。Jr'aupJr'esentations
Oral
Presentations

Wednesday,
Wednesda昂 25
25 September
Septembe陀 2013
2(0 13Hall& MeetingKanazawa Bunka Hall
Ha且＆MeetiIDlg Room,
Room，羞nazawaB口n註aHa且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
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

7EDNESDAY  3EPTEMBERHall
Meeting Room
0LENARY

9:30

PL-06

M. A. Denecke
0LENARY
J. Hatazawa

10:00#OFFEE "REAK

10:20

RPI-01)NVITED

ACI-01)NVITED

10:50

RPI-02

D. S. Wilbur)NVITED

ACI-02

J. Li)NVITED

11:20

RPO-01

11:40

RPO-02

12:00

S. Lahiri
General
ACO-01
E. Aneheim
General
ACO-02
Y. Hatsukawa'ROUP 0HOTO (ALL,UNCH 4IME

Y. Kitatsuji
GeneralA. Kirishima
GeneralH. Hayashi

13:20
13:40 *.23 'ENERAL !SSEMBLY
&OR -EMBER OF *.23
14:00
14:20
14:40

*.23 -EETING

15:00
15:20
15:40

#OFFEE "REAK
RPO-03General

ACO-03

L. Safavi-Tehrani

16:00

FKO-11

16:20

FKO-12

16:40

FKO-13

17:00

FKO-14GeneralE. Rasmussen
GeneralK. Minami
GeneralT. Kawamoto
GeneralD. Parajuli

ACO-04
NCO-13
NCO-14
NCO-15

17:20#OFFEE "REAK
17:50*.23 !WARD 0RESENTATION
/PEN 3ESSION
4 +IMURA

18:30
18:50
0OSTER 3ESSION
20:00－ 69 －

GeneralT.H. Park
GeneralN. Aoyagi
General
A. Toyoshima
GeneralP. Steinegger
GeneralR. Tripathi

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

PL-05

Actinide speciation using synchrotron-based methods
1

M. A. Denecke1

Dalton Nuclear Institute, University of Manchester, Manchester, M13 9PL, UK

Abstract – 3YNCHROTRON BASED TECHNIQUES ARE INCREASINGLYUSED TO CHARACTERIZE MATERIALS AND ELUCIDATE DETERMINANT
PROCESSES RELEVANT TO THE NUCLEAR FUEL CYCLE -OST RECENTADVANCES ARE DRIVEN BY THE NEED TO CHARACTERIZE MATERIALSWITH HIGH SPATIAL RESOLUTION FOR EXAMPLE LOCALIZEDCOMPONENTS
OFHETEROGENEOUS
SYSTEMSOR
INTERSTITIALINTERFACIAL JUNCTIONS )N THIS PRESENTATION
EXAMPLES OF SYNCHROTRON BASED INVESTIGATIONS COVERING A
WIDE RANGE OF WAVELENGTHS INFRA RED TO HARD 8 RAY ANDSPATIAL RESOLUTION NANOMETER RANGE TO BULK WILL BE
INTRODUCED 4HE EXAMPLES ARE CHOSEN TO ILLUSTRATE VARIOUS
THEMES OF RESEARCH AND DEVELOPMENT OVER THE ENTIRE RANGEOF THE NUCLEAR FUEL CYCLE FROM POWER PLANT LIFETIME EXTENSIONSCENARIOS TO NUCLEAR WASTE DISPOSAL AND FUTURE FUELTARGET
DEVELOPMENT
Keywords –Actinide speciation, X-ray techniques, synchrotron
radiation－ 70 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

PL-06

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

RPI-01

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).

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

RPI-02

Generation of nuclear data for the production of 97Ru from 12C+89Y reaction
Moumita Maiti1, Susanta Lahiri2
Department of Physics, Indian Institute of Technology Roorkee, Roorkee-247667, India
2
Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Kolkata-700064, India

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.
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]1

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

¢蛉

9..........、¢

.....
Rh-97
、.、-‑
.
:
...
Ru-97
ｷ‑‑
‑ \.........
Rh-97+Ru-97
・：一

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

140 ‑

Ru‑97

:
C120 ~

IIIII`<:ヽ:i.こ 100 ‑・•
c
o 80

=
よ 60
で

•a一』

>
‑

4o
20

゜

III. RESULTS AND DISCUSSION

1

I

I

＾こロド～寸ドドベ
←1
げ)
r---•
1
m O
OO m
忠
Ji
m I 、iこ `l (iドEnergy[MeV]

97

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

RPO-02

0RODUCTION OF M4C FOR #OMPTON #AMERA )MAGING
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 University
2!BSTRACT – 7ITH THE DEVELOPMENT OF THE #OMPTON CAMERA WHICHCAN REALIZE HIGH POSITION RESOLUTION TECHNETIUM ISOTOPES EMITTINGHIGH ENERGY GAMMA RAYS ARE REQUIRED )N THIS STUDY TECHNETIUM
M WHICH EMITS SOME GAMMA RAYS WITH HIGHER THAN  KE6 WAS
PRODUCED BY THE -OP N M4C REACTION )MAGE OF GAMMA RAYSFROM 4C M WAS TAKEN BY A #OMPTON GAMMA RAY CAMERA+EYWORDS –4ECHNETIUM M #OMPTON GAMMA RAY CAMERA -$0
LABELING -OP N M4C REACTIONI.

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 PA. 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.
S
o
l
v
e
nt
f
r
ont

MEK
Sa
i
l
ne
Di
r
e
c
t
io
nofs
o
l
v
e
ntmovement

Fig.2 Autoradiography images form 95mTc-MDP. MEK
and physiological saline was used as solvents.
2EFERENCE[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￨Elution ￨•=Tc

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 －

ACI-01APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013����������������������������� �������������������������������������
�������������������������������������������
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 verticalaÐ(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.
40

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

353025201510(-O―E二）M6お uwo>l-e-0”
e3

Keywords Ð Actinyl, Relativistic Effects, Spin-Orbit Coupling,
Photoelectron Spectrum, Ab initio Wavefunction Theory

10

15

20

25

30

Poi
nt
sa
l
o
ngLTPath��������. 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 (����).

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

ACI-02

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).

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

RPO-03

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

FKO-11

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

!UTOMATIC #S 5PTAKE $EVICE FOR 2ADIOACTIVE #S %VALUATION IN %NVIRONMENTAL 7ATER
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.

!BSTRACT –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.
+EYWORDS – 0RUSSIAN BLUE RADIOACTIVE CESIUM ENVIRONMENTAL WATERMONITORING

I.

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

Flow

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
MeasuringT
imeofGe1,800sec
Flow
P
a
s
s
Rat
e
Wa
t
e
r
(
L
/
mi
n
) (
L
I

Env i『onmen tal
Wa t e 『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 Pm of pore-size. Dissolved Cs in thefiltrate was adsorbed and concentrated onto PB. This PB

Paddy

03

419

Pond

0
.
3

348

.

Samp
l
e

(
B
q
/
L
)

Coun
t
ing Det
ec
t
ion
E
r
r
o
r
L
imi
t
Bq
/
L
)
ほ Bq/L) (

s
s

0068

00034

00036

PB
Column

0014

00020

00031

s
s

0042

00031

00047

PB
Column

0049

00038

00037

『-Cs※
Concen t『a ti on

Car
tr
i
dg
e

tr
i
dg
e
Car

※ Cs134+Cs137

[1]
[2]

－ 82 －

Yasutaka et al.(2013), Appl. Chem. (in Japanese), in press
Tuji et al. (2013), APSORC13

FKO-13!03/2# TH !SIA 0ACIFIC 3YMPOSIUM ON 2ADIOCHEMISTRY+ANAZAWA *APAN   3EPTEMBER 0ILOT PLANT FOR VOLUME REDUCTION OF #S CONTAMINATED COMBUSTIBLE MATERIALS+IMITAKA -INAMI (IROSHI /GAWA (ISASHI 4ANAKA !KIRA 4AKAHASHI 4ATSUYA 5CHIDA !KIKO+ITAJIMA $URGA 0ARAJULI 4OHRU +AWAMOTO -ASAKI 9AMAGUCHI -ITSUO /SADA .OBUAKI /TAKE
3YUICHI 3ATO 2YUICHI +AMIMURA AND 9UKIYA (AKUTA .ANOSYSTEM 2ESEARCH )NSTITUTE !)34 *APAN
4OKYO 0OWER 4ECHNOLOGY ,TD *APAN!BSTRACT n7E REPORT THE PILOT PLANT TEST FOR VOLUME REDUCTION OF
RADIOACTIVE #S R #S CONTAMINATED COMBUSTIBLE MATERIALS FOR THE
VOLUME REDUCTION OF THE CONTAMINATED WASTE AND TO REDUCE THE R #S
LEACHING FROM THE WASTE THE COMBUSTIBLE WOOD IS INCINERATED BY THE
BIOMASS BOILER 4HE RADIOACTIVE #S STORED IN ASH IS EXTRACTED INTO
THE WATER AND FINALLY IS CAPTURED INTO THE 0RUSSIAN BLUE
NANOPARTICLE ADSORBENTS
+EYWORDS n RADIOACTIVE #S 0RUSSIAN BLUE INCINERATION ADSORBENTS)).42/$5#4)/.

!ROUND &UKUSHIMA AREA THERE ARE SO MUCH COMBUSTIBLE
MATERIALS CONTAMINATED BY THE RADIOACTIVE #S R #S EG THE
WOOD IN FORESTS MUNICIPAL WASTE AND WASTE FROM AGRICULTURE
*APAN GOVERNMENT SHOWED THE POLICY THAT THE MUNICIPAL WASTE
WITH R #S CONTAMINATION SHOULD BE INCINERATED )N ADDITION
THE BIOMASS POWER SYSTEM WITH THE INCINERATION OF THE
CONTAMINATED WOOD MATERIALS IS ALSO PLANNED AROUND&UKUSHIMA AREA
4HERE ARE PROBLEMS IN THE MANAGEMENT OF THE INCINERATION
OF THE COMBUSTIBLE MATERIAL /NE IS THE LARGE AMOUNT OF THE
VOLUME OF ASH AND THE OTHER IS THE R #S LEACHING FROM THE ASH)N ORDER TO SOLVE THE PROBLEMS THE EXTRACTION OF LEACHABLE R#S FROM THE ASH AS THE PRE TREATMENT BEFORE DISPOSAL IS
GATHERING ATTENTION )N ORDER TO CONFIRM THE METHOD FOR THE
SAFETY MANAGEMENT BASED ON THE INCINERATION AND THE R #S
EXTRACTION FROM THE ASH WE CARRIED OUT THE PLANT SCALE TEST&IG  FOR VOLUME REDUCTION OF #S CONTAMINATED COMBUSTIBLE MATERIALS A
BIOMASS BOILER WITH GAS FILTERS FOR #S REDUCTION FROM EXHAUST B !SH
DECONTAMINATION UNIT)) -%4(/$ !.$ 2%3543
4HE FIREWOOD WAS INCINERATED IN A BIOMASS BOILER SHOWN IN&IG A  4O AVOID THE EMISSION OF THE R #S IN THE EXHAUSTTHE BAG FILTER AND (%0! FILTER IS PREPARED 4HE R #S IS TRAPPEDIN ASH MAINLY STORED IN THE BOILER AND THE BOTTOM OF THE BAG
FILTER )N THE NEXT STEP THE R #S IS EXTRACTED FROM THE ASH INTO
THE WATER IN THE ASH DECONTAMINATION UNIT SHOWN IN&IGB ;= &INALLY THE R #S IS CAPTURED BY THE ADSORBENTS
WITH 0RUSSIAN BLUE NANOPARTICLES SHOWN IN &IG
7HEN  KG OF FIREWOOD WAS INCINERATED R #S
CONCENTRATION ^  K"QKG  KG OF ASH WAS OBTAINED4HE HIGHEST R #S CONCENTRATION OF WAS ^  K"QKG AT THE
BAG FILTER 4HE R #S IN THE EXHAUST IN THE INCINERATION WAS
UNDETECTABLE 4HE R #S EXTRACTION RATIO FROM THE ASH INTO
WATER WAS   4HE R #S IN THE WATER AFTER THE
DECONTAMINATION OF THE ADSORBENT WAS ALSO UNDETECTABLE

&IG  6ARIOUS #S ADSORBENTS WITH 0RUSSIAN BLUE NANOPARTICLES;=－ 83 －$ 0ARAJULI ET AL %NV 3CI 4ECH 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.

