knot)
during about 15 minutes on seabed, and next measured
during 1–2 hours at one position. Surface sediments werealso collected in each site and analyzed the density andwater content.
�–ray spectrum data were separated to 4 contributions(134Cs+137Cs, 40K, U series and Th series nuclides) by 4 x 4matrix. Parameters of the matrix were obtained from
calculated �–ray spectrum for radionuclides in sedimentand seawater by Monte Calro simulation with EGS5 code
[1].

St.B (Sand)

134Cs

100

40K

10-1
10-2
10-3
10-4
0

1000

Energy (keV)

2000

3000

Fig. 2 �–ray spectrum measured on seabed by towing system. (1hintegrated data)[1]－ 329 －

Hirayama, H., et. al, 2005, The EGS5 Code System, SLAC-R-730
and KEK Report 2005-8

25-ENP-12

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Radiocarbon dating of molluscan shells and its application
1

Yoshiki MIYATA1, 2, 3, Hiroyuki Matsuzaki2

The Low Level Radioactivity Laboratory (LLRL), Institute of Nature and Environmental Technology, Kanazawa
University, Ishikawa 923-1224, Japan
2

The College of Liberal Arts, International Christian University, 181-8585, Tokyo, Japan
3

4

National Museum of Japanese History, 285-8502, Chiba, Japan
Department of Nuclear Engineering and Management, School of Engineering (MALT), The University of Tokyo, 1130032, Tokyo, Japan

Keywords – Radiocarbon dating; Marine reservoir effect;
Molluscan shell; Marine reservoir correction value ����; Sea
Current

We investigated radiocarbon age differences among
marine shells, terrestrial animal and marine fish bones,
charred wood fragments and charred seeds from layer
IV, at the Higashi michi no ue (3) archaeological site,
Japan, which was occupied during the first half of theearly Jomon period (3900-3750 cal BC) as shown in
Table 1.
We attributed the differences to marine reservoir
effects, which differed among these organisms becauseof differences in their habitats and diets. The ages ofCorbicula japonica, Crassostrea gigas and Ruditapes
philippinarum (molluscan shells) show 180 yrs, 270
yrs and 450 yrs older than the radiocarbon age of thecharred wood fragments, which corresponded to theactual age of the excavated archaeological site,
respectively (Fig.1). This shows the habitats of thesemolluscan shells change from fresh to oceanic water,
so that the salinity of the habitats of these molluscan
shells gradually increases into the level of the sea
water.

Table 1. Radiocarbon ages of marine shells, charrd seeds, charred woods, animal bones, marinefishes and carbonizedmaterials adhering to pottery excavated from the Higashi michi no ue (3) archaeological site.
Sample #Lab code

Sample name14����������
BP(Binomial name)������*1�������*2

14

14

C yr

C yr

AOKH S8

MTC-7412

Japanese walnut(Juglans mandshurica var. sieboldiana)

4910 ± 30--

AOKH C6

MTC-7410

Charred wood

5005 ± 35--

AOKH B11

PLD-6043(wild) boar
(Sus scrofa)

4920 ± 30-30 ± 38

-409 ± 36

AOKH K17

MTC-7444

Corbicula japonica(Ruditapes philippinarum)

5210 ± 150

260 ± 152

-119 ± 151

AOKH K17

MTC-7565

Corbicula japonica*3(Ruditapes philippinarum)

5140 ± 60

190 ± 64-189 ± 63

AOKH K16

MTC-7443

Oyster(Crassostrea gigas)

5230 ± 60

280 ± 64-99 ± 63

AOKH K15

MTC-7442*35380 ± 60

430 ± 64

51 ± 63

AOKH K15

MTC-7562*3

Japanese little neck(Ruditapes philippinarum)

5430 ± 50

480 ± 55

101 ± 54

AOKH B13

PLD-6045

Japanese seabass(Lateolabrax japonicus)

5425 ± 25

475 ± 34

96 ± 32

AOKH 3

MTC-7408

Charred material from inner surface of
potsherd

5505 ± 35

555 ± 42176 ± 40

*3

Japanese little neck(Ruditapes philippinarum)�����������������������
*1 R was subtracted from the average age of Japanese walnut and charred wood (4950±23 BP), excavated from the Higashi michi no ue (3) site.
�������������������������������������������14C age (5329±20 BP), which corresponded to the age of the charred wood (4950±23 BP; 3766-3696 cal BC (68.2%)).

*3 Each same individuals of Corbicula japonica and Japanese little neck were measured twice.

According to the age of Ruditapes philippinarum, the�������������������������������������������������������
Warm Current, which flows around Shimokita
peninsula, is 80 ± 41 14C years (N = 2). The
radiocarbon ages were, in an increasing order, charredwood fragments, charred seeds ~ terrestrial animalbones (deer) < marine molluscan shells ~ marine fishbones < charred materials on potsherds. The different
reservoir effects thus reflect difference in the diets orhabitats of the shellfish, marine fish, and charredmaterials on potsherds found at the site.
This work was partly supported by a Grant-in-Aid forYoung Scientists (B) No. 18700679 (Y.M.), Creative
Scientific Research No.16GS0118 (T.N.) and
Scientific Research (B) No.25282072 (Y.M.) of theJapan Society for the Promotion of Science.

－ 330 －

25-ENP-13

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013���������� ���������� ������� ������������� ������������ �������������
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25-ENP-14

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

USE OF RADON TO CHARACTERISE SURFACE WATER RECHARGE TOGROUNDWATER
N Hermanspahn,1 M Close,1 M Matthews,1 L Burbery,1 P Abraham,11Institute of Environmental Science and Research (ESR), Christchurch

Aims
Many groundwater systems in Canterbury and other partsof New Zealand gain a significant amount of recharge fromrivers. This recharge provides significant storage of water
within the groundwater system and it is used for many
purposes, including domestic and stock water supply,
irrigation and industrial use. There is significant uncertainty
in the amounts of recharge from rivers, particularly large
braided systems, as river flow gauging can only be carriedout under low flow conditions and measurement errors arelarge.
Radon-222 is present in a dissolved state in groundwaterfrom alluvial greywacke gravel aquifers in sufficientconcentration to be easily detectable (10 – 50 Bq/L) while,in contrast, concentrations in surface water are close to zero
(Gregory, 1980). This difference provides a means ofdistinguishing surface recharge water from groundwater.
Surface water infiltrating into groundwater should initiallycontain negligible radon, but would start accumulatingradon as it flows through the aquifer, reaching equilibrium
in approximately 6 half-lives (T1/2 = 3.82d). In addition toproviding a tracer for surface water, this radon ingrowth
also allows flow-rate estimation as the radon concentration
increases with time at a known rate. The use of radon toestimate recharge of surface water into a groundwater
system has been applied at a site in Switzerland (Hoehn &von Gunten, 1989).
The investigation of radon to estimate recharge from rivers
to groundwater systems is presented using a relatively wellcharacterised reach of the Waimakiriri River in Canterbury
to assess the potential for this method.
Methods
A reach from the Waimakariri River near McLeans Island
just north of Christchurch, was selected as the study site.
The river is known to lose water from this reach and there
are a number of shallow wells close to the river that aresuitable for sampling in this area. Two groups of wells
were selected for sampling. The first group of wells wasnear the river and located at increasing distances from theriver. Environment Canterbury had installed 22 wells in 2
arrays at Halketts and Crossbank to study river recharge togroundwater. These wells were sampled on 2-3 occasions.
The second group of wells that were sampled were locatedremote from recent recharge from the river but screened ina similar groundwater environment. This group of wells
provide an estimate of equilibrium radon concentrations

and the likely variability within an alluvial gravel
groundwater system.
Results
The results indicate that radon levels in the river are very
low and concentrations increased with increasing distancefrom the river. These results are consistent with radon
ingrowth processes and the site hydrology.
The eleven wells from the Crossbank array and elevenwells from the Halketts array were sampled, along withwater from the Waimakariri River, at both high and low
flows to determine any variation of radon concentrations
with flow. There was no significant variation in radon
concentration with flow in the Waimakariri River ranging
from 50 to 250 m3/s. The data were modelled using the “ingrowth equation” for radon to determine values for theequilibrium radon value and groundwater velocity. The
groundwater velocities were 350 and 390 m/day for theHalketts and Crossbank sites, respectively. These velocities
are very high but possible near a large braided river.
Estimates of recharge to groundwater over a 20km reachusing this information were similar to estimates derived
from a water balance approach with the largest source oferror being estimates of the effective porosity of thegroundwater system.
References
Gregory, L.P. 1980. Radioactivity of potable waters: Country-wide survey
in New Zealand. NRL report 1980/4. 19 p.
Hoehn, E.; von Gunten, H.R. 1989. Radon in Groundwater: A tool toassess infiltration from surface waters to aquifers. Water
Resources Research 25: 1795-1803.

－ 332 －

25-RPP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Production and Utilization of Radioactive Astatine Isotopes in the 7Li+natPb Reaction
I. Nishinaka1, A. Yokoyama2, K. Washiyama2, R. Amano2, E. Maeda2, N. Yamada2, H. Makii1, A.
Toyoshima1, S. Watanabe1, N. S. Ishioka1, K. Hashimoto1
1

Japan Atomic Energy Agency (JAEA)
2
Kanazawa University

Abstract – Production cross sections of astatine isotopes in 29-57
MeV 7Li+natPb reaction have been measured by �- and �-ray
spectrometry. Excitation functions of production cross sections havebeen compared with a statistical model calculation to study thereaction mechanism of the 7Li+natPb reaction. A chemical
separation of astatine from an irradiated lead target has beenstudied with a dry-distillation method.
Keywords – Astatine, Cross section, Excitation function, Chemical
separation, Dry-distillationI.

INTRODUCTION

An � radioactive nuclide 211At with a half-life of 7.2 h is a
prospective candidate for utilization in targeted alpharadiotherapy. In general, 211At is produced throughbombardment of a bismuth target with 28 MeV helium ionsin the 209Bi(�,2n)211At reaction [1]. However, the nuclear
reactions using lithium ion beams, 6,7Li+Pb, Bi, provide thepossible production routes of 211At. Excitation functions havebeen extensively measured for the 6,7Li+209Bi to study thereaction mechanism involving complete fusion and breakup
reaction for weekly bound nuclei 6,7Li [2-4]. For 7Li+natPb,
however, only reports on production of astatine isotopes 207210
At have been available [5]. Therefore, we have measured
excitation functions of 207-211At isotopes in the reaction of 2957 MeV 7Li+natPb. Besides, a chemical separation of carrierfree radioactive astatine isotopes from an irradiated leadtarget has been studied with a dry-distillation method.
II. EXPERIMENT
Lead targets with thickness of 0.78-1.47 mg/cm2 wereprepared with vacuum evaporation onto a backing sheet ofaluminum. Each target was sandwiched between the backing
and a cover sheet of 2.7 or 5.4 mg/cm2 of aluminum. Six setsof the bismuth target, the backing and the cover sheet were
irradiated with 7Li3+ beams of 50 and 60 MeV from the 20
MV tandem accelerator at JAEA-Tokai. Activities of 207-210At
were determined by �-ray spectrometry to obtain production
cross sections of 207-210At. Details of irradiation and �-ray
spectrometry are described in [6].
The sample used for �-ray spectrometry which consists of
the lead target on the backing and the cover sheet was placedin a test tube with length of 18 cm. After sealing the test tube,
a third of the portion from the bottom of the test tube wasinserted into a furnace. Astatine was distilled at 650�C for1540 min. After cooling and opening the test tube and taking thesample from it, the test tube was rinsed with 1.8 ml ethanol,
water, or diisopropyl ether. The solution is used for the
preparation of a sample for �- and �-ray spectrometry. The
activities of astatine in the solution were measured to obtainproduction cross sections of 211At and chemical yields in thedry-distillation method.
III. RESULTS
The obtained excitation functions of astatine isotopes inthe 7Li+natPb were rather well reproduced with a statisticalmodel calculation by the HIVAP code [7]; the calculation
was independently carried out with the input parameterswhich systematically well reproduce a large number ofexperimental fusion-evaporation cross sections in the similar
heavy-ion reactions without adjusting the input parameters to
fit the present data [8]. Slightly large deviations ofexperimental data from the calculation are observed at higher
incident energies, indicating the effect of breakup reaction of7
Li.
In the �- and �-spectrometry, only activities of astatine
isotopes and their decaying daughters were observed in thesamples prepared from the solution which obtained by the
dry-distillation method. It shows that carrier free radioactive
astatine isotopes were separated from lead targets with highradiochemical purity. Overall recovery yields of astatine in
the dry-distillation method were approximately 65% forethanol and water, and 25% for diisopropyl ether, implying
chemical form of carrier free astatine. Using the ethanol
solution of astatine, astatinated amino acid derivative wasprepared in the high labeling yield, more than 97%, withelectrophilic destannylation [9]. It indicates that the drydistillation method provides carrier free astatine isotopes withhigh chemical purity.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

－ 333 －

S, Lindergren, T. Bäch, H. J. Jensen, Appl. Radiat. Isot., 55 (2001)
157-160; S. Lindegren et al., J. Nucl. Med., 49 (2008) 1537-1545.
H. Freiesleven et al., Phys. Rev.C, 10 (1974) 245-249.
M. Dasgupta et al., Phys. Rev. C, 66 (2002) 04602-1-4; M. Dasgupta etal., Phys. Rev. C 70 (2004) 024606-1-20.
Yu. E. Penionzhkevich et al., J. Phys. G, 36 (2009) 025104-1-12.
K. Roy and S. Lahiri, Appl. Radiat. Isot., 55 (2008) 571-576; M. Maiti
and S. Lahiri, Phys. Rev. C, 84 (2011) 067601-1-4.
I. Nishinaka et al., JAEA-Review 2011-040 (2011) 50-51
W. Reisdolf and M. Schädel, Z. Phys. A, 343 (1992) 47.
K. Nishio, private communication.
S. Watanabe et al., 7th Int. Sym. On Radiohalogens (7ISR), Sep18th(2012), Whistler, BC

25-RPP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Production of actinium-225 from natural thorium irradiated with protons
Aleksandr N. Vasiliev1, Valentina S. Ostapenko1, Ramiz A. Aliev1, Stepan N. Kalmykov1,
Elena V. Lapshina2, Stanislav V. Ermolaev2 and Boris L. Zhuikov2
1

Chemisrtry Department, Lomonosov Moscow State University, Leninskie Gory, Moscow 119991, Russia
Institute for Nuclear Research of Russian Academy of Sciences, 60th October Anniversary Prospect, 7a, Moscow 117312,
Russia2

New procedure for chemical separation and purification of 225Ac
from irradiated metallic Th targets for targeted radiotherapy ofcancer is described.
Keywords – actinium-225, thorium, extraction chromatography

As a result of irradiation of natural thorium with highenergy protons various fission and activation products of232
Th are formed [1, 2]. Among them 225Ac is formed,
which has characteristics that enable to use it inradiotherapy of cancer. There is a growing demand forthis radionuclide, while current methods for producing
actinium have significant limitations and cannot satisfy itcompletely. Production of actinium from 233U is limited
by its inaccessibility. Actinium-225 may be used either
directly for preparation of radioimmunoconjugates or asa mother radionuclide in 213Bi isotope generator. In
addition the formation of 223Ra should be noted, which is������������������-emitter for medicine.
The aim of this work is to develop the new method ofchemical separation and purification of large quantitiesof 225Ac from metallic Th irradiated with high-energy
protons.
Radiochemical separation of Ac and Ra is a difficult task
since a high activity of more than 80 other radionuclides havebeen observed in the gamma- and alpha-spectrum of Thtarget after irradiation.
A developed method for chemical isolation of Ac is basedon combination of liquid-liquid extraction and extraction
chromatography.
Irradiated thorium is dissolved in a mixture ofconcentrated hydrochloric and nitric acids, or in concentrated
nitric acid with the addition of catalytic amounts ofhydrofluoric acid.
Tributylphosphate, trioktylphosphinoxide (TOPO) anddi(2-ethylhexyl)orthophosphoric acid (HDEHP) are used in
extraction experiments. The behavior of radionuclides,
depending on the composition of the aqueous phase is studied.
For additional separation of remaining Th AG 1x8(BioRad) anionite column and extraction chromatographic
sorbent TEVA (Eichrom, mixture of trioctyl and tridecyl
methyl ammonium chloride as extracting agent) are proposed.
Sorption capacity of under experimental conditions (6 M
HNO3) for those sorbents is investigated.
Sorbents DGA Resin (Eichrom), Ln Resin (Eichrom),
TRU Resin (Eichrom), TDi-2 (Karpov Institute) are taken forfurther chromatographic separations. The sorption behaviorof radionuclides, depending on the parameters of the column
and acidity of solution is given. It is shown that 225Ac
quantitatively adsorbed on Ln Resin and TDi-2 (di(2ethylhexyl)orthophosphoric acid (HDEHP) as extracting
agent) from dilute nitric acid (0.05 M HNO3). Desorption iscarried out with acid of higher concentration (3 M).
Significant difference in the sorption behavior of 225Ac for Ln
Resin and TDi-2 is not observed. In 0.05 M HNO3 most of
the fission products (Cs, Ra, Ba, Ag, Pb), are not retained on
the column and are eluted in the first few milliliters. Afterswitching to 3 M HNO3, actinium and rare earth elements (La,
Nd and Ce) and ruthenium are eluted together in the fractionof 3 ml. On DGA Resin (N,N,N`,N` tetroctyldiglicolamide as
extracting agent) Ac absorbed from 6 M nitric acid solution
and desorbed with dilute nitric acid (0.01 M HNO3). In thisway it is possible to separate actinium fraction fromruthenium, this radionuclide makes some difficulties for the
production of final preparation 225Ac.
Actinium is eluted together with cerium and lanthanum.
To separate Ac(III) from rare earth elements the eluted 3 ml
fraction from Ln or DGA Resin (in 3 M HNO3) is loaded
onto extraction-chromatographic columns filled with TRU
Resin (octylphenyl-N,N-di-isobutyl carbomoylphosphineoxide dissolved in TBP as extracting agent).
The possible scheme of separation of 225Ac from theisotopes produced in irradiated thorium target is includes twosequential solvent extractions using HDEHP. After sorption
on DGA Resin, for further separation the 3 M nitric acid canbe passed through the sorbent TRU Resin. The procedureprovides obtaining a pure Ac fraction, containing less than
0.2% 227Ac and no other radionuclides; the chemical yield is
90% or more [3].
[1]

[2]
[3]

－ 334 －

S.V. Ermolaev, B.L. Zhuikov, V.M. Kokhanyuk, V.L. Matushko, S.N.
Kalmykov, R.A. Aliev, I.G. Tananaev and B.F. Myasoedov. Productionof actinium, thorium and radium isotopes from natural thorium
irradiated with protons up to 141 MeV, Radiochim. Acta, 100, 1–7,
2012.
B.L. Zhuikov, S.N. Kalmykov, S.V. Ermolaev, R.A. Aliev, V.M.
Kokhanyuk, Produce of 225Ac and 223Ra from thorium irradiated with
protons, Radiochemistry, 2011, 53, 1, p. 66-72.
B.L. Zhuikov, S.N. Kalmykov, R.A. Aliev, S.V. Ermolaev, V.M.
Kokhanyuk, V.M. Kokhanyuk, I.G. Tananaev and B.F. Myasoedov, A
method of producing actinium-225 and radium isotopes and targets for���� ��������������� ����������� ������� �� ��������� �������� ������������
2009.

25-RPP-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Development of 99Mo-99mTc Domestic Production
with High-Density MoO3 Pellets by (n, �) Reaction

K. Tsuchiya*1, M. Tanase*2, T. Shiina*2, A. Ohta*2, M. Kobayashi*3,
A. Yamamoto*3, Y. Morikawa*3, M. Kaminaga*1, H. Kawamura*1*1 : Japan Atomic Energy Agency, 4002 Narita, Oarai,Higashiibaraki, Ibaraki 311-1393, Japan*2 : Chiyoda Technol Corporation, 3681 Narita, Oarai, Higashiibaraki, Ibaraki 311-1313, Japan*3 : FUJIFILM RI Pharma Co. Ltd., 453-1 Shimo-okura, Matsuo, Sammu, Chiba 289-1592, Japan

Keywords –(n, �)99Mo production, high-density MoO3 pellets,solvent extraction, 99mTc solution, JMTdemonstration tests will be carried out with the irradiated
MoO3 pellets in JMTR.

