Oral Presentations
Tuesday, 24 September 2013
Hall & Meeting Room, Kanazawa Bunka HallTime
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9:00

PL-03

9:30

PL-04

4UESDAY  3EPTEMBERHall
Meeting Room
0LENARY
A. Tuerler
0LENARY
S. Nagao

10:00#OFFEE "REAK

10:20

ENI-01

10:50

ENO-01

11:10

ENO-02

11:30

ENO-03

11:50

ENO-04

12:10
13:20

ENO-05

13:40

ENO-06

14:00

ENO-07

14:20

ENO-08

14:40

ENO-09

15:00

ENO-10

H. Foerstendorf
General
NCI-02
Z.J. Guo
GeneralH. Tuovinen
NCI-03GeneralM.- C. Wu
General
NCO-06
T. Ohnuki,UNCH 4IME
General
NCO-07
S. Sachs
General
NCO-08Y. Iwahana
General
NCO-09J. Krmela
GeneralNCO-10K. Masumoto
GeneralNCO-11
H.W. Gaeggeler
GeneralNCO-12
A. Sakaguchi

15:20
ENI-02

16:10

ENO-11

16:30

ENO-12

17:10)NVITED
S. Dmitriev)NVITED
Ch.E. Duellmann)NVITED
H. Haba
GeneralV. Pershina
GeneralD. Rudolph
GeneralA. Yakushev
GeneralJ. EvenGeneralH. Nitsche
GeneralR. Eichler
General
T.K. Sato#OFFEE "REAK

15:40

16:50

NCI-01)NVITED

ENO-13
FKI-05)NVITED
J.V. Krtaz
GeneralJ.H. Park
GeneralJ. Zheng
GeneralI. Milanovic)NVITED

NEI-01)NVITED

NEI-02

Z.F. Chai)NVITED

NEO-01

A. Goswami
GeneralE. Loefstroem-Engdahl

NEO-02NEO-03

17:40

FKO-0918:00

FKO-10K. Minato
GeneralY. OuraGeneralK. Hirose

NEO-04NEO-0518:50
0OSTER 3ESSION
20:00－ 31 －

GeneralY. Tomobuchi
GeneralF. Poineau
GeneralA. Braatz
GeneralR. ChenAPSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

PL-03

Advances in the Production and Chemistry of the Heaviest Elements
1

Andreas Türler1,2
Laboratory of Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, Villigen-PSI, Switzerland
2
Laboratory of Radiochemistry and Environmental Chemistry, University of Bern, Bern, Switzerland

Abstract – Now that the discovery of all elements in the 7th period
has been announced, has the far end of the Periodic Table of the
Elements been reached? What is the heaviest element in the
Periodic System? Are there still undiscovered ones which mighteven be found in nature? Is there an 8th period and how many
elements will it contain? Will we need to introduce the g-orbitals
and will the current principles governing the groups and periodsof the Periodic Table still be valid for the heaviest elements?
These intricate questions are the topic of current research infundamental nuclear chemistry.

even under optimum conditions a production cross sectionof 1 pb translates into the synthesis of only 1 atom of asuperheavy nuclide every 36 h on average. Second, of themore than 50 new nuclides produced in these experiments a
number of them have t1/2 > 1 s and, thus, live long enoughfor chemical investigations. This result is in strong contrast
to the previously known, more neutron deficient isotopes ofMt, Ds, Rg, and Cn in the range of few milliseconds.

Keywords – APSORC’13 Keywords

B. Chemical Investigations of Heavy Elements

I.

INTRODUCTION

For increasingly heavy nuclei the electrostatic repulsionsof protons cannot be sufficiently compensated by theattractive nuclear force through an increasing number of
mediating neutrons. Therefore, the heaviest stable known
nucleus is already reached with 208Pb. All isotopes ofheavier elements, including some elements such as Bi, Th,
and U that still can be found in nature as remnants of thelast nucleosynthesis process, are radioactive and decay��������������� ��� ����������� �-particle and �¯-particle
emissions back to the last stable element Pb.
A. Synthesis of Heavy Elements
All elements heavier than Pu (Z=94) are man-made.
Transactinide elements (Z�104) are synthesized currently
only in complete heavy ion fusion reactions at high power
accelerators on a “one atom at a time” level. Spectacular
progress was obtained by using the very tightly bound,
doubly magic nucleus 48Ca and actinide target nuclei.
Oganessian et al. were able to synthesize single atoms ofelements 113 through 118 (with 294118 currently being theheaviest observed nucleus) and observe their radioactive
decay [1]. So far, only elements 114 and 116 have beenauthenticated by IUPAC and the element names flerovium,
Fl, and livermorium, Lv, suggested by the team of
discoverers, have recently been made official by IUPAC.
The addition of 6 new elements in the past decade wasremarkable in several ways. First, the maximum production
cross sections of elements Rf through Cn (Z=104-112)
could be described rather well by an exponential decay law,where the cross sections dropped by roughly a factor of 10
when increasing the atomic number by 2 units. In thesynthesis of 277Cn production cross sections of less than 1
pb (10-36 cm2) were determined. However, by using 48Ca
projectiles, this trend was broken and rather constantmaximum production cross sections of several picobarns
were measured for synthesis of elements Cn through Lv(Z=112-116) and even for elements 117 and 118 values
near or slightly below 1 pb were observed. Nevertheless,

The place an element occupies in the Periodic Table is
not only defined by its atomic number, i.e. the number ofprotons in the nucleus, but also by its electronic
configuration, which defines its chemical properties.
Strictly speaking, a new element is assigned its proper
place only after its chemical properties have been
sufficiently investigated. In some cases it has been possible
to experimentally investigate chemical properties oftransactinide elements and even synthesize simple
compounds. Due to the predicted strong influence ofrelativistic effects, the experimental investigation ofsuperheavy elements is especially fascinating.
The difficulties involved in the production and rapid
chemical isolation of few single atoms of a transactinide
element from numerous other reaction products and thesubsequent detection of the nuclear decay require thedevelopment of unique separation methods. Chemical
studies of transactinide elements and simple transactinide
compounds have been accomplished in the liquid as well as
in the gaseous phase. For the heavy transactinides, whichvery likely are volatile in their elemental state, gas phasechemistry is the method of choice [2]. Lately, the required
decontamination factors from interfering nuclear reaction
products grew so large that chemical experiments were
coupled to kinematic preseparators that already remove asubstantial fraction of the primary beam and of transfer
reaction products.
In this contribution the advances made in the synthesis
and chemical investigations of transactinide elements arereviewed [3]. Latest results on attempts to synthesize
elements beyond Z=118 and experiments to chemicallyinvestigate Fl will be highlighted as well as the first
synthesis of volatile transactinide carbonyl complexes.
[1]
[2]
[3]

－ 32 －

Yu. Ts. Oganessian, Radiochim. Acta 99, 429 (2011).
R. Eichler et al., Angew. Chem. Int. Ed. 47, 3262 (2008).
A. Türler, V.G. Pershina, Chem. Rev. 113, 1237 (2013).

PL-04APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013�����������������������������������������������������������������������������
�������������������������
Seiya Nagao
Low Level Radioactivity Laboratory, Institute of Nature and Environmental Technology, Kanazawa University

This study applies a combined use of carbon isotope composition(�14C and �13C) to suspended solids in river waters and surface
sediments from the river mouth, continental shelf off the coast ofJapan. This study is intended to investigate the fate of terrestrial
particulate organic matter that is released from the river to thecoastal marine environment at three river-coastal systems. Our
results indicate that the combined �14C and �13C measurements ofthe particulate organic matter can provide unique information on
the sources and age of sediments and their transport behavior.

Figure 1 shows the �14C values of organic matter in theriverine suspended solids plotted as a function of �13C
values. The paired � 14C vs. �13C distributions vary withsampling site and divided into two groups. Riverine POC in
wetland has lower in �13C and higher in � 14C rather thanthose of rivers in forest and fluvial plain. This indicateshigher contribution of younger organic matter at thewetland river systems.

Keywords Ð�13C, �14C, suspended solids, transport

100

0

-100

14

� C (ä)Global riverine discharge of organic matter to the ocean
represents a substantial source of dissolved terrestrial
matter and organic carbon particulates. Continental margins
are recognized as the dominant reservoir for organic carbon
burial in the marine environment. An accurate inventory for
terrestrial and marine organic carbon in continental margin
sediments is important for quantitative understanding of
biogeochemical cycles.
A variety of geochemical approaches have been
employed to define the mixing ratio of marine andterrestrial organic matter, including �13C and lignin
biomarker analyses. Radiocarbon abundances have become
an additional indicator of terrestrial versus marine sources
because nuclear weapons testing in the 1950s and 1960s
injected large quantities of 14C into the atmosphere. The
�14C values of organic matter in river suspended particles
range from �980 to +75ä, but plankton and particulateorganic carbon in marine environments have enriched 14C
values ranging from � 45 to +110ä. Therefore, thesimultaneous use of � 14C and �13C values adds a second
dimension to isotopic studies of carbon cycling in surface
aquatic environments.
This study investigates the fate of terrestrial particulateorganic matter that is released from the river to the coastal
marine environment at three research fields in Japan.

-200

-300
-30

-28

-26

-24

-22

13

� C (ä)Figure 1 Relationship between �14C and �13C of organic matter in thesuspended solids for the Bekanbeushi (�), Ishikari (�), Kuzuryu (�)and Hino Rivers (�).

Figure 2 shows �14C and �13C values of organic matterin riverine suspended solids and surface marine sediments
at the Kumaki-Nanao Bay system. The � 14C decreased
from the headwater to the middle sites at the Kumaki River,
but increased to the coastal sediments. These results
indicate that the middle and lower watershed area has main
sources of particulate organic matter exported to the costal
marine environments.
100
Headwater

0
-100

Upper

Nanao Bay

-200

14

� C (ä)We selected a river in wetland, Bekanbeushi River, andrivers in forest and paddy field such as the Ishikari,
Kuzuryu and Hino Rivers. The river-coastal systems were
set up at the Bekanbeuchi River-Lake Akkeshi, the TokachiRiver and the Kumaki River-off the coast of the rivers inJapan.
14
C measurements were performed by accelerator mass
spectrometry at the Japan Atomic Energy Agency and theInstitute for Environmental Studies in Japan. The � 14C isdefined as the deviation in parts per thousand from themodern standard. �13C values were determined for subsamples of the CO2 gas generated during graphite
production, using an isotope ratio mass spectrometer.

Middle-300
Kumaki River
-400
-500
-30

-28

-26

-24

-22

-20

-18

13

� C (ä)Figure 2 �14C and �13C of organic matter in the Kumaki River suspended
solids (�) and the Nanao Bay sediments (�).

－ 33 －

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

Surface speciation of dissolved radionuclides on mineral phases – A vibrational and
X-ray absorption spectroscopic study
1

2

H. Foerstendorf1, K. Gückel1, N. Jordan1, A. Rossberg1,2, V. Brendler1

Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Dresden, Germany
Rossendorf Beamline at the European Synchrotron Radiation Facility (ESRF), Grenoble, France

Abstract – Binary and ternary surface complexes of U(VI) and
Np(V) on gibbsite were spectroscopically identified. Se(VI) forms
two different types of outer-sphere complexes depending on the solid
metal oxide.

surface species with a bidendately coordinated carbonate ligand (Fig. 1D).

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Keywords – Surface complexes, minerals, spectroscopy

INTRODUCTION/

A detailed description of the molecular interactions of radionuclides with minerals is required for the prediction of
their dissemination in the environment. In the past decade,vibrational spectroscopy has been developed to a powerfultool for the study of surface complexes of heavy metal ionson solid phases. In particular, a combined approach of vibrational and X-ray absorption spectroscopy potentially provides
comprehensive molecular information. In this study, a surveyof very recent results obtained from sorption reactions of radionuclides, namely U(VI), Np(V) and Se(VI) on metal oxides is given.
RESULTS
A. Surface processes of U(VI) and Np(V) on gibbsite
Gibbsite is widely used as a model system foralumosilicate minerals and clays. In addition, it is a ubiquitous weathering product of these minerals and the mostcommon crystalline aluminum hydroxide.
The results of the U(VI) sorption experiments indicate theformation of a monomeric binary inner-sphere surface complex irrespective of the prevailing atmospheric condition andsurface loading (Fig. 1A). In addition, it was found that
U(VI) surface precipitation occurs at a micromolar concentration level in an inert gas atmosphere. This is circumvented bylowering the initial U(VI) concentration or in the presence of
atmospheric CO2 due to the formation of ternary uranyl
carbonato surface complexes. The ternary complex was identified as a dimeric inner-sphere uranyl surface species containing a bidentately coordinated carbonate ligand by EXAFS
spectroscopy (Fig. 1B)[1].
Inner-sphere complexation was also derived from spectroscopic results of the Np(V)/gibbsite sorption system. Whilst
the neptunyl(V) ion forms a mononuclear surface species under inert gas condition (Fig. 1C), a ternary surface complex in
the presence of atmospherically derived CO2. This ternary
species is most likely a mononuclear Al–O–NpO2–O2CO-

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/
/

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/

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/
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/
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/
/ 

!L

!L

!L

!L

!

"

#

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Fig. 1: Proposed surface complexes of U(VI) and Np(V) on gibbsite.

B. Surface speciation of Se(VI)The sorption of selenate ions on different metal oxide
phases exhibits a new type of outer-sphere complexes. As it
was already postulated for transition metal cations to form
classical and extended outer-sphere complexes [2], this is obviously also true for oxoanions, such as SeO42�. With respect
to the high sensitivity of vibrational spectroscopy to symmetry properties of molecules, the spectra of the sorptioncom�������������������������������������������������������Fe2O3) [4] clearly indicate the formation of different types ofouter-sphere complexes (Fig. 2). These findings are corroborated by macroscopic analytical techniques.

Fig. 2: IR spectra of SeO42� species and the derived surface species.

REFERENCES
[1]
[2]
[3]
[4]

－ 34 －

Gückel, K. et al. (2012) Chem. Geol. 326-327, 27-35.
Lee, S. S. et al. (2010) Langmuir 26, 16647-16651.
Jordan, N. et al. (2011) Geochim. Cosmochim. Acta 75, 1519-1530.
Jordan, N. et al. (2013) Geochim. Cosmochim. Acta 103, 63-75.

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

Adsorption of Eu(III) and Am(III) on granite: Effects of temperature, fulvic acid andbackground electrolyte
Z.J. GUO, Z.Y. CHEN, Q. JIN, W.S. WU
School of Nuclear Science and Technology, Lanzhou University, Lanzhou, 730000, China
E-mail: guozhj@lzu.edu.cn
Abstract –The adsorption of Eu(III) and Am(III) on crushed Beishangranite (BS03, 600m) was investigated as a function of temperature,
background electrolyte and the presence of fulvic acid at different
concentrations. It was found that temperature did not affectapparently the distribution coefficient (Kd) of Eu(III) in the range of
25-80 oC. At pH < 5.0, the Kd value decreased in CaCl2 solution ascompared to that in NaCl solution at the same ionic strength,
suggesting cation exchange reactions occurred in low pH range.
Whereas in high pH range, the Kd values in CaCl2 and NaClsolutions at the same ionic strength are identical, which indicate
inner-sphere surface complexes formed. FA significantly decreased
Kd of Eu(III) especially at pH > 4 and the extent of the decreasedepended on FA concentration and varied with aqueous pH as well.
Aging of freshly crushed granite in synthetic underground water at
150 oC for two weeks did not affect apparently Eu(III) Kd values. A
surface complexation model (SCM) using Generalized Composite(GC) approach was constructed based on experimental data of
Eu(III) in NaCl solutions and verified by experimental data of
Eu(III) in CaCl2 solutions as well as in synthetic underground water.
The SCM was used to predict Am(III) adsorption on the granite andthe calculated results were in accordance with the experimental
data of Am(III)III. RESULTS AND DISCUSSION
In Generalized Composite (GC) approach [2], a rock is
integrally considered and surface reactions on which areassumed to occur on a type of “general sites”, although thechemical environmental of surface sites on different minerals
and even those on different crystal planes of the same mineral
are actually different. In addition, the GC approach ignores
electrostatic effect. As a result, a GC model for a radionuclide
sorption on a rock is actually the simplest model with theleast adjustable parameters.

Keywords –Eu(III), Am(III), adsorption, granite, temperature effect,
fulvic acid, surface complexation modelI.

INTRODUCTION

Beishan granite (Beishan, Gansu province) has been
considered as a preliminary selection of host rock forgeological disposal of high-level radioactive waste in China,[1]. Considering temperature variation, potential change inelectrolytes of underground water, and the presence of humic
substances in the near field of a repository, it is necessary toevaluate adsorption of radionuclides on the granite at variableconditions.
II. MATERIAL AND METHODS
152+154

Eu(III) and 241Am(III) radiotracers were obtained
from Chinese Atomic Energy Institute. All other chemicals
used were of analytical grade. Beishan granite was sampledfrom the borehole BS03 at a depth of 600 m. To simplify theadsorption system, carbonates in Beishan granite wasremoved and the exchangeable cations were transformed into
Na-form or Ca-form. Batch sorption was carried out with
polyethylene tubes in nitrogen atmosphere glove box.

Figure. Eu(III) sorption in CaCl2 and “real” systems, (a) Sorption edge ofEu(III) on Ca-granite, Co = 6.74×10�8 M, m/V = 1 g/L and CCaCl2 = 0.033 M;(b) Sorption isotherm of Eu(III) on Ca-granite, CCaCl2 = 0.033M, m/V = 1g/L
and pH = 4.00±0.10; (c) Sorption isotherm of Eu(III) on Ca-granite, CCaCl2 =0.033 M, m/V = 1g/L and pH = 6.50±0.10; (d) Sorption edge of Eu(III) on
Na-granite with simulated underground water Co = 6.74×10�8 M, m/V = 1
g/L and CNaCl = 0.1 M.
[1]Guidelines for the R&D for geological disposal of high-level
radioactive waste. Beijing: China Atomic Energy Authority (CAEA),
Ministry of Environmental Protection, Ministry of Science andTechnology, 2006 (in Chinese)[2] Davis J A, Meece D E, Kohler M, Curtis G P. Approaches to surface
complexation modeling of Uranium(VI) adsorption on aquifer
sediments. Geochimica et Cosmochimica Acta, 2004, 68: 3621-3641.
[3] Guo Z, Chen Z, Wu W, Liu C, Chen T, Tian W, Li C, The adsorptionof Eu(III) on Beishan granite, SCIENTIA SINICA Chimica, 2011, 41:907-913.

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

ENO-02"EHAVIOUR OF RADIONUCLIDES AND SECONDARY MINERAL FORMATION IN THE
4ALVIVAARA MINING PROCESS
Hanna Tuovinen(1), Esa Pohjolainen(2), Daniela Vesterbacka(1), Caroline Kirk(3),David Read(3), Dina Solatie(4), Jukka Lehto(1),ABORATORY OF 2ADIOCHEMISTRY $EPARTMENT OF #HEMISTRY 5NIVERSITY OF (ELSINKI
0/ "OX  &)  5NIVERSITY OF (ELSINKI &INLAND'EOLOGICAL 3URVEY OF &INLAND "ETONIMIEHENKUJA  &)  %SPOO &INLAND$EPARTMENT OF #HEMISTRY ,OUGHBOROUGH 5NIVERSITY ,OUGHBOROUGH ,EICESTERSHIRE ,% 45 5+

2EGIONAL ,ABORATORY OF .ORTHERN &INLAND &INNISH 2ADIATION AND .UCLEAR 3AFETY !UTHORITY ,ÛHTEENTIE  &) 2OVANIEMI &INLANDThe Talvivaara nickel deposits are located in Sotkamo, Eastern Finland. The deposits comprise one of thelargest known nickel sulphide resources in Europe. Talvivaara is an operational, open cast mine where
Talvivaara Mining Company uses bioheap leaching to extract the metals (Ni, Zn, Cu, Co) from the black schist
ore. In 2010 the company announced the commencement of uranium production as an addition to its normal
mining operations. In heap leaching, uranium dissolves in the pregnant leach solution (PLS) along with mainbase metals and will be extracted using the solvent extraction (SX) process. The uranium produced will be in theform of yellowcake with an estimated annual production of approximately 350 tons. Currently, the uranium isdiverted into a gypsum pond and part of it also ends up in the nickel concentrate as an impurity.
Bioheap leaching is a naturally occurring exothermic process catalysed by indigenous bacteria. The key
parameters are particle size (< 8 mm), pH of the pregnant leach solution (2 – 2.5), temperature (20-90 oC) andthe oxidation and aeration rates. The ore is first extracted using conventional large scale open pit drill and blast
methods, then crushed and screened in four stages. It is agglomerated in a rotating drum, where recirculated PLS
is added to the ore in order to consolidate the finer particles. It is then stacked eight meters high on the primaryheap pad for primary leaching. The heap is irrigated from above and the leachate collected from the base of theheaps. The pregnant leach solution is collected in the PLS ponds where a 10% side flow is taken for metals
recovery; the remaining 90% per cent is recycled back to irrigation to increase the metal grade. The metals are
precipitated from the PLS using hydrogen sulphide and the resulting intermediate products transported forfurther processing in refineries. After approximately 2 years bioleaching on the primary pad, the leached ore isreclaimed, conveyed and restacked onto secondary heap pads. At this stage, the main part of copper and cobalt
is recovered. After secondary leaching, the barren ore will remain permanently in the secondary heaps.
The leaching process oxidizes U(IV) to U(VI) in the form of the uranyl ion (UO22+) at low pH. Radioactive
progeny from the 238U series are also mobilized and fractionate depending on chemical properties and theambient conditions. The aim of this study is to generate new data leading to a better understanding of the
behaviour of radionuclides, especially 226Ra, 210Pb and 210Po, at each stage of the Talvivaara mining process. In
addition the formation of secondary minerals during the leaching process is poorly understood.
Samples were collected from the primary heaps, secondary heaps, the PLS-ponds and gypsum pond in 2011,2012 and 2013. After pre-treatment, gamma spectrometry was used for direct determination of uranium andthorium progeny. Samples were then analysed by X-ray diffraction (XRD) to determine the main minerals
present. The uranium-bearing minerals were determined by electron probe micro-analysis (EPMA). Uranium,
thorium and heavy metals were determined by ICP-MS. For alpha spectrometry, uranium and thorium wereseparated using anion exchange chromatography, 210Po with silver plate precipitation and 210Pb was precipitatedfrom the remaining solution. Leaching experiments were performed in order to determine 226Ra, 210Pb and 210Po– bearing mineral phases.
Preliminary results provide information on the formation of secondary phases and the relative abundance of theinitial ore minerals. Uranium in the gypsum pond is found at least in association with goethite (FeO(OH)). The
high content of sulphate restricts solubility of radium; 226Ra concentrating in precipitated sulphate minerals. For
lead, the formation of anglesite (PbSO4) is probable and polonium is also likely to be bound to secondary
minerals in the heaps. The results of this work will play an important role in estimating radiation doses andpotential health implications to the local population resulting from past and anticipated disposal. A summary of
the main results obtained to date is given in the presentation.