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.

INTRODUCTION

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.

100
80
ま

でコ 60

"C

u

c
~ 40
20

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

゜

ashmass

133‑CsK

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.

1) ~Ir配四（＇団．以 9Am▼)C・ 1 L ‑ . llL ↓」 l 」二』．．．叫2) Evnpom逼 10mLd 臼m pie mu口to dm`迄\
3
) o
,.
.
.
ホ"In 3MHN0,‑1MA~N0, 1,
4) Add1Ma ぬ“はc 配a•F.,,.

5) E
lu¥
82M HNO
,
6
) E
l
u
l
a2M J
;NQ
,
‑
0
.t
M NaNO,
,
,
.
.
• P
u
>
‑‑
ｷp
7
) E
l
u
1
e0
.
5M HNO,and9MHCJ
8
) E
l
u
1
eJ M HClandc
o
l
¥
e
c
l
"
AmundCm

Keywords
Actinides, Extraction chromatography, Radioactive wastes

I.

C
,
,F
,cop
r
e
c
,p
i
t
ai
t
on

a-s p ect『ometry

INTRODUCTIONP
uand

II. EXPERIMENTAL
A radiochemical determination procedure of Pu, andAm/Cm nuclides is illustrated in Scheme 1.

TRUResin

弓A m recove 『y:Management 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.

li 1 ー・ 譴l,9Fo9•)90'/,~TIMS• Pude
t
em,ma
i
t
on
"ペpe ol n;N油吋，，， Pu,,,..四 Pu'

TIMS(w/l OMS) こ 9 ヨ Pu,'"Pu, "'Pu

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

ACO-04

APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013������������������������������������ ������������������������������
���������������� ������������������� ����������������� ������������������������������
���������������������������������������������������������������������������
�������������������������������������������������������������������
������������������������������������������������������������������������������������
�������������������������������������������������������

� ��

�����

��������
��������������������

���

���

�����

�����

�����
���

�����

���

�

�����

�����

�����
�����

���������������������������������������������������
������� �������� �� ����� ���� ���� ���������� ������ ��������
���������� ������������������������������������������������
�������������������� �������������� ��������������������������� ��� ���� ���������� ���� ��� ���� ����� ��� ������������ ��� ����������������������� ������������ ���� ���� ����� ����� ��������
������ � ������������ ������ ��� �������� ����������� ������������ ��������� �� ������������� ���� ����������� ��� ���������������� � ���������� ������ ��� �������� ����������������� ���������� ������ ����������� ���������� ������������������� ������� ���������� ��� � �������������� �������
���������� ��� ���������� ������������� ����� ��� ������ �������� ��������� ������������ ������� ��� ���� ����������� ������������������������������������ ������� ���������������
��������� ����� �������� ���� ���������� � ���� ����� ��������������� �� �������������� ������ ��� �� ������� ��� ��������
���������� ��������� ��� ����� ������������� ���������
��������� ��� ����� ��� ����������� ������� �������������
������� ���������������������� ������� ��� ������������������������������������� ����� �������� ����� ����� ������ ������ ��� ����� ������������ ������������ ���������� ���� ���� ��������� ��� �������� ������ ����������� ������� ��� ��������� ������������� ���� ���� ����������
������� ���� �������������� ��� ����� � ��� ��� �����������
��������� ���������� ��������������������������������������
��������������� ������� ������������� ����� � ���� ���������
�������������������������������������������������������������
���������� �������� ��� ��� ��� ������������� �������� ������������ �������� ��������������������������
��������� �������� ��� ���������������������� � ������
������ �� ������������ ������ ��� ����� �������������� ����������������� ��� ��������� ���������� ������ ������������ �����
����������������������������������������������������������
���������������������������������������� ������ ���� �������� ��� ���� �� ��� ��� ����������� ������������ � ������ ������������ ��������� ��� ���� ��� ����� � ����� ��������� ���������

Keywords Ð Uranium(IV), (VI) complexes, Luminescence, TimeResolved Laser-induced Fluorescence Spectroscopy (TRLFS)

���������������������������������������������������������
������������������������ ��������������� �������� � �������
���� ���� ���������� � ��������� ���� ��� �������� � ��������
����� �������� ���� ��������� ��������� ������� ������ ��� �������� ���� ���� ���� ���� ���� � ��������� �� � ��� ����� ���������������������������������������������������� �������� ������
������ �� �������������� ����� ��� ��� ����� ��� ����� ���� ���������
������ ������ �� ������� ��������� �� ����� �� ���������� ������� ������ ���������� ����� �������� ���� ���� ���� ���� �������� ��� ������ ���� ��� ����� ��� ���� ������ ��� ������� ��������� ���������� ��� ������������� ��� ������ ����� ��� ��������������������������������������������������������������
������������������� ��������������������������������������������
���� ����������������� ������������������������������������ ��� ���������� ����� ������� ��� ��������� ����������� ��������������� ������� ���� �����������������������������

���������������������������

Abstract Ð Syntheses and optical properties of tetravalent or
hexavalent uranium compounds were studied to understandphoto-physics under the unexplored condition such as in nonaqueous media or the cryogenic temperature. Uranium dioxide,
halides or uranium metal were used as starting materials to yield
the luminescent compounds in a series of organic solvents; theluminescence-solvent structure relationship was investigatedusing UV-Vis absorption and time-resolved laser-induced
luminescence spectroscopies.

���

���

���

���������������
������� ������������ ��������������� �������������������� ��� ����� ���������������� �� ������������������������������������������������Chem.
Commun. ����� ������� ��������������� Coord. Chem. Rev. ������������������������ ������������������������������������������������������������
�������� ��� ���������� ��� ��� ���������� ��� ��� ������� RSC
Advances� �������� ������������� �����������������������������������������������������������
����������������Environ. Sci. Technol.� ����� ����������������� ��� ��� ��������� ��� ������� ��� �������� ����� ������� ��� �������
����������������J. Environ. Qual� ��������������������� ��� �������� ��� ��������� ��� ��� �������� ��� ���������� ������������������������������������������������������������
��������Chem. Commun. ����������������������� ����������������Dalton Trans�� ����������������

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

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

NCO-15

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

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.

the 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earlier measurements in····•~1;
19• ‑ 唇喜，‑.lflf
F induced reactions

•;[3-5]. However, the•t••—•comparable
cross
•^
••sections of C and N
PLFs indicate the role %  -E6ofalphacluster
 ..
.
structure, leading to a#large cross section for
"

g•*
"E
even Z C PLF. Also, 12C,I
yield was significantly
larger than the other%  -E6•
isotopes indicating thepreferential break-up of        � 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.

.

l-

二言
l

3上

D�D� MBSR

4

3
入ょ

・六

▲壽

・六
●蚤

傘合上

皐舌入上

......

..

•中．屯心さ

傘綸

．＾書

'▲由

。

LAB

拿〇

*A

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), thatヽf屯III. RESULTS AND DISCUSSION,

傘麿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.

..
a"II. EXPERIMENTAL DETAILS

LAB

●●傘囀

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.

、-t上INTRODUCTION

•’^}

1

I.

▲-*上

1

皐困

▲-↓上入↓

玉一↓上Keywords – Incomplete fusion, angular distribution

LAB

REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

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).

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

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[1]

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).

－ 90 －

PosterPost
erSessionSess』on 3
3
September 2013
Wednesday,Wednesday,25
25Septembe『
2013

1
8
:
5
0~ 20:00
2
0
:
0
0
18:50

Scientific
Topics (Abbrev.)
Sc錮en碑cThpics
伍bbrev。)
1.
Fukushima issues (FK)
1 。JFukush江ma（翌記）
2.
Education in
nuclear andradiochemistry (ED)
2 。匹d1UlCation
innuclearandmad土ochellllllis泣ァ（図D)
3.
3 。 Nuclear
N1UlCIear forensics
foren磁cs (NF)
(N官）
4.
energy chemistry4。 Nuclear
N1UlCIearene喧ychemis切 (NE)(N回）
5.
chemistry (NC)5 。 Nuclear
N1UlCIearchemis切
6.
Actinide chemistry (AC)6。 Ac益n這echemjst巧仏C)
7.
Environmental radiochemistry (EN)7。四mimnmentalra五ochem諏万（四N)8.
chemistry andNuclear medicine (RP)8。 Radiopharmaceutical
Ea凸opha茫llllllace1Ulticalchemist巧andNucleamne五cine
(
B
P
)
9.
materials science9。 Nuclear
N1UlCIear probes forfomnaterials
sc涵ence (NP)(NP)
10.
Activation analysis (AA)10。 Activaもionanalysis
閲
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

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.

II. EXPELIMENTS

2.1
0.
'0
0.
000
m
-2
届 Ul,
0i
. ―
gi”
]d
T』
T
.―
-I
=v
-H

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•Lo.6150high ratio of
238
Pu/239,240Pu

三
中i

.

争

。 。

60
s
o
100
m
(
l
l
o
.
1
c
u
v
1
9yor19’C`’ 恥 I g l

20

』0

120

140

Fig.1 Correlation between 238Pu and 137Cs
09

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 －

＿迎苫u
＿-Oゴ
イ'o
J
u
II
t
Iし
]g ==5三-Sample collection

OS

07

06
05

`“/

00
0.9

01
0.1

゜゜

;o

LOO

J!
'
O

200

2~0

9'’’`’’U ら ,cllvll y orc._13- IB`' ほ I

Fig.2 Correlation between 110mAg and 137Cs

30tl

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

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.
120

Fukushi
ma

100
80
。

6

[·邑
u己[<

40
00
2

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.
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

Oldleaves
Unwashed
Washed!
Pi
neleaves
Newleaves
Unwashed
WashedRice

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.