The renewed JMTR will start rerunning from the later
half of JFY2013, and it is expected to contribute to many
fields not only developments for nuclear materials, but also
the other fields such as medical diagnosis medicine, scienceand technology for fusion reactor, etc. As one of effective
applications of the JMTR, JAEA has a plan to produce
99
Mo by (n, �) method ((n, ��99Mo production), a parent
nuclide of 99mTc. 99mTc is most commonly used as aradiopharmaceutical in the field of nuclear medicine. Incase of Japan up to now, the supplying of 99Mo depends
only on imports from foreign countries. Thus, the (n,��99Mo production was selected from viewpoints of safety,
nuclear proliferation resistance and waste management andthe R&D for domestic production were started in JMTR.
The main R&D items for (n, ��99Mo production are as
follows;(1) Fabrication development of irradiation target for thehigh-density MoO3 pellets,(2) Separation and concentration development of 99mTc
by the solvent extraction from 99Mo/99mTc solution, and(3) Examination of 99mTc solution for a medicine.
In this study, the status of the R&D is presented for the(n, ��99Mo production. Molybdenum oxide (MoO3) is themost commonly used chemical form as irradiation target forthe (n, ��99Mo production. The MoO3 pellet with highsintering density has been developed for large quantity (n,��99Mo production, and the trail fabrication tests of MoO3
pellets were carried out by the plasma sintering method.
The solvent extraction method employs MEK to extract99m
Tc from 99Mo/99mTc solution. The extracted 99mTc
content by the (n, ��99Mo production is less than that by the(n, f) methods and the concentration methods of 99mTc
solution were developed in the 99mTc extraction devices. In
the tests, rhenium (Re) was used instead of 99mTc because
Re and Tc were homologous elements. The R&D will be
carried out with foreign organizations using 99mTc based on
the preliminary results with Re in the present work. It is
important for medical use to determine detailed
specifications of 99mTc solution. In the preliminary tests
with practice solution using Re, chemical purities such as
Mo, Al and MEK were measured in the solution and thecontent of impurities will satisfy the requirement ofradiopharmaceuticals. In future, the solvent extraction－ 335 －

25-RPP-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Preparation of 99Mo–99mTc by using Spallation Neutron
Y. Hayashi*1, N. Takahashi1, K.Nakai1, H. Ikeda2, G. Horitsugi2, T. Watabe2, Y. Kanai2, H. Watabe2,
E. Shimosegawa2, Y. Miyake2, J. Hatazawa2, M. Fukuda3, K. Hatanaka3, K. Takamiya4, S.
Yamamoto5,
Y. Kasamatsu1 and A. Shinohara1
1

Graduate School of Science, Osaka University
Graduate School of Medicine, Osaka University
3
Research Center for Nuclear Physics, Osaka University
4
Kyoto University Research Reactor Institute5
Graduate School of Medicine, Nagoya University
2

Abstract – We developed the method for preparation of 99mTc used
for diagnostic radiopharmaceuticals. We produced 99Mo, themother nuclide of 99mTc, by the 100Mo(n,2n)99Mo reaction using
the spallation neutron which was produced by 400 MeV proton
from a ring cyclotron. The 99mTc was extracted with methyl ethyl
ketone and purified with an aluminum column. Furthermore, we
demonstrated the bone scintigraphy by injecting 99mTc-MDP into
the rats.
Keywords – 99mTc, 99Mo, Spallation neutron, Methyl ethyl ketone(MEK), Aluminum column

I.

INTRODUCTION

The 99mTc is one of most important radioisotopes used
for diagnostic radiopharmaceuticals today. The most of
those are made with the several nuclear reactors in theworld. However, all those reactors using highly enriched235
U fuel are aged more than 50 years, their deteriorations
are anticipated and many alternative methods were
explored for the production of 99mTc, as the 100Mo(p, 2n)
99m
Tc and 100Mo(p, d)99Mo reactions. In our previous work,
we tested to produce 99mTc with spallation neutron by the100
Mo(n, 2n)99Mo reaction which has larger cross section
than the proton induced reactions. The radioactivity of99
Mo produced was 3MBq/(�A h g) and this result
suggested that enough radioactivities of 99Mo for the
medical use can be obtained with this method. However,the specific activity of 99Mo produced by an accelerator isvery low, 99mTc cannot be separated by the conventional
alumina and PZC columns. In this work, we separated
99m
Tc from macro amount of natural Mo by the solvent
extraction with methyl ethyl ketone (MEK) and further
purified it with the aluminum column. In addition wedemonstrated the bone scintigraphy with the purified 99mTc
as a preclinical test.
II.

with a few ml of saline. The solution was passed throughthe neutral aluminum column to remove the Mo species byadsorbing them on the column. Amount of impurities in the
99m
Tc solution were measured with ICP-MS and yield of
99m
Tc was determined by gamma-ray measurement using agermanium semiconductor detector. Furthermore, thepurified 99mTc was labeled into MDP and injected into a rat.
We determined the labeling efficiency of 99mTc-MDP using
a silica-gel-coated thin layer chromatography plate. We
took the bone scintigraphy of the rat using a gamma camera
[1]
.
III.

RESULTS & DISUCUSSIONAs the results of measurement with ICP-MS, we foundthat only less than 10 ppb of Mo and Al coexist in the
purified 99mTc solution. No other impurities were detected
and this solution satisfied the demand of the United States
Pharmacopeia (USP). The yield of 99mTc was 75-90% andthe volume was only 5 mL. The labeling efficiency of the99m
Tc-MDP was higher than 99%, well above the USP
requirement (>90%).We obtained the bone scintigram
which is not different from that obtained using commercial
99m
Tc as shown in Fig.1. Thus, it is thought that thisseparation technique is available for preparation of 99mTc.
We have plan to separate 99mTc from 99Mo produced by the100
Mo(n, 2n)99Mo reaction and to demonstrate the bone
scintigraphy. In this presentation, we will also report theresults of these experiments.

EXPERIMENTAL

We performed separation of 99mTc by the previously
mentioned method using commercial 99mTc and macro
amount of natMo and examined the purity of the 99mTc first.
We prepared the Mo and 99mTc mixture by dissolving 40 gof natMoO3 and 60 MBq of commercial 99mTc solution with
120 mL of 4 M sodium hydroxide solution. The 99mTc
nuclide was extracted with 15 mL of MEK from macro
amount of natural Mo. After the evaporation of the MEK
solution under reduced pressure, the sample was dissolved

Fig.1 Bone scintigram by injecting with 99mTc-MDP into the rat(a: purified 99mTc, b: commercial 99mTc, c:CT image)[1]－ 336 －S Yamamoto et al., Med Phys. 39. 581. 8. (2012)

25-RPP-05
Development of Automated Measurement System for Radioactive Intensities of Sealed Small
Radiation Sources (Iodine-125 Seed Source) for Brachytherapy
M. Sakama,1, ∗ H. Ikushima,2 T. Saze,3 Y. Nagano,4 T. Yamada,5 T. Ichiraku,5 H. Takai,5 Y. Kuwahara,6 and S. Nakayama7
1 Department of Radiological Science (also Advanced Radio-Analytical Chemistry,

Division of Biomedical Information Sciences, Institute of Health Biosciences,
The University of Tokushima,Tokushima 770-8509, JAPAN2 Department of Radiation Therapy Technology, Division of Biomedical Information Sciences,
Institute of Health Biosciences, The University of Tokushima,Tokushima 770-8509, JAPAN3 Otsuka Pharmaceutical Factory, Naruto,Tokushima 772-8601, JAPAN4 Department of Radiological Science, Division of Biomedical Information Sciences,
Institute of Health Biosciences, The University of Tokushima,Tokushima 770-8509, JAPAN
5 Dairyu Co. Ltd., Anan,Tokushima 774-0045, JAPAN
6 Radioisotope Center, The University of Tokushima,Tokushima 770-8503, JAPAN
7 Department of Nuclear Science, Institute of Socio-Arts and Sciences,
The University of Tokushima,Tokushima 770-8502, JAPANWe have developed full automated measurement system for radioactive intensities of sealed small radiation
sources (iodine-125 seed source) for brachytherapy in this work. Today, quality assurance (QA) of I-125 seedradioactive sources for brachytherapy following AAPM (American Association of Physicists in Medicine) Society’s guideline is one of important subjects for hospitals that operate on patients for prostate cancer and medical
companies that manufacture and sell these radioactive sources. In order to survey defective seed products into all
the number of I-125 seed sources (there are usually ﬁfteen seeds, one seed of dimensions is 0.8 mm φ × 4.5 mm
length) within a cartridge, we have applied the method of single slit collimator with moving a radiation detector
to measure each radioactive intensity of these I-125 seeds. As a result, it was found that our developed systemin the present work has good performance of surveying the defective products manufactured with radioactive
intensities out of about ± 15% error (p < 0.05).
I.

INTRODUCTION

Today, there is no doubt about increasing in the patient population of prostate cancer year after year. Since the authorization from the Ministry of Health, Labor and Welfare in 2003,
a brachytherapy using I-125 seeds has been one of most effective therapies of primary and middle stages of prostate cancer in Japan, and all the number of annual clinical operationsin Japan has been probably reached to about 3,500 in 2012.
In terms of safety management on quality assurance (QA) forthe brachytherapy, such kinds of the guidelines stated fromAAPM Society [1] and JASTRO (Japanese Society for Therapeutic Radiology and Oncology) have recommended that eachradioactive intensity of I-125 seed sources should be appropriately surveyed before the therapy of prostate cancer. However,in fact, there are only a few facilities such as surveying the radioactive intensity of I-125 seed source in Japan. It should
be seemed that additional works such as QA make radiologic
workers in hospital bothered due to time consuming and also
exposed due to operations of these radioactive sources using
a dose meter like an ionization chamber. The purpose of thiswork is to develop full automated measurement system for radioactive intensities of I-125 seed source to comply with thedemands of medical workers.
II.

MATERIALS AND METHODS

The system has external dimensions of 600 mm width ×
700 mm depth × 850 mm height and consists of a cartridge
holder, NaI scintillation survey meter and drive mechanism,
and a data analysis module. The survey meter is set behind acopper and stainless steel plate containing a slit (0.1 mm thick-ness). Radioactivity of the seeds within a cartridge is measured by the survey meter that is moved slowly (0.1 mm/sec)
in front of the cartridge by the drive mechanism. The survey
meter detects gamma rays passing through the slit in the plate.
By keeping the seeds inside the cartridge, their individual activities can be measured while maintaining a sterile state.

FIG. 1. Photograph view of our developed system (BSQAS-2).
III.

RESULTS

The system can automatically complete the activity measurement of all seeds contained inside 4 cartridges in less than
15 minutes, with about 15% of errors to detect miss-calibrated
seed. This system enables us to survey the defective products
manufactured with radioactive intensities out of about ± 15%
error (p < 0.05).
IV.

CONCLUSIONS

A full automatic measurement system of I-125 seed activity
shows reliable precision and usability. Future development
will include support for other source delivery methods parallel
to efforts in reducing the size of the system.

[1] AAPM, M ED . P HYS . 26(10), 2054-2076 (1999).

∗ Corresponding author,

electronic address: sakama@medsci.tokushimau.ac.jp, or, minorusakama@tokushima-u.ac.jp－ 337 －

25-RPP-06

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Extraction of astatine isotopes for development of radiopharmaceuticals
E. Maeda1, A.Yokoyama2, T. Taniguchi1, K. Washiyama3 I. Nishinaka41

Grad. School Nat. Sci., Tech. Kanazawa Univ., 2Inst. Sci. Eng., Kanazawa Univ.
3
Sch. of Health Sci., College of Med., Pharma. Health Sci., Kanazawa Univ.
4
ASRC, Japan Atomic Energy Agency

Abstruct�The 211At isotope has gathered attention as a promising�-emitter for radionuclide therapy. We report the dependence ofthe distribution ratio of astatine on the concentration of HCl, andon the polarity of the organic solvent. The results will be usefulfor development of the 211Rn-211At generator.
Keywords�Astatine / radiopharmaceutical / Distribution ratio /Organic solvent

I.

2. Dependence of the polarity of organic solvent
Astatine isotopes are produced and distilled as in theprevious section. Then astatine isotopes were trapped fromtest tube in 8 M HCl solution. They are extracted byshaking with equal volume of several different types ofpolarity of organic solvent ��������������������-activity ofeach two phase was measured by a HPGe detector anddistribution ratio was calculated.

INTRODUCTION

III. RESULTS

Because of the short path length in tissues (<100 �m)
and the high linear energy transfer (~100 keV/�m), �particle therapy is expected to kill specific tumor cells
efficiently with a low level of damage to surrounding
tissues. There are approximately 100 radionuclides thatdecay with �-particle emission. Among them, an 211At
isotope with a proper half-life (7.2 h), has gatheredattention as a promising �-emitter for radionuclide therapy.
Because astatine isotopes are produced via a nuclear
reaction, we have to separate astatine isotopes from
irradiated targets with high purity. But, the chemical
properties of astatine isotopes are not well known for that
purpose. In order to research for preparation of astatine fora radiopharmaceuticals, we prepared for astatine isotopes
by the reaction of natPb(7Li, xn)209-211At at the tandem
accelerator of Japan Atomic Energy Agency– Tokai. We
report dependence of the distribution ratio of astatine on theconcentration of HCl, and on the polarity of the organic
solvent as a part of the study.

Dependence of the distribution ratio on theconcentration of HCl was observed for DIPE as show in
Fig. 1. Tends to increase in concentration of HCl, thehigher the distribution ratio was observed.
The astatine isotopes were well extracted into DIPE andMIBK, but no significant extraction was observed intoluene and decane as show in Fig. 2. It is assumed that theextraction process of astatine is related to polarity of theorganic solvent. These results in this study will be usefulfor development of the 211Rn-211At generator.

II. EXPERIMENTS
Fig. 1 Distribution ratios for several concentrations of HCl with DIPE.

1. Dependence of the concentration of HCl
A lead target (0.74 mg/cm2) was irradiated with 50MeV
Li beam with a current of 120~200 nA using the tandem
accelerator of JAEA-Tokai, so that we prepared for astatine
isotopes by the reaction of natPb(7Li, xn)209-211At. We put on
irradiated target into a test tube and heated up at 650 � forabout 20 minutes in a electric furnace. Then carrier-freeastatine was separated from the lead target by dry
distillation. After the dry distillation, we trapped astatine
isotopes in 4 M HCl solution. We adjusted theconcentration of HCl (1~8 M) and then extracted astatine
isotopes by shaking with an equal volume of DIPE for 5min������ ���� �-activity of each phase was measured by a
HPGe detector, and the distribution ratio of astatine
isotopes was calculated by the measurements.
7－ 338 －

Fig. 2 Distribution ratio for different polarities of organic solventwith 8M HCl.

25-RPP-07

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Lutetium-177 Complexation of DOTA and DTPA in the Presence of Competing
Metals1

Satoshi Watanabe1, Kazuyuki Hashimoto2, Noriko S Ishioka1

Medical Radioisotope Application Group, Quantum Beam Science Directorate, Japan Atomic Energy Agency,
Takasaki, Gunma 370-1292, Japan
2
Medical Radioisotope Application Group, Quantum Beam Science Directorate, Japan Atomic Energy Agency,
Tokai-mura, Ibaraki 319-1195, Japan

Complexation,

DOTA,

DTPA,

III.

I. INTRODUCTION
Lutetium-177 is considered to have potential for
application in radioimmunotherapy, because it emits �particles (E�,max=498 keV) suitable to penetrate small
tumors and its physical half-life of 6.734 days is longenough for 177Lu-labeled antibodies to accumulate to tumor
sites. In addition, real time imaging of biodistribution canbe done by using the 177Lu, because the energy of �-rays(E�=113 keV and 208 keV) emitted from 177Lu is
particularly suitable for imaging by single photon emission
computed tomography.
We have succeeded in the production of high purity nocarrier-added 177Lu of capable of labeling antibodies using
reversed-phase ion-pair liquid chromatography [1]. Usually,
as chelating agents of the labeling antibodies, DOTA
(1,4,7,10-tetraazacyclododecan-N,N’,N’’,N’’’-tetraaceticacid) and DTPA (diethylenetriamine-N,N,N’,N’’, N ’’pentaacetic acid) are mainly used. Therefore, we carried out
the labeling experiment of 177Lu-DOTA-antibody by using
the 177Lu produced in our method in that study. It was
found that metallic impurities such as Ca, Fe and Zn
inhibited the complexation between 177Lu and DOTA.
However, the details of the inhibition by the metallic
impurities have not been understandable. Therefore, inthe present paper, the 177Lu complexation of DOTA andDTPA is investigated by the addition of competing
metals, Ca, Fe and Zn.
II. EXPERIMENTAL

RESULTS AND DISCUSSION

Figure 1(a) shows the results of 177Lu complexation of
DOTA and DTPA by the addition of Ca(II). The 177Lu
complexation yield of DOTA decreases with increasing[Ca(II)]/[Lu], while that of DTPA is constant. This result
indicates that 177Lu complexation of DOTA is more
inhibited by Ca(II) than that of DTPA.
The results of 177Lu complexation by the addition of
Fe(II) and Zn(II) are shown in Figs.1(b) and 1(c). The 177Lu
complexation yield of both DOTA and DTPA decreases
with increasing [Fe(II)]/[Lu] and [Zn(II)]/[Lu]. Fromcomparison between DOTA and DTPA, the decrease of thecomplexation yield of DOTA was rather high comparedwith that of DTPA in both cases of Fe(II) and Zn(II).
Therefore, the inhibition for the 177Lu complexation of
DOTA is higher than that of DTPA.
Consequently, the 177Lu complexation of DOTA was
more inhibited by Ca(II), Fe(II) and Zn(II) than that of
DTPA. Therefore, it was found that the 177Lu complexationof DTPA was rather advantageous compared with DOTAin the presence of competing metals, Ca, Fe and Zn.
100

177Lu Complexation Yield

Keywords – Lutetium-177,
Competing metals

which was defined as a percentage of the radioactivity of
Lu-DOTA or 177Lu-DTPA to that of 177Lu used for thewasdetermined
by
thin
layer
complexation,
chromatography on silica gel ITLC
using aqueous
ammonia : methanol : water (0.2 : 2 : 4) as a developing
solvent. The unreactive 177Lu remains at the origin point ofa silica gel ITLC strip and the 177Lu-DOTA or 177Lu-DTPA
moves to the solvent front.

177

80

100

(a)

60
40
20

DOTA
DTPA

0
0.1

1
10
[Ca(II)]/[Lu]177Lu Complexation Yield

Abstract – 177Lu complexation of DOTA and DTPA is investigatedby the addition of Ca(II), Fe(II) and Zn(II). The 177Lu
complexation yield of DTPA was higher than that of DOTA in thepresence of Ca(II), Fe(II) and Zn(II). Therefore, it was found thatthe 177Lu complexation of DTPA was more advantageouscompared with DOTA in the presence of competing metals, Ca, Fe
and Zn.

100

80

(b)

60
40
20

DOTA
DTPA

0
0.1

1
10
[Fe(II)]/[Lu]The 177Lu used in this experiment was produced by
Lu(n, �)177Lu process. For the experiment of 177Lu
complexation of DOTA and DTPA, to the mixture of 5 �Lof the 177Lu solution (5.0 x 10-5 M as Lu) and 5 �L
solution of the competing metal (Ca(II), Fe(II) or Zn(II))
in a prescribed concentration, 0.875 �L of acetate buffer(3 M, pH=6.0) was added. After that, a 10 �L solution of
DOTA or DTPA (5.0 x 10-5 M) was added. Afterincubating for 1.5 hours at 40�C, the complexation yield,
176

177Lu Complexation Yield

100
80

(c)
Fig.1 177Lu complexation
yield of DOTA and DTPAby the addition of metallic
impurities. (a) Ca(II), (b)Fe(II) and (c) Zn(II).