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

ENO-03

Evaluation of HTO and selenium diffusion behavior in compacted bentonite withdifferent lengths
Chuan-Pin Lee 1, Ming-Chee Wu 1,*,Ching-Yuan Liu 2, Chun-Hua Pan 1, Tsuey-Lin Tsai 3, Hwa-Jou
Wei 3, Lee-Chung Men 3
1* Department of Earth Sciences, National Cheng Kung University, Tainan, Taiwan, 70101
Department of Chemical and Materials Engineering, National Central University, Taoyuan, Taiwan, 32001,
3
Chemistry Divisions, Institute of Nuclear Energy Research, Taoyuan, Taiwan, 32546

2

Abstract – n this study, diffusion behavior of selenium(Se)with a concentration of 0.1mM in bentonite (MX80) wasinvestigated using through-diffusion methods with various
lengths (0.25, 0.5, 0.75, 1.0, 2.0, 2.5 cm), respectively.
Before performing the through-diffusion experiments of Se,
a non-reactive tracer (HTO) was applied and achieved tocharacterize the physical process in compacted MX80
columns with different lengths. It shows that the diffusion
process of Se in synthetic seawater (SW) and groundwater(GW) reached equilibrium after 250 and 300 days,
respectively. Moreover, both retardation factor (Rfcal) anddistribution coefficients (Kdcal ) of Se obtained fromaccumulative concentration’s method in through-diffusion
test showed an obvious discrepancy in an increasing
length/diameter (L/D) ratio. In fact, it presented anagreement of RfH/Se and KdH/Se in an increasing L/D ratio incomparison between HTO and Se. It appears that the RfH/Se
and KdH/Se obtained from the through-diffusion experiments
are higher than those derived from the batch experiments.
Therefore, it demonstrates that reliable Rf and Kd of Se bythrough-diffusion experiments could be achieved at a nonreactive radiotracer(HTO) prior to tests and would be
more confident for long-term performance assessment.
Keywords – Diffusion, Selenium, distribution coefficients,
apparent diffusion coefficient－ 37 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

ENO-04

3ORPTION "EHAVIOR OF $Y))) AND .P6 ON MICROBIAL CONSORTIA
Toshihiko Ohnuki1, Naofumi Kozai1, Fuminori Sakamoto
1

Japan Atomic Energy Agency, Tokai, Ibaraki, 319-1195 Japan

Abstract – To elucidate sorption of trivalent and pentavalentactinides by the consortia of microorganisms sampled atHoronobe, Hokkaido, Japan. In the sorption experiments ofNd(III), Dy(III) (analogue of trivalent actinides), and
Np(V) were contacted with the consortia in the solution at
pH between 3 and 7 in resting condition. The coordination
environment of the sorbed Dy by the consortia wasanalyzed by EXAFS. For the sorption of Nd and Dy on the
consortia, the Kd increased with increasing pH, and wasnearly the same as that by single species of 3 PUTREFACIENS.
For the sorption of Np on the consortia, the K d was higher
than that for a single species of 3 PUTREFACIENS, indicatingthat the sorption behavior of Np on the consortia isdifferent from that by a single species of 3 PUTREFACIENS.
These results indicate that the consortia poses higher
affinity to Np than a single species of S. putrefaciens.
+EYWORDS – .EPTUNIUM TRIVALENT ACTINIDES SORPTION CONSORTIA OF
MICROORGANISMSI.

INTRODUCTION

The presence of actinides (ANs) in radioactive wastes isa major environmental concern due to their long radioactive
half-lives, and its chemical toxicity. The high capacity of
microbial surfaces to bind ANs may affect the migration of
ANs in the environment. Unfortunately, we have only
limited knowledge of the role of microorganisms in the
migration of ANs in the environment.
Many researches have been carried out to study
adsorption of ANs on the cell surface o microorganisms.
Usually in the adsorption experiment single species of
microorganism was used, even though microorganisms
habit in consortia in environment. The adsorption ofdivalent cations of Cd, Cu, Ca, Pb, Sr, and Zn by the
consortia was nearly the same as that by a single species.
However, sorption behavior of ANs by consortia has notbeen elucidated.
In the present study, sorption behavior of trivalentlanthanides of Nd(III) and Dy(III) (alternative use forAm(III) and Cm(III), and of Np(V), by consortia of
microorganisms using batch type sorption experiments..
II. EXPERIMENTAL
Sample locations were at 140 m in depth in the site of
JAEA Horonobe Deep Geological Research Center,
Horonobe, Hokkaido, Japan. Samples were collected 3
different points on February, 2011. The samples were
inoculated in the Fe-reducing bacteria growth medium
containing NaHCO3 1g: NH4Cl 0.6g: KH2PO4 0.24g: KCl
0.04 g: Na-acetate 1 g: Na-citrate 0.4 g: Fe(OH)3 0.4g in 1
L distilled water under anaerobic condition. The pre-grownconsortia were cultured in the medium containing beef

extract or shewanella medium under aerobic condition.
Culture in the consortia were analyzed by 16S rRNA
analysis.
For the sorption experiments of Nd(III), Dy(III), and
Np(V) by the consortia were conducted in resting condition.
The solution sampled at 4 and 24 hrs after the exposure
were centrifuged for 10 min at 4000 rpm. The supernatant
was filtered through a membrane filter of 0.2 Pm tomeasure concentrations of the dissolved elements. The
concentration of Nd and Dy was 0.1 mM, and Np was 0.01
mM. The sorption experiments were performed in aerobic
condition.
The concentrations of Nd and Dy were measured by
ICP-AES, and that of Np by liquid scintillation analyzer.
The coordination environments of the sorbed Dy(III) by
consortia were determined by XAFS analysis using KEK
PF.
III. RESULTS AND DISCUSSION
The consortia contained many kind sof bacteria
involving Pseudomona and 3HEWANELLA family by random
clone analysis.
For the sorption of Nd and Dy on the consortia,
distribution coefficients (Kd) were between 104-105 ml/g at
pH between 3-7. The Kd for Nd and Dy increased withincreasing pH. Higher Kd in Dy than Nd was determined.
The Kd of Nd and Dy for the single species of 3HEWANELLAPUTREFACIENS, was approximately 104 ml/g at pH around 4,
and increased with increasing pH. XAFS analysis showedthat the FT spectrum of Dy sorbed on the consortia
resembled to that of Dy sorbed on a single species of
3HEWANELLA PUTREFACIENS, but not to DyPO4, indicatng thatthe coordination environment of Dy was nearly the same asthat on 0 PUTREFACIENS. These results indicate that thesorption behavior of Nd and Dy on the consortia is nearly
the same as that by a single species of 3 PUTREFACIENS.
For the sorption of Np on the consortia, the Kd wasapproximately 104 ml/g at pH 4. The Kd remained constantwith increasing pH of the solution. The Kd for a single
species of 3 PUTREFACIENS was about 102 ml/g at pH
between 4 and 6.5. The Kd increased with increasing pH.
These results indicate that the sorption behavior of Np on
the consortia is different from that by a single species of 3
PUTREFACIENS. Since higher Kd is measured in the consortia
than a single species of 3 PUTREFACIENS, the consortia poses
higher affinity to Np than a single species of S. putrefaciens.
This research project has been conducted as the regulatory
supporting research funded by the Nuclear Regulation
Authority (NRA), Japan.

－ 38 －.

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

Interaction of Eu(III) with Mammalian Cells as a Function of Eu(III) Concentration
and Nutrient Composition
Susanne Sachs, Anne Heller, Gert Bernhard
Helmholtz-Zentrum Dresden-Rossendorf e.V., Institute of Resource Ecology, P.O. Box 510 119, 01314 Dresden, Germany

Eu(III), interaction, mammalian cells, toxicity, speciationI.

INTRODUCTION

In case of the release of long-lived radionuclides, e.g., actinides, into the environment, knowledge about their behavior
in biosystems is necessary to assess and prevent health risks
for humans. This includes knowledge about bioavailability
and toxicity of actinides for/onto cells, which are governed toa large extent by their speciation [1]. In order to enable a better understanding of these processes, we study interaction
processes of trivalent actinides/lanthanides with mammaliancells on a cellular level combining biochemical and spectroscopic methods. In the present work we studied the cellular
tolerance of FaDu cells (human squamous cell carcinoma cellline) toward Eu(III), as an analog for trivalent actinides, andits uptake into the cells as a function of the metal concentration and the nutrient composition. In parallel, the Eu(III) speciation in the culture media was studied by time-resolved laser-induced fluorescence spectroscopy (TRLFS) to correlate
Eu(III) toxicity and uptake with its chemical speciation.

toxicity is higher in the absence of FBS than in its presence.
This discrepancy is attributed to the different Eu(III) species
in the media and points to an unequal bioavailability ofEu(III). In the presence of FBS, Eu(III) is stabilized in solution by complexation with FBS constituents, most probably
serum proteins, which was verified by ultrafiltration. In contrast, in the absence of FBS, the Eu(III) solubility is very low.
ICP-MS analysis of Eu(III) precipitates as well as TRLFS
point to the occurrence of ternary or higher Eu(III) complexes
with phosphate as the dominant ligand. The additional presence of citrate does not significantly affect the Eu(III) toxicity onto the cells in the presence of FBS. However, in its absence, an excess of citrate decreases the Eu(III) toxicity mostprobably due to a change of the chemical speciation.
Independent from the initial Eu(III) speciation, the Eu(III)uptake by the cells is low. It is predominantly located on thecell surface.
Under the studied experimental conditions, the toleranceof FaDu cells versus Eu(III) appears to be not significantly
influenced by the presence of 152Eu, i.e., there seems to be no
additional radiotoxic effect.

#ELL VIABILITY   OF CONTROLThe Eu(III) toxicity onto FaDu cells is influenced by its chemical
speciation that is determined by the composition of the culture medium. However, independent from its speciation, Eu(III) seems to bebound to the cell surface and does not significantly enter the cells.

II. EXPERIMENTAL
FaDu cells were grown in Dulbecco’s modified eagle medium supplemented with fetal bovine serum (FBS), nonessential amino acids, HEPES buffer, penicillin/streptomycin,
sodium pyruvate (37°C, 5% CO2, 95% humidity) andsubcultivated as described in [2]. The Eu(III) toxicity onto
FaDu cells ([Eu]: 5-2000 µM) and its uptake into the cells([Eu]: 10, 1000 µM) was studied in the presence and absenceof FBS as described in [2,3]. In addition, the impact of citrate
was studied. To differentiate between chemotoxic and radiotoxic effects of Eu(III), first experiments were performed in
the presence of FBS ([Eu]: 10, 1000 µM) applying 152Eu as
radioactive tracer. The Eu(III) speciation was studied by
TRLFS as described in [4].
III. RESULTS



0RESENCE OF &"3!BSENCE OF &"3






;%U=TOT  ±-

Fig. 1: Cell viability after 24 h of incubation with Eu(III).

ACKNOWLEDGMENTS
We thank J. Seibt, S. Heller, A. Ritter, C. Eckardt, and S.
Weiß for experimental and technical support as well as J.
Pawelke and E. Leßmann for the first batch of FaDu cells,
FBS and training in cell cultivation techniques.
[1][2]

As an example, the viability of FaDu cells after 24 h of incubation with 5-2000 µM Eu(III) in the presence and absenceof FBS (no citrate present) is shown in Fig. 1. The Eu(III)



[3]
[4]

－ 39 －

Ansoborlo, E. et al., Biochimie 88 (2006), 1605.
Sachs, S., Bernhard, G., Annual Report 2011, HZDR-013. HelmholtzZentrum Dresden-Rossendorf, Dresden (2012), p. 12.
Sachs, S., Heller, A., Annual Report 2012, HZDR-030. HelmholtzZentrum Dresden-Rossendorf, Dresden (2013), p. 26.
Heller, A. et al., Annual Report 2011, HZDR-013. Helmholtz-Zentrum
Dresden-Rossendorf, Dresden (2012), p. 13.

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ENO-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The Issue of Separation of Uranium from Drinking Water in the Czech Republic
1

Jan Krmela1������������������������� �������������������, The Czech Republic, jan.krmela@ujv.cz

Abstract
Natural ground water used for the preparation of drinking watercontains a number of cations, anions, elements and other substances
depending on the bedrock composition (Ca, Mg, Fe, Mn, heavy
metals, radioactive elements, arsenic, chromium, carbonates,
sulfates, phosphates, silicates, fulvic and humic acids etc.).
Information about composition of drinking water is important tocomply with all the requirements on sanitary of drinking water.
The elements that affect the quality of drinking water mainly fromgroundwater, also includes radioactive elements contained in
bedrock sections where water is extracted. These are the elementswith long half-lives, mainly alpha emitters (U, Ra, Rn, Th, andelements of the decay series).
Uranium and its decay products are found in all environmental
compartments. Radionuclides come to the environment bothnaturally - weathering and leaching of the rocks, and as aconsequence of human activities in connection with the use of raw
materials.
Uranium occurs naturally in four oxidation states. The mostmobility has hexa-valent state (uranyl ion). Uranyl is highly soluble
form of uranium in water. Mobility of uranium in soil and water isaffected by many factors.
Complex processes in soil and rock lead to redox reactions forming
both insoluble compounds (lower valence forms of uranium) andsoluble form of U (VI) (forming by reoxidation), which is again
leachable into groundwater. The content of uranium in groundwater
depends on the geological composition of the ground, and can reachup to hundreds of �g/L.
At present the issue associated with removing uranium fromdrinking water is solved in the Czech Republic. New limit for theconcentration of natural uranium (234U, 235U and 238U) was
recommended ��������������������L as the highest limit based on theWorld Health Organization (WHO). Advice of the Chief Health
Officer of the Czech Republic came into force on 1st January 2010,
which decreased the limit for uranium in drinking water from������������������������������������������� by WHO. However,the WHO ������������������������������������L in 2011 based on a���� ��������� ������ ������� ����� ������L uranium in drinking water
has not negative effect on the human organism (chemical toxicity)[1]. Limit in the Czech Republic remained at the same level �����/L.
Change the limit leaded to solving the issue on the waterworks in
the Czech Republic, which had not any experiences withradioactivity. Some waterworks installed a new device from
Germany (ion exchanges), but did not solve what they do withsaturated ion exchanges. Ion exchanges as the most suitablematerial for removing of uranium from drinking water is not reused(without regeneration), but it is used in the uranium industry, whereis putted to start of processing of uranium ore. Ion exchanges are
replaced with a new one in the waterworks and saturated ion
exchanges are discarded in the uranium industry.
Regeneration of ion exchanges could be cheaper, because ion
exchanges could be reused and processing of ion exchangers could
be cheaper, because it is possible to put the regenerant before theprocess of precipitation of “yellow cake” in the processing of
uranium ore.
This project TA02010044 was supported by TA CR.
Key words - Uranium, Drinking water, Ion exchanger[1]－ 41 －

WHO: Uranium in Drinking-water, Background document fordevelopment of WHO guidelines for Drinking-water Duality,
WHO/SDE/WSH/03.04/118/Rev/1, 2011.

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

ENO-08Air-born contamination caused in a high-energy proton accelerator room
1

K. Mausmoto1, A. Toyoda1, H. Matsumura1, T. Kunifuda2
High Energy Accelerator Research Organization, Tsukuba, 305-0801, Japan
2
Tokyo Nuclear Service, Tsukuba, 300-2646, Japan

Abstract – Surface contamination caused during the operation of
12-GeV proton synchrotron, KEK have been studied by gammaray spectrometry and imaging plate technique. The surface ofaccelerator component was wiped with the filter paper. PSL valueof imaging plate contacted on the filter paper decreased
according to the half-life of 2 weeks. Therefore, it was assumed
that 32P might be produced from Ar by the high-energy protons
and neutrons and deposited on the accelerator components.
Keywords – Air-born activity, High-energy accelerator,
Imaging plate

I.

32

P,

INTRODUCTION

It is well known that various radioisotopes are inducedin the stratosphere by cosmic rays. During the operation ofa high-energy proton accelerator, air components are also
activated by primary protons and secondary neutrons andsimilar radioisotopes are produced. It is interesting to know
the behavior of radioisotopes in an accelerator room. The
radioisotopes are deposited on the surface of accelerator
components and cause surface contamination problem. In
this work, these radioisotopes were wiped with a filter
paper. The radioactivity was measured by the gamma-ray
spectrometry and the imaging plate technique.
II. EXPERIMENTAL
This work was performed at the 12-GeV proton
synchrotron, KEK. After stopping, smeared samples wereobtained from on beam pipes, magnets, wall and floor in
the accelerator room. In order to measure the activity ofbeta and gamma nuclides, a GM-counter, a liquid
scintillation counter, a Ge-detector and an imaging plate
were used.
III. RSULTS AND DISCUSSIONS(1) A liquid scintillation counter
Tritium was only observed. Carbon-14 could notdetected by the background effect.
(2) GM-counter and Imaging plate
Figure 1 shows the decay curves of seven filter papers
sampled from the beam line. It was found that the half-lifeof major activity was 2 weeks. Therefore, it was assumed
that 32P was produced and deposited. As the similar result
was obtained by a GM-counter, Imaging plate was also
detected beta activity. A polyethylene film pasted on thewall and surface was wiped with a filter after beam
stopping. In this case, 32P was also observed as a major
activity.

(3) Ge-detector
Many radioisotopes such as 7Be, 54Mn, were observed.
7
Be was produced by the spallation reactions of oxygen andnitrogen in air and deposited on the surface of beam line.
The gamma activity obtained by the Ge-detector was notcorrelated with the result of imaging plate technique.
Therefore, beta activity is important for surface
contamination.
IV. CONCLUSION
An imaging plate technique is very useful to measure theradioactive decay of many samples simultaneously on thesame condition.
Induced radioisotopes in air were deposited on the beamline. Because, the radioisotopes attached to aerosol anddeposited on the surface of beam line. A major acitivity was
32
P, which might be produced by the spallation reaction of
Ar in air.
In case of high-energy and high-intensity accelerators,
radioactive aerosol formation will become important
problem of radiation control. And this phenomenon wasinteresting subject to achieve the cosmic ray reaction in thestratosphere on the ground level.

－ 42 －

ENO-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Application of 210Pb in Glaciology
H.W. Gäggeler, L. Tobler, M. Schwikowski

Paul Scherrer Institut, Labor für Radio- und Umweltchemie, 5232 Villigen, Switzerland .
Keywords – 210Pb dating, climate research, environmental
pollution, non-dating application of 210Pb
I.

ABSTRACT

Glaciers are increasingly used as proxies for climate change.
Advances and retreats of these ice bodies are prime
information on climate variability. Moreover, glaciers havefound widespread application as archive of current and past
atmospheric information. To fully benefit from suchinformation, the glaciers have first to be dated. 210Pb is one of
the most frequently used radionuclide that enables dating for
one to two centuries BP (before present). 210Pb is ubiquitous
in atmosphere, since it is a decay product of natural radon(222Rn). Attached to aerosol particles 210Pb is then scavenged
by precipitation and deposited on the Earth surface.
210
Pb has proven to be much more versatile as information
species besides dating. This contribution summarizes someexamples that includes (besides dating, see e.g. figure 1);
Determination of annual snow accumulation rates at remotesites using the 210Po/210Pb disequilibria.
Thinning of glaciers as a function of depth caused by theincreasing mass of overlying fresh snow and ice.
Folding of low lying ice layers due to topographic conditions
that lead to non regular age-depth relationships.
Variability of seasonal deposition at high altitudes due toconvective processes in summer.
Study of heavy metal percolation in temperate glaciers

Presented examples originate from glaciers studied at our
institute. Ice core drillings were performed in the European
Alps, the South American Andes, the Russian and Mongolian
Altai, the Mt. Cook area in New Zealand and in Svalbard(Norway).
References

Determination of sublimation rates at glacier sites in arid
areas such as the Andes.
210

Fig. 1: 210Pb activity concentrations along an ice core fromthe Belukha saddle in the Altai mountains (Siberia, Russia)
together with three additional time horizons from the nuclear
weapons testing (1963: measured via tritium), and the wellknown volcanic eruptions from Katmai (1912) and Tambora(1816) identified via increased excess sulphateconcentrations. The right axis depicts the age deduced fromthe 210Pb measurement (deduced from [1])Pb activity concentrations as indicator of air masses, withlow values for precipitation from marine air and high values
for continental air, respectively.