〇）

2

R² = 0.94

1.5

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

25-FKP-05

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 －

100

5

t

80

旦

ｧ

60 m

i
2

40 e
n

八

g

20 ^
ャ冬
ー＇

ol, 1 ,I .
I..‑I・ I I
ｷ
M J
2011

I

•'I

I
‑I

I,
•

‑
1Q

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

25-FKP-08

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

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

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
1

2

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

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

'

00
01

1;;,uuu4o;swno:
J

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.

1000

゜

200

400

600

800

1000

c
h
a
n
n
e
l(
e
n
e
r
g
y
)
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 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-FKP-10

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.
139.2E

140E

1
3
9
.
6
E

1404E
k

’’

.—•..

()

o’

l
376N

&$.00g.'. !BUKUMA．＂・ l9

./

I
珈

1
4
1
,
2
E

｀し

.AKADORI

372N(IGHLANDS
,

372N

III.

High 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.

.
i

C

1396E

140E

• 404E

1408E

RESULTS AND DISCUSSION[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.

“_,r‑‑

ぉ． BN4139.2E

1408E

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.

141.2E

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

25-EDP-01

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

25-NFP-01

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).

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

25-NEP-01

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

25-NEP-02

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

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.

□ only o
:i
mp
.Li
J
iO3
9
9
+
oo
n
l
yD
̲
'
i
m
p
.
L
,
i
J
iO99
2
1
8
•

He+‑D/i
m
p
.L
i
2T
i03

I

w,
/

－ 292 －Ul

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

L.2.LLII. EXPERIMENTAL

0000000"
7654321"
s a O
:
:
i u
oqd .IOS<Ol

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..

Fig. D-TDS spectra for Li2TiO3 and Li1.8TiO2.9 900
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

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

2

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.

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.

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.

‑

.
.
t
CH,

‑ ‑

iで0^\

.
.

l

,
ｷ
ｷ

文cc:
:0
,
}

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\oッ）.................................................

DB18C6.
.
‑ . . .

CH，［で01

1
ｷ

改立：））

＼に，0ジi.............................................“ぷFigure 1 Chemical structure of DB18C6 resin

This work was partially supported by the Grant-in-Aid for
Scientific Research (B) (KAKENHI No. 23360423).
[1][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

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

25-NEP-04

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.

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

25-NEP-05

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

25-NEP-06

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

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

25-NEP-07

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

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.
100

X

ー

;
.l
i
t
s
i
g
l
ep
ke
l
l
(
%
)

゜

J
H
ま）A:><P
I!
U

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

X
X

10

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.

•

i
ng
l
epkef
f
(
%
)
e
xps

＿対数(totaleff(T))

:
.
.
[十←』
J
X

し

t
ot
alef
f(
T
)

IX

X

II. EXPERIMENTAL

f(%)
cascadepkof

•

¥X

100

1000

X

10000

Ene 『gy (keV)

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 －

"$!# @4 ?5-"-/525/$E9<;?5A9;:#-05;/4195?@>E
-:-F-C--<-:  $1<@19.1>

25-NCP-02

           %-7-95E- **;?450- %-:-7- %A655 $A7A@-:5 %$-:; *;?45:; *5:A9- #!7A9A>- $$45.-@#1?1->/4#1-/@;>:?@5@A@1E;@;&:5B1>?5@E
>-0A-@1$/4;;8;2:35:11>5:3E;@;&:5B1>?5@E ""#%&$









%41 01B18;<10 :1A@>;: 5>>-05-@5;: -<<->-@A? @>-:?<;>@
?-9<81? 8;-010 ;: - /->>51> 2>;9 -: 1D<1>591:@-8 >;;9
-06-/1:@@; @41>1-/@;>@;:1->.E@41>1-/@;>/;>1@4>;A34-
4;>5F;:@-8.1-94;81  ;2&# %41?-9<81/->>51>4-?
-/-<-/5@E;2-.;A@/9G/9G /9 -:09-@1>5-8?;2
A< @;  73 /-: .1 8;-010 %41 /->>51> /-: .1 /;::1/@10
C5@4<8-?@5/@A.1?@;9;:5@;>?-:05:?@>A91:@?<8-/10-@@41
1D<1>591:@-8 >;;9 -@ - 05?@-:/1 ;2 -.;A@  9 2>;9 @41
>1-/@;> C-88 5>/A8-@5:3 85=A50 ?-9<81? /-: .1 5>>-05-@10
A?5:3<A9<?-:0@41@A.1



1A@>;: 5>>-05-@5;: 1D<1>591:@? ?A/4 -? :1A@>;:
-/@5B-@5;: -:-8E?5? -:0 5?;@;<1 <>;0A/@5;: 4-B1 .11:
<1>2;>910 A?5:3 B->5;A? -<<->-@A?1? -@ >1?1->/4 >1-/@;>?
!:1 ;2 @41 9;?@ 31:1>-8 -<<->-@A? 5? - <:1A9-@5/ ?E?@19
C45/4 @>-:?<;>@ ?9-88 /-<?A81? 1:/8;?5:3 ?-9<81? 2>;9 -
8-.;>-@;>E@;-:1A@>;:5>>-05-@5;:25180:1->->1-/@;>/;>1
;C1B1> ?5F1? -:0 C1534@? ;2 ?-9<81? ->1 8595@10 .E @41@>-:?<;>@5:3 /-<-/5@E ;2 /-<?A81? -:0 5>>-05-@5:3 85=A50
?-9<81? 5? 05225/A8@ 2;> >1-/@;> ?-21@E 5: @41 <:1A9-@5/
?E?@19  :1C :1A@>;: 5>>-05-@5;: -<<->-@A? 4-? .11:
01B18;<10 -@ E;@; &:5B1>?5@E #1-/@;> &#  (@41>9-8<;C1>@;;B1>/;91?A/48595@-@5;:?

-99->-E;?1#-@19E࣭?

 %#!&%!



%41 :1A@>;: 28AD -:0 3-99->-E 0;?1 >-@1 -@ B->5;A?
<;?5@5;: ;2 5>>-05-@5;: 25180 ;2 @41 -<<->-@A? 4-B1 .11:
91-?A>10 %41 :1A@>;: 28AD C-? 91-?A>10 .E -/@5B-@5;:
91@4;0 A?5:3 3;80 C5>1? %41 3-99->-E 0;?1 >-@1 C-?91-?A>10 .E @41>9; 8A95:1?/1:/1 0;?591@1>? ;@4
91-?A>191:@? C1>1 <1>2;>910 -@ @41 <;?5@5;:? ;2
 @;
/9 -@ 5:@1>B-8? ;2   /9 -:0 ;:8E :1A@>;: 28AD
91-?A>191:@?C1>1/->>510;A@-005@5;:-88E-@ -:0 /92>;9@41>1-/@;>?5011031%41>1?A8@?;2@4191-?A>191:@?
->1?4;C:5:53  %41C501>-:31;2:1A@>;:28AD@4-@5?
:/9 ? C-? ;.?1>B10 C45/4 >1-85F1?
2>;9  @;
B->5;A? 75:0? ;2 :1A@>;: 5>>-05-@5;: 1D<1>591:@? %41
:1A@>;:28AD-:03-99->-E0;?1>-@101/>1-?1-? @41>-:31
2>;9 @41 1031 5:/>1-?1? %41 01/>1-?5:3 @>1:0 ;2 :1A@>;:
28AD /4-:31? ->;A:0 @41 >-:31 -@ /9 .1/-A?1 @41?1/@5;:-8 ?4-<1 ;2 @41 .1-9 4;81 /4-:31? 41>1 %41A:52;>95@E;2:1A@>;:28ADC-? -8?; 91-?A>10.E-/@5B-@5;:
/92>;9@41>1-/@;>
91@4;0A?5:3"%2589?  -@1B1>E
?5011031-:05@C-?2;A:0@41:1A@>;:28AD-@-?1/@5;:5?
A:52;>9

'% ! ) #"   " #"  "$" '!!
!# " $&# %! &%#! &) #*!$#%

1A@>;:28AD:࣭/9 ࣭?

!" " )  %  "#!   $ #! #"   "& "!!$"'"$ !"' "   "#!  " ! "     ! "' "  #"  " " " " "       $ #!
!! &!  #!! "%" #" !  ! !!    " & "!" #"! %" "#! "" (  !# "! '  " & "!  !"" !! "  "   " "       " #"  #&$ #!& "!'% #" #&   
#" "$"'!!  !!#!!!  ' "!  " !"!     " ' " "#! "$' " #"  #&   ' ! "!!# "$ #! "!"
!" #   " #" ! !  "  #!'"' ! !   "    " !"!  " "#!"#"#     ""! #-:312>;9>1-/@;>/;>1/9
53 '->5-@5;:;2:1A@>;:28AD-:03-99->-E0;?1>-@1-@B->5;A?
<;?5@5;:?5:@41 .1-94;81
+ ,－ 299 －

%-7-95E-1@-8">;/#-05;/459/@   APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

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
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).

#%"$ @4 ?5-#-/525/%E9<;?5A9;:$-05;/4195?@>E
-:-F-C--<-:  %1<@19.1>

25-NCP-04

    
 
!5:;95E- &"9;@; $!-7-3-75 !&-7-4-?45 *-?-9-@?A %45:;4->- %%1759;@; *-?459- %%45.-@- &%459-  -@?A9A>-  -35C->- *C-9;@;%-@;4)-2211-:0!5?455FA95
>-0A-@1%/4;;8;2%/51:/1"?-7-':5B1>?5@E$1?1->/4$1-/@;>:?@5@A@1E;@;':5B1>?5@E$1?1->/41:@1>;2!A/81->#4E?5/?"?-7-':5B1>?5@E$-05-@5;:$1?1->/41:@1>534:1>3E//181>-@;>">3-:5F-@5;:!A/81->%/51:/1-:0:35:11>5:35>1/@;>-@1-<-:@;95/:1>3E31:/E1<->@91:@;2#4E?5/?#A>0A1':5B1>?5@E
%<-/1%/51:/1?-.;>-@;>E':5B1>?5@E;2-852;>:5-

*(!#$ + #!$$$%! 
! ! #% &%#!