60
40
20
0
0.1

[1]

－ 339 －

100

DOTA
DTPA
1
10
[Zn(II)]/[Lu]100

Japanese patent application, 2010-223827.

25-NPP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Hyperfine Fields at 140Ce in He-Doped Fe
1
2

Y. Ohkubo1, A. Taniguchi1, Q. Xu1, M. Tanigaki1, K. Sato1 and M. Tsuneyama2

Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka 590-0494, Japan
Grauduate School of Science, Kyoto University, Kitashirakawa, Sakyo-ku, Kyoto 606-8502, Japan

Abstract – Room-temperature TDPAC spectra of 140Ce in an Fe foil
and two He-doped Fe foils, all annealed in vacuum at various
temperatures were taken in order to see whether Ce and He form
complexes in Fe as suggested in first-principles density functional
theory calculations. The TDPAC results are presented.

A22 G 22 (t ) � 2

Keywords – hyperfine fields, 140Ce, He-doped Fe, TDPAC, ion
implantation, ISOL

INTRODUCTION

The magnetic hyperfine fields at impurity elements inferromagnetic metals are important quantities because they canbe used to determine the magnetic moments of nuclear states
having the same atomic number as the impurity elements andmoreover, together with the electric field gradients, to test firstprinciples calculations in condensed matter physics. Recently,
we implanted 140Cs in an Fe foil at room temperature with thehelp of KUR-ISOL and successfully observed an oscillation
pattern due to a unique magnetic hyperfine interaction at 140Ce
arising from those 140Cs in a TDPAC (time-differential
perturbed angular correlation) spectrum, which is identical tothe one seen in Fig. 1(b). From the known magnetic hyperfine
field at 142Ce in Fe, we have obtained the magnetic moment of
the 2083-keV 4+ state of 140Ce [1]. This time, we have taken
room-temperature TDPAC spectra of 140Ce in an Fe foil (forshort, 140CeFe) and 140Ce in two He-doped Fe foils, all annealedin vacuum at various temperatures in order to see whether Ceand He form complexes in Fe as suggested in first-principles
density functional theory calculations [2].

Figure 1 shows a part of the TDPAC spectra obtained forthe three samples. Although the TDPAC spectra for the threesamples before annealing are identical to the one shown in
Fig. 1(b), there can be seen considerable differences among
the samples, which may imply the existence of Ce and He
complexes in He-doped Fe foils.
-0.12(a) 140 Ce Fe irradiated with He

-0.08
-0.04
0.00

(b) 140 Ce He-doped Fe

-0.08
-0.04
0.00

II. EXPERIMENTAL PROCEDURES
Room-temperature implantations of 100-keV 140Cs ions were
performed at KUR-ISOL. Each of three Fe foils was 0.1-mm
thick and of 99.995% purity, which had been annealed in H2
atmosphere at 700°C for 2 h and then polished. 4-keV He
irradiations were carried out at room temperature on two of thefoils, one before 140Cs implantation (140CeHe-doped Fe) and theother after 140Cs implantation (140CeFe irradiated with He).
Before and after 0.5-h isochronous annealing in vacuum atvarious temperatures between 473-1073 K, the timedependences of the coincidence counts N(�, t) of the 329-487
keV cascade � rays for the three Fe samples were taken at room
temperature with two measurement systems, each consisting ofstandard fast-slow electronic modules and four BaF2
scintillation detectors. Here, � and t denote the angle and thetime interval, respectively, between the cascade � rays. The
directional anisotropy A22G22(t) is obtained as follows:(1)

III. RESULTS

A22 G22(t)I.

N (180�, t ) � N (90�, t ).
N (180�, t ) � 2 N (90�, t )(c) 140 CeFe

-0.08
-0.04
0.00
0

5

10

t (ns)

15

20

25

Fig. 1. Room-temperature TDPAC spectra of (a) 140CeFe irradiated with He,(b) 140CeHe-doped Fe, and (c) 140CeFe, all annealed at 673 K in vacuum.

REFERENCES[1][2]－ 340 －

Y. Ohkubo, A. Taniguchi, Q. Xu, M. Tanigaki, N. Shimizu and T.
Otsuka, Phys. Rev. C. 87, 044324 (2013).
W. Hao and W. T. Geng, Nucl. Instru. Meth. B 280, 22 (2012).

25-NPP-02
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Mössbauer studies of lanthanum doped Ni0.4Cu0.2Zn0.4Fe2O4 ferrites by Sol-Gel autocombustion
1

Qing Lin1,2, Chenglong Lei1*, Haifu Huang3, Hui Zhang1, Yun He1

College of Physics and Technology, Guangxi Normal University, Guilin 541004, China
Department of Information Technology, Hainan Medical College, Haikou 571101, China
3
Nanjing National Laboratory of Microstructures and Jiangsu Provincial Laboratory for NanoTechnology,,Department of
Physics, Nanjing University, Nanjing 210093, Chinae-mail:hy@gxnu.edu.cn
2

Abstract:
In this literature, La3+ substituted Ni0.4Cu0.2Zn0.4Fe2xLaxO4(0������������������������������-Gel auto-combustion route
have been prepared. XRD of the powders calcined at 800�/3h show
only single phase cubic spinel ferrites and crystalline size decrease
sharply, but at high temperature 950�/3h that emerge extra phase
LaFeO3 when x�������������������������������������������������������
Mössbauer spectrums at room temperature of samples at 800�/3hvary from magnetic sextets to shrink magnetic sextet and collapse torelaxation doublet(x=0.1). This variation of magnetic order state
confirms the Fe3+-O2--Fe3+ super exchange interaction decrease dueto La3+ substitutions. However, when that processed at 950�/3h,
The hyperfine magnetic field distribution probability moves to highmagnetic field region. The magnetic order for all samples exhibits
relaxation sextet magnetic spectra and does not change obviously up
to substitution x=0.15. A broadening line width observed in
Mössbauer spectra is interpreted as originating from various cation
distributions. The super exchange interaction should have beenenhanced and the Curie temperature increases.
Keywords: Rare earth, Sol-Gel, XRD, Mössbauer, NiCuZn ferrite,
Hyperfine magnetic fieldI.

RESULTS AND DISCUSSION

We have successfully prepared ferrite system La3+ doped
Ni0.4Cu0.2Zn0.4Fe2-xLaxO4(0��������� by Sol-Gel autocombustion method. The XRD patterns of ferrite powders
calcined at 800����������������������������������������
respectively.

Fig.5 show the Mössbauer spectra of samples calcined at 950�������
differences of Mössbauer spectra compared with the sample calcinedat 800�������������������������������������3+ ions need more bondenergy and affect the (Fe3+)A-O2--(Fe3+)B super-exchange interaction
so that the samples show ferromagnetism because of high sintering
temperature.
[1]

[2]

Fig.3 and Fig.4 show the Mössbauer spectra (RT) of
Ni0.4Cu0.2Zn0.4LaxFe2-xO4nano-crystalline

ferritemeasured at room temperatures , respectively.

powders[3]－ 341 －

Gabal, M.A., et al., Structural, magnetic and electrical properties ofGa-substituted NiCuZn nanocrystalline ferrite. Ceramics International,
2010. 36(4): p. 1339-1346.�
Roy, P.K., B.B. Nayak, and J. Bera, Study on electro-magnetic
properties of La substituted Ni–Cu–Zn ferrite synthesized by autocombustion method. Journal of Magnetism and Magnetic Materials,
2008. 320(6): p. 1128-1132.
S.I.Moussa, R.R.Sheha, E.A.Saad, N.A.Tadros, Synthesis andcharacterization of magnetic nano-material for removal of Eu3+ ionsfrom aqueous solutions, Journal of Radioanalytical and Nuclear
Chemistry, 2013. 295: 929–935.

25-NPP-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Analysis of corrosion products formed on anti-weather steel
Matashige OYABU1, Ryo SATOH1, Kiyoshi NOMURA2
1

Math & Science Division, Kanazawa Institute of Technology,
Ohigigaoka 7-1, Nonoichi, Ishikawa, Japan 921-8501
2
The University of Tokyo,
Hongo 7-3-1, Bunkyo-ku, Tokyo, Japan 113-8656

Abstract
Weathering steels (COR-TEN O) were corroded under the salty oracid rain condition in the laboratory. Corrosion products on
weathering steel were analyzed by Mössbauer spectrometry and
X-ray diffraction. The kind of products depended on theatmospheric ������������-FeOOH, which disturbs the performanceof weathering steel, was formed under the existence of chloride or��������� ����� ���� ����������� ��� �-������� �-������� �-FeOOH
and�-Fe2O3 were studied in various conditions.

I. INTRODUCTION
In recent years, use of weathering steel is increasing, and it
became to be used to about 30% as steel materials for abridge. Weathering steel is designed to protect the internal
corrosion of steel by generating stable rust on the surface
without painting. The paint is not needed, and so the cost of
painting and maintenance can be reduced. The life may
exceed 100 years under good atmosphere condition. The
life of weathering steel depends on the environments
largely. Especially it is difficult to use the steel under salty
environment like coastal area. The stable rust on the surface
might be composed of fine �-������� �-FeOOH andmagnetite. Those materials may form protection layer on
the steel. However, �-FeOOH, which is not protective rust,
may be generated under the existence of chloride ion. The
������������������������������������������-FeOOH should
be studied to improve the performance of weathering steel.
In this study, weathering steels were corroded under thedifferent conditions and the corrosion products wereanalyzed by Mössbauer spectrometry and X-ray diffraction.
����������������-FeOOH formation, pure material also wassynthesized by hydrolysis of iron(III) solution and studied
by X-ray diffraction.

III. RESULT AND DISCUSSION
Mössbauer spectra and the hyperfine distributions wereshown in Fig.1. By spraying 5% NaCl solution, strong
paramagnetic doublet was observed. It perhaps is due to the
�-FeOOH and�-FeOOH contained in the rust products.
With respect to acid rain, �-FeOOH, �-FeOOH, and�Fe2O3 were identified. The large amount of sextet with 49T
due to � -Fe2O3 was produced under the condition of
nitrate and sulfate solution. �-FeOOH exhibits the broadand collapsed sextet with 34T at RT. The �-FeOOH is
considered to be poor crystalline or fine grains. Any
corrosion product is composed from fine grains because thebroadening sextets. Detailed discussion will be presented in
the poster.

II. EXPERIMENT
Corrosion test: The steel plate of COR-TEN O with 1mm
thickness was used. It was cut to 80 mm x 60 mm.
Corrosion tests were carried out based on JIS H8502
method. Each piece was sprayed with test solitions and kept
in dry condition followed by wet condition. One cycle took
12 hours. The cycle was repeated 20 times finally. Test
solutions used are 5% NaCl, acid rain (NaCl, HNO3, H2SO4,
pH3.5), acid rain “without NaCl”, 5% NaF, and 5%(NaF+Na2SO4), respectively.
X-ray diffractions patterns were measured by Rigaku
UltimaIV equipped with Cu target and monochromator, andwere analyzed by Rietveld method to identify the
crystalline products. Mössbauer spectra were measured atroom temperature by using 57Co(Cr) source andconventional instrument.

Figure 1 Mössbauer spectra of corrosion products using
sprayed solution; (a) 5% NaCl (b) acid rain, and (c) nitrateand sulfate
Reference
1. “COR-TEN Catalog” published by Nippon Steel
2. Shuichi HARA, Zairyo-to-kankyo,57, 70-75(2008)－ 342 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-NPP-04

Study of the Spin-Crossover Phenomena in 1D Coordination Polymers, [FeII(NH2triazole)3](CnH2n+1SO3)2, by Fe-K edge XAFS and 57Fe Mössbauer Spectroscopy
Hajime Kamebuchi1, Akio Nakamoto1, Masaya Enomoto2, Toshihiko Yokoyama3, Norimichi Kojima1
1

Graduate School of Arts and Sciences, The University of Tokyo, Komaba 3-8-1, Meguro-ku, Tokyo 153-8902, Japan2
Department of Chemistry, Tokyo University of Science, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162-8601, Japan3
Department of Materials Molecular Science, Institute for Molecular Science, Myodaiji-cho, Okazaki 444-8585, Japan
Abstract – The spin transition temperature of 1D spin-crossover
system, [FeII(NH2-trz)3](CnH2n+1SO3)2·xH2O (NH2-trz = 4-amino1,2,4-triazole), was systematically controlled through thechemical pressure derived from the alkyl chain of counter-anion.
We investigated the influence of the chemical pressure on the spintransition temperature and �-back donation from FeII ion to NH2trz ligand with increasing alkyl chain length by means of 57Fe
Mössbauer and XANES spectra.
Keywords – Spin-Crossover, 57Fe Mössbauer, X-ray absorption

I.

INTRODUCTION

When a transition metal ion with an electron
configuration of d4�d7 is octahedrally coordinated byligands, the ground state has a possibility to change the spinstate between high-spin (HS) and low-spin (LS) states byexternal stimuli. Such the HS-LS transition is called spincrossover phenomenon. In the past decades, one
dimensional FeII coordination polymers bridged by 4substituted-1,2,4-triazole (R-trz), whose general formula is[FeII(R-trz)3](A)2·xH2O (A = monovalent anion), haveattracted much attention because of their potential
applications to molecular electronics or molecular devices[1, 2]. The primary reasons for this are that their spintransition behavior occurs around room temperature withwide thermal hysteresis. Furthermore, their spin transition
temperature (T1/2) and hysteresis width (�T1/2) arecontrollable by various chemical and physical approaches[1, 3, 4]. This research aims at the control of the spintransition behavior through chemical pressure effect andthe analysis of the ligand field by X-ray absorption (XAFS)
and 57Fe Mössbauer spectroscopy for [FeII(NH2trz)3](CnH2n+1SO3)2· xH2O (n = 1 – 9).

parameter (B) in the HS state were estimated by analysing
the pre-edge region in Fe-K edge XANES (X-ray
absorption near edge structure) spectra based on the ligand
field theory. It is clear from Figure 2 that the increase of Dq
and the decrease of B were found with increasing n, which
are closely consistent with the relationship between T1/2 andthe 57Fe Mössbauer isomer shift (IS) at 200 K. Judging
from these results, the following result is derived. The backdonation from the 3d orbital of FeII ion to the �* orbital of
NH2-trz (d�-p� back bonding) is enhanced by the uniaxial
chemical pressure due to the fastener effect between thealkyl chains of counter-anion, which induces the expansionof the 3d orbital and the decrease of B of FeII ion. Thus
Dq/B increases with the alkyl chain length, which is the key
parameter determining T1/2 of spin crossover compounds.

Figure 1. Correlation between spin transition temperature (T1/2) and thenearest neighbor Fe-Fe distance (R(Fe-Fe)).

II. RESULTS AND DISCUSSION
In [FeII(NH2-trz)3](CnH2n+1SO3)2·xH2O, T1/2 increases in
the heating and cooling processes with increasing the alkyl
chain length (n). In connection with this, there is a close
relationship between T1/2 and the nearest neighbor Fe-Fe
distance (R(Fe-Fe)) estimated from EXAFS (extended Xray absorption fine structure), which is shown in Figure 1.
These are highly suggestive of the increase of intra-chaininteraction with the alkyl chain length being attributed tothe uniaxial chemical pressure effect induced by selfassembly interaction between alkyl chains, so-called“fastener effect”.
In order to elucidate the effect of uniaxial chemicalpressure on T1/2, the ligand-field strength (Dq) and Racah

Figure 2. Correlation between 57Fe Mössbauer Isomer Shift (IS) of the LS
state and Racah parameter (B).

REFERENCES
[1]
[2]
[3]
[4]

－ 343 －

O. Kahn, C. J. Martinez, Science 279 (1998) 44.
M. M. Dîrtu, F. Schmit, A. D. Naik, A. Rotaru, J. MarchandBrynaert, Y. Garcia, Int. J. Mol. Sci. 12 (2011) 5339.
V. A. Varnek, L. G. Lavrenova, J. Struct. Chem. 36 (1995) 104.
P. Gütlich, V. Ksenofontov, A. B. Gaspar, Coord. Chem. Rev. 249(2005) 1811.

25-NPP-05

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Mössbauer Spectroscopic and Powder X-ray Diffraction Studies on Incorporationof Gaseous Organic Molecules into Intermolecular Nano-voids of Mixed-valence
Trinuclear Iron Pentafluorobenzoate Complex
Yoichi Sakai1, Satoru Onaka1, Ryo Ogiso1, Masashi Takahashi2,
Tadahiro Nakamoto3, and Tsutomu Takayama1
1

DaidoUniversity, Takiharu-cho, Nagoya 457-8530, Japan2
Toho University, Miyama, Funabashi 274-8510, Japan
3
Toray Research Center, Sonoyama, Otsu 520-8567, Japan

Abstract – Incorporation of gaseous organic molecules into
polycrystalline mixed-valence trinuclear iron (Fe3+,Fe3+,Fe2+)
pentafluorobenzoate complex Fe3O(C6F5COO)6(C5H5N)3 withintermolecular nano-voids was studied by 57Fe-Mössbauer
spectroscopic and powder XRD measurements.
Organicmolecule incorporation was mainly chased by using iron-valencefluctuation observed in a Mössbauer spectrum, and also
researched supportively by a powder XRD technique.
Keywords –Intermolecular nano-void, Mixed-valence trinuclear
iron complex, Valence fluctuation, 57Fe-Mössbauer spectroscopy,
powder XRDI.

INTRODUCTION

We have revealed that there is found a valencedetrapped (averaged) state of three iron ions forat room
Fe3O(C6F5COO)6(C5H5N)3·CH2Cl2 (1)temperature in our Mössbauer study, while a valencetrapped (localized) state for Fe3O(C6F5COO)6(C5H5N)3 (2)contrarily.
In complex 1, dichloromethane is contained
as a crystalline solvated molecule. Complexes of 1 and 2
are synthesized in our work both of which are a novelcompound; complex 2 was prepared by heating of 1 undera reduced pressure. It was revealed previously from oursingle-crystal X-ray structure analysis that solvated CH2Cl2
molecules are arrayed in the intermolecular space of thecomplex 1 [2]. This finding led us into anticipating thatgaseous organic molecules may be easily incorporated intosuch intermolecular nano-voids, since complex 2 was
obtained by removing CH2Cl2 molecules of the complex 1.
This expectation of ours was proved to be valid, which isreported elsewhere [2].
In the present work, the incorporation behaviors were
examined by Mössbauer and powder X-ray Diffraction(XRD) techniques. Furthermore, the time constant ofincorporation was also investigated.

All Mössbauer spectra and powder XRD patterns �������
were recorded at room temperature in ordinary ways.
III.

RESULTS AND DISCUSSION

Mössbauer spectra and powder XRD patterns at room
temperature were shown in the left and right sides of Figure
1, respectively, where those for the following three samples
are illustrated; a) polycrystalline powder of complex 2, b)
polycrystalline powder of complex 1, and c) powder of 2
exposed to dichloromethane vapor at 20 ºC for 21 h.
Mössbauer spectrum c) for complex 2 exposed to CH2Cl2
vapor shows that iron ions should be in the same valencedetrapping state as that of complex 1, implying a regain ofsolvated CH2Cl2 molecules to return to complex 1 fromcomplex 2. Such regain and return were confirmed in the
powder XRD patterns shown in Figure 1, where thepatterns a) and c) could be ascribed to a hexagonal crystal
form with a=1.35 and c=2.10 nm..
The re-absorption rate experiments suggested thatbenzene molecules were completely regained with a time
constant of a few tens of seconds, surprisingly swift.

II. EXPERIMENTAL
Complexes of 1 and 2 were prepared according to theprocedures reported in our previous papers [1,2].
Organic-vapor exposure experiments were carried out asdescribed in Ref. [2]; polycrystalline powder of 2 wasplaced in a small-sized vial and then this vial was placed ina large vial. An adequate amount of organic liquid waspoured in the large vial, which then was tightly capped.