[1] Olivier, S.., C. Blaser, S. Brütsch, N. Frolova, H.W. Gäggeler, K.A.
Henderson, A.S. Palmer, T. Papina, M. Schwikowski, Temporal variationsof mineral dust, biogenic tracers and anthropogenic species during the past
two centuries from Belukha ice core, Siberian Altai, J. Geophys. Res.
Atmospheres, 111, DO5309, doi:10.1029/2005/Doo5830 (2006)－ 43 －

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

Depth distributions of uranium-236 and cesium-137 in the Japan Sea;
toward the potential use as a new oceanic circulation tracer
Aya Sakaguchi1, Akinobu Kadokura1, Peter Steier2, Yoshio Takahashi1,
Kiyoshi Shizuma3, Tomoeki Nakakuki1, Masayoshi Yamamoto4
1

Graduate School of Science, Hiroshima Univ.
2
VERA-Laboratory, Univ. of Vienna
3
Graduate School of Engineering, Hiroshima Univ.
4
Low Level Radioactivity Laboratory, Kanazawa Univ.
We present a feasibility study for using 236U as an oceanic
circulation tracer based on depth profiles of 236U and 137Cs in theJapan/East Sea. The concentration of the predominantly
anthropogenic 236U, measured with Accelerator Mass Spectrometry(AMS), decreased from the order of 107 atom/kg in surface water to
106 atom/kg close to the sea floor (3000 m). The profile has asmooth trend with depth and concentration values are generally
proportional to that of 137Cs for the same water sample. The
cumulative inventory of dissolved 236U in the water column was
estimated to be 1012-1013 atom/m2, which is similar to the globalfallout level (17.8x1012 atom/m2) in Japan. Additional analyses ofsuspended solids (SS) and bottom sediments yielded negligible
amounts of 236U. Our results suggest that 236U behaves as aconservative nuclide in seawater, with potential advantages overother tracers of oceanic circulation.

Keywords – the Japan Sea, GEOTRACES, U-236, Cs-137,
globalfallout

II. MATERIAL AND METHOD
Bottom sediments (4 sites) and seawater samples (7 sites)
were collected from the Japan Sea in the research cruise with
R/V Hakuhomaru, 2010 . The sediment core was cut into 1
cm segments from the surface to 5 cm in depth within a few
hours after the sampling. About 20 L of seawater samples
were collected from some depths in each site, andimmediately after the sampling, the water was filtered with
0.45 �m pore-size membrane-filters. After the appropriate
pre-treatment for each sample, uranium isotope and 137Cs
were measured with AMS and Ge-detector, respectively. The
detail of these methods were published in Sakaguchi et al.,(2012)[2].
III. RESULTS AND DISCUSSION
236

I.
137

U was successfully detected for all seawater samples, andU/238U atom ratios in seawater were in the range of (0.191.75)×10-9. The dissolved 236U concentration showed a
subsurface maximum and decreased steeply with depth. The
minimum value was found at a depth of 2500 m and bottom(about 3000 m in depth) in the northern and the southernareas, respectively. These profiles are markedly different
from that of natural 238U which is nearly constant over thedepth, suggesting that 236U has not yet reached steady state.
For the SS sample, 236U could not be detected in significant
levels. The total 236U inventory of the water column was
estimated at 1012-1013 atom/m2. This value is nearly the sameas the global fallout level (17.8×1012 atom/m2)[1][2]. 236U
was also found in the bottom sediments, and the inventory
was about 1/40 compared with that in water column. All
above characters are comparable with 137Cs which isanthropogenic conservative nuclide in ocean. Actually, thediffusion coefficients for both nuclides show the nearly samevalue. The detail discussion of this study has been shown in
Sakaguchi et al., (2012)
236

INTRODUCTION

Cs (T1/2=30.2 y) has been spread all over the world as a
fission product of atmospheric nuclear weapons tests in the
1960s. This nuclide has been used as a powerful tool for
oceanography due to the well-defined origin and conservative
behaviour in water. However, the number of atoms has
decayed already to one thirds compared with its initial levels,and it will become more difficult to measure. In this situation,
we focus on 236U (T1/2=2.342×107 y) as a candidate for a newisotopic tracer for oceanography. The detection of 236U in theenvironment has become possible only recently, by thedevelopment of measuring techniques with high sensitivity
based on AMS. Our group showed that global fallout frombomb tests contains 236U, which might be produced as nuclear
reactions of 235U(n,�) and/or 238U(n,3n)[1]. So 236U has been
therefore globally distributed in the surface environment.
Thus, 236U has a similar potential as a tracer forenvironmental dynamics as 137Cs, especially for
oceanography.
In this study, a comprehensive attempt was made to measure
the concentration of 236U in marine samples such as water,
suspended solid and bottom sediments to clarify theenvironmental behaviour of this isotope. Furthermore, thediscussion of the circulation of deep and bottom water in"Miniature Ocean", the Japan Sea, has been attempted.

[1]
[2]
[3]

－ 44 －

A. Sakaguchi, K. Kawai, P. Steier et al. Science of the Total
Environment. 407, 4238-4242, 2009.
A. Sakaguchi, K. Kawai, P. Steier, et al., Science of the Total
Environment, 408, 5392-5398, 2010.
A. Sakaguchi, A. Kadokura, P. Steier,et al, Earth and Planetary Science
Letters, 333-334, 165-170, 2012.

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

ENI-02Ultratrace Analysis of Long-lived Radionuclides by Resonance Ionization
Mass Spectrometry (RIMS)
J.V. Kratz
Institute for Nuclear Chemistry, Johannes Gutenberg-University, Mainz, Germany
Keywords – Ultratrace analytical method, resonant laser ionization,
isotopic composition, plutonium analyses, actinide ionization potentials,
optical spectroscopy with 255Fm, IONTOF-SIMS coupled with RIMS

Abstract For long-lived radionuclides such as actinides,
conventional radioanalyses by ���������������������������
unsatisfactory limits of detection (LOD). Resonanceionization mass spectrometry, on the contrary, achieves
limits of detection of 106 atoms and is free from isobaric
interferences [1,2]. The multiple step resonant excitation of
evaporated atoms with laser light and the mass selective
detection is presented for isotopes of plutonium as an
example. We use a frequency-doubled Nd:YAG laser witha repetition rate of 10 kHz to pump three titanium-sapphirelasers delivering wave lengths of 420.76 nm, 847.28 nm,
and 767.53 nm to resonantly excite plutonium into a
Rydberg state from where ionization is achieved byapplying an electric field [3]. For isotopic composition
measurements, the wavelengths of lasers 1 and 2 must be
readjusted for each isotope while laser 3 can be maintainedat the same wavelength. The accuracy of isotopic ratios
determined this way is demonstrated with a certified NIST
standard. Applications are presented for fallout plutonium,
reactor plutonium, samples from the Chernobyl area,
wapons plutonium from the Mururoa island, seawater
plutonium from the Northern Sea, and from the Irish Sea.
Migration of plutonium through a granite fracture in theGrimsel underground laboratory has also been investigated[4].
By detecting ionization thresholds as a function of theapplied electric field, accurate ionization potentials IP ofAc, Th, U, Np, Pu, Am, Cm, Bk, Cf, and Es have been
determined by extrapolation to zero field strength [5, 6, 7].
In a first attempt to determine also the IP of Fm, a sample
of 20.1-h 255Fm produced at the HFIR at Oak Ridge has
been investigated. By resonance excitation with a dye laser
and ionization with an excimer laser in a buffer gas cell,
two excited states of Fm (5f12 7s 7p) have been identified
and mass spectra of 255Fm+ and the daughter 251Cf+ havebeen measured by a quadrupole mass spectrometer coupled
to a channeltron detector [8]. By measuring the drift timesof these ions and of 238UO+, ion mobilities in the electricfield could be determined. These are potentially useful todetermine ionic radii of the heavy actinides and superheavy
elements.
By using a commercial IONTOF-SIMS apparatus, analysesof hot micro particles with high lateral resolution in the
sub-micron range have been exploited [9]. For thedetermination of the location of these hot particles (x,ycoordinate on the target holder) their content of fissile
material via fission track analysis [10] has been used.

In order to avoid isobaric interferences, the sputtered ions
(SIMS) were suppressed by a pulsed counter voltage
applied to the target holder, and the abundantly sputteredneutral particles were resonantly excited and ionized by
RIMS. The resulting ions were directed by an alternating
acceleration voltage into the TOF mass spectrometer.
[1] N. Erdmann, G. Herrmann, G. Huber, S. Köhler, J.V.
Kratz, A. Mansel, M. Nunnemann, G. Passler, N.
Trautmann, A. Turchin, A. Waldek
Fresenius J. Anal. Chem. 359, 378 (1997)[2] M. Nunnemann, N. Erdmann, H.-U. Hasse, G. Huber,
J.V. Kratz, P. Kunz, A. Mansel, G. Passler, O. Stetzer, N.
Trautmann, A. Waldek
J. Alloys and Compounds 271-273, 45 (1998)[3] C. Grüning, G. Huber, P. Klopp, J.V. Kratz, P. Kunz, G.
Passler, N. Trautmann, A. Waldek, K. Wendt
Int. J. Mass Spectrometry 235, 171 (2004)[4] S. Bürger, R.A. Buda, H. Geckeis, G. Huber, J.V. Kratz,
P. Kunz, Ch. Lierse von Gostomski, G. Passler, A.
Remmert, N. Trautmann
in: Radioactivity in the environment – Volume 8, series
editor: M.S. Baxter, Elsevier 2006, 581[5] S. Köhler, R. Deißenberger, K. Eberhardt, N. Erdmann,
G. Herrmann, G. Huber, J.V. Kratz, M. Nunnemann, G.
Passler, P.M. Rao, J. Riegel, N. Trautmann, K. Wendt
Spectrochimica Acta, Part B 52, 717 (1997)[6] J.R. Peterson, N. Erdmann, M. Nunnemann, K.
Eberhardt, G. Huber, J.V. Kratz, G. Passler, O. Stetzer, P.
Thörle, N. Trautmann, A. Waldek
J. Alloys and Compounds 271-273, 876 (1998)[7] N. Erdmann, M. Nunnemann, K. Eberhardt, G.
Herrmann, G. Huber, S. Köhler, J.V. Kratz, G. Passler, J.R.
Peterson, N. Trautmann, A. Waldek
J. Alloys and Compounds 271-273, 837 (1998)
8] H. Backe, A. Dretzke, K. Eberhardt, S. Fritzsche, C.
Grüning, G. Gwinner, R. G. Haire, G. Huber, J.V. Kratz, G.
Kube, P. Kunz, J. Lassen, W. Lauth, G. Passler, R. Repnow,
D. Schwalm, P. Schwamb, M. Sewtz, P. Thörle, N.
Trautmann, A. Waldek
J. Nucl. Sci. Tech., Suppl. 3, 86 (2002)[9] N. Erdmann, J. V. Kratz, N. Trautmann, G. Passler
Anal. Bioanal., Chem. 395, 1911 (2009)[10] O. Stetzer, M. Betti, J. van Geel, N. Erdmann, J.V.
Kratz, R. Schenkel, N. Trautmann
Nucl. Instr. and Meth. in Physics Research A525, 582(2004)－ 45 －

ENO-11APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

The Bulk Analysis with TIMS Measurements Performed in KAERI for Nuclear
Safeguards
Jong-Ho Park, Sunyoung Lee, Young-Geun Ha, Seon A Lee, Kahee Jeong, Kyuseok Song
Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, Daejeon 305-353, Korea.

KAERI has been developing the techniques for bulk
analysis of environmental samples to support the internationalsociety for nuclear safeguards purpose. The analytical procedure,
which consists of screening, ashing, acid digestion, chemical
separation, and isotopic measurements by TIMS, was established.
The analytical results of simulated environmental samples preparedfrom certified reference materials fell into the criteria that the IAEA
requires for the NWAL qualification.

rhenium filament with minimized residue. A thermal
ionization mass spectrometer (TRITON, Thermo Fisher
Scientific) was utilized for isotopic measurement.
A simulated samples were prepared with cotton swipe
containing known amounts of uranium (CRM 112-A) andplutonium (REIMEP 16D) reference materials. The routine
procedure was applied for the bulk analysis of the simulated
samples.

Environmental Sample, Safeguards, Isotopic Analysis, TIMS

B. Result

Abstract

I.

INTRODUCTION

Highly accurate and precise analysis of nuclear materials
in environmental samples plays essential roles in monitoring
undeclared nuclear activities.1 The IAEA has been
maintaining a Network of Analytical Laboratories (NWAL)
for nuclear safeguards. Since 2009, Korea Atomic Energy
Research Institute (KAERI) has been developing thetechniques for bulk analysis of environmental samples tosupport the international society as one of the members of
NWAL. The analytical techniques that KAERI is utilizing
with TIMS measurements for bulk analysis are briefly
introduced in this paper.

The analytical results of simulated environmental samples
prepared from certified reference materials are shown in
Table 1. The accuracy and the precision of the result fell into
the criteria that the IAEA requires for the NWAL
qualification. The measured n(235U)/n(238U) of the samples
agreed with the certified value within less than 1% of
accuracy.
Table 1. The result of bulk analysis of simulated environmental samples

Cert.
#1

n(235U)/n(238U)
7.2543e-3n(240Pu)/n(239Pu)
1.110e-1

5.32[±0.52]e-5

7.27[±0.18]e-3

1.150[±0.005]e-1#2

6.71[±0.97]e-5
7.28[±0.11]e-3
1.140[±0.002]e-1
Numbers in parentheses indicate expanded uncertainties U = k·u c

A. Sample Analysis Procedure
Decomposition and acid digestion of environmental
samples were carried out to prepare sample solutions in nitricacid, called as the mother solution. The solutions were
weighed precisely, and then divided into three fordetermination of U isotope ratios and Pu quantity, fordetermination of U quantity and Pu isotope ratio, and forarchive, respectively. Appropriate spike isotopic referencematerials were added to the corresponding mother solution
portion. IRMM 040a (233U) and IRMM 085 (242Pu) were used
for quantification of uranium and plutonium, respectively.
The Pu isotopes were eluted into the conical PFA vial
through the UTEVA columns with 2M HNO3/0.02M ascorbicn(234U)/n(238U)
5.2841e-5[1]Acid/0.02M NH2OH�HCl after loading the sample solution
adjusted with 8M HNO3/0.3% H2O2 on the UTEVA columns.
The uranium isotopes were eluted through the columns with
0.007M ammonium oxalate solution. The purified Pu and U
solutions were evaporated to dryness with concentrated nitricacid, HF and HClO4 until any residue was not found in the
PFA vial. Each sample was loaded on a pre-degassed－ 46 －

D. L. Donohue, J. Alloy Compd. 1998, 271-273, 11.

ENO-12APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of plutonium isotopes at ultratrace level in seawater samples bysector-field ICP-MS combined with chromatographic separation
Wenting Bu1,2, Jian Zheng*2, Qiuju Guo*1, Tatsuo Aono2, Keiko Tagami2, Shigeo Uchida2
1

School of Physics, Peking University, China
National Institute of Radiological Sciences, Japan

2

Plutonium isotopes are released into the environment as a consequence of human nuclear activities
including nuclear weapon testing, nuclear fuel reprocessing and nuclear accident. As the world’s ocean
covers ca. 70 % of the earth surface, it received majority of Pu isotopes released into the environment byatmospheric nuclear weapons tests. For example, it has been estimated that the total global fallout
239+240
Pu released into the environment was about 10.87 PBq, and 6.6 PBq entered the world’s ocean[1].
Besides, a significant amount of Pu isotopes were injected directly to the world’s ocean by close-in fallout
from the nuclear explosions conducted at the Pacific Proving Ground by US and the French Polynesia byFrance.
Due to their radiotoxicity and long half-lives, Pu isotopes are regarded as highly hazardous pollutantsin the marine environment and are of great research interest. Accurate and precise determination of
plutonium isotopes in marine samples is important for radioecological assessment. In addition, Pu
isotopes have also been used for tracing of oceanographic processes, such as water mass circulation,transport and scavenging of particulate matter, etc.
The concentration of Pu in seawater is extremely low (239+240Pu, 1.2-7.4 mBq/m3 in the surface seawaterof the NW Pacific Ocean).[2] By the traditional alpha spectrometry method, usually large volume (~ 200 L)
of seawater sample is needed for the analysis of Pu, and the 240Pu/239Pu atom ratio, which is an important
fingerprint for Pu source identification and for tracing of oceanographic processes, cannot be obtained.[3]Due to the low detection limit and the relatively simple sample preparing procedures, ICP-MS has beentreated as a promising method for the analysis of Pu in environmental samples in recent years. However,when using ICP-MS, the detection of 239Pu and 240Pu can be affected by spectral interferences caused by
238
UH+ and 238UH2+ formations, especially for the environmental samples with high U concentrations. The
concentration of U in seawater in the Pacific Ocean is about several ��/L and the atom ratio of 238U/239Pu
can be up to 1011.[4] Thus, complex procedures for the preconcentration of Pu and separation of Pu from U
were employed for the determination of Pu in seawater prior to the analysis by ICP-MS, which somehow
may lead to a low Pu recovery.
In this work, we presented a simple method for the analysis of Pu concentration and its isotopic
composition in seawater samples by sector field ICP-MS combined with chromatographic separation
technique. High precision and accuracy were achieved by using this method. The detailed analyticalprocedures and the merits of this method will be discussed at the conference.
Acknowledgments
This work was supported by the Ministry of Education, Culture, Sports, Sciences and Technology (MEXT)(24110004), Japan, and partly supported by the Agency for Natural Resources and Energy, the Ministryof Economy, Trade and Industry (METI), Japan.
References[1] Aarkrog, A., Deep-Sea Res. II, 50, 2597-2606, 2003.
[2] Povinec, P. P., Livingston, H. D., Shima, S. et al., Deep-Sea Res. II, 50, 2607-2637, 2003.
[3] Yamada, M. and Zheng, J., Appl. Radiat. Isot., 66, 103-107, 2008.
[4] Chen, J. H., Edwards, R. L., Wasserburg G. J., Earth Planet. Sci. Lett., 80, 241-251, 1986.

－ 47 －

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

Semi-automated Procedure for the Determination of 89,90Sr in Environmental
Samples by Cherenkov Counting���������������, Željko Grahek
Division for marine and ������������������������������������������������, Zagreb, Croatia
Abstract - Development of new chromatographic resins in the lasttwo decades Sr resin, AnaLig-01 and SuperLig 620 has significantly
simplified separation of strontium from various types of samples.
These resins, that have principles based on molecular recognition,
are highly selective for strontium binding. In combination withappropriate detection methods they enable automatic determinationof radioactive strontium. Sequential injection analysis andequilibration based sensor column analysis were developed for thedetermination of long lived 90Sr (28.8 y) in liquid radioactive waste
and water samples.1-3 However, 89Sr that has short half-life (50.5 d),can also be present in samples, especially in those exposed to fresh
fallout from nuclear reactor. Classical analysis of 89Sr requires
isolation of 90Y, usually after attaining of secular equilibrium of90
Sr-90Y and the whole procedure takes at least 16 days. However,by using Cherenkov counting technique, determination time may besignificantly reduced. Unlike 90Sr that emits low energy electrons,
its daughter 90Y as well as 89Sr, generates Cherenkov photons inaqueous media. Consequently, by successive counting within 64
hours, 89Sr and 90Sr via 90Y can be determined. Therefore, the main
aim of this research is development of semi-automated procedure forthe determination of 89,90Sr. It includes solid phase extraction (SPE)of strontium from liquid samples and Cherenkov counting of its
isotopes. The procedure is based on sample - column equilibrationand off-line detection of bound 89,90Sr on the column. Sample ispumped through column at constant flow rate until the breakthroughor saturation point is achieved. The 89,90Sr is determined by counting
on column in PE vial. It will be shown how strontium can beselectively bound on the Sr resin, AnaLig-01 and SuperLig 620
resins and separated from interfering radionuclides. Also, influenceof column geometry, amount of resin and media in PE vial aroundthe column on quantity determination, detection efficiency andachievable lower detection limits will be discussed. The method istested in proficiency testing samples and natural water samples.

Figure 1. Detection efficiency of 89Sr and 90Y bound on AnaLig-01 resin
depending on surrounding media (TriCarb 3180)

REFERENCES
[1]

[2]

[3]

Keywords – semi-automated procedure, solid phase extraction,
Cherenkov counting, 89,90Sr determination－ 48 －

O. B. Egorov, M. J. O’Hara, J. W. Grate, Equilibration-Based
Preconcentrating Minicolumn Sensors for Trace Level Monitoring ofRadionuclides and Metal Ions in Water without Consumable
Reagents. Anal. Chem. 2006 78(15) 5480-5490.
J. W Grate, O. B. Egorov, M. J. O'Hara, T. A. Devol, Radionuclide
Sensors for Environmental Monitoring: From Flow Injection SolidPhase Absorptiometry to Equilibration-Based Preconcentrating
Minicolumn Sensors with Radiometric Detection. Chem. Rev. 2008
108(2) 543-562.
M. J. O'Hara, S.R. Burge, J. W. Grate, Automated radioanalyticalsystem for the determination of Sr-90 in environmental water samples
by Y-90 Cherenkov radiation counting. Anal. Chem. 2009 81(3) 12281237.

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

FKI-04

2ESEARCH AND $EVELOPMENT TOWARDS$ECOMMISSIONING OF &UKUSHIMA $AIICHI .UCLEAR 0OWER 0LANTS
Kazuo Minato
Nuclear Science Research Institute, Tokai Research and Development Center,
Japan Atomic Energy Agency
Tokai-mura, Ibaraki-ken 319-1195, Japan!BSTRACT – 4OWARDS THE DECOMMISSIONING OF &UKUSHIMA $AIICHI.UCLEAR 0OWER 0LANTS SCIENCE BASED RESEARCH AND DEVELOPMENTIS IMPORTANT AND USEFUL AS WELL AS TECHNOLOGY AND ENGINEERINGDEVELOPMENT 2ESEARCH AND DEVELOPMENT ACTIVITIES BASED ON
RADIATION CHEMISTRY RADIOCHEMISTRY THERMODYNAMICS ETC HAVECONTRIBUTED TO SAFE AND EFFICIENT DECOMMISSIONING OF THE PLANTS+EYWORDS – &UKUSHIMA $AIICHI $ECOMMISSIONING 2ADIATION#HEMISTRY 2ADIOCHEMISTRY 4HERMODYNAMICSI.