&%#!  &#%! &4101@1>95:-@5;: ;2/>;???1/@5;:?.E:1A@>;:5:0A/10
:A/81-> >1-/@5;: 5? B1>E 59<;>@-:@ 5: @41 B51C <;5:@ ;2
?<-/1 -:0 <8-:1@->E ?/51:/1? @; 5:B1?@53-@1 @41 45?@;>E ;2
/;?95/ >-E 1D<;?A>1 &41?1 0-@- ->1 -8?; >1=A5>10 2;>1?@59-@5;:;2>1?50A-8>-05;-/@5B5@51?5:-//181>-@;> 2-/585@51?
;C1B1> />;???1/@5;:91-?A>191:@?5:@411:1>3E>135;:
 1( 4-B1 ?/->/18E .11: A:01>@-71: .1/-A?1 ;2 @41
05225/A8@E5:;.@-5:5:345341:1>3E9;:;1:1>31@5/:1A@>;:?
%; :1A@>;:5:0A/10 />;???1/@5;:? ->1 1?@59-@10 .E -<>;@;:5:0A/10 />;???1/@5;: C5@4 @41 ?-91 1:1>3E ;>
/-8/A8-@10A?5:3@41;>1@5/-89;018?
"A>3>;A<4-? 01B18;<10-91@4;02;>01@1>95:-@5;:;2
4534 1:1>3E 9;:;1:1>31@5/ :1A@>;: />;???1/@5;:? -@ @41
$1?1->/4 1:@1> 2;> !A/81-> #4E?5/? $!# "?-7-':5B1>?5@E + , &45? 91@4;0 5? .-?10 ;: @C; :1A@>;:
5>>-05-@5;:1D<1>591:@?<>;0A/10 .E 5<: 1 >1-/@5;:
C5@4@C;05221>1:@-:381?2;>@41-D5?;2@41<>59->E<>;@;:
.1-9 @;/;>>1/@@41/;:@>5.A@5;:;2@418;C1:1>3E :1A@>;:
>1-/@5;: + , : @45? ?@A0E C1 <1>2;>910 />;???1/@5;:
91-?A>191:@? C5@4  -:0  1(:1A@>;:?2;>A-:0!.
88 :1A@>;: 5>>-05-@5;: 1D<1>591:@? C1>1 <1>2;>910 -@! .1-985:15:$!#)1;.@-5:10=A-?59;:;1:1>31@5/:1A@>;:28A1:/1C5@4  -:0  1(2>;9-:0   1( 5:/501:@ <>;@;: .1-9 >1?<1/@5B18E &41
01@-58? ;2 @41 1D<1>591:@-8 91@4;0? C1>1 C>5@@1: 5:
18?1C41>1 + , #>;0A/10 ?4;>@85B10 >-05;:A/8501? C1>1
501:@52510.E4534<A>5@E31>9-:5A9 01@1/@;>?-:0:1A@>;:/>;???1/@5;:?C1>101@1>95:10)1-8?;<1>2;>910<>;@;:
5>>-05-@5;: 1D<1>591:@? -@ @41 ?-91 .1-9 85:1 @; ;.@-5:<>;@;:/>;???1/@5;:?C5@4@41?-915:/501:@1:1>351?

&411D/5@-@5;:2A:/@5;: ;2  ;2;>A@->31@.E<>;@;:
-:0 :1A@>;:5:0A/10 >1-/@5;:? ->1 ?4;C: 5: 53A>1 C5@4@41 >18-@10 85@1>-@A>1 B-8A1? + , )1 2;A:0 @41 />;??
?1/@5;:? ;2 :1A@>;:>5/4 :A/8501? ?A/4 -?  ; .E :1A@>;:
.;9.->091:@ >1-/@5;:? 4-B1 - @1:01:/E 8->31> @4-: @41?1
.E<>;@;:>1-/@5;:?-:0<>;@;:>5/4:A/8501? ?A/4-? ;
4-B1 -: ;<<;?5@1 @>1:0 : @41 <>1?1:@-@5;: C1 C588 >1<;>@@41 01@-581D<1>591:@-8/>;???1/@5;:0-@- -:005?/A???A/4
/>;???1/@5;: 05221>1:/1 .E <>;61/@581 A?5:3 19<5>5/-8
9;018?2;>:A/81->?<-88-@5;:>1-/@5;:?



;
fi
—― oo仕 a/>;???1/@5;:9.

$%#%+  #*! ! #% &%#!  &#%! $!'   '   $%& !# &    %#%$)%%! & %! $!$!#%'#! &$ (#%# *#*$"%#!%#* $!$&##!$$$%! $*"#!%!  & #%! $ (% % $  #* #   
!"# (%  !%#  #!$$$%! $ ! &%#! #&$ * &%#!  & #%!  (# $*$%%* ##% %$*"#!%!  &#%! $

ロ

ロ？



i

  1(:1A@>;:@45?C;>7   1(<>;@;:@45?C;>7
    1(:1A@>;:+ , 1(:1A@>;:+ ,  1(<>;@;:+ ,  1(<>;@;:+,<>;61/@5811:1>3E 1(
53A>1 D/5@-@5;:2A:/@5;:2;>:-@A:D ;-:0:-@A<D ;
>1-/@5;:?
+ ,
+ ,
+ ,
+ ,
+,

－ 301 －

!5:;95E- 1@-8#!!%  %5?@1>?;:1@-8& $%#& %   59 1@-8&  !  &4%451718 1@-8& $%#& %   % 588?1@-8"" % $!%    

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

$EVELOPMENT 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!BSTRACT –! RAPID SOLVENT EXTRACTION SYSTEM WITH FLOW INJECTIONANALYSIS BASED ON MICROCHIP CHEMISTRY WAS DEVELOPED TO STUDYCHEMICAL PROPERTIES OF SUPERHEAVY ELEMENTS 5SING THIS SYSTEMSOLVENT EXTRACTION EXPERIMENTS OF G.B WERE PERFORMED AS MODEL
EXPERIMENTS OF ELEMENT  DUBNIUM 4HE EXTRACTION EQUILIBRIUM OF.B WAS REACHED IN APPROXIMATELY  S &OR ON LINE LIQUID LIQUID
PHASE SEPARATION A PHASE SEPARATOR WAS ALSO DEVELOPED BY USE OF A
MEMBRANE FILTER+EYWORDS – MICROCHIP FLOW INJECTION ANALYSISEXTRACTION NIOBIUM PHASE SEPARATIONI.

LIQUID LIQUIDINTRODUCTION

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.
Reservoi
rc
oi
lwi
t
h
g
amco
ra
q
ueous
o
r
p
h
a
s
ei
.d
.2m m

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..

•

nat

l

Ex
t
r
a
c
t
i
onc
o
i
l Membranep
h
a
s
es
e
p
a
t
a
t
o
r

B了pressurecoil
‑a
q

o
r
g

•

D
o
u
b
l
ep
l
u
n
g
e
rp
um
p
Figure 1. Schematic view of the FIA system[1]－ 302 －

Y.Kasamatsu et al, J. Nucl. Radiochem. Sci. , 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

/FF LINE ISOTHERMAL GAS CHROMATOGRAPHY OF :R AND (F COMPOUNDSY.Oshimi, S.Goto, T.Taguchi, T.Tomitsuka, K.Ooe, H.Kudo
Department of Chemistry, Faculty of Science, Niigata University, Niigata 950-2181, Japan!BSTRACT –7E OBTAINED ISOTHERMAL CHROMATOGRAPHIC DATA OF :R AND(F CHLORIDES IN A MACRO SCALE ABOUT  MOLECULES  4HE
Adsorption enthalpies(ΔHA OF THE :R AND (F CHLORIDES ON A QUARTZ
SURFACE WERE DETERMINED TO BE ABOUT – K*MOL AND – K*MOLRESPECTIVELY WITH ANALYZING THESE RETENTION CURVES The present ΔHAVALUES ARE VERY DIFFERENT FROM THE EARLIER WORK;= IN MICRO SCALE
BUT AGREE WITH THE VOLATILITY DEDUCED FROM THE VAPOR PRESSURE IN
MACRO SCALE+EYWORDS – ISOTHERMAL GAS CHROMATOGRAPHY
HAFNIUM ADSORPTION ENTHALPYI.

ZIRCONIUM AND

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, 2ADIOCHIM !CTA , 169 (1996)
A. Türler ET AL, * !LLOYS #OMP , 287 (1998)
I. Zvara, 2ADIOCHIM !CTA , 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

3OLVENT EXTRACTION OF HEXAVALENT -O AND 7 USING  ISOPROPYLTROPOLONE (INOKITIOLFOR 3EABORGIUM 3G 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
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!BSTRACT – 3OLVENT EXTRACTION OF M-O AND 7 USING ISOPROPYLTROPOLONE (INOKITIOL (4 WAS INVESTIGATED %XTRACTIONMECHANISM OF -O AND 7 WITH (4 WAS EXAMINED BY SLOPE ANALYSIS4HE SLOPSE OF THE DISTRIBUTION RATIO OF -O AND 7 VS ;(4= IN
LOGARITHMIC SCALE ARE  AND  RESPECTIVELY+EYWORDS – 3UPERHEAVY ELEMENTS 3OLVENT EXTRACTION (INOKITIOL-OLYBDENUM 4UNGSTEN 3EABORGIUMI.

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 J-rays of 93mMo and 102 keV J-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.

l

1000

• 93mMo

1
0
0

1
0

゜

II. EXPERIMENTAL
93m

176

89

7

93m

Mo and W were produced in the Y( Li, 3n) Mo 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 and

. .•
. ..
I

01

175

:

■ 1a1w

•

I
•

001
1
0
‑
6

I

,
‑
5
1
0

' ‑4
1
0

1
0
‑
3

1
0
‑
2

[
HT
]

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 －

A. Toyoshima et al., 2ADIOCHIM !CTA  , 323
J. P. Omtvedt et al., %UR 0HYS * $ , , 91

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

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
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

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 DISCUSSIONI.

INTRODUCTION

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

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

25-NCP-11

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)

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

25-NCP-12

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

25-NCP-13%XPLORING THE 3YNTHESIS AND #HARACTERIZATION OF "INARY 4ECHNETIUM #HLORIDES
AND "ROMIDES
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.

+EYWORDS –4ECHNETIUM SOLID STATE SYNTHESIS BINARY TRANSITIONMETAL HALIDESTechnetium (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.

" "INARY 4ECHNETIUM "ROMIDES
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]! "INARY 4ECHNETIUM #HLORIDES
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., * !M #HEM 3OC, , , 15864-15865.
Poineau, F., et. al. * !M #HEM 3OC, , , 8814-8817.
Poineau, F., et. al. )NORG #HEM, , , 4915-4917.

T9•Cl2p,’`‘IIcr

T9•Cl2

I
F
T
e
C
IJ

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. )NORG #HEM. , , 8462-8467.
Poineau, F., et. al. * !M #HEM 3OC , , 910-911.
Johnstone, E. V., et. al., )NORG #HEM, ,  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].

：二：H ［口ロ＼口叉＼: O O H

Ll‑Cl
fs

L1‑CF3Figure 1.

L2‑
pz

L
2
‑p
y

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.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-ACP-02

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

•`•~~

00

倉i



~~
i



i

-O/

3;
09

][

i

[i

-O/
:R/
'D/
#E/
3R/
.D/
0D/
2U/
,A/
3M/
0R/

XC

[ｷ
[i
[

;(/=;(/=O

•[•·

][

.~

g2



][



・～



.~

▼♦•

＊・・。◇

INTRODUCTION

偽1\

◄

2U/

I.

.i

0D/

.O METAL OXIDE

•i•·

.i
.i



＼へ



Keywords – Uranyl peroxo-carbonato complex, Hydrogen
peroxide, Metal oxides, Absorption spectra

g
ｷ
ｻ

"`g‘

か『

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.



4IME 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).


4IME HOUR










!BSORBANCE

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.







II. RESULTS AND DISCUSSION







7AVELENGTH NM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.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-ACP-04

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

こ号 U①さelq」

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.