Figure 1. 57Fe-Mössbauer spectra (left) and powder XRD patterns(right) at room temperature: a) Fe3O(C6F5COO)6(C5H5N)3·CH2Cl2, (1)b) Fe3O(C6F5COO)6(C5H5N)3, (2) c) Fe3O(C6F5COO)6(C5H5N)3 (2)exposed to CH2Cl2-vapor at 20 ºC for 21 h
[1]
[2]

－ 344 －

Y. Sakai et al., Hyperfine Interactions, 205 (2012) 1-5.
S. Onaka et al., to be submitted to an international journal (2013).

25-NPP-06

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Dynamic Perturbation to 111Cd(�111Ag) Doped in AgI Nanoparticles
W. Sato1,2, R. Mizuuchi2, N. Irioka3, S. Komatsuda2, S. Kawata4, A. Taoka1,2, and Y. Ohkubo5
1

Institute of Science and Engineering, Kanazawa University, Kanazawa, Ishikawa 920-1192, Japan
Graduate School of Natural Science and Technology, Kanazawa University, Kanazawa, Ishikawa 920-1192, Japan3
School of Chemistry, Kanazawa University, Kanazawa, Ishikawa 920-1192, Japan
4
Department of Chemistry, Faculty of Science, Fukuoka University, Fukuoka, Fukuoka 814-0180, Japan
5
Research Reactor Institute, Kyoto University, Kumatori, Osaka 590-0494, Japan

2

Abstract – Dynamic behavior of the extranuclear field relative tothe 111Cd( � 111Ag) probe doped in an ionic conductor silver
iodide (AgI) was investigated by means of the time-differential
perturbed angular correlation (TDPAC) technique. The roomtemperature TDPAC spectrum for as-precipitated AgI powder
shows no perturbation, reflecting the zinc blende crystal structure(�-AgI); whereas in polymer-coated AgI nanoparticles, the111
Cd( � 111Ag) probe is dynamically perturbed. This result
signifies that Ag+ ions in the latter sample can move around evenat room temperature in the time scale of the present time window.
Keywords – Silver Iodide, Perturbed Angular Correlations,Dynamics, PVP, Nanoparticles, Superionic Conductivity

I.

INTRODUCTION

It is well known that silver iodide (AgI) offers
superionic conductivity as in its high-temperature � phase,and applications of this solid-state conductivity are desired
in a wide field of industry. This conducting phenomenon,
however, emerges at high temperature because of
temperature-dependent crystal structures, which is indeed abarrier to the practical applications of this compound.
Recently, an epoch-making technique was reported tobreak through this situation: AgI powder coated by a polyN-vinyl-2-pyrrolidone (PVP) can partially preserve theconducting � phase even at room temperature, recording
the conductivity of 1.5 × 10-2 �-1 cm-1[1]. The authors
report that this achievement is due to successful control ofthe particle size as small as nanoscale. For a detailed
understanding of ionic conductivity of this compound, it isof great importance to examine lattice-to-lattice hopping
motion of Ag+ ions on an atomic scale. For that purpose, inthe present work, dynamic behavior of Ag+ ions has been
observed by means of the time-differential perturbed
angular correlation (TDPAC) technique using the probe of111
Cd( � 111Ag) nuclei. Here, preliminary results ofsuccessful observation of room-temperature dynamic
motion of Ag+ ions are reported.
II.

work, two different samples were prepared: PVP-free andPVP-coated. We confirmed by transmission electron
microscope that microscopic particles with sizes of 10-100
nm were expectedly synthesized for 111Ag-free PVP-coated
AgI.
TDPAC measurements of the 111Cd( � 111Ag) probe
were performed for both samples at various temperatures toobserve temperature dependence of the spectra.
III.

RESULTSFor the PVP-free AgI polycrystals, time variation was
not seen in the TDPAC spectrum at room temperature,
which suggests that the 111Cd(�111Ag) probe duly occupies
tetrahedral lattice site of Ag+ in zinc blende crystal
structure as in � phase. At high-temperature (> 419 K) �
phase, the TDPAC spectra showed an exponential
relaxation, signifying dynamic motion of the extranuclear
field relative to the probe nucleus.
As regards the PVP-coated AgI nanoparticles, on theother hand, typical dynamic perturbation was observed
even at room temperature as shown in Fig. 1. The
directional anisotropy of the spectrum shows a relaxation in
the time scale of 10-7 s, which corresponds to nuclear
relaxation time by the dynamic perturbation arising fromfast fluctuation of the extranuclear charge distribution,
namely, hopping motion of Ag+ ions. It is considered that
PVP-coating has made it possible for the � phase to survive
at room temperature, realizing superionic conductivity.
For the hopping rate of Ag+ ions, it is essential to obtainthe value of nuclear quadrupole frequency as they are stillat their lattice site. Experiments for the data acquisition are
now in progress.

EXPERIMENTS

For the production of the TDPAC probe, Pd foil was
irradiated by thermal neutrons in Kyoto University Reactor
to produce 111Pd. After radioequilibrium was achieved
between 111Pd and 111Ag, the Pd foil was dissolved in
HNO3 aq. solution, and carrier-free 111Ag was isolated byan anion exchange chromatography. The separated 111Ag
was incorporated together in AgI samples when the powder
sample was synthesized by precipitation. In the present－ 345 －

Fig. 1. TDPAC spectrum of 111Cd(� 111Ag) in PVP-coated AgI at
room temperature, where A22 stands for the angular correlation
coefficient and G22(t) the time-differential perturbation factor as afunction of the time interval of the cascade �-ray emission, t.
[1]

R. Makiura et al. Nature Mater. 8, 476 (2009).

25-AAP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

A prototype of a simple collection system for the determination of 14C
Tzu-Han Chuang, Tsuey-Lin Tsai, Hwa-Jou Wei, Lee-Chung Men
Chemistry Division, Institute of Nuclear Energy Research, Longtan, Taoyuan 32546, Taiwan, R.O.C.

Abstract
This study presents a simple and relatively costeffective system for sampling 14C in biologicalsamples or the radwaste from nuclear power plants.
The proposed system uses a CO2 absorption
technique to collect 14C. This technique involves
placing a sample in a quartz tube inside a furnace
in a flowing stream of oxygen, and then heating thetube to a minimum temperature of 3000C at heating
rate of 14 °C/min. In the combustion zone, CuO
catalytic oxidation ensures that any CO produced
from the incomplete combustion of the sample
carbon present in the gas stream is oxidized toform CO2. This process uses dilute sulfuric acid(5%) for steam absorption. The proposedcollection technique also provides a simple
procedure for subsequent sample preparation andactivity measurement using a liquid scintillation
counting When combined with several counting
vials, this trapping design can solve theovercapacity problem of carbon absorption foreach collector. The following sample pretreatment
also facilitates counting. This system achieves aminimum detectable activity level of 20 mBq/g foran l-g solid sample. This level of sensitivity isappropriate for the routine monitoring of radwaste
at nuclear facilities.
14
Keywords:
C;
CO2
absorption;
scintillation counting; radwaste

liquid－ 346 －

25-AAP-02

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Elemental analysis of Korean adult toenail using of instrumental
neutron activation analysis
Sun-Ha Kim1, Jong-Hwa Moon1, Yong-Sam Chung1, Ok-Hee Lee2

1

Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon, 305-353, Korea
Dept of Food Science and Nutrition, Yongin University, 470, Samga-dong, Cheoin-Gu, Yongin, 449-714, Korea

2

Abstract – The elemental contents in a toenail as a biologicalsample may depend on the dietary habit and health status. In thisstudy, the inorganic elements in Korean adult toenail were
determined by an instrumental neutron activation analysis (INAA).
Toenail samples were collected from Korean adults, and the total
number of samples was 50. The collected samples were pretreated
and analyzed using INAA facilities at the HANARO research
reactor. 15 elements, i.e., Al, As, Br, Ca, Cl, Co, Cr, Fe, Hg, K,
Mn, Na, Se, V, and Zn in the toenail samples were determined andevaluated for the level of elemental concentration. Finally,correlation between 15 elements was examined. It is found that
Mn-V, Na-Cl, Br-K, and Cr-Fe seem to be in close correlation.
Keywords–Instrumental Neutron Activation Analysis, Inorganic
Elements, Toenail, Elemental CorrelationI.

INTRODUCTION

Fig. 1. Mean elemental concentrations in toenail samples

The correlation between the 15 elements was examined
and Mn-V, Na-Cl, Br-K and Cr-Fe seem to be in close
correlation. Fig. 2 shows the Cr-Fe correlation.

The organic elements in a human organism such asserum, hair, nail, and internal organs are able to provide
valuable information to estimate the health status of thehuman body. The elemental contents in a toenail as a
biological sample may depend on the dietary habit andhealth status. In this study, the inorganic elements in a
Korean adult toenail were determined using instrumental
neutron activation analysis (INAA). For this purpose, theanalytical condition for INAA was established, and 15
elements were determined. Finally, correlation between theelements was examined.

Fig. 2. Correlation between Cr and Fe in toenail samples

II. EXPERIMENTALACKNOWLEDGEMENT

The toenail samples were collected from Korean adults,
and the total number of samples was 50. The collected
samples were pretreated by cutting, cleaning, andhomogenizing for INAA. The prepared samples were
irradiated using NAA #1 or #2 irradiation holes at the
HANARO research reactor. For the measurement of
gamma-rays of the detectable nuclides, a HPGe detector
coupled to a 16k-multichannel analyzer was used. The
elemental concentration in the samples was determined by
the absolute and/or relative method.

This work was carried out under the Nuclear Researchand Development Program of the Korean Ministry of
Education, Science, and Technology.
REFERENCES[1][2]

III. RESULTS
15 elements, i.e., Al, As, Br, Ca, Cl, Co, Cr, Fe, Hg, K,
Mn, Na, Se, V, and Zn in the toenail samples were
determined by INAA. The mean elemental concentration isshown in Fig. 1.

－ 347 －

Rita Mehra, Meenu Juneja: Fingernails as biological indices of metal
exposure, Journal of Bioscience 2005, 30(2):253-257.
World Health Organization (2006) Trace elements in humannutrition and health. Geneva, WHO, Belgium

25-AAP-03

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of Vanadium at ppb Levels in Relatively High-Salt
Biological Materials without Chemical Separation and using Neutron Activation
coupled to Compton Suppression Gamma-Ray Spectrometry
W. Zhang and A. Chatt
Trace Analysis Research Centre, Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3, Canada
III.

Abstract – APSORC’13 Abstract
Keywords – vanadium, INAA, Compton suppression, biologicalmaterials

I.

INTRODUCTION

The toxicity of V has been known for some time. It isonly recently that V has been recognized as an essentialtrace element. Its determination with high precision andaccuracy in tissues, foods and other biological materials isneeded. Techniques such as atomic absorption, X-ray
fluorescence, and neutron activation analysis (NAA) can beused for this purpose. Vanadium can be determined by
NAA through the interference-free 1434.2-keV gamma-rayof its short-lived (half-life of 3.74 min) nuclide 52V
produced via the 51������52V reaction. It has been reported
that 52V has sufficient sensitivity for its measurement down
to nanogram levels [1]. However, it is seldom assayed inpractice by instrumental NAA (INAA) in conjunction withconventional gamma-ray spectrometry (INAA-CONV), in
particular for low V content in relatively high-salt
biological materials, due to the Compton backgroundinterference from nuclides such as 28Al, 38Cl, 56Mn, and
24
Na. Preconcentration NAA (PNAA) and radiochemical
NAA (RNAA) methods are commonly used to separate V
from the major and interfering elements [2-3]. Compton
suppression spectrometry (CSS) counting technique can bealternatively used under such situations [4]. One of theobjectives of the present work was to fully explore theadvantages of INAA coupled to CSS (INAA-CSS) for thedetermination of low levels of V without any chemical
separation in biological materials in general, nutritional
materials in particular, containing varying amounts of
sodium chloride.

RESULTS AND DISCUSSION

The application of CSS can reduce the Compton
background under the 1434.2-keV peak, improve thestatistical accuracy of the peak and lower the detection
limit, if Cl and Na levels are not too high [4]. For example,
the V content of Wheat Flour (NIST SRM 1567a) was
determined by INAA-CSS as 9.0±2.9 ppb compared to the
Information value of 11 ppb; the detection limit was 1.8
ppb by INAA-CSS relative to 8.6 ppb by INAA-CONV. In
the case of Peach Leaves (NIST SRM 1547) our measured
value of 355±17 ppb agreed well with the certified value of
370±30 ppb; the detection limit of 13 ppb by INAA-CSS
was about 3 times lower than that of 34 ppb by INAACONV.
The overall background around the 1434.2-keV region
was reduced by a factor of 5 to 10 for several biological
RMs and SRMs in the Compton suppression counting
mode compared to conventional counting. Consequently,
the detection limits were lowered by factors of 3 to 5 in
INAA-CSS compared to INAA-CONV making rapid andreliable V determinations possible above 1.5 ppb levels
without any chemical separation. The agreement between
the certified (information) and measured values for the RM
and SRM analyzed in this work was generally within ±10%.
References[1]

A.J. Blotcky, F.G. Hamel, A, Stranik, A. Ebrahim, and R.B. Sharma,
J. Radioanal. Nucl. Chem., Articles, 131(1989)319-329.
[2] A.J. Blotcky, W.C. Duckworth, and A. Ebrahim, J. Radioanal. Nucl.
Chem., Aritcles, 134(1989)151-160.
[3] A.I. Kulathilake, A. Chatt, Trans. Am. Nucl. Soc., 65(1992)172.
[4] W. Zhang, Ph.D. Thesis, Dalhousie University, Halifax, NS,
Canada,1997.

II. EXPERIMENTAL
A total of 16 biological reference material (RM) andstandard reference material (SRM) containing 1.4 to 1100
ppb V with low to high levels of sodium chloride wereanalyzed by INAA-CSS. Between 200 and 700 mg ofthese materials were irradiated in the Dalhousie University
SLOWPOKE-2 Reactor facility at a neutron flux of 5×1011
cm-2 s-1 for 1 min, allowed to decay for 1 min, and counted
for 10 min. The average sensitivity for V standard
solutions under these conditions was 5025 counts ��-1 in
the Compton suppression counting mode. The CSS usedhere consisted of a HPGe detector and a 10"x10" NaI(Tl)guard detector with a 3"x3" NaI(Tl) plug. The peak-toCompton plateau ratio of this system was about 590:1.
－ 348 －

25-AAP-04

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Radiochemical neutron activation analysis of halogens (Cl, Br and I) in geologicaland cosmochemical samples
Mitsuru Ebihara1 and Shun Sekimoto2
1

Tokyo Metropolitan University
Kyoto University Research Reactor Institute

2

I.

INTRODUCTION

Accurate and reliable data of halogen abundance havebeen rarely reported for terrestrial samples, such as crustalrock and mantle material. Since halogens differ in volatility
from element to element, their content and relative
abundance are highly informative when discussing thepetrogenesis of such samples. Among the halogens, iodine
is the most informative element in discussion of thegeochemical circulation of crustal materials (oceanic crustand continental crust) and mantle. Halogens are also
important in meteorite samples, and in particular, iodine isof particular interest and of high importance in discussionsof the cosmochemical behavior of its extinct nuclide 129I
(half-life of 15.7 million years) in the early solar system.
However, the scarcity of halogen data for meteorite
samples is more worrying.
There is a shortage of accurate and reliable data of
halogens in meteorites, as well as in terrestrial rock samples,
as can be witnessed in the data libraries, where only
preferable, not certified values, and for some rocks, novalues are listed. This deficit must be largely related todifficulties in determining trace amounts of halogens withinthese samples. To determine trace halogens in rock samples,
either inductively coupled plasma mass spectrometry (ICPMS) or neutron activation analysis (NAA) have commonly
been utilized. Bromine and iodine are conventionallydetermined by ICP-MS after using pyrohydrolysis of rockpowder, but neither fluorine nor chlorine can be reliably
determined by this method. In principle, four halogens canbe determined using NAA. However, only three halogens(chorine, bromine, and iodine) have been routinely
determined by NAA with radiochemical purification.1
In this study, trace three halogens (chlorine, bromine,
and iodine) were determined by radiochemical NAA(RNAA) for geological and cosmmochemical powder
samples. Similar studies have been conducted for many
years by a senior author of this paper and his colleagues
with use of different types of reactors. Now that the Kyoto
University reactor (KUR) is currently the only research
reactor running in Japan, we initiated to perform RNAA of
three halogens by using KUR. Our first goal was to present
a modified radiochemical procedure for RNAA of three
heavy halogens, which was to be more effective andconvenient compared with the previous one. A part of ouroutcomes will be published soon.2 In this paper, wedemonstrated that RNAA data for bromine and iodine are
more reliable and accurate than the data obtained by ICPMS coupled with pyrohydrolysis preconcentration. Anothergoal was to apply our RNAA procedure to geological andcosmochemical samples for discussing geochemical andcosmochemical implications based on the analytical data
for such samples. A part of the progress related to this goalis presented here.
II. EXPERIMENTAL
Both geological rocks (mantle xenoliths) andcomochemical samples (Antarctic meteorites) wereanalyzed, along with several geological reference rockpowders. Approximately 100 mg of each powder sample
was weighed, inserted into a clean, small plastic vial.
Chemical standard solutions of the three halogens wereprepared for their quantifications. An appropriate amountof each solution was dropped onto a paper disk (17 mm �),
weighed, dried under a heat lamp and doubly sealed intopolyethylene bags. Two rock samples, together with a setof three reference halogen samples, were irradiated for 10
min with a thermal neutron flux of 3.3 x1012 n/cm2/s at
Kyoto University Research Reactor Institute. After
irradiation, the rock samples were cooled for a few minutes
to enable the decay of 28Al, and were then subjected toradiochemical separation of neutron-induced radionuclidesof 38Cl, 82Br, and 128I. We basically followed theradiochemical procedure for RNAA of three heavy
halogens, as described by Ozaki and Ebihara,3 and others
cited within this paper. Chemical yields were determinedby reactivation method.
III. RESULTS AND DISCUSSION
Our RNAA procedure was applied to several rocksamples in powder. In addition, the Smithsonian Institution
Allende meteorite powder sample, which has been
repeatedly analyzed for many years, was also analyzed as acontrol sample. Our present data are consistent with theprecious results. RNAA results of halogens for the
Antarctic meteorite recovered from the Ice were comparedwith those for meteorites recovered from the bare ice field
and a similar enrichment was observed for both of them,suggesting that halogens were added during the storage in
Antarctic ice.
Reference: [1] Ebihara M. et al. (1997) JRNC, 216, 107112. [2] Sekimoto S. and Ebihara M. (2013) Anal. Chem,in press. [3] Ozaki H. and Ebihara M. (2007) Ana. Chim.
Acta, 583, 384.

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25-AAP-05

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Multielement analysis of KIGAM reference samples by INAA, ICP-AES and ICPMS
Naoki Shirai1, Meiramkhan Toktaganov2, Hiroki Takahashi1, Yuta Yokozuka1, Shun Sekimoto3,
Mitsuru Ebihara1
1

Tokyo Metropolitan University
National Nuclear Center Republic of Kazakhstan Institute of Atomic Energy
3
Kyoto University Research Reactor Institute

2

I.

INTRODUCTION

III. RESULTS AND DISCUSSION

Bulk chemical compositions of geochemical andcosmochemcial materials provide us the information ofevolution processes and magmatism of planetary bodies.
Instrumental neutron activation analysis (INAA),
inductively coupled plasma mass spectrometry (ICP-MS)and X-ray fluorescence (XRF) have been used for thedetermination of bulk chemical compositions of thesesamples. For these analytical methods, reference materials
are used as standard samples. Therefore, the quality ofanalytical data depends on accuracy and precision of suchreference materials. Many kinds of reference materials
having a wide range of chemical compositions wereprepared and distributed by different institutions. Korean
Institute of Geology, Mining and Materials (KIGAM)
issued geological reference materials. However, the numberof published values is very limited [1] and recommended
values are not established. In this study, we aimed todetermine chemical compositions for KIGAM referencematerials by using three analytical methods.

About 40 elements were determined by INAA, ICP-MSand ICP-AES for each reference sample. Figure 1 shows
CI-chondrite normalized REE abundance patterns for KB-1
and KGB-1. INAA and ICP-MS data are in good agreementwith each other for comparable elements. REE abundances
patterns for KB-1 and KGB-1 obtained by Sakamoto et al.
[1] show small zigzag patterns in middle REEs, while ourabundances patterns are smooth. CI-normalized REEs
abundances patterns for KB-1 and KGB-1 are very close toeach other and similar to those for continental crustal
materials.