INTRODUCTION

Two and a half years have passed since the accident at
Fukushima Daiichi Nuclear Power Station Units 1-4,
Tokyo Electric Power Company, Inc. (TEPCO). The
research and development towards decommissioning of theplants, concerning the removal of fuels from spent fuelpools, removal of fuel debris, processing and disposal ofradioactive waste, and remote control equipment anddevices, have been being made as national projects, which
are based on the Mid-and-Long-Term Roadmap towards
the Decommissioning of TEPCO's Fukushima Daiichi
Nuclear Power Station Units 1-4 [1]. Besides TEPCO, plantmakers, research institutes, etc., jointly participate in the
projects. Among them the Japan Atomic Energy Agency isplaying an important part in science-based research anddevelopment to support the decommissioning of the plants.
II. RADIOLYSIS OF SEAWATER
One of the distinguishing features of the accident is thatseawater was injected to the damaged reactor cores andspent fuel pools in the early stage of actions. The
accumulated radioactive water, including seawater, in thereactor and turbine buildings has been being processed fordecontamination and desalination. This process generates
spent zeolites highly contaminated with radioactive cesium.
For safe storage of the spent zeolites, hydrogen generation
should be clarified.
Gamma-ray irradiation experiments revealed that theyield of hydrogen from seawater was larger than that frompure water and comparable to the primary yield, indicatingthat oxidation of hydrogen by radical products of waterradiolysis is not effective in seawater due to the presence of
Cl- and Br- ions. Furthermore, hydrogen generation wasincreased by addition of the zeolite to seawater. This meansthat the radiation energy deposited on zeolite is involved inhydrogen formation [2].
Based on the experimental data, hydrogen generation in
the vessels was evaluated, and the procedures to represshydrogen generation in the spent zeolite were suggested.

III. RADIOCHEMICAL ANALYSIS OF WASTE
The radioactive materials were released into theenvironment by the accident. A huge amount of the waste
contaminated with the radioactive materials was generated.
To classify the waste and to establish ways of processing
and disposal of the waste, inventory of radioactive
materials in the waste should be clarified.
The analysis of rubbles, trees, and accumulated water
sampled in the site of the nuclear power station revealed
that the main radionuclide was 137Cs (and 134Cs) with verysmall amounts of fission products, actinides, and activation
products, which is quite different from those of theradioactive waste generated from ordinary nuclear power
stations and reprocessing plants. The development of
separation method of a target nuclide before radiochemical
analysis was inevitable, and the analytical scheme andmethods have been developed for the nuclides, such as 3H,
14
C, 36Cl, 79Se, 90Sr, 99Tc, 129I, 60Co, 94Nb, 137Cs, 152Eu,
154
Eu, 238Pu, 239Pu, 240Pu, 241Am, and 244Cm.
IV. THERMODYNAMIC ANALYSIS OF FUELS
A large amount of seawater was injected into the reactor
pressure vessels in the accident. Several elements contained
in seawater possibly reacted with degraded fuel debris andmolten corium. These reactions may have affectedvolatilization of fission products, property of fuel debris,and formation of corrosive gases.
Thermodynamic evaluation indicated that volatility ofCs, Sr, and Te was potentially increased due to the change
in stable chemical species, and that corrosive gases, such as
HCl and H2S, were possibly generated, depending on
temperature and oxygen potential [3].
Experiments on the high temperature reaction between
sea salt deposit and (U,Zr)O2 simulated fuel debris (simdebris) were also made. A dense layer of calcium andsodium uranate formed on the surface of a sim-debris under
airflow. When the oxygen partial pressure was low,
calcium was dissolved into the cubic sim-debris phase toform solid solution (Ca,U,Zr)O2+x [4].
REFERENCES
[1]
[2]
[3]
[4]

－ 49 －

http://www.meti.go.jp/english/earthquake/nuclear/decommissioning/index.html
Y. Kumagai, R. Nagaishi, et al., At. Energy Soc. Jpn., 10, 235-239(2011).
M. Kurata, N. Shirasu and T. Ogawa, Trans. At. Energy Soc. Jpn., inpress.
M. Takano and T. Nish, J. Nucl. Mater., 443, 32-39 (2013).

FKO-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of atmospheric radiocesium on filter tapes used at automated SPM
monitoring stations for estimation of transport pathways of radionuclides from
Fukushima Daiichi Nuclear Power Plant
Yasuji Oura1, Mitsuru Ebihara1, Haruo Tsuruta2, Teruyuki Nakajima2, Toshimasa Ohara3
Mitsunori Ishimoto4, Yosuke Katsumura4
1

Department of Chemistry, Tokyo Metropolitan University
Atmosphere and Ocean Research Institute, The University of Tokyo
3
Center for Regional Environmental Research, National Institute for Environmental Studies
4
Nuclear Professional School, The University of Tokyo
2

I.

INTRODUCTION

Enormous amount of artificial radionuclides were emitted
into the atmosphere by a nuclear accident at Fukushima
Daiichi nuclear power plant (FDNPP) in March 2011. The
radionuclide in the atmosphere was transported withatmospheric stream into eastern Japan area widely. Sincesome institutes in Kanto region monitored atmosphericradioactivity periodically, it was partially evident that whenradioactive plumes passed through Kanto region. However,data on atmospheric radioactivity during an initial period in
Tohoku region in where FDNPP presents is nothing, thus
passing routes of radioactive plumes in Tohoku region andhow radioactivity went though is not clear.
A lot of automated air pollution monitoring stations areplaced by local governments around in Japan. Suspended
particulate matters (SPM) are also monitored hourly in thestation. SPM collected during the accicdent at the stations in
Tohoku and Kanto region must play an important role tosolve when and how much atmospheric radionuclides passed
through in Tohoku and Kanto regions. So we determined134
Cs and 137Cs contents in SPM collected on filer tapes at
SPM monitoring stations. The determined contents are also
expected to help a development of air pollution transportmodel calculation.
II. EXPERIMENTAL

Fukushima, 8 stations in Ibaraki, 4 stations in Saitama, and 6
stations in Chiba prefectures were subjected to gamma
spectroscopy. SPM was collected on roll paper tapecontinuously and SPM on a paper tape was visible as a black
circle (we call it spot in this article). �Spots of SPM
collected from 15 to 16 March and from 20 to 23 March in2011 were cut one-by-one. Each spot was sandwiched
between medical papers, and it was fixed on a thin plastic
sheet by an adhesive tape. Gamma rays from samples were
measured for 1 to 3 hours with a Ge detector.
III. RESULTS AND DISCUSSION
We observed the different arrival time of radioactive
plume on 15 and 20-21 March among stations. For example,
137
Cs concentrations at 3 stations in Fukushima city and 4
stations in Ibaraki prefecture are shown in Figs. 1 and 2,
respectively. It was found that high 137Cs concentration (> 10
Bq/m3) continued for about 12 hours in Fukushima city. This
peak was not observed by radiation dose monitoringaround that time. In Ibaraki prefecture, a high 137Csconcentration (> 200 Bq/m3) appeared at 8 am, 21 March at 2
stations in Tsuchiura but not observed in both Shimozuma
and Tsukuba. This difference is expected to be helpful forsolving passways of radioactive plume in Ibaraki. Analysis ofradioactive Cs on filter tapes collected by automated SPM
monitoring stations even at 1 - 2 years after FDNPP accident
is concluded to give very valuable information.

Filter tapes used at 3 stations in Miyagi, 19 stations in

Fig.1 Atmospheric 137Cs concentration at 3 stations in Fukushima city.

－ 50 －

Fig.2 Atmospheric 137Cs concentration at 4 stations
in Ibaraki prefecture.

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

FKO-10

Two-Years Trend of Monthly 137Cs Deposition Observed within 300 km of the
Fukushima Dai-ichi Nuclear Plant
1

Katsumi Hirose 1,2
Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioicho,
Chiyodaku, Tokyo 102-8554, Japan2
Geosphere Research Institute, Saitama University, 255 Shimo-okubo, Sakura-ku, Saitama, 338-8570, Japan

Abstract – Monthly depositions, which directly reflect
atmospheric processes including emission from the Fukushima
Daiichi nuclear power plant (FDNPP), are an important tool tore-construct accident sequence. In order to elucidate deposition
behavior of the FDNPP-derived radionuclides after the major
emission in March 2011, two-years trends of the monthly 137Cs
deposition at monitoring stations within 300 km of the FDNPP
were examined. The monthly 137Cs deposition showed marked
peaks in winter 2012 and winter 2013 at the Futaba site about 5
km of the FDNPP, whereas 2013 winter the peak at the sites insouth Kanto and Tohoku regions was not pronounced. We discuss
two-years trend of the monthly 137Cs deposition taking into
account its spatial variation and effect of precipitation amount.
Keywords – Fukushima Dai-ichi nuclear power plant, monthly
deposition, 137Cs, temporal variation, emission historyI.

INTRODUCTION

The 2011 Great East Japan Earthquake and resulting
tsunami caused severe accident in the Fukushima Dai-ichi
nuclear power plant (FDNPP). As a result, large amounts ofradionuclides have been released in the environment. In
order to trace long-term trend of FDNPP-derived
radionuclides emitted into atmosphere, it is important to docontinuous monitoring of radionuclides in surface air anddeposition. Especially monthly deposition of the FDNPPderived radionuclides is one of the powerful tools to
elucidate long-term environmental effects of the FDNPP
accident. The results of monthly 137Cs deposition [1,2]revealed that the effects of the FDNPP accident at least
continued until the early 2012. In this paper, we describe
two-years trend of the monthly 137Cs deposition observed in
the Kanto and Tohoku regions and discuss processes
controlling temporal variation of the monthly 137Cs
deposition.
II. SAMPLING AND METHOD
Monthly deposition samples (rainwater and falling dust)
were collected by rainwater samplers with surface areas of
0.5 m2, respectively, which are usually installed on the roofof main monitoring building in each monitoring site.
Monthly deposition sampling in 45 monitoring sites
covering Japanese Island has been stationary performed tomonitor basic levels of radioactivity deposition. Monthly
rainwater and falling dust samples was collected inappropriate bottles on the first day morning of every month.
Water sample was transferred into an evaporation dish anddried on a hot plate. The resultant residues were weighted
after drying in an oven at 110�C and then transferred to aplastic container. Dried residue sample in a plastic

container was subjected by gamma spectrometry. Gamma
spectrometry was performed in each measurementlaboratory of local government. Major radionuclides inmonthly deposition samples were radiocesium (134Cs and137
Cs). In this analysis, we focused 137Cs deposition because
at initial stage, the 134Cs/137Cs activity ratio was constant(Hirose, 2012). All of monthly deposition data has beenrecorded in NRA homepage.
III. RESULT AND DISCUSSION
Two-years trend of the monthly 137Cs deposition at themonitoring stations within 300 km of the FDNPP was
examined. The FDNPP-derived 137Cs has been stillmeasured in January 2013 at most of the monitoring
stations within 300 km of the FDNPP. A typical time
sequence of the monthly 137Cs deposition is as follows: 1.
Pronounced high 137Cs deposition (3.34 MBq m-2) occurredin March 2011 at the Futaba monitoring station, where islocated about 5 km of the FDNPP. 2. The monthly 137Cs
deposition at Futaba rapidly decreased in April 2011 as aresult of cease of major radioactivity emission from the
FDNPP. 3. A minimum monthly 137Cs deposition (1.55
kBq m-2) appeared in October 2011 and then gradually
increased to a maximum (19.5 kBq m-2) in February 2012.
4. A cause of higher 137Cs deposition in winter, 2012 waspresumed to be resuspension of 137Cs-enriched particles [2].
5. After a peak in February 2012, the monthly 137Cs
deposition deceased and reached a minimum in August
2012. However, the monthly 137Cs deposition increased in
winter, 2013 (January 2013: 18.9 kBq m-2).
The temporal variations of the monthly 137Cs depositionat the monitoring stations within 300 km of the FDNPP
spatially differed from each other. In order to have better
understanding of temporal variations of the monthly 137Cs
deposition and its spatial difference, we calculate 137Csconcentrations in rainwater from the 137Cs deposition andprecipitation amount to eliminate effect of precipitation
amount. The temporal variation of the 137Cs concentrationin rainwater at Hitachinaka is similar to that at Futaba. Thisfinding suggests that the temporal change of the 137Csconcentration in rainwater at Hitachinaka waspredominantly affected by that at Futaba, in other words,
source intensity at the FDNPP.
REFERENCES[1][2]－ 51 －

Hirose, K., J. Environ. Radioact., 111, 13-17, 2012.
Hirose, K., Appl. Radiat. Isot. doi.org/10.1016/j.apradiso.2013.03.
076

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

NCI-01Synthesis and study of properties of superheavy elements
status, problems, and prospects
S. Dmitriev
The Flerov Laboratory of Nuclear Reactions, JINR, Dubna,
dmitriev@jinr.ru
The study of nuclear physical and chemical properties ofrecently discovered superheavy elements (SHE, Z = 112–118) as well as synthesis of new elements (Z>118) remain
one of the most crucial tasks in modern science. Over the
past decade, the unique results [1] have been obtained thatare of utmost importance both in nuclear physics andastrophysics (experimental evidence of existence of islandsof increased stability of SHE) as well as in chemistry(influence of relativistic effects on the chemical propertiesof the elements 112–114). As per the IUPAC decision, thetwo new elements are now officially called Fl - Flerovium(element 114) and Lv - Livermorium (element 116).
The discovery of elements 117 [2] and 118 closed the 7th
period of Mendeleev’s Periodic Table of the Elements.
Possibilities to study synthesis of heavier elements inreactions with the double-magic 48�������������������������
because production of actinides with Z>98 (Es, Fm, etc.) in
necessary quantity (several mg) is impossible in neutroncapture reactions within the framework of existing today
reactor technologies. One needs to use ions heavier than48
�����������������50Ti, 58Fe, and 64Ni; however, production
cross sections with these ions are expected to be at least
one order of magnitude less. Implementation of the largescale program on the study of earlier synthesized SHE
requires, in turn, significant experiment efficiency
improvement.
Further development implies the construction of a first-everSHE factory at JINR FLNR, which shall include thefollowing:- a new accelerator complex with the average-mass ion
beam intensity 10-20 times higher than that of today;- physical and chemical new-generation experimental setups (highly effective gas-filled recoil separator, gas catcher,selective laser ionization, etc.).
The work was carried out with the financial support
from the Russian Foundation of Basic Research (projectcode # 13-03-12058-ofi-m-2013).
[1][2]

Yu. Ts. Oganessian, S. N. Dmitriev, Russian Chem.Review, 78,
1077, 2009.
Yu. Ts. Oganessian et al., Phys. Rev. Lett., 104, 142502, 2010.

－ 52 －

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

The Search for New Chemical Elements and the Possibilities to Synthesize
Transactinide "Chemistry" Isotopes
1

Christoph E. Düllmann1,2,3

Johannes Gutenberg-Universität Mainz, 55128 Mainz, Germany
GSI Helmholtzzentrum für Schwerionenforschung, 64291 Darmstadt, Germany
3Helmholtz Institute Mainz, 55099 Mainz, Germany

2

On overview on nuclear reactions leading to isotopes of thetransactinide (Z�104) elements with sufficiently long half-lives forchemical study will be presented.
Transactinides, Superheavy elements, Nuclear fusion reactions

Elements up to Z=112 as well as 114 and 116 are
officially recognized as discovered and have been
named [1]. The current literature contains reports about
the synthesis of all elements up to Z=118 [2], meaningthat more than 10% of all elements are members of thetransactinide series with Z=104-118. Searchexperiments for the new elements with Z=119 and
Z=120 have been performed, e.g., at the GSI Darmstadt.
Elements up to Hs (Z=108) as well as Cn (Z=112) andFl (Z=114) have been chemically investigated [3], using
isotopes with half-lives of at least about one second,which is the current limit for chemical studies. The
figure shows the cutout of the current chart of nuclei ofthe more than 100 transactinide isotopes. These can besynthesized in nuclear fusion reactions. Traditionally,
these are grouped into different classes depending on
the excitation energy of the compound nucleus ifformed at a beam energy corresponding to the height of
the Coulomb barrier.

the more than 100 transactinide isotopes, synthesized innuclear fusion reactions. Selecting the optimum nuclear
reaction to synthesize a certain isotope is a sensible
topic, which requires proper attention in any experimentwith the heaviest elements, regardless of the specificaspect under study. The figure shows that isotopes
suitable for chemistry studies with current technology
exist for all elements up to Fl (Z=114).
I will first present the search for new elements using therecoil separator TASCA [4] at GSI and then discuss the
optimum reactions leading to the relatively long-lived
isotopes of the transactinides as they are frequently usedin chemical studies of these elements, including
elements which were not studied chemically to date.
[1]
[2]
[3]
[4]

R. D. Loss and J. Corish, Pure Appl. Chem. 84, 1669 (2012).
Y. Oganessian, Radiochim. Acta 99, 429 (2011).
A. Türler and V. Pershina, Chem. Rev. 113, 1237 (2013).
A. Semchenkov et al., Nucl. Instrum. Meth. B 266, 4153 (2008)

Chart of nuclei of transactinide elements. Half-lives are given, and decay modes color coded. Isotopes often used in chemical studies are shown in a red border.
Long-lived isotopes of elements that were not studied chemically so far are shown in a blue border. Dashed lines show nuclear shell closures.

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

NCI-03

Production and Decay Studies of Transactinide Nuclides with GARIS at RIKEN
Hiromitsu Haba
Nishina Center for Accelerator-Based Science, RIKEN, Wako, Saitama 351-0198, Japan
Abstract – The isotopes of 261Rf, 262Db, and 265Sg were produced
248
248
in
the
Cm(18O,5n)261Rf,
Cm(19F,5n)262Db,
and
248
22
265
Cm( Ne,5n) Sg reactions, respectively, using a gas-jet
transport system coupled to the gas-filled recoil ion separator,
GARIS at RIKEN. Production and decay properties of those
nuclides were investigated in detail with a rotating wheel
apparatus for � and spontaneous fission spectrometry under low
background conditions.
Keywords – Superheavy elements; RIKEN gas-filled recoil ion
separator, GARIS; 261Rf; 262Db; 265Sg

Chemical characterization of superheavy elements(SHEs, atomic numbers Z � 104) is an extremelyinteresting and challenging research subject in modern
nuclear and radiochemistry [1,2]. We have been developing
a gas-jet transport system coupled to the RIKEN gas-filled
recoil ion separator GARIS as a novel technique for the
next-generation SHE chemistry [3–5]. With this method,
breakthroughs in SHE chemistry are expected: (i) the
background radioactivities originating from unwanted byproducts are strongly suppressed, (ii) the intense primary
heavy-ion beam is absent in a gas-jet chamber and hencehigh gas-jet yield is achieved, and (iii) the beam-free
conditions also make it possible to investigate newchemical reactions. In this work, we investigatedproduction and decay properties of isotopes of 261Rf (Z =104), 262Db (Z = 105), and 265Sg (Z = 106) available forchemical studies using the GARIS gas-jet system.
A schematic of the experimental setup is shown in Fig. 1.
Oxygen-18, 19F, and 22Ne beams were extracted from the
RIKEN Linear Accelerator, RILAC. The isotopes of261
Rfa,b, 262Db, and 265Sga,b were produced in the reactions
248
248
Cm(18O,5n)261Rf,
Cm(19F,5n)262Db,
and
of
248
22
265
Cm( Ne,5n) Sg, respectively. The evaporation
residues of interest were separated in flight from the beamand the majority of the nuclear transfer products by GARIS
and were guided to a gas-jet chamber at the focal plane of
GARIS. The evaporation residues were thermalized in He
gas, attached to KCl aerosol particles, and were transported
through a Teflon capillary to a chemistry laboratory. Alphaand spontaneous fission (SF) decays of 261Rfa,b, 262Db, and265
Sga,b were then investigated with the rotating wheel
apparatus MANON (Measurement system for Alphaparticle and spontaneous fissioN events ON line) under low
background conditions.
The 1.9-s isomeric state (261Rfb) in 261Rf was directly
populated in the 248Cm(18O,5n)261Rfb reaction for the firsttime [6]. The identification of 261Rfb was based on six �-�correlations linking � decays of 261Rfb and its daughter
257
No. The �-particle energy of 261Rfb was measured to beE� = 8.52 ± 0.05 MeV. The half-life was determined to be
T1/2 = 1.9 ± 0.4 s based on both 8.52-MeV � and SF decays.
The SF branch is bSF = 0.73 ± 0.06. The cross section forthe 248Cm(18O,5n)261Rfb reaction is �(261Rfb) = 11 ± 2 nb at

95.1 MeV, which gives a cross section ratio of
�(261Rfa)/�(261Rfb) = 1.1 ± 0.2. In the 265Sg experiment [7],eighteen and twenty four events were assigned to 265Sga and265
Sgb, respectively, based on �-�(-�) and �-SF correlations.
The half-life and �-particle energy of 265Sga were measured
to be T1/2 = 8.5+2.6–1.6 s and E� = 8.84 ± 0.05 MeV,
respectively, and those of 265Sgb were T1/2 = 14.4+3.7–2.5 s
and E� = 8.69 ± 0.05 MeV. As a daughter product of
265
Sga,b, the decay properties of 261Rfb were derived: T1/2 =2.6+0.7–0.5 s, E� = 8.51 ± 0.06 MeV, and bSF = 0.82 ± 0.09.
These results confirm and refine the complicated decay
pattern suggested for the decay chain 265Sga,b � 261Rfa,b �
257
No � in [8]. The production cross sections for 265Sga
and 265Sgb were determined to be �(265Sga) = 180+80–60 pb
and �(265Sgb) = 200+60–50 pb at 117.8 MeV. Recently, decay
properties of 262Db and its �-decay daughter 258Lr were
investigated [9]: E� = 8.46 ± 0.04 MeV (� intensity I� = 70
± 6%) and 8.68 ± 0.04 MeV (I� = 30 ± 6%), T1/2 = 34+4–3 s,and bSF = 55 ± 4% for 262Db; T1/2 = 3.5+0.5–0.4 s and bSF(and/or bEC) = 2.6 ± 1.8% for 258Lr. Based on those decay
properties, the cross section for the 248Cm(19F,5n)262Db
reaction in [10,11] was revised to �(262Db) = 2.2 ± 0.7 nb at
103 MeV. In the conference, perspectives of SHE nuclear
chemistry opened by GARIS will be also presented.
(a) GARIS(b) Gas-jet transport system

Differential pumping section
Beam from
RILAC

Evaporation Residues
Focal plane(ERs)
Gas inlet

Mylar window~100 kPa

Beam dump

ERs
Rotating
targetElastic scattering
beam monitor

~0.1
kPa
D1

Irradiation room

Q1

Q2

0

1

Chemistry laboratory

D2

He/KCl2m0(c) MANON
7 pairs of Si PIN photodiodes
Rotating wheel

100 mmTeflon capillary(10 m)
Mylar

ExhaustFig.1. (a) RIKEN gas-filled recoil ion separator, GARIS. (b) Gas-jet
transport system coupled to the focal plane of GARIS. (c) The rotating
wheel apparatus MANON for �/SF-spectrometry.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

M. Schädel, Angew. Chem. Int. Ed. 45, 368 (2006).
A. Türler and V. Pershina, Chem. Rev. 113, 1237 (2013).
H. Haba et al., J. Nucl. Radiochem. Sci. 8, 55 (2007).
H. Haba et al., J. Nucl. Radiochem. Sci. 9, 27 (2008).
H. Haba et al., Chem. Lett. 38, 426 (2009).
H. Haba et al., Phys. Rev. C 83, 034602 (2011).
H. Haba et al., Phys. Rev. C 85, 024611 (2012).
Ch. E. Düllmann and A. Türler, Phys. Rev. C 77, 064320 (2008).
H. Haba et al., EuCheMS International Conference on Nuclear andRadiochemistry (NRC8), Sept. 18, 2012, Como, Iraly.
[10] Y. Nagame et al., J. Nucl. Radiochem. Sci. 3, 85 (2002).
[11] K. Tsukada et al., Radiochim. Acta 97, 83 (2009).