900

850

800

750

700

Ramanshift[cm 11—

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
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.



 



CURRENT  !

B

CURRENT  !

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.

 



 



 



 



A
C


 



 







0OTENTIAL  6 VS 33%



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.

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.
100

U in solution [%]1\‘^---

ー•.i............`......................9...........

-—

I‘`..._

入｀｀｀｀へ—`iン｀｀

ー・し．・・ 1・・・・・・・・・・・・・•...........

..

.......,..

..

......

L.,:.ーさ．牛．一―-=·---.
.
:

0
0

II. EXPERIMENTAL

t=ーごき巴•-Oxalic acid
Tartaric acid
Citric acid＼ヽ、―T-- EDTA
60
Acetic acidiヽ、· • Adipic acid
40 ···\I·······················•..........
No additionalorganic acid
20

80

50

100

150

Time [h]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 periodicallyFig. 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 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa,Japan, 22-27September 201325-ACP-08

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




.P

 -E6)NTENSITY





0U



 -E6











%NERGY -E6
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

2EFERENCE '!"URNEY AND 2-(ARBOUR 2ADIOCHEMISTRY OF
NEPTUNIUM .UCLEAR 3CIENCE 3ERIES .3  － 317 －

25-ACP-09

APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013����������������������������������������������������������
a
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.
����������� 、人、)l���I���������

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/���������

I���������

������

�

•••
�

�
�

���

���

���

���������

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).

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

25-ENP-01

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.

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

25-ENP-06

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

二」

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.

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

25-ENP-07

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

Abstractof 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.
350~3500

に三：：：

‑

{

I

‑

1-0滋 "..'ool●: : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9

:

:

i

IIII
l,ooo 琶
!
,
o1
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.1. 、.....................................
>
琶 ,oo I

500

NO

゜

Uヽ

"
,
D
,

0
.
0
1

0
.
1

1

゜

1
0

A
e
r
o
d
y
n
ami
cdi
ame
t
e
ront
nei m pactor 申ge (µm)

Figure 1 size distribution of specific radioactivity of activated piping_S p ec fi C 「ad i oa ctiYil v [
Bq
/
e
la
tt
hest琴C＿如 era g e o f allo f琴 rosols c
o
l
l
e
c
t
edatE
l
P
I

゜

"

g

{/
3b
＄3ー。さとnu•o!P←
°p
'd
,5
,
al0
a

54321
9299
EEEEE
90999
lllll
ー

。

u

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 weight

U
.
l

l

lO

Aerodvnamlcdi
amet
e
ront
heImp
ac
t
o
rs
t
ag
e(ｵm)

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

           &)3-;01 )<;=6)/) &)3)01:7!)3)61;01  ):137<):);016,70 :16)&)3-=+01 )<;=67:1
&;=,=31 %A=;)3=!1;015=:) =67):);01 %01/-A7;01"<7;)3) &;=<75=%)<7 %-1A)!)/)7

!=+4-):%+1-6+-)6,6/16--:16/1:-+<7:)<-)8)6<751+6-:/A/-6+A&73)15=:)*):)31   )8)6
1>1;1767.%=;<)16)*4-$-;7=:+-;6/16--:16/:),=)<-%+07747.6/16--:16/733)1,7'61>-:;1<A%)887:7 )8)6
7?->-4$),17)+<1>1<A)*7:)<7:A6;<1<=<-7.!)<=:-)6,6>1:765-6<)4&-+06747/A)6)B)?)'61>-:;1<A;013)?)
 )8)6
#$"$   &$& ($ #  $ " $ ##&$  "$& $"#  "&" '$" # 
&   &$ # $ # $"% $" ##  $ $ "%""$&$( (## $# $ "&#   "$%$( "$ "$")$  #%#  $"# #  $#  $ !%$$# " $ #&" $#  "# #$(# $#$%#
('"#&"%# ###&$
$"$"%# $"# ##&$"#

!&$"'&"!

&0- 51/:)<176 *-0)>17: 7. )<57;80-:1+)44A ,-:1>-,
:),176=+41,-;)6,+0-51+)4;76<7:1>-:+)<+05-6<;0);*--6
-@<-6;1>-4A ;<=,1-, <0=; .):  &:)6;87:< 7. <0-;- 5)<-:1)4;
<0:7=/0:1>-:;+)6*-<0-57;<16.4=-6<1)4-@87:<8:7+-;;<7,7?6;<:-)5 :-/176; &0-;- 16>-;<1/)<176; 07?->-: 0)>-
7.<-6 -6+7=6<-:-, -;;-6<1)4 ,1..1+=4<1-; 76- 7. ?01+0 1; 16
;)58416/.:-9=-6+A$)16.)44->-6<;84)A)61587:<)6<:74-
16.4=>1)4<:)6;87:<7.+76<)516)6<;7?->-:1<1;,1..1+=4<<7 +)::A 7=< .:-9=-6< 5)66-, 7*;-:>)<176; .7: <0-;-;<7+0);<1+->-6<;67<0-:,1..1+=4<A1;<0-)*141<A<7+744-+<-67=/0 ;=;8-6,-, 5)<-:1)4 .7: +0):)+<-:1B)<176 8=:87;-;
;=+0 ); +0-51+)4 -@<:)+<176; )6, 516-:)47/1+)4 )6)4A;-;
&0- ).7:-5-6<176-, )6)4A;-; /-6-:)44A :-9=1:- ;->-:)4
/:)5; 7. ;=;8-6,-, 5)<-:1)4 &0- +76+-6<:)<176 7. ;=+0
5)<-:1)4; 16:1>-:?)<-:<A81+)44A:)6/-;.:75).-?5/4<7)*7=< 5/4 5-)616/<0)<<-6<7)<07=;)6,41<-:;7.
?)<-: ):- :-9=1:-, ++7:,16/4A 0)6,416/ ;=+0 4):/-
)57=6<; 7. ?)<-: +)6 *- ,1;<:-;;16/ -:- ?- :-87:< )6
1667>)<1>-A-<;1584-+744-+<1765-<07,.7:;=;8-6,-,)6,
,1;;74>-,+75876-6<;16:1>-:?)<-: &"% $#%#  $#&?7.14<-:>-;;-4; 550-1/0< 55?1,<0%
% ,>)6<-+ &7A7 )1;0) <, ?-:- =;-, ;-9=-6<1)44A
?1<0 ,1..-:-6< 67516)4 87:-;1B-, .14<-:; 5 )6, 5 )+0 >-;;-4 +76<)16-, ;1@ +):<:1,/- .14<-:; 7.
?7=6, <A8- 874A8:78A4-6-   55 4-6/<0 $1>-: ?)<-:
?);4-,<7<0-;A;<-56)<=:)44A=;16/),:787.<0-:1>-:*-,
*A 07;- .:75 =8;<:-)5 .<-: )6 )88:78:1)<- 6=5*-: 7.
,)A; 7. 78-:)<176 <0- .14<-:; )6, <0- 5=, ,-87;1<; 76 <0-
*7<<757.<0->-;;-4;?-:-:-+7>-:-,6<0-4)*7:)<7:A<0-
;=;8-6,-,5)<-:1)4<0)<?);+744-+<-,76<0-?7=6,.1*-:;

?); ?);0-, 7=< ?1<0 ?)<-: 16 ) *=+3-< &0- ?);0?)<-:
;)584-; )6, <0- 5=, ;)584-; ?-:- +76+-6<:)<-, >1)+-6<:1.=/)<176  +7587;1<- 7. <0- 5=, ;)584- ?);7*<)16-, )6, ;=*2-+<-, <7 ?-< ;1->16/ ;=+0 <0)<+75876-6<; 7. .7=: ;1B-; ?-:- 7*<)16-,   5  5   5)6,  5168:16+184-
&0-.1:;<)6,;-+76,+75876-6<; ?-:-)1:,:1-,&0-<01:,
)6, .7=:<0 +75876-6<; ?-:- .:--B-,:1-, <7 7*<)16 .16)4
;)584-;7.;=;8-6,-,5)<-:1)4
 $##& $#&0-,1;;74>-,+75876-6<:),17+-;1=516<01;;<=,A?);
+744-+<-, .:75 8):< 7. <0- 7=<4-< ?)<-: .:75 <0- .14<-:>-;;-4;!)5-4A <0-7=<4-< ?)<-: ?);8=<<0:7=/0);-:1-;
7. <?7 #( +74=56;   +5 166-: ,1)5-<-: +5 4-6/<0?01+0+76<)16;;8-+1.1+),;7:*-6<5)<-:1)46.-B0$%'&%!%'%%"!
&0- -..-+<1>-6-;; 7. <01; 5-<07, ?); >)41,)<-, 7>-: )
8-:17,7. 576<0;7..1-4,78-:)<176<15-;16+--+-5*-:
 &0-<-;<;1<- ?);)0144A .7:-;<-,+)<+05-6<7. 
35  +76<)1616/ ) ;<:-)5 47+)<-, 16 <0- !7:<0-:6 ):-) 7.
-6<:)4)8)6*):)31#:-.-+<=:-&0-;1<-?);)..-+<-,*A
.)447=< .:75 <0- =3=;015) 6=+4-): )++1,-6< 6 <01;
>)41,)<176 ;<=,A <0- )15 ?); <7 7*<)16 ;)584-; .7::),17+-;1=5 )6)4A;-; =:16/ <0- <-;< 8-:17, <-6 ;-<; 7.
;=;8-6,-, 5)<-:1)4 ;)584-; ?-:- ;=++-;;.=44A :-+7>-:-,
6<-:>)4; ?-:- +0)6/-, .:75 <?7 <7 ;1@ ?--3; ,-8-6,16/
76 <0- 0A,:747/1+)4 ;1<=)<176 88:7@15)<-4A   / 7.
;=;8-6,-, 5)<-:1)4 ?); :-+7>-:-, 8-: +744-+<176 8-:17,
>):1)6+- ,-8-6,-, 76 <0- 4-6/<0 7. <0- 8-:17, )6,
8:-+181<)<176 +76,1<176; ,;7:*-6< +74=56; .7: ,1;;74>-,
:),17+-;1=5 ?-:- ),,-, ).<-: !7>-5*-:   &0-
+744-+<176-..1+1-6+A7.,1;;74>-,:),17+-;1=5 ?);); 01/0);     +76;1;<-6< ?7:316/ 5-<07, .7: +744-+<176 7.
,1;;74>-, +75876-6<; )6, ;=;8-6,-, +75876-6<; 0);
<0-:-.7:-*--6-;<)*41;0-,
("!'%"! 8);;1>- A-< ;1584- +744-+<176 5-<07, .7: :),17)+<1>-
5)<-:1)4;16:1>-: ?)<-: 0);*--6,->-478-,)6,>)41,)<-,
&0- 5-<07, 1; ),>)6<)/-7=; ); 1< 1 )447?; -..1+1-6<:-+7>-:A7. ?074-;1B-.:)+<176;7.;=;8-6,-, 5)<-:1)411
+)6 *- =;-, 16 :-57<- 47+)<176; ?1<07=< -4-+<:1+1<A 111 1;
;=1<)*4-.7:=65)66-,78-:)<176;7>-:476/8-:17,;7.<15-

－ 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

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.