II. EXPERIMENTAL
Eleven KIGAM reference materials (KB-1, KGB-1, KD1, KT-1, KF-1, KF-2, KP-1, KP-2, KP-3, KG-1 and KG-2)
were analyzed. In addition, JB-2 published by GSJ was
analyzed as control sample. In INAA, samples were
irradiated two times with different irradiation periods
which are adjusted for half lives of nuclides usable fordetermining elements. Samples weighing about 0.04 g were
irradiated for 10s at a neutron flux of 4.6 x 1012 cm-2s-1 at
Kyoto University Research Reactor Institute (KURRI) andwere immediately measured for their emitting gamma ray.
The samples were reirradiated for 4 hrs at a neutron flux of
5.6 x 1012 cm-2s-1 at KURRI. After irradiation, samples
were measured for gamma rays several times with different
cooling intervals at KURRI and the RI Research Center ofTokyo Metropolitan University. ICP-AES and ICP-MS
were used for determination of major and minor elements,
and rare earth elements (REEs), Th and U, respectively.
Samples were digested with HF, HNO3 and HClO4.
Dissolved samples were dried and redissolved in HNO3. Byusing a 10 % aliquot sample solution, REEs, Th and U
abundances were determined by ICP-MS. Remaining
sample solutions were used for determination of major andminor elements by using ICP-AES.

Reference: [1] Sakamoto K. et al. (1997) J. Radioanal. Nucl.
Chem., 215 (1), 69-76.

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25-AAP-06

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Comparison of Calculated Results with NTD Measured Data for Establishment of
Burned Core Model for Monte Carlo Simulation of HANARO Reactor
Dong-Keun Cho and Myong-Seop Kim

Korea Atomic Energy Research Institute, Dukjin-dong 150, Yuseong, Daejeon 305-353, Republic of Korea
Keywords – Monte Carlo Simulation, MCNP, Research Reactor

HANARO is a multipurpose research reactor operated formaterial testing, production of key radioisotopes, neutron
activation analysis of nuclear-grade materials, and neutron
radiography. To support various researches, HANARO has
a very heterogeneous configuration with 25 verticalirradiation thimbles and seven horizontal beam tubes.
Although the reactor core is predicted by HANARO coremanagement system, called HANAFMS, equipped withWIMS and VENTURE, heterogeneity of the core andnewly installed device for specific experiment makes theneutronic analysis difficult and sometimes doubtable. To
resolve these limitations, MCNP has been utilized forneutron transport calculation in the HANARO reactor.
For HANARO, MCNP core model filled with fresh fuels
has been used to support the experiments in addition to
HANAFMS. And, the model has supplied acceptable
analysis results for a design of experimental devices andfacilities. However, it is definite that burned core model
can provide better result than that obtained from the coremodel with fresh fuels. In this study, MCNP burned coremodel was established and then its viability wasinvestigated through comparison of calculated result fromthe burned core model and measurement data from neutrontransmutation doping (NTD) for producing silicon
semiconductor.
Burned full-core model for MCNP simulation wasestablished by using the data generated by WIMS and
VENTURE codes. Brunup-dependent number density wascalculated for each rod for each fuel assembly by WIMS toassign appropriate isotopic number density to each regionof irradiated fuel of the core. The power and burnup of eachregion of fuel region were calculated by VENTURE for theequilibrium core of HANARO. Based on the burnupdependent number density library calculated by WIMS, thenumber densities of major nuclides corresponding to theburnup of each region were assigned to each region of theirradiated fuel of MCNP model.
HANARO has two vertical holes in the heavy waterreflector tank for the NTD- NTD1 and NTD2 holes having
diameters of 22 and 18cm respectively. Because these twoholes showed excellent conditions for NTD in the aspectsof high thermal neutron flux and large hole size, and low
fast neutron flux and gamma heating, commercial service
for a 5 in., silicon ingot has been provided to produce
silicon semiconductor at NTD hole. And measurement wasalso performed to check radial and axial uniformity ofneutron irradiation in silicon ingots.
The actual irradiation geometry for silicon ingots as wereused for the experiment were described almost exactly in
the MCNP burned core model. Absolute and relative
neutron flux distributions along radial and axial direction of
the ingots for NTD were calculated by using MCNP burned
core model. The neutron flux was averaged over each ringradially divided with the same thickness from the center ofingots. The reason why the calculated neutron fluxes wereaveraged azimuthally is to consider the rotation of the ingot
during irradiation to obtain low RRG (radial resistivity
gradient). Three axial positions of a silicon ingot - the top,bottom, and middle planes – were obtained as well. The
longitudinal length of each plane was 2 cm.
Finally, these calculated data were compared with thosefrom the measured data for silicon ingots for neutrontransmutation doping carried out at NTD-1 and NTD-2
irradiation holes of HANARO research reactor.
1. M.S. Kim, et al., “Radial Uniformity of Neutron
Irradiation in Silicon Ingots for Neutron Transmutation
Doping at HANARO,” Nuclear Engineering andTechnology, 38(1). 2006.

－ 351 －

25-AAP-07

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Neutron Activation Analysis of JCFA-1, JCu-1 and JZn-1
Shun Sekimoto1, Yuta Homura1, Ryo Okumura1, Naoki Shirai2
1

Kyoto University Research Reactor Institute2
Tokyo Metropolitan University

Abstract – We present NAA results of JCFA-1, JCu-1 and JZn-1
reference samples prepared by GSJ. Through NAA of those threereference samples, appropriate reference samples forquantification by INAA are discussed. We also report fundamental
property of each irradiation port, such as neutron fluence rate, at
Kyoto University Reactor after renewal of the reactor fuel.
Keywords – JCFA-1; JCu-1; JZn-1; Neutron activation analysis;
Kyoto University Reactor; GSJ reference sample

I.

INTRODUCTION

Geological Survey of Japan (GSJ) has prepared various
kinds of geochemical reference materials [1]. In the most of
igneous rock samples and sedimentary rock samples, theirchemical compositions are presented as the certified values
through compilation of a lot of data [2, 3]. In several
reference samples, however, certified values have not been
given yet, and provisional, recommended, or information
values are given, and then multielement analysis by neutron
activation analysis (NAA) has never been performed. In
this work, the first NAA results of a coal fly ash reference
sample (JCFA-1) and ore reference samples (JCu-1 andJZn-1), where certified values have never been given, arereported and compared to the literature data obtained byatomic absorption spectrometry (AAS), inductively coupledplasma-atomic emission spectrometry (ICP-AES), etc. [4,5] Through NAA of the above three reference samples, weinvestigate appropriate reference monitor samples forquantification by INAA. The characteristics of the NAA
systems using Kyoto University Reactor (KUR) after the
furl conversion to low-enriched uranium intend to bepresented.
II. EXPERIMENTAL
A. Sample preparation
Three reference samples analyzed in this work are
JCFA-1 as coal fly ash, JCu-1 as copper ore, and JZn-1 aszinc ore, which were prepared by GSJ and werecommercially distributed [4-5]. As reference monitor
samples for quantifications by NAA, JA-1 (andesite), JB1b (basalt), JG-1 (granite), and JP-1 (peridotite) are also
prepared [2]. All the samples were in powder, and were notsubjected to any additional treatment such as drying.
Approximately 100 mg of each powder sample wasweighed, doubly sealed into clean polyethylene bags.
B. Neutron irradiation

irradiation, the outer bag of the sample was replaced by a
new one and then the sample was immediately subjected to
gamma-ray spectrometry for measurement of short half-life
nuclides: 28Al, 52V, 49Ca, 27Mg, etc. Next the three reference
samples together with all reference monitor samples wereplaced in one capsule and irradiated for 4 h at Pn-2. After 4
h irradiation, samples whose outer bags were also replacedin a similar manner as 10 s irradiation were subjected to
gamma-ray spectrometry for measurements of long half-life
nuclides: 59Fe, 60Co, etc.
C. Kyoto University Reactor
Kyoto University Reactor (KUR), a 5 MW research
reactor in Japan, has worked as the central place to support
the university researchers using NAA for their analyticalstudies. After four-year shutdown period for fuelconversion to low-enriched uranium fuel, KUR restarted in
May 2010, and thereby a new inter-university research
project using NAA system at KUR also restarted. During
this renewal of the reactor fuel, the control system of thepneumatic irradiation system was refurbished to digitalcontrol type. This improvement has been introduced
elsewhere [6] and operated well after KUR restarted. To
promote this inter-university research project successfully,
fundamental properties of the irradiation sites, such as
neutron fluence rate, cadmium ratio of gold, andtemperature inner capsules during neutron irradiation ateach pneumatic irradiation system used for NAA are shownin the presentation.
III. RESULTS AND DISCUSSION
Elemental contents of the three reference samples
measured by NAA are reported. Among four referencemonitor samples (JA-1, JB-1b, JG-1 and JP-1),
inconsistencies in the activities of radionuclides producedby (n,�) reaction per amounts of their corresponding
elements was found in several elements determined.
Through NAA of the three reference samples, we also
investigate which reference sample is suitable or not foreach element determined.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]

First, each sample was irradiated one by one for 10 s atpneumatic transport system No. 3 (Pn-3). After the 10 s
－ 352 －

http://riodb02.ibase.aist.go.jp/geostand/welcome.html
N. Imai et al., Geochem. J. 1995, 29, 91-95
N. Imai et al., Geostand. Newslett. 1996, 20, 165–216.
S. Terashima et al., Geostand. Newslett. 1998, 22, 113-117.
S. Terashima et al., Geostand. Newslett. 2003, 27, 259-271.
K. Takamiya et al., J. Radioanal. Nucl. Chem. 2008, 278, 719-721.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-AAP-08

Prompt Gamma-ray Analysis of Chloride Concentration in Blended Cement Concretes
1

A. A. Naqvi1*, M. Maslehuddin2, O.S.B. Al-Amoudi3, Khateeb-ur-Rehman1 and M. Raashid1

Department of Physics, 2Center for Engineering Research, and 3Department of Civil and Environmental Engineering
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia

Abstract – The chloride concentration in plain and blast furnace
slag cement concrete has been measured using a D-D portableneutron generator.. The setup has been used to measure chloride
concentration in specimens using chlorine prompt gamma-rays
with different energies. Out of several chlorine gamma ray data, an optimum and aunique chlorine gamma-ray line has been chosen for the detectionof chloride in all the blended cement concretes specimen
including fly ash, blast furnace slag and superpozz cement
concrete utilizing the portable neutron generator-based PGNAA
setup

Keywords – Chloride detection, blended concrete
specimen, BGO detector , Portable D-D neutron generator
based PGNAA setup, Monte Carlo simulations,I.

INTRODUCTION

Industrial by-products, such as fly ash, silica fume and blast
furnace slag, are added to concrete, as partial replacementof cement, to increase its denseness and impermeability.
The increased impermeability of blended cement concretes
decreases the rate of diffusion of chloride ions to the steel
surface. Since reinforcement corrosion is predominantly
attributed to the presence of chloride ions at the steel
surface, a non-destructive technique is required to assess
the level of chloride concentration in concrete. A portableneutron generator-based prompt Gamma-ray Neutron
Activation setup has been designed by the authors tomeasure the chloride concentration in plain and blended
concretes using a cylindrical 100 mm x 100 mm (diameterx height) BGO detector.

The setup has been used to measure chloride concentrationin fly ash and blast furnace slag cement concrete specimens
using chlorine prompt gamma-rays with different energies.
An excellent agreement has been observed between thechlorine prompt gamma-ray experimental yield and thecalculated values obtained through Monte Carlosimulations. The optimum choice of unique chlorine
gamma-ray line for the detection of chloride in the blended
cement concretes utilizing the portable neutron generatorbased PGNAA setup data taken in present study and earlier[1,2] is presented.
[1]

[2]

－ 353 －

Naqvi, A. A., Zameer Kalakada, Faris A. Al-Matouq, M.
Maslehuddin and O.S.B. Al-Amoudi. Prompt Gamma-Ray Analysis
of Chlorine in Superpozz Cement Concrete .Nuclear Inst. andMethods in Physics Research, A Vol. 693 (November 2012), pp. 6773
Naqvi, A. A., Zameer Kalakada, Faris A. Al-Matouq, M.
Maslehuddin and O.S.B. Al-Amoudi. Chlorine Detection in Fly Ash
Concrete using a Portable Neutron Generator. Applied Radiation and
Isotopes Vol70(2012) pp.1671-4.

25-AAP-09

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Cold Neutron and Thermal Neutron PGAA facilities
at The HANARO Research Reactor
G.M. Sun1, E.J. Lee1, B.G. Park1, J.H. Moon1

1

Neutron Utilization Technology Division, Korea Atomic Energy Research Institute, 305-353, Korea

A new cold neutron prompt gamma activation analysis facility has
been developed at a cold neutron source of the HANARO research
reactor and be prepared to open to users until the end of
2013.The performance tests were carried out and compared withan old thermal neutron facility. The neutron beam characteristics
such as neutron flux, spatial distribution and energy spectrum
were investigated and a background was also studied in detail.
The measurements for the standard reference material provide
the performance of the new facility and comparison with the oldthermal neutron facility
Keywords –cold neutron, thermal neutron, prompt gamma
activation analysis, HANAROI.

INTRODUCTION

Prompt gamma-ray activation analysis (PGAA) is basedon the radiative neutron capture, which has been considered
to be a complementary method to the conventional
instrumental neutron activation analysis though in principle
it can analyze almost elements in the elemental table. If a
guided cold neutron beam with a relatively low backgroundcan provide a possibility that a PGAA itself becomes acomplete elemental analysis tools. We operated a thermal
neutron PGAA (SNU-KAERI PGAA) [1] on the horizontal
ST1 beam line of the HANARO research reactor and newly
developed a cold neutron PGAA (CN-PGAA) on the CG2B
cold neutron guide from a cold neutron source. Figure 1
shows a SNU-KAERI PGAA facility, which was developedby a group from Seoul National University, has a neutron
flux of 1x108 n/cm2s and detection limit for boron
elemental of about 60 ng. Figure 2 shows a new CN-PGAA
facility. Neutron guide after the end of the guide to asample position is normally made of aluminum but Teflon
chopper and The Teflon tube has a length of 100 cm and adouble-layer structure and the space between double layers

is introduced as material for the flight tube between disk
chopper and is filled with 95% enriched 6Li2CO3 powder,whose thickness is 1 cm. Lithium layer catches neutrons
scattered out from the path. Neutron beam is shaped with a
6
LiF beam cutter to have a reactangular shape of 2 cm x 2
cm. We investigated neutron characteristics such a neutron
flux and its spatial distribution by using a gold foil
activation method and neutron energy spectrum by using atime-of flight method. True integrated neutron flux a thesample position is a about 5x108 n/cm2s. The total beamcharacteristics of the CN-PGAA were compared with thatof the SNU-KAERI PGAA and background wasinvestigated in detail.

Figure 2. Cold Neutron Activation Station, where a cold neutron PGAA
(CN-PGAA) was installed.
[1]

[2]

Figure 1. Thermal neutron PGAA (SNU-KAERI) facility at the ST1
horizontal beam line of the HANARO research reactor.

－ 354 －

S.H. Byun, G.M. Sun and H.D. Choi, "Development of a Prompt
Gamma Activation Analysis Facility Using Diffracted
Polychromatic Neutron Beam", Nuclear Instruments and Methods inPhysics Research A, Vol. 487, (2002), pp. 521 ~ 529.
G.M. Sun, “Development of HANARO Cold Neutron Activation
Station”, 2012 Asia-Pacific Winter Conference on plasma
spectrochemistry, Jeju, Aug. 2012.

25-AAP-10

��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Exposing dogs to uranium contained in commercial diets
Camila Elias,1 Elisabete A. De Nadai Fernandes,1 Márcio A. Bacchi,1 Peter Bode2
1. University of São Paulo, Nuclear Energy Center for Agriculture, P.O. Box 96, 13400-970 Piracicaba, SP, Brazil
2. Reactor Institute Delft, Delft University of Technology, Mekelweg 15, 2629 JB, Delft, The Netherlands
Abstract

III. RESULTS AND DISCUSSION
The presence of uranium in dry dog food samples wasinvestigated by instrumental neutron activation analysis (INAA).
Some commercial brands showed uranium concentration as highas 4 mg kg-1, which may lead to chronic exposure of dogs to alevel about a thousand higher than the normal ingestion level forhumans according to the US-EPA.
Keywords � Food safety, dog food, INAAI.

INTRODUCTION

Dry dog food is intended to be a complete andbalanced diet and may be the unique source feeding theanimal in all stages of life. Therefore, it is extremely
important to choose a product capable of providing optimal
nutrition, with all necessary substances at adequate levels
and free of contaminants, for promoting long-term health.
The safety of dog diets has recently received
increasing attention since the contamination with melaminecaused the death of several animals and a major recall ofpet food in the United States. In fact, the use of low quality
ingredients in the pet food composition can introduce
residues of pesticides, mycotoxins, hazard chemicalelements and other toxic substances. Products derived from
phosphate rocks, as dicalcium phosphate (DCP), normallyused as feed additives to supplement phosphorus may havehigh concentrations of uranium [1].
Experiments with dogs, rabbits and rats havedemonstrated that the animals are sensitive to both
inhalation and oral exposure to uranium compounds.
Uranium accumulates mainly in the bones, kidneys andliver, and presents both chemical and radiological toxicity.
The overexposure to uranium may cause pathologicalalterations to the kidneys, leading in extreme cases to renal
failure. In this context, this work investigated the presenceof uranium in several commercial brands of dry dog foods
produced in Brazil.
II. EXPERIMENTAL
For this work, 61 dry dog food samples of 37 different
commercial brands, including food for puppies and adults,
were purchased in the local market of Piracicaba, SP,
Brazil. After homogenization, a 300 g subsample of eachdog food package of 1 kg was reduced in a knife mill for
analysis by INAA. For analytical quality control, certified
reference materials were used. Test portions of 200 mg
were inserted in polyethylene vials and irradiated in the
nuclear research reactor IEA-R1 of IPEN/CNEN at athermal neutron flux of 7x1012 cm-2 s-1 for 4 h. Element
concentrations and expanded uncertainties were calculatedby the k0-method, using the software package Quantu [2].

����� ������ ��� ��� �������� ���� ��� ��� ������� ��������
������������������������� ����������������������� ���������
����� ������� �������� ����� ����� �������� ��� ��������������
������������������������������������������ ���� ���������
���� �������� ������� ���� ����������� ���� ���������������
������������ ������������� ���� �������� ������� ���������������������������������������������������������
������������������������������������������������������
�����������������
�������� ����� ��������� ��� ������� ��������� ��� ��������������������������������������������������������
�������������������������������������������������������
�������� �������� ���� �������� ����� ����� �������� ��������������������������������������������������������������
����� ������������� ��� ���� ������ ������ ���� ������������� �����������������
�
Table 1. Uranium concentration (mg kg-1) in dry dog foods compared withresults published in previous work [3].�
This study

Previous work

Min

0.24

0.46

Max

3.61

3.99

Median0.91

0.70

Average

1.49

1.36

Stdev (%)

81

85

N

14

13

�

��� �������� ����������� ������ ���� ������ ������������ ��� ���� ������ �������� ���� ������������ ��������
������ �������� ���� �� ����� ������ �������� ������ ����������
���������� ��� ��� �������������� ����������� �������
���������������������������������������������������������
����������������������������������������������������������� ���� ��� ��� ��� ����� ��������� ������ ���� �� ��� ���� �����
�������������������������������������������������������
������������������������������������������������������
�����������������REFERENCES

[1]
[2]
[3]
[4]

－ 355 －

Casacuberta N, Masquéa P, Garcia-Orellana J, Bruach J M, Anguita
M, Gasa J, Villa M, Hurtado S, Garcia-Tenorio R (2009) J. Hazard.
Mater. 170: 814-823.
Bacchi M A, Fernandes E A N (2003) J. Radioanal. Nucl. Chem.
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Elias C, Fernandes E A N, Bacchi M A (2012) J. Radioanal. Nucl.
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United States Environmental Protection Agency (2010)
Understanding
radiation
in
your
life,
your
world.
http://www.epa.gov/radiation/radionuclides/uranium.html.

��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Authors Index
A
Åberg
S.
NCO-07Abraham P.
25-ENP-14
Ackermann D.
NCO-07Adachi K.
25-FKP-08
Aguilar E
23-APP-03
Aitken D.
23-ACP-01
Akabori M.
ACO-02
Akata
N.
23-ENP-06, 23-FKP-03
Akimune N.
24-ENP-03
Akiyama K.
24-APP-04, 24-APP-07
Al-Amoudi O. S. B. 24-AAP-08, 25-AAP-08
Aliev Ramiz A.
25-RPP-02
AllardS.
23-ACP-04
Amano R.
25-RPP-01
Andersson
L.-L.
NCO-07
Andrieu C.
23-APP-04
Aneheim E.
NEO-01 RPO-01 24-NEP-03
AnsoborloE.
EDI-01Anton
J.
23-NCP-10
Anvia
M.
APO-03
Aono
T.
ENO-12, 23-FKP-21, 25-FKP-05
Aoshima H.
24-APP-07
Aoyagi N.
ACO-04 25-ACP-03
Aoyama M.
FKI-03, 23-FKP-23, 24-FKP-12
24-FKP-14
Arai
M.
23-APP-07
AraiY.
24-AAP-06
Arisaka M.
NEO-05, 24-FKP-05, 25-NEP-04
Arporn B.
AAO-01Asai
M.
NCO-09, NCO-12, NCO-13,
RPO-02, 24-NCP-09, 25-NCP-03,
25-NCP-08, 25-NCP-09, 25-NCP-10
Asai
Miyuki NEO-05, 24-FKP-05
Asano
A.
24-NCP-06
Atarashi-Andoh M. 25-ENP-08
Augustín J.
24-NEP-02
Awaludin R.
23-NCP-02

B
Bae
S.-E.
ACO-03Bagla
H. K.
23-ENP-02
Bai
J.
NCO-01
BalkinE. R.
RPI-01
Bacchi M. A.
25-AAP-10
Behe
M.
23-RPP-02
Bernhard G.
ENO-05Bessho K.
24-ENP-03
Bi
J.
23-APP-01, 24-ENP-02
Bilewicz A.
23-RPP-05
Bjugren J. M.
23-NCP-04
Block
M.
NCO-07
Bode
P.
25-AAP-10
Bogulski Z.
23-RPP-01
Bojanowska-Czajka A.

Bond
E. M.
Braatz
A.
Brand
H.
Breen
J.
Bremen K. vonBrendler V.
Brennetot R.
Brown S. A.
Brown T. A.
Bu
W.
Buesseler K.
Bunka
M.
Burbery L.
Burton-Pye B. P.
Buttigieg C.

24-NEP-04
NFO-03NEO-04
NCO-07, NCO-09
23-ENP-17
23-FKP-18
ENI-0123-APP-04
APO-03
NFO-02
ENO-12, 23-FKP-21
FKO-0623-RPP-02
25-ENP-14
NEO-0323-RPP-01

C
CaffeeM. W.
Camargo C.
Carlsson B.G.
Caussignac C.
Chai
Z.-F.
Chajduk E.
Chatt
A.
Chen
R.
Chen
Y.
Chen
Z.Y.
Chen
Zi
Chiba
K.
Chiba
KoichiChieraN. M.
Chikuchi Y.
Childs
B. C.
Cho
D.-K.
Cho
Y.-H.
Choi
G.-S.
Choi
Y. S.
Chuang T.-H.
Chung
D.-Y.
Chung
K.-H.
Chung
Y. H.
Chung
Y.-S.
Chyan
M.-K.
Clark
S. B.
Close
M.
Colin-Garcia M.
Coppo
M.
Cox
D.
�uba
V.
Czerwinski K. R.

25-NCP-04
23-APP-03
NCO-07
APO-04API-02, EDI-02, NEI-01,23-ACP-06
24-NEP-01
23-RPP-05, 24-NEP-05
AAI-01, AAO-04, 25-AAP-03
NEO-05, 24-FKP-05, 25-NEP-04
24-APP-03
ENO-0125-NCP-12
24-APP-04
24-ENP-06
23-NCP-05
23-ENP-06
24-ENP-07, 25-ENP-05
25-AAP-06
ACO-0324-ENP-16
ACO-0325-AAP-01
25-ACP-02
23-ENP-15, 24-ENP-16
23-RPP-06, 24-NCP-02, 25-EDP-01
24-AAP-04, 25-AAP-02
RPI-01
PL-07
25-ENP-14
24-APP-01
APO-04
NCO-07
EDI-01
NCO-02, NEO-03, 24-ENP-07,
24-NCP-04, 25-NCP-13,25-ENP-05

D
DaileyA. R.
Dararutana P.

－ 357 －

NFO-0323-APP-09

��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Dastegeer M.
de Souza P.
Degros J.P.
Denden I.
Denecke M. A.
Derkx
X.
Despotopulos J. D.
Dmitriev S.
DorrerH.
Dote
H.
Dressler R.
Düllmann Ch.E.
Dvorakova Z.
���������� R. S.

23-APP-02
NPO-01, 23-ENP-17, 24-APP-06
NCO-04NEO-03PL-05
NCO-07
APO-06, NFO-02
NCI-01
23-RPP-02
NPO-03, 24-APP-05
NCO-14
NCI-02, NCO-07, NCO-09
23-FKP-18
HMA-01

Fujimura S.
FujitaH.
Fujiwara M.
Fujiwara T.
Fukuda K.
Fukuda M.
Fukuda S.
Fukushima C.
Fukushima M.
Fukutani S.
Funabashi T.
Furukawa J.
Furusawa Y.
FurutaE.
Furutaka K.

NCO-07
AAO-02, AAO-05, FKO-09,
24-AAP-07, 25-FKP-10,25-AAP-05
25-AAP-04
24-APP-06
25-ACP-01
NCO-09, NCO-11, NCO-14,
23-NCP-05, 23-NCP-09
EDI-01, NEO-01, 23-ACP-04
24-NEP-03
NEO-0125-AAP-10
25-FKP-09
25-NPP-04
23-NCP-04
25-RPP-02
NFO-01, 25-NFP-01
NCO-10
EDI-01
NCO-07 NCO-09

G

E
Eberhardt K.
Ebihara M.
Egg
Eguchi
EichlerM.
M.
R.

EkbergC.

Elfversson H.
Elias
C.
Endo
K.
Enomoto M.
Eriksson J.
Ermolaev S. V.
Esaka
F.
Esker
N. E.
Evans
N.
Even
J.

F
Fahlander C.
NCO-07
Fan
F.-L.
NCO-01Fan
F.-Y.
NCO-01Fan
Q.
FKI-02, 23-ENP-09
FangliF.
NCO-09Fattahi M.
NEO-03Fernandes E. A. D. N.
25-AAP-10
Ferrier M.
NEO-03FichetP.
APO-04, NCO-04
Foerstendorf H.
ENI-01
Forsberg U.
NCO-07
Forster P. M.
NCO-02, 24-NCP-04,25-NCP-13
Francesconi L. C. NEO-03
Fujihara K.
24-NCP-05
Fujii
A.
24-FKP-18
Fujii
T.
24-FKP-11, 25-ACP-04,25-FKP-01
25-NCP-02
Fujimoto K.
24-ENP-13

Gäggeler H.W.
Gates
J. M.
Gautier C.
GerlJ.
German C.
German K. E.
Gharibyan N.
Golubev P.
Gondal M. A.
GosticJ. M.
Goswami A.
Gothe
O. R.
Goto
K.
Goto
N.
Goto
S.
Goutelard F.
Grahek ��Grambow B.
Gregorich K. E.
Gross
C.J.
Gückel K.
Gunawan A. H.
Guo
L.
Guo
N.
Guo
Q.
Guo

Z. J.

GütlichP.

23-FKP-05, 23-FKP-20
23-FKP-13
24-FKP-10
FKO-0224-FKP-22
25-RPP-04
FKO-14NEO-05, 24-FKP-05
AAO-0425-NCP-02, 25-FKP-01, 24-FKP-11
FKO-1223-FKP-01
24-ENP-13
24-AAP-03
AAO-02
ENO-09, 23-NCP-01
NCO-07, NCO-10
NCO-04, APO-04
NCO-07
FKO-06NEO-03
APO-06, NFO-02
NCO-0723-APP-02
NFO-02
NEI-02
NCO-1023-FKP-04
25-NCP-05, 23-NCP-03
23-NCP-03, 24-NCP-07, 25-NCP-05
25-NCP-07
APO-04, NCO-04, 23-APP-04
ENO-13, 23-ENP-01
FKI-04
NCO-07, NCO-10
NCO-07
ENI-0123-NCP-02
23-ENP-16, 24-ENP-04
23-ENP-12
ENO-12, 23-FKP-21, 23-ENP-05
23-ENP-16, 24-ENP-04, 24-ENP-05
25-ENP-03, 25-ENP-04
ENO-01, 23-ACP-08, 23-ENP-12
23-ENP-13
24-APP-06

H
Ha
Ha
Haba

－ 358 －

Y.-K.
Y.-G.
H.

NCO-03
ENO-11
NCI-03, NCO-09, NCO-13
23-NCP-03, 23-NCP-06, 23-NCP-07
24-APP-08, 24-NCP-07, 24-NCP-09
25-NCP-03, 25-NCP-05, 25-NCP-06
25-NCP-08, 25-NCP-09��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Haga
M.
Hagiwara M.
Hakuta Y.
Halldin N.
Halleröd J.
Hamajima Y.

AAO-0425-NCP-04
FKO-1323-NCP-04
23-NCP-04
API-03, FKI-03, 23-FKP-25,
24-ENP-13, 24-ENP-14, 25-NCP-01
Hamano T.
24-APP-04
Hamataka K.
24-ENP-11
Hamlin D. K.
RPI-01
Hamon C.
23-APP-04
Hanafua R.
24-APP-02
Hanson B.
EDI-01Hara
K.
AAO-02Hara
T.
24-FKP-20
Harada H.
API-01, AAO-02
Harada N.
24-FKP-12
Haratani T.
25-NEP-03
Hardie S. M. L.
PL-02
Hartmann W.
NCO-09Hasegawa A.
24-FKP-12, 24-FKP-14
Hasegawa H.
23-ENP-06, 23-ENP-14, 23-FKP-03
Hashimoto K.
RPO-02, 23-RPP-03, 23-RPP-04,
25-RPP-01, 25-RPP-07
Hashimoto R.
25-FKP-03
Hashimoto S.
23-RPP-03
Hatanaka K.
25-RPP-04
Hatazawa J.
PL-06, 25-RPP-04
Hatsukawa Y.
RPO-02, 23-RPP-03
Hayashi H.
ACO-02
Hayashi Y.
25-RPP-04
He
Y.
24-NPP-04, 25-NPP-02
HellerA.
ENO-05
Henderson R. A.
APO-06, NFO-02
Herlina23-NCP-02, 24-NCP-08
Hermanspahn N.
25-ENP-14
Herzberg R.-D.
NCO-07
Heßberger F.P.
NCO-07
Hibino K.
24-ENP-10
Hidaka Y.
AAO-05
Higaki S.
FKO-07
Higemoto W.
AAO-03, NPO-04, 24-NCP-05
Higley K. A.
FKO-08
Hioki
A.
AAI-02Hirai
S.
NPO-01, 24-ENP-06
HiroseA.
APO-01HiroseK.
25-NCP-11
HiroseKatsumi FKO-10, 23-FKP-10
HiroseM.
23-FKP-10
Hisamatsu S.
23-FKP-03, 23-ENP-04, 23-ENP-06
23-ENP-07, 23-ENP-08, 23-ENP-14
Hitomi K.
NCO-05
Hohn
A.
23-RPP-02
Holgersson S.
23-APP-06
Homura Y.
25-AAP-07
Honda
M.
FKO-02, 23-FKP-08, 23-FKP-22
Honda
M. C.
FKO-06

Honda
T.
Horitsugi G.
Horng
M.-C.
Horník M.
Hoshi
S.
Hu
D.
Huang
C.-C.
Huang
H.
Huang
M.
Huang

W.

23-FKP-07, 23-FKP-10
25-RPP-04
23-ENP-10
24-NEP-02
AAO-0423-ENP-05
23-ENP-10
24-NPP-04, 25-NPP-02
NCO-09, 23-NCP-03, 23-NCP-06
24-APP-08, 24-NCP-09, 25-NCP-06
25-NCP-09
25-NEP-07

I
Ibuki
R.
Ichikawa S.
Ichiraku T.
Igarashi T.
Igarashi Y.
IijimaK.
Iinuma Y.
Ikarashi S.
Ikeda
H.
Ikeda
Hayato
Ikeda
K.
Ikeda
S.
Ikka
T.
Ikushima H.
Im
H.-J.
Imamura T.
Inagaki M.
Inagawa N.
Inaki
M.
Inoue
A.
Inoue
M.
Inubushi K.
IriokaN.
Ishihara M.
Ishihara S.
Ishii
K.
Ishii
N.
Ishii
Y.
Ishikawa Y.
Ishimaru T.
Ishimoto M.
Ishioka N. S.
Ishizaki M.
Isoda
Y.
Ito
A.
Ito
T. U.
Ito
T.
Ito
Y.
Itono
T.
Iwahana Y.
Iwamoto H.

－ 359 －

24-APP-07
NCO-12, 25-NCP-10
25-RPP-05
FKO-0325-FKP-08
24-ENP-15
AAI-02, 24-AAP-03, 25-NCP-02
FKO-0525-RPP-04
APO-0523-APP-08
24-ENP-01
25-ENP-06
25-RPP-05
25-ACP-07
24-AAP-06
AAO-03, NPO-04, 24-NCP-05
FKO-04, 23-FKP-19
23-ACP-07, 23-RPP-08
25-FKP-03
23-FKP-25, 24-ENP-01,24-ENP-13
24-ENP-14
23-FKP-17
25-NPP-06
23-NCP-02
24-AAP-03
NCO-0523-ENP-11, 24-ENP-12
25-NCP-08
25-FKP-09
25-FKP-05
25-FKP-10, FKO-09
23-RPP-07, 25-ACP-09,25-RPP-01
25-RPP-07
NEO-05, 24-FKP-05, 25-NEP-04
24-ENP-13
APO-05NPO-04
NCO-0525-FKP-05
24-FKP-19
ENO-0624-ENP-06

��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Iwamoto N.
Iwamoto O.
Iwamoto Y.
Iwasaki N.
Iwata
K.
Iwata
R.
Iwatani H.
Izumi
Y.

23-RPP-03
23-RPP-03
25-NCP-04
24-AAP-03
23-ENP-11
APO-0124-FKP-08
25-FKP-09

J
Jacob
T.
Jäger
E.
Jeanson A.
Jensen
H.
Jeong
K.
Jiang
F.
Jin
Q.
John
J.
Johnston K.
Johnstone E. V.
Jordan
N.
Jung
S.-H.

23-NCP-10
NCO-07, NCO-09
23-ACP-01
RPO-01
ENO-1125-NEP-07
ENO-01
EDI-01, 25-NEP-05, 25-ENP-13
23-RPP-02
NEO-03, 25-NCP-13
ENI-01
APO-02K
Kabuki S.
Kadir
A.
Kadokura A.
KajiD.
Kajino M.
Kakimoto H.
KakitaK.
Kakitani S.
Kakiuchi H.
Källvenius G.
Kalmykov S. N.
Kamebuchi H.
Kameo Y.
Kamimura R.
Kaminaga M.
Kanai
Y.
Kanai
YutakaKanamori M.
Kanasashi T.
Kanatzidis M. G.
Kanaya J.
Kanda
J.
Kaneko M.
Kaneshiki T.
Kaneya J.
Kaneya Y.
Kang
M.-J.
Kanno
A.
Kar
A.
Kasamatsu Y.

RPO-0224-ENP-05
ENO-10
NCO-09, 23-NCP-03, 24-NCP-09
25-FKP-08
24-FKP-18
24-ENP-06
FKO-07, 24-FKP-03
23-ENP-06, 23-FKP-03
23-ACP-04
25-RPP-02
25-NPP-04
FKO-01
FKO-12, FKO-13, FKO-14
25-RPP-03
25-RPP-04
23-FKP-09
25-FKP-06
24-FKP-21
25-NCP-13
NCO-09, 23-NCP-06, 24-APP-08
24-NCP-07, 24-NCP-09, 25-NCP-06
25-NCP-09
25-FKP-05
NPO-0325-NEP-03
25-NCP-05
NCO-09, NCO-12, NCO-13
25-NCP-03, 25-NCP-09, 25-NCP-10
23-ENP-15, 24-ENP-16
24-FKP-04, 24-FKP-16
25-ACP-08
23-NCP-06, 23-NCP-07, 24-NCP-01

24-NCP-05, 24-NCP-06, 24-NCP-09
25-NCP-04, 25-NCP-06, 25-NCP-08
25-RPP-04
Kashiwaya K.
24-FKP-19
Kato
M.
24-ENP-11
Katsumura Y.
FKO-09, 25-FKP-10
Kawabata H.
23-ENP-06, 23-ENP-14
Kawabata M.
23-RPP-03, 23-RPP-04
Kawabata T.
24-FKP-18
Kawahara O.
23-FKP-04
Kawakami H.
FKO-06
Kawamoto T.
FKO-12, FKO-13, FKO-14
NEO-05, 23-FKP-11, 23-FKP-16
24-FKP-02, 24-FKP-05
Kawamura H.
25-RPP-03
Kawamura Hidehisa 23-FKP-03
Kawamura N.
AAO-03, NPO-04
Kawano T.
23-FKP-23
Kawano Y.
25-ENP-09
Kawashima S.
25-ENP-10
Kawasumi K.
23-FKP-06
Kawata S.
25-NPP-06
Kawatsu K.
25-FKP-09
Kawatsu K.
24-FKP-04, 24-FKP-16
Kazahaya K.
23-APP-07
KerlinW. M.
APO-06, NCO-02, NEO-03
25-ENP-05
Khateeb-ur-Rehman
23-APP-02, 24-AAP-08,
25-AAP-08
Khedekar N.B.
25-ACP-08
Khilnani R. P.
23-ENP-02
Khoo
K. S.
EDO-01
Khuyagbaatar J.
NCO-09, NCO-07
Kikawada Y.
23-FKP-07, 23-FKP-10
Kikunaga H.
23-NCP-07, 24-APP-08, 24-NCP-09
25-FKP-09, 25-NCP-11
Kikutani Y.
24-NCP-09
Kim
C.-J.
24-ENP-16
Kim
C.-H.
APO-02Kim
E.
NEO-03, 25-NCP-13
Kim
H.
23-ENP-15
Kim
J.-B.
APO-02Kim
J.-Y.
ACO-03Kim
J.-S.
NCO-03Kim
K.-W.
25-ACP-02
Kim
M.-S.
25-AAP-06
Kim
S.-Y.
NCO-05Kim
S.-H.
24-AAP-04, 25-AAP-02
Kimura A.
AAO-02, 23-NCP-02
Kimura H.
24-APP-08, 25-FKP-02
Kimura Hiroyuki RPO-02
Kimura T.
JNRS, ACO-04, 25-ACP-05
25-ACP-03
Kin
T.
23-RPP-03
Kindler B.
NCO-07, NCO-09
Kino
A.
23-NCP-06, 24-NCP-01－ 360 －

��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Kinoshita N.
Kirakosyan G.
Kirishima A.