－ 54 －

NCO-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Theoretical Predictions of the Electronic Structure and Properties of the Heaviest
Elements
Valeria Pershina11Helmholtzzentrum für Schwerionenforschung, Planckstr. 1, D-64291 Darmstadt, Germany

Abstract - Recent theoretical works on predictions of chemical
properties and experimental behaviour of the heaviest elements arepresented and critically compared
Keywords – Superheavy elements/Electronic structure/Relativistic
calculationsI.

INTRODUCTION

One of the main aims of studies in the area of the chemistryof the heaviest elements is to place a newly produced elementin the proper position of the Periodic Table [1]. It is achievedby comparing behaviour of the new element with that of its
lighter homologs in the chemical group. Having this in mind,
a large number of interesting and important chemical
experiments on the heaviest elements were performed in the
recent years [2]. Theoretical investigations in this area havealso been very fruitful and resulted in some remarkableachievements [2, 3]. In the presentation, recent advances in
the relativistic electronic structure calculations for theheaviest elements and predictions of their experimental
behaviour are overviewed. An emphasis is put on thereliability of the theoretical approaches and models withrespect to the experimental outcome.
II. THEORETICAL METHODS AND RESULTS
For the heaviest elements, electronic structure
calculations should be made with the use of methods thattreat relativistic and electron correlation effects at the highest
possible level of theory. In the recent years, the relativistic
quantum theory and computational algorithms received
tremendous developments [4]. As a result, very accurate
calculations of the electronic structure and properties ofsuperheavy atoms and molecules became possible. On theirbasis, reliable predictions of experimental behaviour of theseelements in the sophisticated and expensive experiments withsingle species have been made [5].
For atoms, Dirac-Coulomb-Breit (DCB) calculations withelectron correlation at the highest level of theory, i.e., acoupled-cluster (CC) method, were performed for elements
till Z=122 [6]. Accurate predictions of such properties likeelectronic
configurations,
ionization
potentials,
polarizabilities, that are important for the placement of theelements and for the chemical experiments, have been made.
In the molecular theory, fully relativistic (4-component)
and 2-component wave-function (ab initio Dirac-Fock) [7]and Density-Functional-Theory (DFT) [8] methods have beendeveloped to such an extent that very accurate predictions ofbinding molecular energies, optimized geometry, electronic
density distributions, etc. are now available. On their basis,
predictions of experimental behaviour for gas-phase andaqueous chemistry chromatography experiments have been
made [2, 3, 5]. For the gas-phase experiments, direct
calculations of adsorption energy of atoms and molecules on
metal or other surfaces using relativistic DFT methods are
now possible via a cluster approach [9].
In the presentation, we will overview results of atomic
calculations till Z=122 that are important for placing theseelements in the Periodic Table. They are also used forpredictions of adsorption of atoms of these elements onneutral surfaces to guarantee their transportation from anaccelerator to the chemistry set up.
For the gas-phase chemistry experiments, predictions ofvolatility of group-4 through 8 compounds are presented andcompared. General trends and a common character of thechemical behaviour are outlined. Predictions of volatility ofelements in the atomic state, like of element 112, Cn, element
113, and element 114, Fl, as adsorption on neutral and metal
surfaces are also described and compared [9]. Interestingcases of volatility of even heavier elements, like 115, or 119
and 120 are considered.
Influence of relativistic effects on properties andexperimental behaviour of the heaviest elements is elucidated.
Future perspectives for the chemical studies on theheaviest elements from the theoretical point of view are
outlined.
Acknowledgment: The author is thankful to her free-willcollaborators J. Anton, T. Jacob, A. Borschevsky, E. Eliav and U.
Kaldor. She also thanks her colleagues, experimentalists, forvaluable discussions of experimental results.

REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

－ 55 －The Chemistry of Superheavy Elements, M: Schädel ed., Kluwer,
Dorderecht, 2003.
A. Türler and V. Pershina, Chem. Rev. 113, 1237 (2013).
V. Pershina, Radiochim. Acta 99, 459 (2011).
Relativistic Electronic Structure Theory, P. Schwerdtfeger ed., Parts I
and 2, Elsevier, Dordrecht, 2002 and 2004.
V. Pershina, In: Relativistic Methods for Chemists, Y. Ishikawa, M.
Barysz, eds., Springer, Dordrecht (2010), pp. 452-520.
U. Kador, E. Eliav, In: Ref. [4], Part 2, pp. 279-350.
K. G. Dyall and K. Faegri, Relativistic Quantum Chemistry, Oxford
University Press, 2007.
J. Anton, B. Fricke, E. Engel, Phys. Rev. A 69, 012505 (2004).
V. Pershina, J. Anton and T. Jacob, J. Chem. Phys. 131, 084713 (2009).

NCO-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Spectroscopy of Element 115 Decay Chains
D. Rudolph1, U. Forsberg1, P. Golubev1, L.G. Sarmiento1, A. Yakushev2, L.-L. Andersson3,
Ch.E. Düllmann2,3,4, J.M. Gates5, K.E. Gregorich5, F.P. Heßberger2,3, R.-D. Herzberg6, J. Khuyagbaatar2,3,
J.V. Kratz4, K. Rykaczewski7, M. Schädel2,8, S. Åberg1, D. Ackermann2, M. Block2, H. Brand2,
B.G. Carlsson1, D. Cox6, X. Derkx3,4, A. Di Nitto4, K. Eberhardt4, J. Even3, C. Fahlander1, J. Gerl2,
C.J. Gross7, E. Jäger2, B. Kindler2, J. Krier2, I. Kojouharov2, N. Kurz2, B. Lommel2, A. Mistry6,
C. Mokry4, H. Nitsche5, J.P. Omtvedt9, P. Papadakis6, I. Ragnarsson1, J. Runke2, H. Schaffner2,
B. Schausten2, P. Thörle-Pospiech4, T. Torres2, A. Türler10, A. Ward6, D. Ward1, N. Wiehl3,4
1

Lund University, S-22100 Lund, Sweden
GSI Helmholtzzentrum für Schwerionenforschung GmbH, D-64291 Darmstadt, Germany
3Helmholtz Institute Mainz, D-55099 Mainz, Germany
4
Johannes Gutenberg-Universität Mainz, D-55099 Mainz, Germany
5
Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
6
University of Liverpool, Liverpool L69 7ZE, United Kingdom
7
Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
8
Advanced Research Center, Japan Atomic Energy Agency, Tokai, Japan
9
University of Oslo, NO-0315 Oslo, Norway
10
Paul Scherrer Institute and University of Bern, CH-5232 Villingen, Switzerland

2

During the past decade, a number of correlated �-decay
chains, which all terminate by spontaneous fission, have been
observed in several independent experiments using 48Cainduced fusion-evaporation reactions on actinide targets [1].
These are interpreted to originate from the production ofneutron-rich isotopes with proton numbers Z = 113 to 118.
However, neither their mass, A, nor their atomic number, Z,
have been measured directly.
In November 2012, a three-week experiment was conductedat the GSI Helmholtzzentrum für SchwerionenforschungGmbH in Darmstadt, Germany, using high-resolution �-,electron, X-ray and �-ray coincidence spectroscopy to observe
�-X-ray events to identify uniquely atomic numbers of
isotopes in Z = 115 decay chains. The reaction 48Ca+243Am
was used, with fusion-evaporation products being focused
into the TASISpec set-up [2-4], which was coupled to thegas-filled separator TASCA [5,6].
A beam integral of roughly 7·1018 48Ca particles led to theobservation of about 25 correlated �-decay chains withcharacteristics similar to those previously published [7,8].
Results from the ongoing data analysis will be presented.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

Yuri Oganessian, J. Phys. G 34, R165 (2007).
L.-L. Andersson et al., Nucl. Instrum. Meth. A 622, 164 (2010).
L.G. Sarmiento, L.-L. Andersson and D. Rudolph, Nucl. Instrum.
Meth. A 667, 26 (2012).
U. Forsberg et al., Acta Phys. Pol. B 43, 305 (2012).
A. Semchenkov et al., Nucl. Instrum. Meth. B 266, 4153 (2008).
J.M. Gates et al., Phys. Rev. C 83, 054618 (2011).
Yu. Ts. Oganessian et al., Phys. Rev. C. 69, 021601 (2004).
Yu. Ts. Oganessian et al., Phys. Rev. Lett. 108, 022502 (2012).

－ 56 －

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－ 57 －

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NCO-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

3G#/  – 4HE &IRST /RGANOMETALLIC 4RANSACTINDE #OMPLEX OPENING A 7INDOW TO A
.EW #OMPOUND #LASS
J. Even 1, A. Yakushev2, Ch.E. Düllmann1,2,3, H. Haba4, M. Asai5, T.Sato5, H. Brand2, A. Di Nitto3,
R. Eichler6,7, F. Fangli8, W. Hartmann2, M. Huang4, E. Jäger2, D. Kaji4, J. Kanaya4, Y. Kaneya5,
J. Khuyagbaatar1, B. Kindler2, J.V. Kratz3; J.Krier2,Y. Kudou4, N. Kurz2, B. Lommel2, S. Miyashita5,
K. Morimoto4, K. Morita4, Y. Nagame5, H. Nitsche9,10, K. Ooe11, M. Schädel5, J. Steiner2, T. Sumita4,
K. Tanaka4, A. Toyoshima5, K. Tsukada5, A. Türler 6,7, I. Usoltsev 6,7, Y. Wakabayashi4, Y. Wang8,
N. Wiehl1,3, S. Yamaki4,12, Q. Zhi8
1

Helmholtz-Institut Mainz, Johannes Gutenberg-Universität, 55099 Mainz, Germany;
GSI – Helmholtzzentrum für Schwerionenforschung, Planckstr. 1, 64291 Darmstadt, Germany;
3
Johannes Gutenberg-Universität Mainz, 55099 Mainz, Germany;
4
Nishina Center for Accelerator-Based Science, RIKEN, Wako, Saitama 351-0198, Japan;
5Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan;
6
University of Berne, Freiestrasse 3, CH-3012 Berne, Switzerland;
7
Paul Scherrer Institute, CH-5232 Villigen, Switzerland;
8
Institute of Modern Physics Lanzhou; Chinese Academy of Sciences, 509 Nanchang Road, CN-730000 Lanzhou, China;
9
University of California, Berkeley, CA 94720-1460; U.S.A.;
10
Lawrence Berkeley National Laboratory, Berkeley, CA 94720-8169 U.S.A.,
11
Niigata University, Niigata, Niigata 950-2181, Japan,
12
Saitama University, Saitama 338-8570, Japan.
2!BSTRACT – 7E REPORT ON THE SYNTHESIS AND CHEMICAL INVESTIGATION OF
THE FIRST ORGANOMETALLIC COMPOUND OF A TRANSACTINIDE ELEMENTNAMELY SEABORGIUM HEXACARBONYL
+EYWORDS – 3EABORGIUM #ARBONYL #OMPLEX !DSORPTION (OT
CHEMISTRYIn the last decades, simple inorganic compounds of thetransactinde elements (TAN) were studied in gas phasechemical reactions [1]. Accessing, e.g., metal complexes
with organic ligands or organometallic compounds was
impossible due to technical restrictions, like the destructive
plasma present behind the target created by the intense heavy
ion beam. Thanks to the novel approach of physicalpreseparation in a recoil separator to reject the beam [2],these limitations could be overcome [3]. In previous
experiments, we demonstrated the formation of volatile delement carbonyl complexes with recoiling ions thermalized
in a carbon monoxide containing atmosphere [4]. Short-lived
isotopes of the lighter homologs of seaborgium –molybdenum and tungsten showed this to be an appropriate
method to study group 6 elements under conditions relevant
for a transactinide chemistry experiment.
Seaborgium hexacarbonyl has been predicted to be stable[5]. The π-back bonding, characteristic for the metal-carbon
bond in carbonyl complexes, is expected to be stronger thanin the complexes of the lighter homologues due to therelativistic expansion of the d-orbitals. Furthermore, Sg(CO)6
is predicted to be as volatile as tungsten hexacarbonyl andtherefore suitable for, e.g., thermochromatography studies [6].
Based on previous studies with molybdenum and tungsten, an
experiment aiming at the study of seaborgium hexacarbonyl

was conducted at the gas-filled recoil ion separator GARIS at
RIKEN. In our experiment, 265a,bSg (t1/2=8.5 s, 14.4 s) [7] wassynthesized in the reaction 248Cm(22Ne,5n). Seaborgium wasseparated within GARIS from the primary beam and was
guided to the recoil transfer chamber (RTC) mounted in the
focal plane of GARIS [8]. The 265Sg was thermalized within
the RTC in a helium carbon-monoxide mixture under ambientconditions. This way it formed volatile carbonyl complexes
and was transported in the gas stream to the radiochemistrylaboratory. There, its adsorption on silicon dioxide wasstudied with the thermochromatography detector COMPACT.
The combination of preseparation with GARIS and detection
in COMPACT allowed the study of seaborgium underbackground-free conditions.
Our results indicate the observation of Sg(CO) 6 and allow
to compare its behavior to that of W(CO)6 and to theoreticalpredictions. At the moment, the data analysis is ongoing.
Experimental details and results will be presented at theconference.
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

A. Türler and V. Pershina, #HEM 2EV. , , 1237−1312.
Ch E. Düllmann et al., .UCL )NSTR -ETH ! , , 528–539.
Ch.E. Düllmann et al., 2ADIOCHIM !CTA , , 403-418.
J. Even, et al., )NORG#HEM , , 6431-6422.
C.S. Nash, B. E. Bursten, * !M #HEM 3OC  , 10830-10831.
V. Pershina and J. Anton, SUBMITTED TO * #HEM 0HYS .
H. Haba et al., 0HYS 2EV # , , 024611.
H. Haba et al, #HEM ,ETT , , 426-427.

4HIS EXPERIMENT WAS PERFORMED AT 2) "EAM &ACTORY OPERATED BY2)+%. .ISHINA #ENTER AND #.3 5NIVERSITY OF 4OKYO 7E THANK THE ION
SOURCE AND 2),!# OPERATORS &INANCIAL SUPPORT FROM THE 'ERMAN "-"&UNDER CONTRACT -: AND FROM *!%! 4OKAI !DVANCED 3CIENCE
2ESEARCH #ENTERgS 2EIMEI RESEARCH PROGRAM IS GRATEFULLY ACKNOWLEDGED－ 58 －

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

Superheavy Element Z and A Measurements at the Berkeley Gas-Filled Separator
H. Nitsche 1, 2, G. K. Pang 2, J. M. Gates 2, K. E. Gregorich 2 N. E. Esker 1, O. R, Gothe 1
12

University of California, Berkeley, Department of Chemistry, Berkeley, CA 94720-1460, USA
Lawrence Berkeley National Laboratory, Nuclear Science Division, Berkeley, CA 94720-8169, USA

Since the dawn of the new Millenium, six new superheavy
elements (SHE) (113, 114, 115, 116, 117, and 118) have been
produced in reactions of 48Ca beams with actinide targets. So
far, these experiments have led to the discovery of 52 newisotopes [1,2]. Several independent confirmation experiments
led to the recent naming of flerovium, Fl, and livermorium,
Lv, for elements 114 and 116, respectively [3-6��� � ���� �decay chains of these SHE terminate by spontaneous fission,
before reaching the part of the Chart of the Nuclides where Z
and A are well-established. The SHE Z and A assignments������������������������������������������-particle decayenergies with model calculations [7], supplemented withcross-bombardment information. Thus, neither Z nor A have����� ��������� ���������� � ������� ������ ��������� �-decayenergies to adjust mass models, these Z and A assignments
must be proven to be correct. Otherwise a situation could
arise where data from incorrect assignments are used tomodify mass models which, in turn, reinforce the incorrect
assignments. Identifying Z by detecting �� - K x-ray
coincidences [9], known as x-ray fingerprinting, is an alreadyestablished process. The first results of x-ray finger printing
experiments conducted for element 115 produced in the243
Am(48Ca,3n)288115 reaction using the Berkeley Gas-Filled
Separator (BGS) at the 88-inch cyclotron at Lawrence
Berkeley National Laboratory will also be presented.
However, to simultaneously identify both Z and A with the
BGS, we are making several upgrades to its detection setup,
design and construct a new mass analyzer, as well a gas
catcher and a radiofrequency quadrupole ion trap (RFQ) to
match the output of the BGS to the acceptance of the mass
analyzer. The first SHE to be studied using these new
upgrades at the BGS will be 289Fl [9] produced in the fusion
evaporation reaction of 244Pu(48Ca,3n). Z-identification isconducted in the same manner as described above andcoupling of the x-ray fingerprinting setup with a mass
analyzer, then provides a simultaneous determination of A
and Z.
[1]
[2]
[3]
[4]
[5]

[6]
[7]
[8]
[9]

Acknowledgement:This work is supported by U.S. Department of Energy, Office of Science,
Nuclear Physics, Low Energy Physics Program, and was performed atLawrence Berkeley National Laboratory under Contract No. DE-AC0205CH11231.

Y.T. Oganessian, J. Phys. G 34, R165 (2007).
Y.T. Oganessian, Radiochim. Acta 99, 429 (2011)
L. Stavsetra, K. E. Gregorich, J. Dvorak, P. A. Ellison, I. Dragojevic´,
M. A. Garcia, and H. Nitsche, Phys. Ref. Let. 103, 132502 (2009).
Ch. E. Düllmann et al., Phys. Ref. Let. 104, 252701 (2010).
P. A. Ellison, K. E. Gregorich, J. S. Berryman, D. L. Bleuel, R. M.
Clark I. Dragojevic´, J. Dvorak, P. FallonC. Fineman-Sotomayor, J. M.
Gates, O. R. Gothe, I.Y. Lee, W. D. Loveland, J. P. McLaughlin, S.
Paschalis, M. Petri, J. Qian, L. Stavsetra, M. Wiedeking, and H.
Nitsche, Phys. Ref. Let. 105, 182701 (2010).
J. M. Gates et al., Phys. Rev. C 83, 054618 (2011).
A. Sobiczewski et al., Prog. Part. Nucl. Phys. 58, 292 (2007).
C.E. Bemis et al., Phys. Rev. Lett. 31, 647 (1973).
Y.T. Oganessian et al., Phys. Rev. C 69, 054607 (2004).

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

NCO-11

Intermetallic Actinide compounds for SHE Production Targets

a

d
c
a
R. Eichlera,b, I. Usoltseva,b, J.P. Omtvedt, O. V. Petrushkin, D. Piguet, A. V. Sabel’nikovc, A.
a,bcc
Türler , G. K. Vostokin , A. V. Yeremin

Laboratory for Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, CH-5232 Villigen, Switzerlandb
Department of Chemistry & Biochemistry, University of Berne, Freiestrasse 3, CH-3012 Berne, SwitzerlandcFlerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, 141980 Dubna, RussiadUniversity of Oslo, 0316 Oslo, Norway

Recent experiments with superheavy elements require highintensive heavy ion beams and highly sophisticated target
technologies able to stand the harsh irradiation conditions.
Especially, stationary target technologies based on painting
and molecular plating of actinide oxides onto thin Ti foils
reveal severe target degradation by the intensive beams.
These effects lead to a considerable drop in the production
rates and transport yields of SHE to chemical setups.
Seeking for better target material possibilities we focusedour research onto metallic targets. These metallic targets
are expected to be superior to the widely used nowadays
solely electroplated targets due to higher thermal
conductivity, electrical conductivity, chemical stability, andmechanical stability. We proposed a simple method whichallows producing Pd-based intermetallic targets for highintensity irradiations [1]. Based on the molecular plating
technique [2] followed by coupled reduction [3] thismethod was successfully applied to different lanthanide andactinide isotopes [1]. First irradiation experiments withintermetallic targets were carried out at the Oslo Cyclotron
Laboratory, University of Oslo, Norway. Here, a 3.5 µm
238
U/Pd target was irradiated at the MC-35 Scanditronix
cyclotron using a 0.5 �A proton beam with cyclotron
energy of 30 MeV. This experiment showed the possibilityof safe handling of such targets in accelerator environments.
Two 243Am/Pd intermetallic targets have been prepared andirradiated at the U-400 cyclotron at the Flerov Laboratory
for Nuclear Reactions for several days. Both 243Am targets
were characterized by alpha-particle spectroscopy and lightmicroscopy before and after irradiation with high intensity
beams of 48Ca. For direct comparison, the performance of a‘classical’ electroplated 243AmO2/Ti target was investigated.
Figure 1 shows optical micrographs revealing the clear
superiority of intermetallic targets. Challenges andpossibilities connected to the use of intermetallic
compounds as high power irradiation targets will bepresented.