210Pb0,(mBq
l
g
)
10

100

3
0
00

TOCF
l
u
x
jmgC/口n9/y)

4513C （知）

8.;io

‑
2
5

°「―

_E::>)4~aー

4｀口――::)------i-------LL-『95し°----"---

8

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.

p

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 －

20

1
4

J
0

10

C/Nn叫ar r
a
t
io

20

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)

Collected by SS-cartridge
��4
SS-C�2
0.1

6

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 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.

-ARKER"OAT

II. SYSTEM AND METHOD
4OWING
3YSTEM-OORING
3YSTEM
6IDEO#AMERA

3EABED

6IDEO#AMERA#4$ 3ENSOR
5NDERWATER .A)4L$ETECTOR

Fig. 1 Illustration of field operation of underwater gamma-ray
spectrometry systems (mooring and towing system).
101
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].

134Cs

、口、

100

I二

St.A (Mud)St.B (Sand)

I

40K

10-1
10-2
10-3
10-4
0

1000

2000

3000

Energy (keV)

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

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

25-ENP-12

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.

Sample #Lab code

14

Sample name����������
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*3

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

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.

Tsug
a
r
uWarmCurrent

,1)

5500

會 600

w
t
: :

Fresh

200
5000

1
mq(p
―

』eo

pooM p a』
A1-U

4500

Arcl}lleol~ 竺a i ns (4950 士 23 B
P)
nu1eMasaueder‑t－ 330 －

eOOp
!
e~
uoqJ

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.

i
7
j
S
e
a

land

Ag
eofhumant
ee
t
h
(
Y
o
n
e
d
a
,2006)器g)3(d

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.

6000

i
ｷ ]且社
ュし一

"

号る舟

角卓諄

竺

S

三＄

J p aJJ
(
sJ1:a
1 i
a J!O
I
I
JasaJ au苓 Zl.:

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.

Sコ

1

0 ：：で

i §角 3騒

Fi
g
.1
.Radi
o
c
a
r
b
o
na
ge
so
fa
r
c
h
a
e
o
l
o
g
ic
a
lremai
n
s
f
r
omH
i
g
a
s
hi
mi
ch
inoue(
3
)a
r
c
h
a
e
o
l
og
ic
a
ls
i
t
e
.

!03/2# TH !SIA 0ACIFIC 3YMPOSIUM ON 2ADIOCHEMISTRY+ANAZAWA *APAN   3EPTEMBER 25-ENP-13

���������� ���������� ������� ������������� ������������ �������������
���������� ������������������ ��������� ������������������ �������������� ����!���������"��������#����$��%&� �'�����������(��&��������������# �)�������* �++,�+-�$��%&� �� ����.��&������������

����%����������/����%���������������/��������#�������
(���&�� �������������� ������������������ ��( �&����&� �(����&�(��� � 0����1 � 2/���� � (�� � ���������� � �( � &����&� � (���&����&�3�������������0�����0�����4�1%1�0�����0�����(��������% ���� �������% ��( � &����&� � 0���� � (��� � �&����� �(&�������������%5 � ����� � ���� � ���� � �( � ����������� � ��� � ����(��������������������&���(����/����������(�&����&��(�������
0�����0�������&�����������#�������(&�&����������(�&����&�1��������������������������(�������������������3��������������( � &����&� � (��� � ���&��� � 0����� � (����0�� � �# � &����&�������������� � ��� � �����&� � �������� �� � ������6&�� � �&�� � ��!.7�8������81�$��������������(�&����&���/���������(��������0���������
���� � �&����� � �( � ������� � ������������� � ���(������� � 4�1%1!������ � ������%� � �� � ��� � .������# � �( � "����&� � (���8��0��������+-9:;� ���8����������������%��<:+<����15�����������������#�����&���������������0��#�)�����=+>�����������#�# � ?�� � =<>1 � �� � ��� � � ��� � .��&���� � &����&�3���������
����%����������/����%������%��������������(��������������(�����&��0������(����&����&�����&���# ������#�&����%��&��0���� �&����&��������%�����3��������0���� ���������0����
0�����(����&����%��&���&����&���������%�����������������
����� � ��&������ � (�� � ������������� � �( � &����&� � ��������
����������� � (��&���% � �� � ��������%���� � ��� � ���&��� � <@A"�������1
����%�������������(�����%�����%����������/����%����(����� � ����� � ������ � �&������ � �#������ � ������&� � ���/���
4����������� ����!�B5���������&�����������4��������������
��!�B5��������������1�$�����������(�!�B�������!�B�0��������0�� � �# � 7���� � =@>1 � ���� � ��� � ����� � �( � ���0 � �(
���3�/����%� � ���������� � �( � �#������ � ������&� � �/��� � ���
����&������������������#��������1�!������������������%���(�����������/����%����(������&������3��������������������������
���&((������ � ���������� � ��������# � =+>1 � !� � ������� � �����������# � ��� � �������� � ��������� � ��� � �� � �������� � ���� � �������%������/1�����(�������#���#����������4$��5���������������������
����� ��� �!�������� �"��������#����$��%&� ����� �&��������
������%������/�(���(����#�������������%��������������1 �!��%������ � ������&�� � (�� � ��� � ����������� � �( � ��� � ���&����%����%����3��%��������������������������������������������
�(��&�����#�%��������������������������� =C>1�!�����������
�(��������������������#�������&�����-:�D�40E05������#�����&�1�!�� � ��� � �( � ���� � ��&�# � 0�� � �� � ����(# � ����������# � �(�/�������� � �( � &����&� � 0��� � !�B3$�� � ��� � ��!�B3$��
��������� ���������� ����������� ����������� � �(������ ��0�����������������������&���0����������#�����������������(��&����&�������������(�����&�(�������E���0�����0�����1
F#������ � ������&� � �/��� � 4!�B5 � ��� � ����&� � ��������
4��!�B5�3���� � ������ � ���������� � �( � ��� � ���������
����������3�0�������������(�������&��������������������(�������&�������(�������&��0����1�8��������������&���0���&����� � ������� � ��� � !�B3$�� � ��� � ��!�B3$�� � ���������
���������� =C>1��� ������/��������� �������������������0����
0����&���������������������(�&������(�����0�������������1
�F��(������((�&����0������������&�����&���%������������1�!������&�������0����������������������������������#�4+:D�����3����&%�5 � (��� � ���� 0���� � ���������% � <1@� G%� "1�73+
����&�������(��0�������(�+::�)H1� 3+�0���I�C1A��%�����I�+1,
�% � �( � &����&� � ��� � �� � �( � �0����� � !�B3$�� � ���
��!�B3$�� � �������� � �����������#1 � !�� � ��/��&� � (��0����� �����A:�)H1�3+� ����A:3+::�)H1�3+� (���!�B3$������
��!�B3$�� � ��������� � �����������# � ��������% � �� � ������������������(�&����&��4<1@�3�<@:��%�"173+51�2�&������(&����&� � ��� � ��%��������� � �( � ��� � �������� � ��# � �������������� � �# � :1+ � ���173+� �� � �����%�� � ���&����� � �(
�#����������������(���������������������1
F���� �!�B3$���������!�B3$����������������������
0��� � ������ � �� � �� � ���������� � (�� � �/�������� � �( � &����&�(��� � �6&��&� � ���&�����1 � J��� � ������� � �� � ��� � ����&�����������������������������# �!�B3$������������������������
���� � �&������ � (�� � ��� � &����&� � ���������� � (��� � �&�(������E���0�����0����1�� �������

"����&���/�������� �!�B3$�� ���!�B3$�� ����������
�������� �(�����0����
=+>
=<>
=@>

=C>

－ 331 －

)�������4+-9,5�������������"����&��B���$��������%�����.������#(��� � ���3������������ � .���&����1 � ��2�3!�3C-+E+91 � ��2�H����� �<-?���� �!��&����� ���#���.! �B#����K �8�����! ��������� �'���88���������2 �8������'�4<:+@5�8�����8���!�������C9L�@A*3@9*7���� � � � 4+-9*5 � 8���&� � !������� � (�� � 8�����(������� � �( � .����������
J����� � 3 � $���������� � 8��&��&�� � ��� � ��� � $���������1 � ��������
'����������� � "��������# � �( � F�������1 � .����� � 8����� � ��.������������#�,E+-9*����������4+--*5���.����������&��������<<:L�**399

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

25-ENP-14

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.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-RPP-03

Y

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 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-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 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.

INTRODUCTIONIII.

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].
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.
(
a
)

(
b
)

(
c
)

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) #$!"' # ('#!' &(%!"' *&'! #% #') "'"&'& #   !
'#" #(%& #"  #(% #% %*'%$*" (.8.:.    8B@56:. ) (.G2 + #.4.;< ) +.:.1. ) 056?.8B  ).8.6 + BD.5.?. .;1 ( #.8.F.:.
",-/)"*/ +# !&+(+$& (  &"* " (.+ !1* "! !&+*(2/& ( %")&./-2
&1&.&+* +# &+)"!& ( *#+-)/&+*  &"* ". *./&/0/" +# "(/% &+. &"* ".
%" *&1"-.&/2 +# +'0.%&)+'0.%&)   
",-/)"*/ +# !&/&+* %"-,2 " %*+(+$2 &1&.&+* +# &+)"!& ( *#+-)/&+*  &"* ".
*./&/0/" +# "(/% &+. &"* ". %" *&1"-.&/2 +# +'0.%&)+'0.%&)   
/.0' %-) "0/& (  /+-2 -0/++'0.%&)   
 ",-/)"*/ +# !&+(+$& (  &"* " &1&.&+* +# &+)"!& ( *#+-)/&+*  &"* ".
*./&/0/" +# "(/% &+. &"* ". %" *&1"-.&/2 +# +'0.%&)+'0.%&)    &-20 + /! **+'0.%&)
   !&+&.+/+," "*/"- %" *&1"-.&/2 +# +'0.%&)+'0.%&)
  