24-ENP-03
NEO-03
ACO-01, ACO-04, 23-ACP-05
24-FKP-22
Kirk
C.
ENO-02Kita
K.
FKO-07, 24-FKP-03
Kitagawa A.
24-NPP-07
Kitagawa J.
FKO-05
Kitajima A.
FKO-12, FKO-13, 23-FKP-16
24-FKP-02
Kitamura A.
23-ACP-02
Kitamura K.
24-ENP-06
Kitamura N.
APO-05
KitanoM.
ENO-06
Kitatani F.
AAO-02
Kitatsuji Y.
ACI-02, NCO-13, 25-ACP-04
25-ACP-05
Kitayama K.
24-FKP-04, 24-FKP-16
Kitayama Y.
NCO-13, 24-APP-08 25-NCP-03
25-NCP-09
Klein
E.
PL-02
Klimek F.
25-NEP-05
Klingelhöfer G.
24-APP-06
Koarashi J.
25-ENP-08
Kobayashi M.
25-RPP-03
Kobayashi Makoto 25-NEP-02
Kobayashi Natsuko I.
APO-01
Kobayashi T.
23-FKP-20
Kobayashi Taishi 23-ACP-03
Kobayashi Y.
24-FKP-11, 25-FKP-01
Kobayashi Y.
AAO-03, 24-NPP-01, 24-NPP-02
24-NPP-03, 24-NPP-07
KofujiH.
23-FKP-25, 24-ENP-01, 24-ENP-13
24-ENP-14, 25-ENP-11
Koga
F.
25-FKP-09
Koibuchi Y.
24-ENP-08
Koike
Y.
ENO-06, 24-FKP-10
Koivula T.
EDI-01
Koizumi M.
AAO-02
Kojima A.
23-FKP-04
Kojima H.
AAO-05
Kojima I.
24-ENP-06
Kojima N.
NPO-01 25-NPP-04
Kojouharov I.
NCO-07
���������� K.
24-NEP-04
Koma
Y.
23-FKP-02
Komatsuda S.
NPI-01, 24-NPP-05, 25-NPP-06
Komori Y.
23-NCP-06, 23-NCP-07, 24-NCP-01
24-NCP-09, 25-NCP-06
Kondo T.
23-FKP-06
Kondo Y.
25-ENP-10
Konno
C.
23-RPP-03, 23-RPP-04
Kosako K.
24-ENP-15
KösterU.
23-RPP-02
Koyama T.
25-NCP-05, 23-NCP-03
Kozai
N.
ENO-04, 23-ENP-03, 25-FKP-07

Kratz

J. V.

Krier
Krmela
Kubo

J.
J.
M. K.

KubotaKubuki
Kudo

T.
S.
H.

Kudo
Kudou

I.
Y.

Kulyako Y. M.
Kumamoto Y.
Kunifuda T.
Kurihara M.
Kurihara Y.
Kurz
N.
Kusakabe M.
Kutoba T.
Kuwahara Y.

25-ACP-06, 25-ENP-02
ENI-02, NCO-07, NCO-12
23-NCP-01, 25-NCP-09, 25-NCP-10
25-NCP-03
NCO-07
ENO-07
AAO-03, NPO-04, 24-NCP-05
24-NPP-07
25-FKP-01, 24-FKP-11
24-APP-07, 24-APP-04
24-NCP-07, 24-NCP-09, 25-NCP-05
25-NCP-07
24-ENP-11
23-NCP-03, 23-NCP-06, 23-NCP-07
24-APP-08, 24-NCP-01, 24-NCP-09
25-NCP-06
23-ACP-03
23-FKP-23
ENO-08NEO-05, 24-FKP-05, 25-NEP-04
24-FKP-10
NCO-0724-FKP-23, 24-FKP-24
FKO-0325-RPP-05

L
LahiriS.
Lamxay S.
Lan
J.-H.
Lapshina E. V.
Laszak I.
LaZar
S.
Le
V. S.
Lee
C.-P.
Lee
E.J.
Lee
E.-H.
Lee
K.-Y.
Lee
O.-H.
Lee
S. A.
Lee
S.
Lehto
J.
Lei
C.
Lerum
H. V.
Li
J.
Li
P.
Li
Q.-N.
Li
W.-X.
Li
Z.
Li
Z. J.
Li
Z.
Liang
J.
Lim
J.-M.
Lin
Q.
Lindegren S.
Liu
C.-C.
Liu
C.-Y.

－ 361 －

RPI-0224-ENP-08
24-NEP-01
25-RPP-02
APO-04, NCO-04
FKO-11
23-RPP-01, 24-NCP-03
ENO-0325-AAP-09
25-ACP-02
25-ACP-02
25-AAP-02, 24-AAP-04
ENO-11
ENO-11
EDI-01, ENO-02
24-NPP-04, 25-NPP-02
NCO-13, 25-NCP-03, 25-NCP-09
ACI-0123-ACP-08
25-NEP-06, 25-NEP-07
25-NEP-06
NCO-0125-NCP-08
23-APP-01, 24-ENP-02
24-ENP-05
23-ENP-15, 24-ENP-16
24-NPP-04, 25-NPP-02
RPO-01
23-ENP-10
ENO-03��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Liu
P.
Liu
Z.
Löfström-Engdahl
LommelLong
Lubis
Lukens

B.
D.-W.
H.
W.

23-APP-01, 24-ENP-02
23-ACP-08
E.
NEO-01, 23-NCP-04
NCO-0725-NEP-07
23-NCP-02
NEO-03

M
Ma
R.
Mae
K.
Maeda E.
Maejima Y.
Maekawa A.
Maekawa A.
Magara M.
Mahajan M.A.
Mahara Y.
Mahata K.
Maiti
M.
Majid
A. A.
Maki
T.
Makii
H.
Makino T.
Malliakas C. D.
Malmberg M.
Manganini S.
�����
K. V.
Maruk
A.
Maslehuddin M.
Masumoto K.
Matsukawa S.
Matsumoto K.
Matsumura H.
Matsumura M.
Matsunaga T.
Matsuno H.
Matsuo K.
Matsuo M.
Matsushi Y.
Matsuzaki H.

Matsuzaki T.
Matthews M.
Mausmoto K.
McBrayer J.
McKinley I. G.
Mclain D. R.
Men
L.-C.
Mihara M.
Mikami M.
��������� I.
MillerG. E.
Mimura H.

23-ENP-16
24-NPP-07
24-APP-08, 25-RPP-01, 25-RPP-06
23-FKP-22
23-FKP-12
24-FKP-20
NFO-01, 25-NFP-01
25-ACP-08
FKO-03
NCO-15
RPI-02
EDO-0125-FKP-08
25-RPP-01
23-FKP-24
25-NCP-13
23-NCP-04
FKO-0625-NEP-05
NEO-0325-AAP-08, 24-AAP-08
ENO-08, 24-ENP-03, 24-ENP-15
24-NPP-06
24-FKP-16
ENO-08, 24-ENP-03, 25-NCP-04
24-ENP-08
25-ENP-08
23-FKP-07
23-FKP-06
24-AAP-05
23-FKP-22
FKO-02,
FKO-03,
FKO-0423-APP-07, 23-FKP-08, 23-FKP-22
24-ENP-08, 24-FKP-06, 24-FKP-14,
25-ENP-12, 25-FKP-03
23-FKP-19
25-ENP-14
ENO-0823-RPP-01
PL-02
NFO-03
ENO-03, 24-AAP-01, 25-AAP-01
24-NPP-07
25-FKP-08
ENO-13, 23-ENP-01
RPO-0323-ACP-05

Minai
Y.
Minakawa M.
Minami K.
Minato F.
Minato K.
Minowa H.
Misonoo J.
MistryA.
Miura
T.
Miura Tsutomu
Miyake Y.

24-ENP-06
24-ENP-14
FKO-12, FKO-13
23-RPP-03
FKI-05, ACO-02
24-FKP-13
24-FKP-24, 23-FKP-25
NCO-07NPO-04, 24-NCP-05
AAI-02, 24-ENP-06
AAO-03, NPO-04, 24-NCP-05
25-RPP-04
Miyake Yasuto FKO-02, 23-FKP-08
Miyamoto Y.
NFO-01Miyashita S.
NCO-12, NCO-13, 25-NCP-03
25-NCP-09, 25-NCP-10
Miyata Y.
25-ENP-12
Miyatani R.
24-NPP-01
Miyazaki J.
24-NPP-07
Mizuno S.
24-FKP-11, 25-FKP-01
Mizuno T.
25-FKP-05
Mizuuchi R.
25-NPP-06
Modolo G.
24-NEP-03
Mogi
M.
25-FKP-09
Mohamed F.
EDO-01
Mokry C.
NCO-07
Momoshima N.
23-FKP-12, 24-ENP-10, 24-FKP-20
Monjushiro H.
24-ENP-03
Moody K. J.
APO-06, NFO-02
Moon
J. H.
AAO-01, APO-02, 25-AAP-09
Moon
J.-K.
25-ACP-02
Moon Jong-Hwa
25-AAP-02, 24-AAP-04
Morcos N.
23-RPP-01
Morikawa Y.
25-RPP-03
Morimoto A.
24-ENP-13
Morimoto K.
23-NCP-03, 24-NCP-09
Morita A.
25-ENP-06
Morita K.
23-NCP-03, 24-NCP-09
Mosqueira F.G.
24-APP-01
Motl
A.
25-ENP-13
Motoishi S.
23-RPP-03, 23-RPP-04
Müller C.
23-RPP-02
Müller K.
23-ACP-03
Munakata H.
23-FKP-17
Muneda A.
25-FKP-02
Murakami M.
23-NCP-03, 24-NCP-07, 24-NCP-09
25-NCP-05
Murakami Michio 24-ENP-08
Murakami T.
23-FKP-25
Muramatsu H.
23-FKP-06
Muramatsu Y.
FKO-04, 23-APP-07, 23-FKP-19
23-FKP-20, 23-FKP-08, 24-FKP-06
25-FKP-03, 25-FKP-04
Murata A.
23-FKP-23
Murayama S.
25-FKP-09
Mutalib A.
24-NCP-08, 23-NCP-02
Myasoedov B. F.
23-ACP-03－ 362 －

��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

N
Nagai
H.
Nagai
Y.
Nagame Y.

23-FKP-22, 24-FKP-12, 24-FKP-14
RPO-02, 23-RPP-03, 23-RPP-04
25-NCP-10, 25-NCP-09, 25-NCP-08
NCO-12, 25-NCP-03, NCO-13
Nagano Y.
25-RPP-05
Nagao
S.
PL-04, FKO-06, 23-FKP-25
24-ENP-09, 24-ENP-11, 24-ENP-13,
24-ENP-14, 24-FKP-17, 24-FKP-19,
25-ENP-08, 25-ENP-09, 25-FKP-06
Nagaoka M.
23-FKP-13
Nagatomo T.
AAO-03, NPO-04
Nagatomo T.
24-NPP-07
Nakagaki R.
25-NCP-04
Nakai
K.
25-RPP-04
Nakajima T.
FKI-01, FKO-09, 25-FKP-10
Nakajima Y.
23-FKP-02
Nakakuki T.
ENO-10Nakama A.
23-FKP-12
Nakamachi K.
23-FKP-07
Nakamoto A.
25-NPP-04
Nakamoto T.
25-NPP-05
Nakamura H.
24-ENP-15
Nakamura K.
23-NCP-06, 23-NCP-07,24-NCP-01
24-NCP-09, 25-NCP-06
Nakamura M.
23-FKP-02
Nakamura S.
AAO-02
Nakamura T.
ENO-06
Nakamura Y.
AAO-04
Nakanishi T.
25-FKP-02
Nakanishi Takahiro 25-ENP-08
Nakanishi T. M.
APO-01, 23-FKP-01, 24-FKP-15
Nakano C.
23-FKP-22
Nakano M.
23-FKP-13
Nakano Y.
24-ENP-13, 24-ENP-14
Nakashima S.
NPO-03, 24-APP-05
Nakayama S.
25-RPP-05
Nankawa T.
NEO-05, 24-FKP-05
Naqvi
A. A.
23-APP-02, 24-AAP-08, 25-AAP-08
Negrón-Mendoza A. 23-APP-03, 24-APP-01
����� M.
EDI-01, 24-ENP-17, 25-ENP-13
Neville D. R.
FKO-08Nguyen C. D.
24-NCP-03
Ni
B. F.
AAO-01
Niibori Y.
23-ACP-05
Niitsuma K.
23-FKP-05
Nilsson M.
NEO-04, RPO-03, 25-NEP-01
Ninomiya K.
AAO-03, FKO-07, NPO-04
24-FKP-03, 24-NCP-05, 25-NCP-04
Nishiizumi K.
25-NCP-04
Nishimura S.
25-ENP-08
Nishinaka I.
25-RPP-01, 25-RPP-06
NishioS.
24-ENP-10
Nitsche H.
NCO-07Nitto
A. D.
NCO-07, NCO-09
Niu
Z. L.
23-ENP-12
Nobuhara F.
24-ENP-15

Noda
NodiloNogami
NomuraNomuraNomuraNomuraNozaki
NurbaitiH.
23-FKP-01
M.
23-ENP-01
M.
25-NEP-03
Kazunori
23-FKP-02
Kiyoshi NPO-01, NPO-02, 25-NPP-03
M.
NEO-02, 23-RPP-08, 25-NEP-03
R.
24-ENP-01
T.
25-EDP-02
S.
24-NCP-08

O
Ochiai
Ochiai

K.
S.

Oda
Oda
Ogata
Ogawa

H.
K.
Y.
H.

Ogawa K.
Ogiso
R.
Ohara
T.
Ohata
M.
Ohkubo Y.
Ohno

T.

OhnukiT.

Ohse
K.
Ohshima Y.
Ohta
A.
Ohta
T.
Ohtsuka Y.
Ohtsuki T.
Ohzawa R.
Oi
T.
Oikawa S.
Oishi
A.
Oishi
K.
Okabe
N.
Okada
A.
Okada
S.
Oki
T.
Oki
Y.
Okumura R.
Okuno
K.
Ollington R.
Omoto T.
Omtvedt J. P.
Onaka
Onda

－ 363 －S.
Y.

23-RPP-03
23-FKP-25, 24-FKP-17, 24-FKP-19
25-ENP-09, 25-FKP-06
23-APP-08
FKO-04, 23-FKP-20
24-APP-02
FKO-12, FKO-13, 23-FKP-16
24-FKP-02
25-EDP-02
25-NPP-05
25-FKP-10, FKO-09
AAI-02
NPI-01, 24-NPP-0, 25-NPP-06
25-NPP-01
FKO-04, 23-FKP-19, 23-FKP-20
24-FKP-06, 25-FKP-04
ENO-04, 25-ACP-06, 25-ENP-02
23-ENP-03, 25-FKP-07
24-FKP-04, 24-FKP-16
23-RPP-07
25-RPP-03
FKO-03, 24-FKP-11, 25-FKP-01
23-ENP-08
23-NCP-07, 24-NCP-10, 25-FKP-09
25-NCP-11
23-FKP-12
23-FKP-10
24-FKP-23, 24-FKP-24, 23-FKP-25
24-FKP-09
24-ENP-15
23-APP-07
24-ENP-06
23-FKP-04
24-ENP-08
24-ENP-03
AAI-02, 24-AAP-03, 24-AAP-05
24-FKP-11, 25-AAP-07, 25-FKP-01
25-NCP-02
25-NEP-02, 25-ENP-06
23-ENP-17
25-NCP-04
EDI-01, NCO-07, NCO-11
NCO-13, 25-NCP-03
25-NPP-05
24-FKP-08

��������� - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Ono
Ooe

R.
K.

Osa
A.
Osada
M.
Osada
N.
Osawa T.
Oshimi Y.
Ostapenko V. S.
Otake
N.
Otobe
H.
Otosaka S.
OtsukiT.
OuraY.
Outsuki
Oya
Oyabu
Ozeki

M.
Y.
M.
K.

24-NPP-08
NCO-12, NCO-13, 24-NCP-01
24-APP-08, 24-NCP-07, 25-NCP-03
25-NCP-05, 25-NCP-07, 25-NCP-09
25-NCP-10
NCO-12, 25-NCP-10
FKO-1324-ENP-03
24-AAP-02
NCO-13, 25-NCP-07
25-RPP-02
FKO-1325-ACP-05
23-FKP-21, 25-ENP-08
FKO-09, NCO-13, 24-AAP-06
25-FKP-10, 25-NCP-09
23-FKP-19
25-ENP-06, 25-NEP-02
25-NPP-03
24-NCP-09

P
Pagel
J. M.
Pan
C.-H.
Pan
D.
Papadakis P.
Parajuli D.
Park
B.G.
Park
H.-K.
Park
J.-G.
Park
J.-H.
Park
M.-S.
Park
S.-D.
Park
T.-H.
Park
Y.-S.
Pearson J.
PerretP.
Pershina V.
Petrushkinc O. V.
Phillips A. J.
Phillips G.
Pigueta D.
������� M.
Pohjolainen E.
Poineau F.

RPI-01
ENO-0325-ENP-01
NCO-07
FKO-13, FKO-14, 23-FKP-11
25-AAP-09
23-ENP-15
APO-02
ACO-03, ENO-11
25-ACP-02
NCO-03
ACO-03
NCO-0325-NEP-01
23-APP-04
NCO-06, 23-NCP-10
NCO-11
FKO-0823-RPP-01
NCO-1124-NEP-02
ENO-02
NCO-02, NEO-03, 24-ENP-07
25-NCP-13
Polkowska-Motrenko H.
23-RPP-05, 24-NEP-05
Press
O. W.
RPI-01
PujariP. K.
NCO-15

Q
Qi
Qin

R

W.
Z.

23-APP-01, 24-ENP-02
NCO-01

Raashid M.
25-AAP-08, 23-APP-02, 24-AAP-08
Ragnarsson I.
NCO-07
Rahman I. A.
EDO-01
Rahman W. Y.
24-NCP-08
Raindl
J.
24-ENP-17
Ramakumar K. L. 25-ACP-08
Ramos-Bernal S.
24-APP-01
Rao
D. R. M. 23-ACP-09
Rasmussen E.
FKO-11Rawat
N.
25-ACP-08
Read
D.
EDI-01, ENO-02
Reber
J.
23-RPP-02
Rego
D. B.
NEO-03, 24-NCP-04
Retegan T.
EDI-01
Ritawidya R.
24-NCP-08
Roman A. R.
NFO-03
Roques J.
23-ACP-01
Rossberg A.
ENI-01Rudolph D.
NCO-07Runke
J.
NCO-07
Rykaczewski K.
NCO-07Rykov
A. I.
NPO-02

S
Saas
J. N.
NCO-04������������ A. V. NCO-11
Sachs
S.
ENO-05
Saeki
H.
23-RPP-03, 23-RPP-04
Safavi-Tehrani L. G. RPO-03
Safi
S.
23-ACP-01
Saha
M.
24-ENP-08
Saino
T.
FKO-06
Saito
T.
AAO-03, 24-FKP-10
Saito
Takashi FKO-07, 23-FKP-05, 23-FKP-24
Saito
Takayuki
APO-01
Saito
Takumi FKO-02, 25-ACP-03
Saji
H.
RPO-02
Sakaguchi A.
FKI-02, ENO-10, 24-FKP-08
24-FKP-17
Sakaguchi H.
24-FKP-10
Sakai
R.
24-NCP-09
Sakai
Y.
25-NPP-05
Sakama M.
25-RPP-05
Sakamoto F.
ENO-04, 25-FKP-07
Sakamoto S.
AAO-03
Sakamoto S.
23-APP-08
SakataT.
AAO-04
Sakatani K.
FKO-01
Sakuda E.
APO-05
Sakuma Y.
23-FKP-05
Salbu
B.
EDI-01Salim
N. A. A. AAO-01
Samsonov M.
23-ACP-03
Sanchez W. M.
AAI-01
Sandmaier B. M.
RPI-01Sano
T.
25-NCP-02－ 364 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Saotome T.
Sarmani S. B.
Sarmiento L.G.
Sarmini E.
Sasa
K.
SasakiI.
SasakiT.
Sasaki
Y.
Sato
A.
Sato
K.
Sato
M.
Sato
MamoruSato
MisakiSato
Mutsuto
Sato
N.
Sato

Nobuaki

Sato
Sato
Sato
Sato
Sato

Norio
NozomiShinji
Syuichi
T. K.

Sato
Sato

Tsutomu
W.