A:

B:
Figure 1: Micrographs of irradiated targets. A) titanium
based target after irradiation with 48Ca particles at
intensities of up to 7�1012 48Ca per second for about 120
hours; B) palladium based target after irradiation with 48Caparticles at almost two times higher intensities compared tothe titanium based target of up to 1.2�1013 48Ca per second
for about 60 hours. The Pd foil and the actinide distribution
remain nearly unchanged.
Acknowledgments: We thank the crews form the ion sourceand U-400 cyclotron of FLNR Dubna for providing intense
beams of 48Ca. This research was supported by Swiss
National Science Foundation grant 200020_126639.
References[1]I. Usoltsev, et al., Preparation of Pd-based intermetallic targets for highintensity irradiations, Nucl. Instr. and Meth. Phys. Res.A691, 5–9 2012.
[2]W. Parker, et al., Nucl. Instr. and Meth. 26, 61 (1964).
[3]S. Möbius, L. Hellwig, C. Keller, J. Less-Common Met. 121, 43 (1986).

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

NCO-12The First Successful Observation of Mass-separated Lawrencium (Lr, Z = 103)
Ions with ISOL Technique
T. K. Sato1, M. Asai1, N. Sato2, Y. Kaneya1,3, K. Tsukada1, A. Toyoshima1, S. Miyashita1,
Y. Nagame1, M. Schädel1, A. Osa3, S. Ichikawa1,4, K. Ooe5, T. Stora6, J. V. Kratz7
1

Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
3
Graduate School of Science and Engineering, Ibaraki University, 2-1-1, Bunkyo, Mito, Ibaraki 310-8512, Japan3
Department of Research Reactor and Tandem Accelerator, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
4
Nishina Center for Accelerator-Based Science, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
5
Institute of Science and Technology, Niigata University, Niigata 950-2181, Japan
6
ISOLDE, CERN, CH-1211 Geneva 23, Switzerland
7
Institut für Kernchemie, Universität Mainz, D-55099 Mainz, Germany
2

Abstract – In order to determine the first ionization potential of
the heaviest actinide lawrencium (Lr, Z=103), we have developed
a surface ionization ion-source as part of the JAEA-ISOL (Isotope
Separator On-Line) setup, which is coupled to a He/CdI2 gas-jet
transport system. We will report on the first successful ionizationand mass separation of 27-s 256Lr produced in the 249Cf+11B
reaction.
Keywords – Lawrencium (Lr), Heavy actinide, Ionization
potential, ISOL, Surface ionization, Ion source

I.

INTRODUCTION

The ground-state electronic configuration of lawrencium(Lr, Z = 103) that is the heaviest actinide element ispredicted to be [Rn]5f147s27p1/2, which is different from thatof the lanthanide homolog lutetium (Lu) [Xe]4f146s25d. The
reason for this change in the ground state configuration isthat the 7p orbital of Lr is stabilized below the 6d orbital bystrong relativistic effects [1]. The weakly-bound outermost
electron results in a significantly lower first ionization
potential of Lr as compared to its neighboring heavy
actinides [2]. The ionization potential of Lr, however, has
not been determined experimentally owing to its low
production rate and short half-life. In order to determine theionization potential of Lr, we have developed a surface
ionization type ion-source for the JAEA-ISOL coupled to agas-jet transport system [3]. As a step to determination of
the ionization potential of Lr, we conducted to ionize ashort-lived Lr isotope by using the ion-source in several
ionization conditions.
II. EXPERIMENTAL
The isotope 256Lr (T1/2 = 27 s) was produced in thereaction of 249,250,251Cf(11B, xn)256Lr [4]. A 249,250,251Cf target(249Cf: 63%, 250Cf: 12%, and 251Cf : 25%) with 185 ± 25
�g/cm2 on a 1.85 mg/cm2 thick Be backing foil was
irradiated with a 67.9-MeV (63 MeV in the middle of thetarget) 11B4+ beam from the JAEA tandem accelerator. For
comparison the lutetium isotopes 168mLu and 168gLu, withhalf-lives of 6.7 min and 5.5 min, respectively, weresynthesized in the 162Dy(11B, 5n) reaction. The nuclear

reaction products recoiling from the targets weretransported to the ion-source by a He/CdI2 gas-jet transportsystem. The products were ionized in the ion-source,
accelerated with 30 kV, and then mass-separated with amass-separator in ISOL. The amount of ions collected at
the end of the ISOL after mass-separation was determinedby �- or �-ray measurements. To calculate ionization
efficiencies, nuclear reaction products transported from atarget recoil chamber were collected directly and measured
prior to the ionization experiments. To compare theionization efficiencies on different surface material of theion-source, a rhenium (Re) surface and a tantalum (Ta)surface were employed in this study.
III. RESULTS AND DISCUSSION
We successfully ionized and mass-separated 256Lr for
the first time by using the developed ion-source andapplying the ISOL technique. The Ionization efficiencies of
Lr and Lu on the Re surface were obtained to be 42 + 20-1
9 % and 19.9 ± 7.0 %, respectively. In the case of the Ta
surface, the efficiency of Lr was 19 + 9-8 % while that of Lu
was 4.0 ± 1.4 %. The ionization efficiency of each elementon the Re surface was larger than that on the Ta surface
because the work function of Re is higher than that of Ta.
Under both conditions, the ionization efficiencies of Lr
are larger than those of Lu. The results indicate that theionization potential of Lr must be lower than that of Lu.
This is consistent with the theoretical prediction from acoupled cluster (CC) calculation that takes into accountrelativistic effects [3].
In the presentation, we will report on the firstexperimental determination of the first ionization potentialof Lr based on our latest results.
[1]
[2]
[3]
[4]

－ 61 －

Zou, Y. and Fischer, C. F. Phys. Rev. Lett. 88 (2002) 183001.
Borschevsky, A. et al. Eur. Phys. J. D45 (2007) 115.
Sato, T. K. et al. Rev. Sci. Instrum. 84 (2013) 023304.
Sato, N. et al. JAEA Rev. 2010-056 (2010) 52.

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

NEI-01

Nuclear Energy Chemistry in China: Present Status and Future Perspectives
Zhi-Fang Chai
Nuclear Energy Chemistry Group, Key Laboratory of Nuclear Analytical Techniques
Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
E-mail: chaizf@ihep.ac.cn
Nuclear energy chemistry is one of the most challenging
subjects in modern science, and its development is tightly
related to the advanced nuclear fuel cycle and persistentdevelopment of nuclear energy. Nuclear energy chemistryin China is now experiencing a renaissance, which is being
strongly motivated by China’s huge energy demand. In thistalk, the recent progresses in nuclear energy chemistry of
China are selectively highlighted, with emphasis on thefront-end chemistry, actinide solid-state chemistry
associated with nuclear fuel fabrication, actinide solution
chemistry and nuclear fuel reprocessing as well as
chemistry in nuclear waste disposal and management.
Some positive measures about how to promote the nuclear
energy chemistry in China are discussed, and future
perspectives are briefly outlined as well.
Acknowledgement – This work was supported by Natural Science
Foundation of China (Grants 91026007, 91226201 and 11275219) andthe "Strategic Priority Research Program" of the Chinese Academy of
Sciences (Grants.XDA030104).
[1]

WQ Shi, YL Zhao, ZF Chai. Radiochim Acta. 2012, 100: 529.

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

NEI-02

Evaluation of new extractants relevant to the back-end of nuclear fuel cycle
A. Goswami
Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai – 400 085, INDIA
E-mail: agoswami@barc.gov.in

Abstract:. Conventionally, PUREX and THOREX processes have been proposed for the reprocessing of U and Th based spent fuels
employing tri-n-butyl phosphate (TBP) as extractant. However, some major limitations of TBP have been identified and need to beaddressed. Evaluation of alternative extractants is, therefore, desirable which can overcome at least some of these problems. Extensive
studies have been carried out on the evaluation of N,N-dialkyl amides as extractants in the back-end of the nuclear fuel cycle foraddressing the issues related to the reprocessing of U and Th based spent fuels. Similarly, efforts have been made on the evaluation of
new solvents for the partitioning of minor actinides (MA) from high-level waste (HLW) solutions. This talk presents an overview ofstudies carried out at Radiochemistry Division on (a) spent fuel reprocessing of U/Th based spent fuels employing N,N-dialkyl amides
as extractants, and (b) partitioning of minor actinides using novel solvents .
Keywords – Reprocessing; Actinide partitioning; Tributyl phosphate; Dialkyl amides; Diglycolamides

chemical properties (including extraction/stripping) of these
extractants for hydrometallurgical applications. A flow sheet
has been proposed using DHOA as extractant. Merits of flowsheets proposed for the separation and recovery of minor
actinides from HLW have also been discussed. Detailed batchas well as mixer settler studies have shown that tridentate
diglycolamide based ligands such as TODGA and TEHDGA
have excellent properties for the partitioning of actinides from
HLW solution.

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

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The challenging task of recovery and purification of 239Pu from
irradiated U and of 233U from irradiated Th are accomplishedpresently by the well known PUREX and THOREX processes,
respectively [1]. These processes employ tri-n-butyl-phosphate(TBP) in n-dodecane as solvent. However, a few drawbacks
associated with the use of TBP have been identified: (i)deleterious nature of its degradation products (ii) relatively
lower distribution coefficient of Pu(IV) as compared to that ofU(VI) (iii) significant solubility of TBP towards aqueous phase,and (iv) non-incinerable nature of the spent solvent yielding
large volumes of secondary radioactive waste. These
shortcomings may pose a serious challenge particularly during
the reprocessing of short-cooled (MOX) thermal reactor,
Advanced Heavy Water Reactor (AHWR, being developed inIndia based on Th) as well as fast reactor spent fuels with larger
Pu content and significantly higher burn up [2]. In this context,
large number of eco-friendly N,N-dialkyl amides were evaluatedas alternative extractants at Radiochemistry Division, BARC,
Mumbai, India. Amongst these amides, N,N-dihexyloctanamide(DHOA) and N,N-di(2-ethylhexyl)isobutyramide (D2EHIBA)
received considerable attention as potential alternatives
extractants for the reprocessing of U and Th based spent
nuclear fuels, respectively [3]. Batch extraction, mixer settler/
centrifugal contactor runs were carried out with these reagents
under Pu rich feed (relevant to fast reactor) and AHWR feed
conditions, respectively. These data were compared with thoseobtained with TBP as extractant under identical experimental
conditions and a flow sheet for AHWR spent fuel reprocessing
has been proposed [4].
Actinide partitioning is the proposed strategy for
effective mitigation of the long term hazards associated withhigh-level waste (HLW). Octyl-(phenyl)–N,N-diisobutyl
carbamoyl methyl phosphine oxide (CMPO) has been studied
extensively during eighties for actinide partitioning from wastes
of different origin. However, the last two decades, substituted
malonamide extractants such as N,N’-dimethyl-N,N’-dibutyl
tetradecyl malonamide (DMDBTDMA) and N,N’-dimethylN,N’-dioctyl hexylethoxy malonamide (DMDOHEMA) haveemerged as viable green alternatives to phosphine oxides.
Recently, diglycolamide based extractants such as N,N,N�,N�tetraoctyl diglycolamide (TODGA) and N,N,N�,N�-tetra-2ethylhexyl diglycolamide (TEHDGA) have received
considerable attention due to overwhelmingly favorable
extraction and stripping efficiencies of minor actinides fromdifferent types of transuranium (TRU) wastes (Fig.1) [5,6]. We
have carried out comparative evaluation of the key physical and

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Fig.1: Variation of DAm with HNO3 concentration; Extractants: 30%
TRPO, 0.2M CMPO+1.2M TBP, 1M DMDBTDMA, 0.1M TODGA +0.5M DHOA and 0.2M TEHDGA + 30% iso-decanol; Diluent: ndodecane; Temperature: 25°C

Acknowledgement: Author thanks Dr. P.K. Mohapatra and
Dr. P.N. Pathak for their help in preparing this paper.
References
1.
2.
3.
4.
5.
6.

－ 63 －“Reactor Hand Book”, S.M. Stoller and R.B. Richards (Eds.), v. 2,“Fuel reprocessing”, Interscience Publishers & Inc., New York,1961.
R.K. Sinha, A. Kakodkar, A. Nucl. Engg. Design, 2006, 236, 683.
V.K. Manchanda, P.N. Pathak, Sep. & Purif. Technol., 35(2004) 85.
N. Kumari, D.R. Prabhu, A.S. Kanekar, P.N. Pathak. Ind. Engg.
Chem. Res., 51 (44) (2012) 14535.
S.A. Ansari, P.N. Pathak, Prasanta K. Mohapatra, Vijay K.
Manchanda. Chemical Reviews, 112(3) (2012) 1751.
Seraj A. Ansari, Priyanath Pathak, Prashant K. Mohapatra andVijay K. Manchanda. Sep.& Purif. Reviews, 40 (2011) 43.

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

NEO-01

Hexanoic acid as alternative diluent in a GANEX process based on TBP and
CyMe4-BTBPElin Löfström-Engdahl1, Emma Aneheim1, Christian Ekberg1, Hanna Elfversson1 and Gunnar
Skarnemark1
Nuclear chemistry , Industrial Materials Recycling2, Department of chemical and Biological Engineering,
Chalmers University of Technology, SE 412 96 Gothenburg, Sweden
1

Abstract – Used nuclear fuel is radiotoxic for mankind andits environment for a long time. However, if it can betransmuted the radiotoxicity can be reduced.
Simultaneously the long term heat load is decreased,making a final storage more volume efficient. Before thetransmutation the actinides within the used fuel need to be
separated from the fission, corrosion and activation
products. This separation can be achieved by using thetechnique liquid-liquid extraction.
One extraction process that can be used for such a
separation is the GroupActiNideEXtraction (GANEX)
process. In a GANEX process all the actinides are to be
separated from the rest of the fuel as one group. This
extraction leaves all the fission, corrosion and activation
products in the aqueous stream. One GANEX process thatcan successfully accomplish the An(III)/Ln(III) separation
utilizes the diluent cyclohexanone in combination with theextractant tributylphosphate (TBP) (30 % vol) and asecond ligand, CyMe4-BTBP (10 mM). However, there aresome issues when using cyclohexanone as diluent, forexample; it has a low flash point and it degrades in contact
with the acidic aqueous phase. In this work an alternative

diluent has therefore been tried in order to rule out if it canreplace cyclohexanone. The diluent used was hexanoic acid.
In the system containing 12 mM CyMe4-BTBP and 30 %vol TBP in hexanoic acid and the aqueous phase being 4 M
HNO3 the distribution ratio for plutonium is high (DPu = 76
± 17), while the one for uranium is lower (DU = 2.2 ± 0.25).
The distribution ratios for americium and curium are
unfortunately much lower than that of plutonium (DAm= 1.1± 0.27, DCm=1.6 ± 1.81). The concentration CyMe4-BTBP
ligand, the extractant of curium and americium, could
unfortunately not be increased, because of limited solubility
in hexanoic acid. The distribution ratios for fission,
corrosion and activation products were low for mostly
metals; however, silver, cadmium, palladium andmolybdenum all have distributions ratios above 1 istherefore troublesome. Europium is used as arepresentative lanthanide, which are similar to the trivalentactinides and therefore hard to separate. The distribution
ratio for europium is low in this system (D Eu = 0.12 ±0.016). However, to conclude, the low americium andcurium extractions indicate that hexanoic acid cannot
replace cyclohexanone in a GANEX process.

－ 64 －

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

Effect of alcohols on separation behavior of rare earth elements using
benzimidazole-type anion-exchange resin in nitric acid solutions
1

Tomobuchi Yusuke1, Yu Tachibana1, Masao Nomura2 and Tatsuya Suzuki1
Department of Nuclear System Safety Engineering, Graduate School of Engineering, Nagaoka University of Technology,
2
Laboratory for Nuclear Reactors, Tokyo Institute of Technology

Abstract - Chromatographic separation experiments of trivalentrare earth elements were performed using benzimidazole typeanion-exchange resin in nitric/alcohol mixed solvent systems atroom temperature. As a result, it was found those trivalent rareearth elements are able to be separated mutually in a 20 % HNO3
and 80 % MeOH mixed solvent. Based on these results, we
systematically examined using various alcohols to make clear therole of alcohols in anion-exchange reactions at various
temperatures.
Keywords - rare earth elements, alcohols, benzimidazole-typeanion-exchange resin, mutual separation
I. INTRODUCTION
As a final disposal method for the high level liquid
waste(abbreviated as HLLW) generated by spent-nuclear-fuelreprocessing plants, the geologic disposal concept of thevitrified HLLW has been proposed and investigated globally.
Especially, from the viewpoint of minimizing the long-term
radiological risk and facilitating the management of HLLW, a
separation of the long-lived minor actinides(MA = Am andCm) from HLLW is strongly desired.1) Moreover, a mutual
separation of Am and Cm is also required after the separationof MA from HLLW because the relatively high decay heat ofCm makes it difficult to fabricate nuclear fuels reproduced
from spent nuclear fuels.2) On the other hand, it has been wellknown that the difficulty of a mutual separation between
trivalent Am and Cm is due to similar chemical properties.2)
In fact, although a few reports by Hale et al. using
diethylenetriaminepentaacetic acid and Suzuki et al. withtertiary pyridine have been reported, little systematic
information is available on the mutual separation mechanisms
between Am and Cm.2,3) Therefore, as a part of thefundamental researches to innovate conventional separation
technologies, we have studied on the chromatographic
separation of trivalent rare earth elements(abbreviated as
REE (REE = La, Ce, Pr, Nd, Sm, Eu, and Gd)) which havethe same valence level in solutions and the similar ion radii ascompared with those of MA, using benzimidazole type anionexchange resin (abbreviated as AR-01) embedded in highporous silica beads in nitric acid/alcohol mixed solvent
systems.
II. EXPERIMENTAL
All REE were used without further purification. The purityof all REE was more than 98.0%. All chemicals for sample
preparations were of special pure grade. AR-01 resin

consisted of styrene-divinylbenzene copolymers with 4-(1methylbenzoimidazole-2-yl)phenyl and 4-(1,3-dimethylbenzoimidazole-2-yl)phenyl, was supplied from Asahi Kasei
Corporation. Each concentration of REE species in thesolutions were determined by ICP-MS(7700x, Agilent).
III. RESULTS
Chromatographic separation experiments of trivalent REE
were performed using AR-01 resin in a nitric acid solvent
system and a nitric/alcohol mixed solvent system at room
temperature. As a result, it was found that mutual separationsof REE cannot be achieved completely in HNO3
solutions(data no shown), but REE are able to be separated
mutually in a 20 % HNO3 and 80 % MeOH mixed
solvent(see Figure 1). In addition, retention times obtained
from these chromatograms of the REE increase withincreasing the ion radii in order of Gd, Eu, Sm, Nd, Pr, Ce,and La, i.e., it could be estimated that the separation
mechanisms proceed through anion-exchange reactions
between 4-(1,3-dimethyl-benzoimidazole-2-yl)phenyl groupsof AR-01 and [Ln(NO3)n]3-n (n �� �� . Based on these results,
we concluded that the examined separation technique isapplied to mutual separation of Am and Cm.

ACKNOWLEGEMENT
This work was partially supported by the Grant-in-Aid for
Scientific Research (B) (KAKENHI No. 23360423).
REFERENCES
[1]
[2]
[3]

－ 65 －

Kolarik, Z., Journal of Nuclear Fuel Cycle and Environment, 5, 21-35(1998)
Suzuki, T., Otake, K., Sato, M., Ikeda, A., Aida, M., Fujii, Y., Hara, M.,
Mitsugashira, T.,Ozawa, M., Journal of Radioanalytical and Nuclear
Chemistry, 272, 257-262 (2007)
Hale, W.H., Lowe, J.T., Inorganic and Nuclear Chemistry Letters, 5,363-368 (1969)

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

Speciation and Reactivity of Heptavalent Technetium in Concentrated Acids.
Frederic Poineau1, Philippe Weck2, Benjamin P. Burton-Pye3, Alesya Maruk4, Gayane Kirakosyan4,
Ibthihel Denden5, Daniel. B Rego1, Erik V. Johnstone1, William Kerlin1, Eunja Kim1, Mairlynn Ferrier1,
Alfred P. Sattelberger7, Wayne Lukens6, Massoud Fattahi5, Lynn C. Francesconi3, Konstantin E. German4,
and Kenneth R. Czerwinski1.
1

Department of Chemistry, University of Nevada Las Vegas, Las Vegas, NV, USA.
2
Sandia National Laboratories, Albuquerque, NM 87185, USA.
3
Department of Chemistry, Hunter college of the City University of New York, NY, USA
4
A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, RussianFederation
5 Laboratory Subatech, Ecoles des Mines de Nantes, Nantes, France
6
Energy Engineering and Systems Analysis Directorate, Argonne National Laboratory, Lemont, IL, USA.
7
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, 94720, USA

Keywords – Technetium, Speciation, EXAFS spectroscopy.