 ",-/)"*/ +# 0 ("-  &"* " *./&/0/" +# + &+-/. *!  &"* ".
%" *&1"-.&/2 +# +'0.%&)+'0.%&)   
*2 5.C2 12C29<=21 3B99 .BA<:.A21 :2.@B?2:2;A @F@A2: 3<? ?.16<.0A6C2 6;A2;@6A62@ <3 @2.921 @:.99 ?.16.A6<;@<B?02@ 6<16;2  @221 @<B?02 3<? /?.05FA52?.=F 6; A56@ D<?8 )<1.F >B.96AF .@@B?.;02 & <3   @221?.16<.0A6C2 @<B?02@ 3<? /?.05FA52?.=F 3<99<D6;4 %" :2?60.; @@<06.A6<; <3 %5F@606@A@ 6; "21606;2 (<06
2AF@ 4B61296;2 6@ <;2 <3 6:=<?A.;A @B/720A@ 3<? 5<@=6A.9@ A5.A <=2?.A2 <; =.A62;A@ 3<? =?<@A.A2 0.;02? .;1 :2160.9
0<:=.;62@ A5.A :.;B3.0AB?2 .;1 @299 A52@2 ?.16<.0A6C2 @<B?02@ ; <?12? A< @B?C2F 12320A6C2 @221 =?<1B0A@ 6;A< .99
A52 ;B:/2? <3   @221 @<B?02@ A52?2 .?2 B@B.99F 3A22; @221@ <;2 @221 <3 16:2;@6<;@ 6@  ::    ::92;4A5 D6A56; . 0.?A?6142 D2 5.C2 .==9621 A52 :2A5<1 <3 @6;492 @96A 0<996:.A<? D6A5 :<C6;4 . ?.16.A6<; 12A20A<?
A< :2.@B?2 2.05 ?.16<.0A6C2 6;A2;@6AF <3 A52@2   @221@ @ . ?2@B9A 6A D.@ 3<B;1 A5.A <B? 12C29<=21 @F@A2:
6; A52 =?2@2;A D<?8 5.@ 4<<1 =2?3<?:.;02 <3 @B?C2F6;4 A52 12320A6C2 =?<1B0A@ :.;B3.0AB?21 D6A5 ?.16<.0A6C2
6;A2;@6A62@ <BA <3 ./<BA   2??<? =     )<1.F A52?2 6@ ;< 1<B/A ./<BA 6;0?2.@6;4 6; A52 =.A62;A =<=B9.A6<; <3 =?<@A.A2 0.;02? F2.? .3A2? F2.? (6;02 A52 .BA5<?6G.
A6<; 3?<: A52 "6;6@A?F <3 2.9A5 !./<? .;1 *293.?2 6;
. /?.05FA52?.=F B@6;4   @221@ 5.@ /22; <;2 <3 :<@A 23
320A6C2 A52?.=62@ <3 =?6:.?F .;1 :61192 @A.42@ <3 =?<@A.A2 0.;02? 6; .=.; .;1 .99 A52 ;B:/2? <3 .;;B.9 096;60.9 <=2?.A6<;@
6; .=.; 5.@ /22; =?</./9F ?2.0521 A< ./<BA  6;; A2?:@ <3 @.32AF :.;.42:2;A <; >B.96AF .@@B?.;02 & 3<?
A52 /?.05FA52?.=F @B05 86;1@ <3 A52 4B61296;2@ @A.A21 3?<:
%" (<062AF , - .;1 ()'$ .=.;2@2 (<062AF 3<? )52?.
=2BA60 '.16<9<4F .;1 $;0<9<4F 5.C2 ?20<::2;121 A5.A 2.05?.16<.0A6C2 6;A2;@6AF <3   @221 @<B?02@ @5<B91 /2 .==?<=?6
.A29F @B?C2F21 /23<?2 A52 A52?.=F <3 =?<@A.A2 0.;02? <D2C2?
6; 3.0A A52?2 .?2 <;9F . 32D 3.0696A62@ @B05 .@ @B?C2F6;4 A52 ?.
16<.0A6C2 6;A2;@6AF <3   @221 @<B?02 6; .=.; A @5<B91/2 @22:21 A5.A .116A6<;.9 D<?8@ @B05 .@ & :.82 ?.16<9<460
D<?82?@ 6; 5<@=6A.9 /<A52?21 1B2 A< A6:2 0<;@B:6;4 .;1 .9@<
2E=<@21 1B2 A< <=2?.A6<;@ <3 A52@2 ?.16<.0A6C2 @<B?02@ B@6;4. 1<@2 :2A2? 9682 .; 6<;6G.A6<; 05.:/2? )52 =B?=<@2 <3 A56@
D<?8 6@ A< 12C29<= 3B99 .BA<:.A21 :2.@B?2:2;A @F@A2: 3<? ?.
16<.0A6C2 6;A2;@6A62@ <3   @221 @<B?02 A< 0<:=9F D6A5 A52
12:.;1@ <3 :2160.9 D<?82?@       )52 @F@A2: 5.@ 2EA2?;.9 16:2;@6<;@ <3  :: D61A5  :: 12=A5   :: 52645A .;1 0<;@6@A@ <3 . 0.?A?6142
5<912? #. @06;A699.A6<; @B?C2F :2A2? .;1 1?6C2 :205.;6@:
.;1 . 1.A. .;.9F@6@ :<1B92 )52 @B?C2F :2A2? 6@ @2A /256;1 .
0<==2? .;1 @A.6;92@@ @A229 =9.A2 0<;A.6;6;4 . @96A   :: A5608

;2@@ '.16<.0A6C6AF <3 A52 @221@ D6A56; . 0.?A?6142 6@ :2.@B?21 /F A52 @B?C2F :2A2? A5.A 6@ :<C21 @9<D9F   :: @20
6; 3?<;A <3 A52 0.?A?6142 /F A52 1?6C2 :205.;6@: )52 @B?C2F:2A2? 12A20A@ 4.::. ?.F@ =.@@6;4 A5?<B45 A52 @96A 6; A52 =9.A2
F 822=6;4 A52 @221@ 6;@612 A52 0.?A?6142 A526? 6;16C61B.9 .0
A6C6A62@ 0.; /2 :2.@B?21 D5692 :.6;A.6;6;4 . @A2?692 @A.A2

  %5<A<4?.=5 C62D <3 <B? 12C29<=21 @F@A2: (&(  

)52 @F@A2: 0.; .BA<:.A60.99F 0<:=92A2 A52 .0A6C6AF :2.@B?2:2;A <3 .99 @221@ 0<;A.6;21 6;@612  0.?A?6142@ 6; 92@@ A5.;
 :6;BA2@ D6A5 ./<BA  <3 2??<?@ A< 12A20A :6@@0.96/?.A21@221 )56@ @F@A2: 2;./92@ B@ A< @B?C2F A52 12320A6C2 =?<1B0A@:.;B3.0AB?21 D6A5 ?.16<.0A6C2 6;A2;@6A62@ <BA <3 ./<BA  2??<? =    

 3B99 .BA<:.A60 :2.@B?2:2;A @F@A2: <3   @221 .0A6C6AF@5<D@ ?296./92 =?206@6<; .;1 B@./696AF BAB?2 12C29<=:2;AD699 6;09B12 @B==<?A 3<? <A52? @<B?02 1296C2?F :2A5<1@ =.?.9929
A< 233<?A@ 6; ?21B06;4 A52 @6G2 <3 A52 @F@A2:

, - %" "   % +(    <??2@=<;16;4 .BA5<?

2920A?<;60 .11?2@@ @.8.:.:21@06A<8B@56:.
B.07= +- :6;<?B@.8.:.A<8B@56:.B.07=－ 337 －

   APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-RPP-06

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.
2
1
.6

゜
E

I2

i
=

.::

と言•と

08

2
04

.
.

.

ヽ

3

4

6

6

8

2

t、

。 。

II. EXPERIMENTSー』：

Concentr
at
ionofHCI/t,I

MIBK ・

■

DIPE

'
■ C
H
2
C
l
2
ー

16

8

e

lo

0

－ 338 －,t。

ol-Euo」l
q[)
JS
Q!
n

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.

血 10010101
細0
血01

Fig. 1 Distribution ratios for several concentrations of HCl with DIPE.

1. Dependence of the concentration of HCl
7

. .
.

・ニ：

■ C
HCl3

I

16

2

26

Polat
i
t
yofo
rg
ani
cs
o
l
v
e
nt[
ｵ
I
D
]

Fig. 2 Distribution ratio for different polarities of organic solventwith 8M HCl.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-RPP-07

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

0‑̲

一呈
..

~

゜

一

>

|~e

1.

l‑

一

rr

.

J

.
.

」
み

mo
ー[-

00

10

ぷ

mrｭ

mo.

•ro•—•

C. t

一v
シ

一

0.

oo‑

•一

゜

r‑

二

』[町

oo5 g 5 5

『｀~

00000

,

‑J

{uH‑9‑

00

一。＾

L
_

Lし
〉-『

——

r
ｰ

[

‑00

‑
=
‑

ぎ

['ｭ

TO
一0
.

o
n

[

コ

ai

゜

n
'

{•-

‑5‑.‑

ー一＂

,

＼＾ーー、
"^ｰ"ET9CF9 にし OITIF
lg 4,ho0
1
3
1
.
.
.
b
u
9
l
o
nof""oornnQ m ngno9i
o nok
ivI
th x‑00.
.cn9oInodn9eoo`—
9
.
.
.
1
.
.
.
.
Qーし。
louolun

.
.
.
.
,

~

3
‑

. ` . , . . .,, ,,

,, ,

鳴

i

Il,',a0,

UO!SS!WSUOJJ.a>‑=e‑au

g函 m 曰皿 mm”

calcined at 800����������������������������������������
respectively.

0

UO!SS!Es』u←e
3>Pe-3”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

玉g曰”mma” 泣ga g

RESULTS AND DISCUSSION• L•F•O,

.
‑
里言｛嘩浬
嘩

̲ ̲ ̲ ̲ -.5

I.

’l 遷

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 field

‑
9
9 •99

亀'`

9 0 2

』'.

" "

.
.
,
a"'
...,、

.
.
...,。

,

LoFeO

x•0.16

a.
.
.

y[
m
m
l
s
]
V• loclly [
m
m
l
s
]
V
e
l
o
c
ll
g.5 lhemoss 図 uer spectra(RT)o 『 N i.. Cu..
Zn..La̲Fe.̲O̲ (
x
=
0
,
0
.
0
5
,
0
.
1
,
0
.
1
5
)c
a
lc
inedal950 ℃
Fi•A
02.., } •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]

鴫＂鵡

[2]

99.. 、9..........,0,....,

2•Th«•I••91'’"

99,.,9...,,.,9F 炉tゆ XRD patternso
rsamp
l
e
sc
a
l
ci
noca
l80

2•T 閲 •1 00g)

閲＂Fl, 』 2m.XRO 四畑 m, or,amol•• 臼!coin 虻 at 950 ℃

Fig.3 and Fig.4 show the Mössbauer spectra (RT) of
Ni0.4Cu0.2Zn0.4LaxFe2-xO4nano-crystalline

ferritepowders[3]

measured at room temperatures , respectively.

－ 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.

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

25-NPP-03

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

1

.""a

.』 a,

、・四i

g:f叫四

̲T
3
a

t a

[:I,'9,’^.

郎

IDJJ四

．曲，．．
・
•1,
.
e..
;.
.
.

こ

1』関!J)

“.a

1•

D

伽ml,

・ー・

4』.,.O....am.'

•四工甚必

珈

皿

り・

9 皿・

r.
.
2,aa.?9

四•

....

.3
t

h 仙り、’

i皿I

.
., ..
a
.

‘‘

』ヽヽ＇

3↓頂田・

出

r
.
.
.
/
,

八＼
‑,
グ一

直・

0

.
一｝

直血 r

•s

a

40 40 4

ヽ

l
:
u皿・

．匹
:'s3:

軋＂， 9

｝四0 •

皿り

『9-9 〕●ー

¥

合濾い・

訂皿 l

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.