Satoh
D.
Satoh
R.
Satoh
S.
Satou
C.
Satou
Y.
Sattelberger A. P.
Sawant R. M.
Saze
T.
Schädel M.
Schaffner H.
Schausten B.
Schibli R.
Schwikowski M.
Scott
B. L.
ScullyP. J.
Šebesta F.
Seike
M.
Sekimoto S.
Sekine T.
Sekiyama T.
Shaughnessy D. A.
She
C.-F.
Shi
W.-Q.
Shi
Y.
Shibahara Y.

25-FKP-05
EDO-01, 23-APP-05
NCO-0724-NCP-08
FKO-05, 24-ENP-08
23-RPP-07
23-ACP-03
23-ACP-05, 25-ACP-09
24-NPP-06
25-NPP-01
25-FKP-04
FKO-0425-NEP-02
23-FKP-05, 23-FKP-24
NCO-12, 24-FKP-11, 25-FKP-01
25-NCP-10
ACO-01, ACO-04, 23-ACP-05
24-FKP-22
23-FKP-05
23-RPP-03, 23-RPP-04
24-NPP-07
FKO-13
NCO-09, NCO-12,NCO-13, RPO-02
25-NCP-03, 25-NCP-08, 25-NCP-09
25-NCP-10
25-ENP-08
NPI-01, 24-NPP-05, 24-NPP-07
24-NPP-08, 25-NPP-06
25-NCP-04
25-NPP-03
23-FKP-01
23-FKP-19
FKO-05, 24-ENP-08
NCO-02, NEO-03, 25-NCP-13
23-ACP-09, 25-ACP-08
25-RPP-05
NCO-07, NCO-12, NCO-13
23-NCP-01, 25-NCP-03, 25-NCP-08
25-NCP-09, 25-NCP-10
NCO-07
NCO-0723-RPP-02
ENO-0925-NCP-13
EDI-0125-ENP-13, 25-NEP-05
25-ACP-01
AAI-02, AAO-05, 24-AAP-07
24-ENP-03, 25-AAP-04, 25-AAP-05
25-AAP-07, 25-NCP-04
APO-0525-FKP-08
APO-06, NFO-02
25-NEP-07
API-02, 23-ACP-06, 24-NEP-01
AAI-0124-FKP-11, 25-FKP-01

Shibata A.
Shibata S.
Shibata T.
Shibayama N.
Shibukawa M.
Shiga
K.
Shigeyoshi Y.
Shiina
T.
Shima
N.
Shima
T.
Shimada A.
Shimada T.
Shimamoto M.
Shimasaki T.
Shimizu R.
Shimoda S.
Shimomura K.
Shimosegawa E.
Shinohara A.

Shinohara H.
Shiohara N.
ShiraiN.
Shiraishi Y.
Shizuma K.
Shozugawa K.
Simoni E.
Skarnemark G.
Skipperud L.G.
Sodaye S.
Solatie D.
Song
K.
Sonoda S.
Špendlíková I.
SriyonoStamets P.
SteierP.
Steinegger P.
Stora
T.
Strasser P.
Su
J.
Su
T.-Y.
Sudowe R.
Sueki
K.
Suenaga S.
Sugihara S.
SugitaR.
Sugiura Y.
Sugiyama M.
Sugo
Y.
Sumita T.
Sumiya S.

－ 365 －

23-FKP-02
24-ENP-03, 25-NCP-02, 25-NCP-04
24-FKP-11
24-ENP-08
24-ENP-06
24-NPP-02
24-APP-08
25-RPP-03
23-ENP-06
25-NCP-04
FKO-0125-ENP-07
23-FKP-04
23-FKP-04
24-NPP-03
23-ACP-02
AAO-03, NPO-04
25-RPP-04
AAO-03, APO-05, FKO-07, NPO-04
23-NCP-06, 24-FKP-03, 24-FKP-10
24-NCP-01, 24-NCP-05, 24-NCP-09
25-ACP-01, 25-NCP-06, 25-NCP-04
25-RPP-04
24-APP-04
23-NCP-07
AAO-05, 24-AAP-07, 25-AAP-05
25-AAP-07
23-FKP-04, 25-FKP-09
ENO-1024-AAP-05
23-ACP-01
EDI-01, NEO-01, 23-NCP-04
EDI-01
NCO-15
ENO-02
ACO-03, ENO-11, NCO-03
25-ACP-07
RPO-0224-ENP-17, 25-ENP-13
23-NCP-02
FKO-11
ENO-10, 24-FKP-17
NCO-14
NCO-12, 25-NCP-10
AAO-03, NPO-04
ACI-0124-AAP-01
APO-06, NFO-03
FKO-05, 24-ENP-08
24-FKP-16
23-FKP-12, 24-ENP-10, 24-FKP-20
APO-01, 23-FKP-01
24-FKP-21
25-FKP-04
23-RPP-07, 25-ACP-09
23-NCP-03
23-FKP-13

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Sun
Sun
SuzukiSuzukiSuzukiSuzukiSuzukiSuzukiSuzukiSuzukiSuzukiT

G.M.
25-AAP-09
K.
25-ENP-03
C.
24-FKP-04, 24-FKP-16
D.
NFO-01, 25-NFP-01
Hirokazu 23-FKP-17
Hisashi APO-01
T.
AAO-03
Tatsuya NEO-02, 23-ACP-07,
25-NEP-03
Toshitaka 23-ENP-06
Yasukazu 23-FKP-17
Yoshinori 25-ACP-06

Tachibana Y.

23-RPP-08

NEO-02, 23-ACP-07, 23-RPP-08
25-NEP-03
Tachiya T.
25-FKP-09
Tada
T.
NCO-05Tadai
T.
24-APP-07
Tagami K.
ENO-12, 23-ENP-11, 23-FKP-14
23-FKP-15, 23-FKP-21, 24-FKP-01
24-FKP-07, 24-ENP-12
Taguchi M.
25-ACP-09
Taguchi T.
25-NCP-07
Takada H.
24-ENP-08
Takada T.
24-ENP-09, 24-FKP-17
Takahashi A.
FKO-13, 23-FKP-11
Takahashi Hiroaki 23-FKP-10
Takahashi Hiroki 25-AAP-05
Takahashi K.
24-ENP-15
Takahashi Kazuhira
23-FKP-24
Takahashi Kuniaki
FKO-01
Takahashi M.
23-APP-07
Takahashi Masashi 24-NPP-06, 25-NPP-05
Takahashi N.
23-NCP-06, 23-NCP-07, 24-NCP-01
24-NCP-06, 25-NCP-04, 25-NCP-06
25-RPP-04
Takahashi Naruto FKO-07, 24-FKP-03
Takahashi T.
24-FKP-11, 25-FKP-01
Takahashi Tsutomu 24-ENP-08
Takahashi Yoshio FKI-02, ENO-10, 23-ENP-09
24-FKP-08
Takahatake Y.
23-FKP-02
Takai
H.
25-RPP-05
Takaku Y.
23-ENP-04, 23-ENP-08, 23-ENP-14
Takakura K.
23-RPP-03, 23-RPP-04
Takamiya K.
AAI-02,23-NCP-07,24-AAP-05
24-FKP-11, 24-NCP-01, 25-FKP-01
25-NCP-02, 25-NCP-11, 25-RPP-04
Takasaki M.
23-FKP-16
Takase T.
25-FKP-09
TakataH.
24-FKP-23, 24-FKP-24
Takayama T.
APO-05, 25-NPP-05
Takeda A.
23-ENP-04, 23-ENP-07
Takenaka C.
24-FKP-21

Takeuchi E.
Takeyama M.
Takigawa M.
Takikawa T.
Tamura N.
Tan
C.-M.
Tanaka H.
Tanaka Hisashi

24-APP-04, 25-ENP-08
23-NCP-03
FKI-01
24-ENP-13
23-NCP-03
NCO-0125-NCP-02
FKO-12, FKO-13, FKO-14, NEO-05
23-FKP-11, 23-FKP-16, 24-FKP-02
24-FKP-05, 25-NEP-04
Tanaka K.
23-NCP-03
Tanaka Kazuya FKI-02, 24-FKP-08
Tanaka M.
23-ENP-09
Tanaka T.
25-ENP-07
Tanaka Taichu
25-FKP-08
Tanaka Y.
24-AAP-06
Tanase M.
23-NCP-02, 25-RPP-03
Tancharakorn S.
23-APP-09
Tanigaki M.
24-FKP-11, 25-FKP-01, 25-NPP-01
Taniguchi A.
25-NPP-01
Taniguchi T.
25-RPP-06
Tanihata I.
24-FKP-10
Tanimori T.
RPO-02
Tanoi
K.
APO-01, 23-FKP-01
Tanthanuch W.
23-APP-09
Taoka
A.
25-NPP-06
Tatunuma K.
25-NEP-02
TayaraK. E.
23-NCP-04
TeiaraM. B. A. 23-APP-05
Tereshatov E.
APO-06, NFO-02
Theresia R. M.
AAO-01
Thörle-Pospiech P. NCO-07
Tian
L.-L.
NCO-01
Tian
L.-F.
25-NEP-07
Tian
W.
NCO-01
Tietzea S.
23-NCP-08
Timms G.
23-ENP-17
Tišáková L.
24-NEP-02
ToblerL.
ENO-09Toda
K.
24-NCP-06
Toda
K.
25-ENP-06, 25-NEP-02
Togimitsu T.
24-NPP-08
Togo
Y. S.
FKI-02Toh
Y.
AAO-02
Toktaganov M.
25-AAP-05
Tokuda H.
NCO-05Tokuyama H.
23-FKP-08
Tomar
B. S.
23-ACP-09, 25-ACP-08
Tomita J.
24-ENP-09
Tomitsuka T.
25-NCP-07
Tomobuchi Y.
NEO-02, 23-ACP-07
Tooyama Y.
23-FKP-17
TorresT.
NCO-07
Toyama T.
23-FKP-19
Toyoda A.
ENO-08, 24-ENP-15
Toyomura K.
25-NCP-06, 24-NCP-01, 23-NCP-07
23-NCP-06－ 366 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Toyoshima A.

Tripathi R.
Triyanto
Trojanowicz M.
Tsai
T.-L.
Tsai
W.-H.
Tsuchiya K.
Tuchiya S. Y.
Tsuduki K.
Tsuji
H.
Tsujita K.
Tsukada H.
Tsukada K.
Tsukamoto A.
Tsuneyama M.
Tsuruta H.
Tsuto
S.
Tumey S. J.
Tuovinen H.
TürlerA.

U

UchidaUchidaM.
S.

Uchida T.
Uchimura H.
Ueda
S.
Uehara A.
Uematsu Y.
Ueno
H.
Ueno
S.
Uesugi M.
Umemura M.
Usoltseva I.
Usuda
S.

V

Vahlbruch J.-W.
ValéryJ. F.
Vasiliev A. N.
van der Walt N.T.
Vesterbacka D.
Vian
A.
Vlk
M.
Vostokinc G. K.

NCO-12, NCO-13, RPO-02
24-APP-08, 25-NCP-03, 25-NCP-06
25-NCP-08, 25-NCP-09, 25-NCP-10
25-RPP-01
NCO-1524-NCP-08
24-NEP-04
ENO-03, 24-AAP-01, 25-AAP-01
23-ENP-10
23-NCP-02
25-RPP-03
23-FKP-22
25-ENP-08
25-ENP-10
24-FKP-12
23-ENP-04, 23-ENP-07, 23-ENP-14
23-FKP-17, 23-FKP-24, 24-FKP-04
24-FKP-16
NCO-12, NCO-13, RPO-02
24-APP-08, 25-NCP-03, 25-NCP-08
25-NCP-09, 25-NCP-10
23-FKP-10
25-NPP-01
FKI-01, FKO-07, FKO-09
25-FKP-10
24-NCP-07, 23-NCP-03
NFO-02
ENO-02PL-03, NCO-07, NCO-11, NCO-14
23-FKP-18, 23-NCP-09, 23-NCP-05
23-RPP-02
25-FKP-09
ENO-12, 23-ENP-11, 23-FKP-14
23-FKP-15, 23-FKP-21, 24-ENP-12
24-FKP-01, 24-FKP-07
FKO-1325-ENP-06, 25-NEP-02
23-FKP-03
24-FKP-11, 25-ACP-04, 25-FKP-01
24-ENP-06
PL-08
24-NCP-06
25-FKP-02
24-FKP-21
NCO-11, 23-NCP-09
23-ACP-05
EDI-01
NCO-0425-RPP-02
23-RPP-02
ENO-02
NCO-0425-NEP-05
NCO-11Vu

C. D.

AAO-01W

Wada
A.
NCO-13, 25-NCP-03, 25-NCP-09
Wakabayashi Y.
23-NCP-03
Walther C.
EDI-01
Wang
C.-Z.
24-NEP-01
Wang
Jing
23-APP-01, 24-ENP-02
Wang
Junhu
NPO-02Wang
L.
23-ACP-06
Wang
S.
25-ENP-04
Wang
Y.
NCO-01
Wang
Zhongtang
23-ENP-05
Wang
Zheming 25-ENP-01
Ward
A.
NCO-07
Ward
D.
NCO-07
Washiyama K.
25-RPP-01, 25-RPP-06
Watabe H.
25-RPP-04
Watabe T.
24-FKP-24, 25-RPP-04
Watanabe A.
24-FKP-03
Watanabe H.
23-FKP-13
Watanabe M.
ACO-04, NEO-05, 24-FKP-05
25-NEP-04,
Watanabe R.
25-FKP-02
Watanabe S.
25-RPP-01
Watanabe Satoshi 25-RPP-07
Watanabe Shigeki 23-RPP-07
Watanabe Shuichi FKO-06
Weck
P.
NEO-03, 25-NCP-13
Wei
H.-J.
ENO-03, 25-AAP-01
Wei
Y.
24-APP-03, 25-NCP-12
Wiehl
N.
NCO-07
Wilbur D. S.
RPI-01
Wilden A.
24-NEP-03
Witman-Zając S.
24-NEP-05
Won-in K.
23-APP-09
Wu
G.-Z.
25-NEP-06
Wu
H.-C.
24-AAP-01
Wu
M.-C.
ENO-03Wu
X.-L.
NCO-01
Wu
Y.-W.
23-ENP-10
Wu
W. S.
EDI-02, ENO-01, 23-ACP-08
23-APP-01, 23-ENP-13, 25-ENP-01
24-ENP-02
Wu
Y.
25-NCP-12

X

Xu
Xu

Q.
Y.

Y

Yahaya R. B.
Yajima Y.
Yakushev A.
Yamada N.

－ 367 －

25-NPP-01
NCO-05
EDO-01
23-FKP-17
NCO-08, NCO-07, NCO-09
23-FKP-18
25-RPP-01

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Yamada T.
25-RPP-05
Yamada Takahiro 24-ENP-06
Yamada Yasuhiro NPI-01, 24-NPP-01, 24-NPP-02
24-NPP-03, 24-NPP-07
Yamada Yoshimune
24-FKP-18
Yamagata T.
24-AAP-05
Yamagata Takeyasu
FKO-02, 23-FKP-08, 23-FKP-22
24-FKP-12, 24-FKP-14
Yamaguchi M.
FKO-13
Yamaguchi Y.
FKO-07, 24-FKP-03
Yamaki S.
23-NCP-03
Yamamoto A.
25-RPP-03
Yamamoto H.
24-FKP-10
Yamamoto M.
PL-01, ENO-10, 23-FKP-25
24-ENP-09, 24-ENP-11, 24-ENP-13
24-ENP-14, 24-FKP-17, 24-FKP-19
25-ENP-09, 25-FKP-06
Yamamoto S.
25-RPP-04
Yamamura T.
23-ACP-07
Yamana H.
24-FKP-11, 25-ACP-04, 25-FKP-01
Yamanishi K.
23-ACP-05
Yamasaki T.
24-APP-02
Yamashita R.
24-ENP-08
Yamauchi T.
23-FKP-05
Yamazaki Y.
23-ACP-07
Yanaga M
24-FKP-09
Yang
G.
24-FKP-07
Yang
H.-B.
25-ACP-02
Yang
S.
23-RPP-06
Yang
W.
23-NCP-09
Yashima H.
25-NCP-04
Yasir
M. S.
EDO-01Yasu
H.
23-APP-08
Yasuda K.
25-NFP-01
Yasuhara H.
24-APP-05
Yasuike K.
24-FKP-18
Yasutaka T.
FKO-12, 25-ENP-10
YeY. L.
23-ENP-12
Ye
T.
23-ENP-13
Yeon
J.-W.
ACO-03
Yereminc A. V.
NCO-11
Yin
X.-J.
NCO-01
Yokokita T.
23-NCP-06, 23-NCP-07, 24-NCP-01
24-NCP-06, 25-NCP-06
Yokoyama A.
EDI-03,
NCO-13,24-APP-08
24-NCP-06, 25-FKP-02, 25-NCP-09
25-RPP-01, 25-RPP-06
Yokoyama H.
23-FKP-13
Yokoyama T.
25-NPP-04
Yokozuka Y.
25-AAP-05
Yonezawa C.
24-ENP-06
Yoshida G.
AAO-03, NPO-04, 24-NCP-05
Yoshida K.
24-ENP-13, 24-ENP-14
Yoshida S.
25-FKP-05
Yoshida Y.
25-NCP-02

Yoshihara Y.
Yoshikawa M.
Yoshimura T.
Yoshinaga H.
Yoshino H.
Yoshino K.
Yoshioka K.
Yuan
L.-Y.

Z

Zaizen
Zhang
Zhang
Zhang

Y.
H.
Lan
Lei

Zhang
Zhang
Zhang
Zhao
Zhao
Zheng
Zheng

R.
W.
Z.
L.
Y.-L.
H.-Y.
J.

Zhernosekov K.
Zhi
Q.
Zhuikov B. L.

－ 368 －

24-AAP-03
24-FKP-11
APO-05, FKO-07, 23-NCP-06
23-NCP-07, 24-FKP-03, 24-NCP-01
25-ACP-01
24-FKP-11, 25-FKP-01
24-FKP-11, 25-FKP-01,25-NCP-02
23-FKP-16
23-FKP-05, 23-FKP-24
API-02 23-ACP-06
25-FKP-08
24-NPP-04
25-NPP-02
25-NEP-06
23-ENP-16, 24-ENP-04, 24-ENP-05
25-ENP-03, 25-ENP-04
23-ENP-12
25-AAP-03
FKO-07 24-FKP-03
24-APP-03
API-02 24-NEP-01
25-NEP-07
ENO-12, 23-FKP-21, 24-FKP-01
24-FKP-07
23-RPP-02
23-NCP-09
25-RPP-02

Co-sponsorship
Ishikawa Prefecture

Kanazawa City

Kanazawa University

The Chemical Society of JapanThe Japanese Society of Nuclear Medicine

The Physical Society of Japan

Japanese Society of Radiation Chemistry

Atomic Energy Society of Japan

Japan Association of Solvent Extraction

The Geochemical Society of JapanThe Rare Earth Society of JapanThe Pharmaceutical Society of Japan

Japan Atomic Energy Agency (JAEA)The Japan Society for Analytical Chemistry

Advanced Science Research Center, JAEA

IUPAC Sponsorship
IUPAC sponsorship implies that entry visas will be granted to all bona fide chemists provided application
is made not less than three months in advance. If a visa is not granted one month before the meeting,
IUPAC Secretariat should be notified without delay by the applicant.

IUPAC(International Union of Pure and Applied Chemistry)

Exhibitors
Hitachi Aloka Medical, Ltd.
TRISKEM INTERNATIONAL
raytest Isotopenmessgeräte GmbH
Canberra Japan K.K.
Saint-Gobain K.K.

－ 369 －

Sponsorship Company
Nuclear Safety Technology Center
Niki Glass Co. Ltd.
Nakayama Co. Ltd.
Tokyo Nuclear Services Co., Ltd.
Japan Environment Research CO., Ltd.
Hokuriku Nuclear Conference
Spectra-Physics KK
Chiyoda Technol Corporation
Ozushoukai. Inc.
ING Corporation
Fujimoto Science
Art Kagaku
Rikoh Kagaku
Marubuntsushou co. Ltd.

－ 370 －

－ 371 －－ 372 －－ 373 －－ 374 －－ 375 －－ 376 －－ 377 －－ 378 －