Discovered 75 years ago, technetium is the lightest
radioelement. Thirty four isotopes are known; the mostcommon isotopes being 99Tc (t1/2 = 2.1 x 105 y) and 99mTc (t1/2= 6 h). The isotope 99Tc is a fission product of the nuclear
industry, while the isotope 99mTc is used in nuclear medicine
as an imaging agent. Current researches focus on thedevelopment of 99mTc radiopharmaceuticals, and on thedevelopment of separation process and waste form storage for99
Tc. Technetium exhibits nine oxidation states (-1 to +7).
Under oxidizing conditions, the aqueous chemistry of Tc(+7)
is dominated by the pertechnetate anion, TcO4-. In high acidconcentration, TcO4- can be protonated and pertechnetic acid,HTcO4, is formed. The structure and reactivity of HTcO4 ispoorly studied. Studying the chemistry of Tc(+7) inconcentrated acids is relevant to the fundamental and appliedchemistry of technetium; it will allow to better understand the
behavior of Tc(+7) in separation processes whereconcentrated acids are used. In this work, the speciation andreactivity of Tc(+7) in concentrated HNO3, H2SO4 and HClO4
is investigated. The resulting complexes are characterized by
NMR, UV-visible and EXAFS spectroscopy and DFT
calculations. Results show the formation of TcO3(H2O)2(OH)in concentrated H2SO4 and HClO4 while TcO4- inconcentrated HNO3. The complex TcO3(H2O)2(OH) reacts in
13 M H2SO4 with MeOH to produce TcO(HSO4)3(OH)-. In
HNO3 > 7 M , the pertechnetate anion reacts with hydrogen
peroxide to produce TcO(O2)2(H2O)OH. The results
demonstrate the complex and little explored chemistry of Tc
in concentrated acids.

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

NEO-04

Fluorescence Studies of Complex Stoichiometry of Metal ions in Extraction
Systems Combining Dibutyl Phosphoric Acid and Tri-n-butyl Phosphate
Alexander Braatz and Mikael Nilsson
University of California, Irvine
Department of Chemical Engineering & Materials Science
916 Engineering Tower
Irvine, CA 92697-2575
abraatz@uci.edu
Advanced nuclear fuel cycles are dependent on successful
chemical separation of the various elements present in theused fuel. Numerous extraction systems have beendeveloped for the recovery and separation of the various
metal ions present in the used fuel. Extraction oflanthanides and actinides by tri-n-butyl phosphate (TBP)
and dibutyl phosphoric acid (HDBP) is of importance forone of these processes, the PUREX process.
The
combination of these two extraction reagents have beenshown to synergistically enhance metal ion extraction anddisplay characteristics of microemulsion aggregates ofreverse micelle type. To improve our understanding of thecomplexes formed in this system we further studied theextraction of lanthanides and actinides, in our casedysprosium, Dy, and uranium, U, with TBP and HDBP in
conjunction with 2D fluorescence spectrometry. Aqueous
samples containing Dy3+ and UO22+ in nitric acid were
contacted with organic phases containing varying ratios of
TBP and HDBP in n-dodecane and the distribution was
followed by neutron activation analysis. 2D Fluorescence
spectra were examined for all lanthanides and uranium.
Typically, europium is used as a benchmark for lanthanides
in fluorescence studies but we show here that several otherlanthanides exhibit excellent spectroscopic characteristics
using this technique. The effects of acid on the fluorescence
spectra will be investigated. Possible explanations ofphenomena and comparison to existing Eu studies found inliterature will also be presented.

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

NEO-05

Column study on electrochemical separation of cesium ions from wastewater using
copper hexacyanoferrate film
Rongzhi Chen 1), Hisashi Tanaka 1), Miyuki Asai 1), Chikako Fukushima 1), Tohru Kawamoto 1), Manabu Ishizaki 2),
Masato Kurihara 1,2), Makoto Arisaka 3), Takuya Nankawa 3) and Masayuki Watanabe 3)
1)
Nanosystem Research Institute, AIST, Tsukuba central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan2)
Department of Material and Biological Chemistry, Faculty of Science, Yamagata University, 1-4-12 Kojirakawamachi, Yamagata 990-8560, Japan
3)
Japan Atomic Energy Agency, 2-4 Shirane Shirakata, Tokai-mura, Naka-gun, Ibaraki 319-1195, Japan
Abstract – We coated the copper hexacyanoferrate (CuHCF) on
the gold electrodes, and then performed the Cs removal byelectrochemical separation (ES). The prepared CuHCF
nanoparticles can be simply and uniformly coated on electrodes
by wet process like conventional printing methods, so any sizes orpatterns are feasible at low cost, which indicated the potential asa promising sorption electrode of large size in the columns forsequential removal and recycle of Cs from wastewater.

Metalhexacyanoferrate
complex,
Keywords:
Electrochemical separation, Cesium, Radioactive waste,
Nanoparticle ink, Prussian blue complex.
Introduction

Transition metal hexacyanoferrates (HCFs) are
preferred to be competitive ion exchangers over othermaterials due to their selectivity and high capacity. Amongthem, copper (II) hexacyanoferrate (III) (CuHCF) is often
selected as the agent in practical analysis. This compound
has been much used as precipitants for alkali metal cations,especially cesium, to remove them from aqueousradioactive wastes [1].
However, small sized CuHCF particles can easily
contaminate water, which restricts its direct use for column
operations. Herein, we developed and coated the waterdispersible CuHCF nanoparticles on the electrodesubstance, and then performed Cs removal. This study
evaluates the electrochemical Cs sorbability of CuHCF NPs
film and estimates the potential as a promising sorption
electrode of large size in the columns for sequential
removal and recycle of Cs from wastewater.

Fig. CV of a Cu-HCF film under different temperatures (from 298
to 338 K), and effect of temperature on Cs sorption using CuHCF
film

In order to using our film for practical analysis in thefield-scale applications, column study is needed. We
synthesized water-dispersed nanoparticle CuHCF ink andthen coated its nanoparticles on SUS316L sheet electrodes.
The Cs adsorption and desorption were alternately repeatedfor 5 cycles (30 min/cycle), initial Cs conc. is 9.858 ppm.
The well balance of Cs desorption and adsorption,
indicated the CuHCF film has a long life in the columns forsequential removal and recycle of Cs from wastewater.

Experimental & Results

The Cs adsorption was performed in a three-electrodecell in which an Hg/Hg2Cl2/KCl (saturated solution) as
reference electrode, a platinum electrode (as counterelectrode), and the CuHCF film coated adsorbent electrodewere used as the working electrodes. The redox reaction for
Cs separation process is proposed as follows [1]:Cu3[Fe III (CN)6]2) + 2e� + 2Cs+ � Cs2Cu3[Fe II (CN)6]2
To examine the effect of temperature, electrochemical
characterization of CuHCF film and its Cs adsorptions wereconducted at 298, 313, and 323 K, respectively. Cs removal
decreased with the increase in temperature for CuHCF film
(Fig. 3b). Namely, the Cs adsorption process was
exothermic in nature.

Fig. Cs alternate adsorption and desorption performance using
CuHCF film

Effective regeneration and large surface coating willallow it to be used in the column for sequential removal
processes.
[1] RZ. Chen, et al., Electrochimica Acta, 2013, 87
119－ 68 －

Poster Session 2
Tuesday, 24 September 2013
18:50 ~ 20:00

Scientific Topics (Abbrev.)
1. Fukushima issues (FK)
2. Education in nuclear and radiochemistry (ED)
3. Nuclear forensics (NF)
4. Nuclear energy chemistry (NE)
5. Nuclear chemistry (NC)
6. Actinide chemistry (AC)
7. Environmental radiochemistry (EN)
8. Radiopharmaceutical chemistry and Nuclear medicine (RP)
9. Nuclear probes for materials science (NP)
10. Activation analysis (AA)
11. Application of nuclear and radiochemical techniques (AP)－ 195 －

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

$ETERMINATION OF SHORT LIVED 0U IN ENVIRONMENTAL SAMPLESBY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY
Jian Zheng*, Keiko Tagami, Shigeo Uchida
Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences

Plutonium isotopes have been released into the environment mainly from the atmospheric nuclear
weapons tests in last century, the discharges from nuclear fuel reprocessing facilities, and the nuclear
accidents, such as the Chernobyl and the Fukushima Daiichi Nuclear Power Plant (FDNPP) accidents [13] Accurate determination of Pu isotopic composition is important for the source identification ofradioactive contamination in the environment since Pu isotopic composition is characteristic for various
Pu sources. Among Pu isotopes (238Pu, 239Pu, 240Pu, and 241Pu) observed in the environment, the shortlived 241Pu (t1/2 = 14.4 y), a beta emitter, is a sensitive indicator for the identification of any newcontamination of Pu isotopes resulted from nuclear power plant accident. For 241Pu originated from theglobal fallout, the activity of 241Pu in the environment is quite low due to the dacay with time. The
activity ratio of 241Pu/239+240Pu is ca. 1.2 in 2011 for the global fallout-sourced Pu isotopes. Therefore,
higher activity ratio of 241Pu/239+240Pu in the environment will provide evidence of additional Pu input.
Due to its short half-life and beta emission, determination of 241Pu in environmental samples has beena great analytical challege. Conventional technique is the low level liquid scintillation counting, which
requires tedious sample preparation and long measurement time (typically 13-24 h). In the past years, wehave developed sensitive analytical method using inductively coupled plasma mass spectrometry for thedetermination of 241Pu in various environmental samples, such as atmospheric fallou material, marine
sediments, and seawater reference material [4-6]. In this work, we report the determination of 241Pu in
environmental samples, such as litter, soil and marine sediments collected in Fukushima Prefecture after
the FDNPP accident in 2011. Fig. 1 shows the results of 241Pu activity in litter and surface soils collected
in 20-30 km zone of the FDNPP, and in Cities of Mito, Kamagaya and Chiba. High activities of 241Pu
ranging from 4.5 to 34.8 mBq/g were detected in the J-Village surface soil (0-2 cm) and two litter
samples. This finding of high 241Pu activities in environmental samples after the FDNPP accidnet
provided evidence of the release of Pu isotopes from the accident.

－ 196 －

N.D.

N.D.

N.D.

Chiba

濃 度 範 囲 （ 推 定 ）2011年 に お け る

N.D.

N.D.

Kamagaya

N.D.

Mito

N.D.

S1 SoilN.D.:
Not detected

G 241
lo b a l f a llo u t

Global fallout
source in 2011
241
Pu
Pu activity range

濃 度 範 囲 （ 推 定 ）1963年 に お け る

1963 Global fallout
241
Pu
Pu activity range
G lo
b a l f a llo u t
241

1S1 Litter

サ ン プ ルSamples

千 葉

鎌 ヶ 谷

水 戸

J-village
Jビ レ ッ ジ

S3土 壌

S3 Soil

S2土 壌

S3落 葉 層S3 Litter

S2 Soil

S2落 葉 層S2 Litter

S1土 壌

0.1

S1落 葉 層[1] J. M. Kelley, L. A. Bond, T. M. Beasley. Sci. Total Environ.
237/238 (1999) 483-500.
[2] M. E. Ketterer, K. M. Hafer, J. W. Mietelski. J. Environ.
Radioact. 73 (2004) 183-201.
[3] J. Zheng, K. Tagami, Y. Watanabe et al. Sci. Rep. 2:304;
DOI:10.1038/srep00304. 2012[4] J. Zheng, M. Yamada. J. Oceanogr. 64 (2008) 541-550.
[5] J. Zheng, M. Yamada, Appl. Radio. Isot. 70 (2012) 19441948.
[6] Y. S. Zhang, J. Zheng, M. Yamada et al. Sci. Total Environ.
408 (2010) 1139-1144.

10

241

References

100

241Pu
P u 濃 activity
度（m B q (mBq/g)/g )Acknowledgement: This study was partially supported by the
Agency for Natural Resources and Energy, Ministry of
Economy, Trade and Industry (METI), Japan.

Figure 1. Results of activities of 241Pu detected in theenvironmental samples collected after the FDNPP accident.

24-FKP-02

APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013������������������������������������������������������������������������
��������������������������������������������Hiroshi Ogawa, Akiko Kitajima, Hisashi Tanaka, and Tohru Kawamoto
Nanosystem Research Institute, Advanced Industrial Science and Technology (AIST), Tsukuba, 305-8568, Japan.

Abstract Ð Amount of Cs adsorption in PB column was
numerically evaluated based on extended Langmuir formula andone-dimensional adsorption model. The extended Langmuir
formula successfully reproduced the experimental Kd distribution
coefficient of Cs adsorption that cannot be explained bytraditional Langmuir model. The time-variation of the Cs
adsorption in column experiment was also explained by onedimensional adsorption model.
Keywords Ð Cs decontamination, Cs adsorption, extended
Langmuir formula, column experiment, simulationI.

INTRODUCTION

The accident of the Fukushima-daiichi nuclear plant inMarch, 2011 has caused heavy radioactive pollution insurrounding regions.
Decontamination of radioactive
elements, especially Cs-134 and Cs-137, is an urgent issue.
One of the most effective procedures for the Csdecontamination from contaminated water is to use
Prussian-Blue (PB) as a Cs adsorbent [1,2]. In this paper,
the authors propose a numerical method for expecting theamount of Cs reduction by PB adsorbent based on extended
Langmuir formula and one-dimensional adsorption model.
II. METHOD
The Langmuir formula is extended as,
w = �i � Ni wi ,wi = Ki c (wimax Ð wi),

(1)
(2)

where w is the total amount of the adsorbed Cs in theadsorbent, Ni the number of adsorption site, wi the amountof the adsorbed Cs at i-th adsorption site, Ki the equilibrium
constant between liquid and adsorbent at the i-th site, wimax

Fig. 1 Experimental and calculated Kd values of the adsorbent usedin this study.

the saturation value of the Cs adsorption at the i-th site, andc the Cs concentration in the liquid.
Time-variation of Cs reduction in a column experiment
was calculated by one-dimensional adsorption model as,dc (x, t) / dt« = Ð c (1 Ð � (x, t)) / � max �,(3)where x, t, t«, � (max), and � are the one-dimensional positionin the column, wall-clock time, contact time of the waterwith the adsorbent, (maximum capacity of) Csconcentration in the adsorbent, and time constant of Csconcentration reduction, respectively.
The column and shaking experiments were carried out
by using granular adsorbent with PB nanoparticle suppliedby Kanto Chemical Co. Inc. [2]III. RESULTSIn Fig. 1 the experimental Kd values are shown as afunction of initial Cs concentration in comparison with theresults of Langmuir fittings of Ni = 1 and 2. Large
discrepancy is found in the case of Ni = 1 (dashed line)
especially at high Cs concentration. The fitting is, however,drastically improved if the second adsorption site isincluded (solid line).
Figure 2 gives the comparison between experimental
and calculated time-variation of Cs concentration incolumn experiment. Our one-dimensional model gives
time-variation of the Cs concentration after column
adsorption accurately. It is expected that precise simulationof the Cs adsorption in actual plant will be possible bycombining extended Langmuir formula and onedimensional adsorption model.
[1][2]

Kitajima et al., Chem. Lett., 41, 1403 (2012).
Kitajima et al., in APSORC 13 abstract.

Fig. 2 Experimental and calculated (solid lines) time-variation of Cs
concentration in liquid after column adsorption.

－ 197 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-03

Secular distribution of radioactive concentration in the atmosphere at Fukushima,
Hitachi and Marumori
ZiJian Zhang1, Shunsuke Kakitani1, Kazuhiko Ninomiya1, Naruto Takahashi1, Yoshiaki Yamaguchi2,
Takashi Yoshimura2, Kazuyuki Kita3, Akira Watanabe4, Atsushi Shinohara1
1

Graduate School of Science, Osaka University, 2 Radioisotope Research Center, Osaka University,
3
Faculty of Symbiotic Systems Science, Fukushima University,
4
College of Science, Ibaraki University

Abstract - Our group started gamma ray measurement of air dust
sample after the Fukushima Dai-ichi nuclear power station
accident. Air dust filters was collected at Hitachi, Fukushima andMarumori. The activity of Cs-134 and Cs-137 was determined by
germanium semiconductor detector. The radiocesium activity
concentration in air dust(Bq/m3) after October 2011 were stableand 6.2×10-6 at Hitachi, 3.0×10-4 at Fukushima and 1.3×10-4
at Marumori.
Key word –radioactive cesium, air dustI.

INTRODUCTION

On 11th March 2011, the earthquake occurred and alarge tsunami destroyed coasts of Eastern Japan. As a result,the nuclear accident of Fukushima Dai-ichi nuclear power
station (in the following FD-NPS) was arisen. The accident
caused massive release of radioactivity into the atmosphere.
Many material transportation models were used for
simulating the behavior of radioactive nuclides inenvironment. From these simulations, we can estimate theamount of radioactive deposition to land and sea, andcalculate the internal exposure. However, there are someunclear points about nuclides transportation in theenvironment, and the accuracy of precision simulation was
limited by these problems. We need accurate measurement
data of radioactive nuclides in the atmosphere. Our group
started collection of air dust after the accident of FD-NPS
at three locations. In this study, we discuss about theseculer distribution of radioactive concentration in theatmosphere.

the concentration in April. The average of radiocesium
activity concentration after October 2011 were 6.2×10-6
Bq/m3 at Hitachi, 3.0×10-4 Bq/m3 at Fukushima and 1.3×
10-4 Bq/m3 at Marumori. Ratios of Cs-134/Cs137 wereabout 1 in three locations. There are many studies thatobserve the same results in environmental samples.
The activity concentration of beryllium-7 was always
about 10-3 Bq/m3. The seasonal variation was likely someprevious report [1]. Beryllium-7 is known for attaching toaerosol and being transported to all over the world. We
could not find out some correlation between Be-7 and Cs137. Therefore, main sources of Cs-137 in environment
behave differently with cosmic ray radionuclides. We
suggest that most of radiocesium in the atmosphere comefrom some local sources, likely releasing from soil andforest.

II. MEASUREMENTOur group has been collecting air dust in Fukushima
City, in 68 km east of FD-NPS, Hitachi, in 87 km south andMarumori, in 50 km north. Sampling duration was 3-4 days.
All gamma ray measurements were carried out at Osaka
University in low background condition with 1-2 days.
Radioactivities in air (Bq/m3) of I-131, Cs-134 and Cs-137
were determined. We also measured Be-7 that is one ofindex of cosmogenic radionuclides, to discusstransportation process of Cs-137.
III.

Fig.1. Cs-134, Cs-137 and Be-7 activity concentration. Upper one isdata of Hitachi and Under one is data of Fukushima

RESULT AND DISCUSSION

The time variation of activity concentration in Hitachi
and Fukushima is shown in Fig.1. In Hitachi, activity
concentrations for Cs-134 and Cs-137 were very high at
April 2011(�Bq/m3).They were rapidly decrease with time
passing, and in October, they were about one-thousandth of－ 198 －

[1]R.Winkler and F.DIETL, Atmospheric Environment 32,
No6, 983-991(1998)

24-FKP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

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

Abstract – Concentration of 137Cs in atmospheric coarse and fineparticles was determined in Fukushima city and Date city collected
every 2 weeks from August 2012 to January 2013. Total average
concentration of 137Cs in Fukushima and Date were 182 and 173
�Bq m-3, respectively and the range was within a factor of 2. The
concentration of 137Cs in the coarse fraction was higher than that in
the fine fraction except for one sample collected in Fukushima city.
The variation of 137Cs concentration in the fine fraction was smaller
than that in the coarse fraction and the concentration ratio of 137Cs
in the fine fraction to that in the total was approximately 1/3.
Keywords – 137Cs, fine particle, coarse particle, Fukushima city,
Date cityI.

a) Fukushima city
#S ACTIVETY CONCENTRATION  ±"Q M 

1











INTRODUCTION























b) Date city

II.

RESULTS AND DISCUSSION

Total concentration of 137Cs in coarse and fine particles inFukushima was ranged from 84 to 347 µBq m-3 with anaverage of 182 µBq m-3 (Fig. 1-a). The total 137Csconcentration of Date was in the range of 103 to 311 µBq m-3
where the average was 173 µBq m-3 (Fig. 1-b). The range of








METHODCoarse and fine particles were collected from two sites
such as 62 km (Fukushima) and 55 km (Date) distant from
Fukushima Dai-ichi Nuclear Power Plant from August 2012
to January 2013. Fukushima is in the urban site and Date is in
the rural site. Coarse and fine particles were divided at 50 %cutoff diameter of 1.1 �m with an Andersen sampler (AH600,
Tokyo
Dylec),
andwerecollectedon
polytetrafluoroethylen filters at flow rate of 566 L min-1. The
filters were exchanged every two weeks.
The sampled filters were cut into small pieces andcompress into a plasitic bottle. Radioactivety of 137Cs in thesamples was measured for 0.5-2 days by Ge detector.
III.

#S ACTIVETY CONCENTRATION  ±"Q M On 11 March, 2011, the Fukushima Dai-ichi Nuclear
Power Plant accident was caused by the tsunami following
the earthquake to release radioactive nuclides into theatmosphere. Cesium-137 is a major radionuclide released into
the environment and is important to estimate radiation dose
for the public. In order to estimate radiation dose frominhalation, the particle size distribution of 137Cs in theatmosphere is required. In this study, concentration of 137Cs
in atmospheric coarse and fine particles was determined in
Fukushima city and Date city.

Fig. 1 Concentration of 137Cs in atmospheric coarse and fine particles.
Error bars indicate one sigma of deviation.

the concentration of 137Cs in the total particles was within afactor of 2. Tsukada et al. (2012) reported that 137Csconcentration in Fukushima city was 164 mBq m-3 in early
April 2011 and the value decreased to one thousandth in
September 2011. The observed values in the study also
maintained a similar order of magnitude to the value in
September 2011.
The concentration of 137Cs in the coarse fraction was
higher than that in the fine fraction except for one sample
collected in Fukushima. The variation of 137Cs concentrationin the fine fraction was smaller than that in the coarse fraction
and the concentration ratio of 137Cs in the fine fraction to thatin the total was approximately 1/3. However, massconcentration ratio in the fine fraction to the total wasapproximately 1/2. It may attribute that the sources of coarse
and fine particles were different.
[1]－ 199 －

Tsukada H. et al. (2012) Atomic Energy Society of Japan, Hiroshima.