L•9-.-

l四·

匹

'‑̲.
g a ggggg血疇g

ご三、4 凶·“→

II. EXPERIMENT

,.a

E

□
’
[
]
〗

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.

』 i
:
u
,
0
|
:

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

9

匹I. •,'.••,9,..,’9：ーロ
j....'

』“置置

IllD

四

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

8

7

6

4

2

,

R(Fe'Fe)/
A

.
.
o
.
.
.
.F
e
‑
F
ed
i
s
t
a
n
c
e

28293031
立 333435

Cool i ng

33333333

ｮ

Heating

•

A)

•

2
6
0

A
l
ky
l
c
h
ai
nl
e
ng
th(
n
)
Figure 1. Correlation between spin transition temperature (T1/2) and thenearest neighbor Fe-Fe distance (R(Fe-Fe)).

840

8

780

9ｷ
9ｷ
99
99

8
0
0

'ｭ

8
2
0

ゑ

',

ふ

99
99

`,
7

6
5
4
3
2

II

99

99
99

43
0.

Tを

J
・
＇
h

0
.
4
4

860
Blem

0.
45

B(XANES)·•.,... ..
',.’

9,'

0.
46

ｷ
ｷ
ｷ
O
ｷ
ｷ
ｷJS(
M
o
s
s
b
a
u
e
r
)

•?"'

,
.,
,
.'ｷ
.
.
.
,
"
"
5
,

047

3
ｷ
,
'
.
.
.
.
.
.
'
,
'
,.
.
,.
,
..
.
.
.
，．口『＇
.
.
..
'互
.
. ,..,'▲3,
...
,

u
r
w/SI

s

-‘

賓｀

048

II. RESULTS AND DISCUSSION
In [Fe (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.. .. ..

ｷA

2
8
0

A9

...

..

Q
e

の＂

.... ......

00
0
2
33

u
‑

·:•O

....
.... ..

A0・汀

3
4
0

令

▲る

3
6
0

Q̀'

3
8
0

xl4

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.

Alkylchai
nl
e
n
g
t
h(
n
)
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.

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

25-NPP-05ooo

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.

INTRODUCTIONIII.

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.
a)竺

Sll:llll! g
l.-r A'!

3an8
一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.

‑
2

II. EXPERIMENTAL

0

2

4

Do
ppl
e
rv
e
l
o
c
i
t
y/mm/sComplexes 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.

10

20

2t
het
a/
d
g
ree

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).

30

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

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
1

2

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

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.

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.

For 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.
‑
0
.
3

‑
0
.
2
<

ヽ

N

¥
:
,
N‑
0
.
1

<

EXPERIMENTS

R
i
゜

II.

RESULTSFor 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 －

0
.
1
0

50

100

150

200

250

300

t(
n
s
)

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

25-AAP-02

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

2

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

0
1
ー（旦咎―)石名

0000
o
ool
001

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.

103。

Al As Sr Ca Cl Co Cr Fe Hg K Mn Na Se ¥'Zn
EIOIICIII

Fig. 1. Mean elemental concentrations in toenail samples

Keywords–Instrumental Neutron Activation Analysis, Inorganic
Elements, Toenail, Elemental CorrelationI.

INTRODUCTION

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.

10000

s
o
o
oI

♦

.

6000

ぃ゜

.
.
函:b-

‑
1000

0.0

~00.0

1,00.01000.02000,02~00,0C 』·

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

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

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

25-AAP-04

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.

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

25-AAP-05

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◇―●一 INAA(Th iswork)·,o、「 ICP-MS(Thiswork)¥ ··•••

NAA,PAA(
(
1
)
)

̀-Q、
(
a
)KB‑1

ー

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.

100

00
10

II. EXPERIMENTAL

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.

'
‑
0
z
1
1
e
wo
saouepunqepa
JuBulk 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.

(b)KGB‑1

10
ｷ

La Pr smGd Dy Er Yb
Ce Nd Eu Tb ‑Ho Tm Lu

Fi
g
.l
.C
I
‑
n
o
r
m
a
li
z
e
dREEa
b
u
n
d
a
n
c
e
sf
o
rKB‑1(a)
andKGB‑I(b).

Reference: [1] Sakamoto K. et al. (1997) J. Radioanal. Nucl.
Chem., 215 (1), 69-76.

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

25-AAP-06

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

25-AAP-07

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.

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

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

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, HANARO

I.

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.

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

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.

$3625&¶ - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

25-AAP-10

        

,847,74,> 74>,-0?00 ,/,40=9,9/0> F=.4:,..34 "0?0=:/0'94A0=>4?D:1%G:",@7: @.70,=90=2D09?0=1:=2=4.@7?@=0"!:C "4=,.4.,-,%"=,E47
$0,.?:=9>?4?@?0071?071?'94A0=>4?D:1&0.39:7:2D0607B02   071?&30 0?30=7,9/>
 !!

 $%'&% %'%%!     ""  &     $ # !! &  !"! "! !#! &    
  $""!!as highas 4 mg kg-1 $ &  !  % "    ! 
#"!!" !! !#
" !! 
&$ ±  !&





 &$!'&! =D /:2 1::/ 4> 49?09/0/ ?: -0 , .:8;70?0 ,9/-,7,9.0/ /40? ,9/ 8,D -0 ?30 @94<@0 >:@=.0 100/492 ?30,948,7 49 ,77 >?,20> :1 7410 &30=01:=0 4? 4> 0C?=0807D
48;:=?,9??:.3::>0,;=:/@.?.,;,-70:1;=:A4/492:;?48,7
9@?=4?4:9 B4?3 ,77 90.0>>,=D >@->?,9.0> ,? ,/0<@,?0 70A07>
,9/1=00:1.:9?,849,9?>1:=;=:8:?4927:92?0=830,7?3&30 >,10?D :1 /:2 /40?> 3,> =0.09?7D =0.04A0/
49.=0,>492,??09?4:9>49.0?30.:9?,849,?4:9B4?3807,8490
.,@>0/ ?30 /0,?3 :1 >0A0=,7 ,948,7> ,9/ , 8,5:= =0.,77 :1
;0?1::/49?30'94?0/%?,?0>91,.??30@>0:17:B<@,74?D
492=0/409?> 49 ?30 ;0? 1::/ .:8;:>4?4:9 .,9 49?=:/@.0
=0>4/@0> :1 ;0>?4.4/0> 8D.:?:C49> 3,E,=/ .3084.,7
070809?>,9/:?30=?:C4.>@->?,9.0>"=:/@.?>/0=4A0/1=:8
;3:>;3,?0 =:.6> ,> /4.,7.4@8 ;3:>;3,?0 " 9:=8,77D
@>0/,>100/,//4?4A0>?:>@;;70809?;3:>;3:=@>8,D3,A0
3423.:9.09?=,?4:9>:1@=,94@8* +C;0=4809?> B4?3 /:2> =,--4?> ,9/ =,?> 3,A0
/08:9>?=,?0/ ?3,? ?30 ,948,7> ,=0 >09>4?4A0 ?: -:?3
493,7,?4:9 ,9/ :=,7 0C;:>@=0 ?: @=,94@8 .:8;:@9/>
'=,94@8 ,..@8@7,?0> 8,497D 49 ?30 -:90> 64/90D> ,9/
74A0=,9/;=0>09?>-:?3.3084.,7,9/=,/4:7:24.,7?:C4.4?D&30:A0=0C;:>@=0?:@=,94@88,D.,@>0;,?3:7:24.,7,7?0=,?4:9>?:?3064/90D>70,/492490C?=080.,>0>?:=09,7
1,47@=09?34>.:9?0C??34>B:=649A0>?42,?0/?30;=0>09.0
:1@=,94@849>0A0=,7.:880=.4,7-=,9/>:1/=D/:21::/>
;=:/@.0/49=,E47
 )"$ &
:=?34>B:=6 /=D/:21::/>,8;70>:1 /4110=09?
.:880=.4,7-=,9/>49.7@/4921::/1:=;@;;40>,9/,/@7?>
B0=0 ;@=.3,>0/ 49 ?30 7:.,7 8,=60? :1 "4=,.4.,-, %"=,E47 1?0= 3:8:2094E,?4:9 ,2 >@->,8;70 :1 0,.3
/:2 1::/ ;,.6,20 :1  62 B,> =0/@.0/ 49 , 69410 8477 1:=,9,7D>4> -D   := ,9,7D?4.,7 <@,74?D .:9?=:7 .0=?4140/
=010=09.0 8,?0=4,7> B0=0 @>0/ &0>? ;:=?4:9> :1 82
B0=0 49>0=?0/ 49 ;:7D0?3D7090 A4,7> ,9/ 4==,/4,?0/ 49 ?30
9@.70,= =0>0,=.3 =0,.?:= $  :1 "    ,? ,
?30=8,7 90@?=:9 17@C :1 C
.8 >  1:= 3 70809?
.:9.09?=,?4:9> ,9/ 0C;,9/0/ @9.0=?,49?40> B0=0 .,7.@7,?0/
-D?306 80?3:/@>492?30>:1?B,=0;,.6,20#@,9?@* +����� ������ ��� ��� �������� ���� ��� ��� ������� ��������
������������������������� ����������������������� ���������
����� ������� �������� ����� ����� �������� ��� ��������������
������������������������������������������ ���� ���������
���� �������� ������� ���� ����������� ���� ���������������
������������ ������������� ���� �������� ������� ���������������������������������������������������������
������������������������������������������������������
�����������������
�������� ����� ��������� ��� ������� ��������� ��� ��������������������������������������������������������
�������������������������������������������������������
�������� �������� ���� �������� ����� ����� �������� ��������������������������������������������������������������
����� ������������� ��� ���� ������ ������ ���� ������������� �����������������
�
&,-70 '=,94@8.:9.09?=,?4:98262 49/=D/:21::/>.:8;,=0/B4?3
=0>@7?>;@-74>30/49;=0A4:@>B:=6* +�
&34>>?@/D"=0A4:@>B:=6

49

 

 

,C

 



0/4,9

 

 

A0=,20

 

 

%?/0A

 







�
��� �������� ����������� ������ ���� ������ ������������ ��� ���� ������ �������� ���� ������������ ��������
������ �������� ���� �� ����� ������ �������� ������ ����������
���������� ��� ��� �������������� ����������� �������
���������������������������������������������������������
����������������������������������������������������������� ���� ��� ��� ��� ����� ��������� ������ ���� �� ��� ���� �����
�������������������������������������������������������
������������������������������������������������������
�����������������
$$ %
* +
* +
* +
* +

－ 355 －

,>,.@-0=?, ,><@H,",=.4,!=077,9,=@,.392@4?,
,>,(477,@=?,/:%,=.4,&09:=4:$ ,E,=/
,?0=    ,..34   0=9,9/0>       $,/4:,9,7 @.7 308 
74,>0=9,9/0> ,..34$,/4:,9,7 @.7308     
'94?0/ %?,?0> 9A4=:9809?,7 "=:?0.?4:9 209.D '9/0=>?,9/492 =,/4,?4:9 49 D:@= 7410 D:@= B:=7/
3??;BBB0;,2:A=,/4,?4:9=,/4:9@.74/0>@=,94@83?87