24-FKP-05
APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013����������������������������������������������������������� ������������������������
��������������������������
����������������������������������� ��������������� ������������������������������������������������������������
���������������������������������������������������������� ������������������������
�������������������������������������� ������������������������������������������������������������������
������������������������������������������������������������������������������������������� �������������������������
������������������������
����������������������������� ��������������������������������������������������������������������
Abstract Ð Copper hexacyanoferrate (CuHCF) is known as a good
adsorbent for Cs. We developed water-dispersible CuHCF ink by
nanoparticulation and surface treatment, and fabricated the thinfilm of CuHCF on metal electrodes. Cs adsorption/desorption canbe controlled electrochemically using this thin film CuHCF
electrode, repetitively. Cs sorption capability under coexisting otherions were examined for alkali metals, alkali earth metals, transition
metals, etc, and determined to be few affected.
Keywords Ð Copper hexacyanoferrate, Prusian blue analogues,
Nanoparticle ink, Electrochemical adsorption/desorption, Cs
adsorption, Nuclear waste water, Fukushima daiichi nuclear
disaster��

desorption, ������� ������������� ����������������������� ������������������ ����������������������������������������������
���� ����� ��� ����� ���� ������ ����������� ����� ������ ��� ������������� ���� ��� �������������� ����� ������ ��� ���� ����������������������������������������������� ���������������
����������� ��� ��� ���� ����� ���� ������� ���� ���������������� ������������ ����������� ��� ������ ����� ������ ���� ��� ��������� �������������������������������������������� �����������������������
�����������������������������������������������������������������
����� ����������������������������������� 18��������

������������

���� ������������ ������� ����� ��� ������ �T��� �� ����� ������� ������� ��� ����� �������� ��� ������������ �������� ��� ������� ���������������� ��������� ���������� �������� ����� ����� ����� ������
������ ������������������ ��������� ������ ����� �� ����������
���������������� ��������������������������������������������
����������� ������������ ������� ����������������� ��������
�������������������������������������������� ������������� ��������� ����� ��� ����� ��� ������ ����������� ��� �������������
����� ������� ��� ���������� ��� ����������� ������������������� �������������������������������������������������������
���������������������� �������� ���� ��� ��������� �����������
����������������������������
II. ������������ ���������
�������������������������������������������������������� ���� �������� ����� ����� �������� ���� a����� �������� ������������� ���� ����������� ��� ����� �������� ��� ��� �����������
������ ��������������� ��������� ���� ������ ���������� ���� �����
����������� ������������������������������������� ����������������� ��������� ���� ��������� ����� ������������ �������� �������
������������������������������������������������������
���� ���������������� ��� ���������������������� ����������������������������������������������������������������
���������� ������� ����� ��� �������� ����������� ����������
�������� ���������� ������ ��� ���������� ����������� ���� ��� �������� �������� ����������� ���� �������� ������������ ��������� ��������������� ���������� �� ��� ��� ���� � ��� ����� ���� �������������������������� ��� ���� ������������������������������
���� ����������� ��������� ���������� ��� ���� ����� ��� ���� �������� �� ���� ���. After executing 5 cycle adsorption and������������������������������������������������������
����������������������

������������������������������������������������������
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－ 200 －

24-FKP-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of 129I in Fukushima Soil Samples by ICP-MS
Takeshi Ohno1, Yasuyuki Muramatsu1, Hiroyuki Matsuzaki2
1

Faculty of Science, Gakushuin University
School of Engineering, The University of Tokyo

2

Abstract – A method was developed for the determination of 129I in
soil samples, which uses a ICP-MS with an octopole reaction system,
permitting the investigation of radioiodine released by the
Fukushima Daiichi nuclear power plant (FDNPP) accident. The
determination of 129I by ICP-MS is capable of providing a highsample throughput compared to other methods.
Keywords – Radioiodine, Fukushima Daiichi nuclear power plant
accident, 129I, ICP-MS, Octopole reaction systemI.

INTRODUCTION

The accident at the Fukushima Daiichi nuclear power
plant (FDNPP) resulted in a substantial release ofradionuclides into the environment, including atmospheric ofradioiodine and radioceium.1, 2 The distribution of radiocesium has been studied, and a map of the radiocesium
contamination was made. On the other hand, 131I could only
be determined within a couple of months, due to its short halflife (8 days), resulting in a lack of data on the deposition ofthis nuclide. Because iodine is an essential element, andplays an important role in thyroid development, radioiodinethat is ingested readily and becomes enriched in the human
thyroid. In the event of a nuclear plant accident, an effective
dose estimation of released 131I is important.
Another iodine isotope, 129I (half-life: 1.57 × 107 y), wasreleased simultaneously with 131I, although the amount wasvery small. To reconstruct the early distribution of 131I in theenvironment, 129I has been used as a follow-up tracer due to
its much longer half-life. The determination of 129I in soils inFukushima is of importance to investigate the distribution ofradioiodine released from the FDNPP. Recent advances in
inductively coupled plasma mass spectrometry (ICP-MS)
using a octopole reaction cell have enabled us to determine
the long-lived radionuclide 129I in soil samples.3
II. EXPERIMENTAL
The analytical method used in this study is based on themethod for AMS measurements.4 Soil samples (about 2 g)
were mixed with V2O5 in a ceramic boat before being placedin a quartz tube. The sample was heated at 1000°C in a tube
oven for 30 min under a flow of oxygen with water vapor.
The iodine released by heating was collected with a trap
containing 10 ml of a solution of 1% TMAH. The iodine
fraction was then purified by a combination of solventextraction and back extraction using carbon tetrachloride as
the solvent. The back-extracted solution was concentrated toabout 1 mL on a hotplate at 100°C. The purified samples

were subjected to measurements of 129I/127I by the ICP-MS.
Any mass-discrimination effect in the mass spectrometer wasmonitored using NIST SRM 3231 Level 1.
III. RESULTS AND DISCUSSION
In order to improve the precision and accuracy of theI/ I isotopic ratio measurements, interfering signals, suchas 129Xe+, must be reduced. In this study, 129Xe+ was
suppressed by O2 as a reaction gas using the following
reaction: Xe+ + O2 � Xe + O2+. The oxygen flow rate was
optimized while aspirating an iodine solution (10 ppb,
129 127
I/ I=10-13) so as to maximize the 127I intensity/background(m/z = 129) ratio. When increasing the oxygen flow ratefrom 0 L/min to the optimum value at 0.8 mL/min, a twenty129
I
background-equivalentfold
improvementofconcentration was observed.
We investigated the production ratio of 127IH2+/127I+ while
aspirating iodine solution (100 ppm, 129I/127I=10-13). The
results demonstrated that the production ratio of 127IH2+/127I+
in the ICP-MS was about 3 × 10-8. The contribution from thisinterference could be corrected by subtracting of 127IH2+
according to the production ratio. The production ratio wasmonitored before and after measuring the samples, and thecontribution of 127IH2+ was subtracted from the signal
intensity of 129I when calculating the 129I/127I isotopic ratios.
In order to confirm the applicability to measurements of
the 129I/127I ratios of soils we measured 129I in six samples
which were collected from an orchard in Ohkuma-machi(about 5 km from the FDNPP), a rice paddy in Iitate-muraand Namie-machi (about 30 km from the FDNPP) and an
orchard in Koriyama-shi (about 60 km from the FDNPP).
The measured 129I/127I ratios in the samples by ICP-MS areconsistent with the value determined by AMS within theanalytical error, suggesting the applicability of this method tomeasurements of 129I/127I in Fukushima soil samples. Our
results indicate that 129I can also be determined outside of the
30 km districted area, i.e. 60 km or more from the FDNPP.
This method could provide a powerful tool for theinvestigation of the radioiodine contamination.
129 127

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

－ 201 －

M. Chino, H. Nakayama, H. Nagai, H. Terada, G. Katata, and H.
Yamazawa, J. Nucl. Sci. and Tech., 2011, 48, 1129.
N. Kinoshita, K. Sueki, K. Sasa, J. Kitagawa, S. Ikarashi, T. Nishimura,
Y.-S. Wong, Y. Satou, K. Handa, T. Takahashi, M. Sato, and T.
Yamagata, PNAS, 2011, 108, 19526.
T. Ohno, Y. Muramatsu, C. Toyama, K. Nakano, S. Kakuta, and H.
Matsuzaki, Anal. Sci., 2013, 29, 271.
Y. Muramatsu, Y. Takada, H. Matsuzaki, and S. Yoshida, Quarter.
Geochronol., 2008, 3, 291.

24-FKP-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Measurement of soil-to-crop transfer factor of tellurium for estimation of potential
radiotellurium ingestion from crops
Guosheng Yang, Keiko Tagami*, Jian Zheng, Shigeo Uchida
Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences



4RANSFER FACTORThe Fukushima Daiichi Nuclear Power Plant (FDNPP)
accident discharged large amounts of radionuclides into theenvironment, including 127mTe (T1/2=109 d), 129mTe (T1/2=33.6d), 131mTe (T1/2=30 h) and 132Te (T1/2=3.204 d) [1]. Since
relatively long-lived 127mTe could transfer from soil to crops
through roots, people would ingest 127mTe; however, theisotope is a beta-emitter and the concentration data in foodcrops were unavailable. Now, 127mTe has been decayed out
and it is difficult to measure 127mTe in crops samples.
However, it is still important to estimate how much amountof 127mTe might have been ingested from food for public
safety purpose. The soil-to-crop transfer factor (TF) is a
useful tool to estimate Te concentrations in crops.
Unfortunately, the TF data of Te are scarce in the world [2]and there are no data for crops native to Japan.
In order to obtain the TF data of Te for crops, we
focused on stable Te as an analogue of radioactive Te. We
measured 79 soil and associated crop samples collectednationwide to calculate TFs of Te. Te concentrations in soil
and crop samples were measured by using sector field
inductively coupled plasma mass spectrometry (SF-ICP-MS)
after aqua regia digestion and appropriate dilution to reducethe matrix effect [3]. The Te contents in Japanese soil andcrops ranged from 12.6 to 479 ng g-1 (mean: 55.3 ng g-1) andfrom 0.06 to 3.8 ng g-1 (mean: 0.7 ng g-1), respectively. The
Te concentrations in soil were higher than previous report inJapan (10–109 ng g-1), while Te contents in plant samples
were much lower than those (18–33 ng g-1) in Japanese plants[4]. Then, TF values from 8.7 × 10-4 to 1.1 × 10-1 (mean: 1.8
× 10-2) were obtained for the first time in Japan (Figure 1),
which were relatively low compared to those reported by
IAEA-TRS-472 (0.1–1) [2]. These data could be used toestimate the internal radiation dose from 127mTe after the
FDNPP accident.



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Figure 1. The variations of soil-to-crop transfer
factors of Te from different crop groups in Japan.
Bars show maximum and minimum values. Boxes
show the 75% and 25% values.

Acknowledgement: This work was partially supported by the
Agency for Natural Resources and Energy, the Ministry of
Economy, Trade and Industry (METI), Japan.
[1]
[2]
[3]
[4]

METI (Ministry of Economy, Trade and Industry), Data on the amountof released radioactive materials, http://www.meti.go.jp/press/2011/08/
20110826010/20110826010-2.pdf. 2011.
IAEA. Handbook of Parameter Values for the Prediction ofRadionuclide Transfer in Terrestrial and Freshwater Environments.
Technical Reports Series No. 472, IAEA, 2010.
G. Yang, J. Zheng, K. Tagami, S. Uchida, Direct determination of
tellurium in Japanese soil and plant samples by sector-field inductively
coupled plasma mass spectrometry (submitted).
T. Asami, Metal pollution in Japanese soils (in Japanese), Heiwa
Kogyo Co., Ltd., Tokyo, Japan, 2010, p. 447.

* Corresponding author. Tel: +81 43 206 3268; fax: +81 43 206 3267. E-mailaddress: k_tagami@nirs.go.jp (K. Tagami).

－ 202 －

24-FKP-08
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Retention of radiocesium incorporated in tree leaves contaminated by fallout of theradionuclides emitted from the Fukushima Daiichi Nuclear Power Plant
1

Kazuya Tanaka1, Hokuto Iwatani2, Aya Sakaguchi2, Yoshio Takahashi2, Yuichi Onda3

Institute for Sustainable Sciences and Development, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima,
Hiroshima 739-8530 Japan2
Department of Earth and Planetary Systems Science, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama,
Higashi-Hiroshima, Hiroshima 739-8526 Japan
3 Graduate School of Life and Environmental Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8572,
Japan
Abstract – We analyzed fresh and dead leaves collected in forests inFukushima after the Fukushima Daiichi Nuclear Power Plant(FDNPP) accident using autoradiography. We examined how
strongly radiocesium was incorporated in contaminated leaves of
Cryptomeria japonica, Quercus serrata and Pinus densiflora. Morethan half of radiocesium in the contaminated leaves remained in leaf
tissues after leaching treatment using pure water, surfactant andacetone.
Keywords – Fukushima, radioactivity, radiocesium, tree leaves,autoradiography

I.

INTRODUCTION

A large amount of radionuclides was emitted by the
Fukushima Daiichi Nuclear Power Plant (FDNPP) accident.
Tree canopies and underlying litters above the soil layers are
critical parts when forests are directly contaminated by falloutof radionuclides. Considering cycles of radiocesium inecosystems, it is very important to know the distribution ofradionuclides that were deposited directly on litters orintercepted by tree canopies [1-3]. In this study, weinvestigated the distribution of radioactivity in various
samples of fresh and dead leaves contaminated by the falloutof radionuclides after the FDNPP accident, and examined
how strongly radiocesium was incorporated in the leaves [4].
II. SAMPLES AND METHODS
We collected fresh and dead leaf samples (Cryptomeria
japonica, Quercus serrate and Pinus densiflora) from
Kawamata Town in Yamakiya District, in the northern part of
Fukushima Prefecture on December 15, 2011. Leachingexperiments were carried out to examine how strongly
radiocesium was incorporated in leaf tissues. Leachingexperiments consisted of three steps using leachates in theorder of pure water, 0.14% of fatty acid potassium salt
(surfactant) solution and 100% acetone. Leaf samples were
immersed in each leachate and sonicated in an ultrasonicwater bath at room temperature for 30 min. Leaf samples
before and after each treatment were analyzed using
autoradiography. All the samples were treated in the same
way to obtain comparable autoradiographs. Reduction ofradioactivity by each leaching treatment was evaluated using

the differences in signal intensity of autoradiographs before
and after leaching treatments.
III. RESULTS AND DISCUSSION
It was clearly observed in autoradiographs that both freshand dead leaves of C. japonica were contaminated byradionuclides (134Cs and 137Cs). Contamination of the fresh
leaves was possibly attributed to interception of radionuclides
by tree canopies, whereas the dead leaves indicated the direct
deposition of radionuclides by fallout and/or washout ofradionuclides intercepted by tree canopies. Fallen leaves of Q.
serrata, which started growing after the FDNPP accident, did
not show radioactivity. This means that significant amountsof translocation from other parts to new leaves did not occur.
Fallen leaves of Q. serrata collected from a litter showed hot
spots originating from direct fallout. Needles of P. densiflora
were also contaminated by fallout. Leaching with pure water
removed soluble fractions of radiocesium and radiocesiumbearing particles from the surface of the contaminated leaves,
but significant amounts of radioactivity remained. Thissuggests that foliar absorption occurred in both fresh anddead leaves. The surfactant was used to remove the wax
coating from leaf surfaces. This treatment showed that 10 to
20% of radiocesium was removed as a wax fraction of leaf
surface. However, the further treatment using acetone did noteffectively removed radiocesium. After the three stepleaching experiments using pure water, surfactant andacetone, more than half of radiocesium remained in thecontaminated leaves. In conclusion, our results indicate thatradiocesium in the contaminated leaves is strongly fixed inleaf tissues and is not readily released unless leaf tissues aredecomposed.
REFERENCES
[1]
[2]
[3]
[4]

－ 203 －

Desmet G, Myttenaere C (1988) J Environ Radioact 6:197-202
Bunzl K, Schimmack W, Kreutzer K, Schierl R (1989) Sci Total
Environ 78:77-87
Ronneau C, Sombre L, Myttenaere C, Andre P, Vanhouche M, Cara J(1991) J Environ Radioact 14:259-268

Tanaka K, Iwatani H, Sakaguchi A, Takahashi, Y, Onda Y (2013) J
Radioanal Nucl Chem 295:2007–2014

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-09$ECONTAMINATION OF 2ADIOACTIVE #ESIUM IN THE 3OIL
Makoto YANAGA, Ayumi OISHI
Department of Chemistry, Graduate School of Science, Shizuoka University!BSTRACT – $ECONTAMINATION OF RADIOACTIVE CESIUM FROM THE
AGRICULTURAL SOIL WAS ATTEMPTED BY EXTRACTION METHOD USINGPOTASSIUM SOLUTION 4HE RESULT OF EXPERIMENTS USING THE SOIL
ARTIFICIALLY CONTAMINATED WITH #S SHOWED THAT RADIOACTIVECESIUM WAS EXTRACTED BY POTASSIUM SOLUTION (OWEVER THE
EXTRACTION RATE DECREASED WHEN TIME AFTER CONTAMINATION PASSED

70

Pure water
1M KNO3
1M KI
2M KI

60
50

I.

2ADIOACTIVE CESIUM.UCLEAR抽出率(%)+EYWORDS – $ECONTAMINATIONPOWER PLANT ACCIDENT SOIL

40
30
20

INTRODUCTION

A huge amount of radioisotopes was released by the
Fukushima Daiichi Nuclear Power Plant accident in March
2011. The radioactive materials released in the atmosphere
contaminated not only air but also the earth surface.
Decontamination of the radioactive cesium from the soil is
one of the current serious problems. In the present work,
the decontamination of radioactive cesium from soil,
especially agricultural soil, was attempted using thecontaminated soil which was made artificially.
II. EXPERIMENTAL

10
0

0

2

4

6

4IME
AFTER CONTAMINATION  WEEK
汚染させてからの経過時間(週)Fig. 1 Time variation of removal rate of 137Cs from the gardening soil.

On the other hand, when time after soil was
contaminated by radioactive cesium passed, in the case ofany solution used in the present work, the removal rate
decreased. It is thought that cesium ion moved to the sitethat is strongly combined with cesium ion in minerals.

Many commercial plastic containers usually for storingand preserving food were prepared. About 400 grams ofcommercially obtained mixture of many kinds of soil, used
for gardening, was put into each plastic container. Then, 5
ml of 137Cs solution (1 kBq/ml) was dropped in eachcontainer. After selected time (from several hours todozens of weeks) was passed, one container was opened
and homogenized in another container.
The homogenized soil was separated to by 60 grams,
and each radioactivity was measured. Then, 200 ml of purewater, 1M KNO3, 1M KI, or 2M KI solution was poured
into the beaker which soil was in and the mixture wasstirred. After two days standstill, radioactivity of eachextract was measured.
III. RESULTS AND DISCUSSION
Relation between the removal rate and time after
contamination is shown in Fig. 1. As shown in Fig. 1, it
was hardly extracted in pure water. The extraction rate for
1M KI solution and the 1M KNO3 solution was about thesame, and the extraction rate for the 2M KI water solution
was higher than them. This indicates that radioactive
cesium in the soil was extracted by ion exchange withpotassium.

－ 204 －

24-FKP-10
APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013��������������������������������������������������������������
��������������������������������������������
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��������������������������������������������������������������������������
Abstract Ð Altitude distributions of radioactive cesium (134Cs and
137Cs) fallout at Mt. Fuji due to Fukushima No.1 nuclear power
plant accident have been investigated. Radioactive cesium from
Fukushima No.1 nuclear plant is found to reach at the height of
2700 m. It is inferred that some amounts of radioactive cesium are
attributable to the global fallout due to the nuclear weapons tests inthe atmosphere.
Keywords Ð radioactive cesium, altitude distribution, Mt. Fuji��������������

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－ 205 －

24-FKP-11
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Isotope Compositions of Strontium in Environmental Samples
in Fukushima Prefecture
Y. Shibahara1, S. Fukutani1, T. Fujii1, T. Kubota1, M. Yoshikawa2, T. Shibata2, T. Ohta3, K. Takamiya1,
N. Sato1, M. Tanigaki1, Y. Kobayashi1, R. Okumura1, H. Yoshinaga1, H. Yoshino1, A. Uehara1,
S. Mizuno4, T. Takahashi1, and H. Yamana1
1

Research Reactor Institute, Kyoto University
Institute for Geothermal Sciences, Kyoto University
3
Faculty of Engineering, Hokkaido University
4
Nuclear Power Safety Division, Fukushima Prefectural Government2

Abstract – Strontium was recovered from environmental samples inFukushima prefecture. The isotopic composition of 84Sr, 86Sr, 87Sr,
88Sr, and 90Sr was evaluated by mass spectrometry and �
spectrometry. The source of radioactive strontium released during
the Fukushima Daiichi nuclear power plant accident was discussed.
Keywords– strontium-90, strontium isotope ratio, mass spectrometry

On the accident of Fukushima Daiichi nuclear power plant,huge amount of fission product containing radioactive
strontium were widely released. The most importantradioactive strontium are 89Sr and 90Sr, whose half-lives are
50.5 days and 28.90 years, respectively. The cumulative
yields of thermal neutron induced fission of 235U are 4.73%(89Sr) and 5.77% (90Sr) [1]. As shown in Fig. 1, the isotopic
composition of Sr via fission of uranium and plutonium [1]are totally different from the natural abundance. The
information on the origin of radioactive strontium releasewould also be obtained from the analytical data.

)SOTOPIC ABUNDANCE &ISSION 0RODUCTS.ATURALLY OCCURING ISOTOPES















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-ASS NUMBER

Fig. 1 Isotopic abundances of Sr. The sum of cumulative fission yields of Sr
isotopes from 235U by thermal neutron irradiation [1] was set to 100% forcomparing them with the natural abundance. The natural abundance of 84Sr is
0.56%. The fission yields of 84Sr and 86Sr are less than 10-4%.

precision isotopic analysis in parallel. The isotopic
composition of 84Sr, 86Sr, 87Sr, 88Sr, and 90Sr was evaluatedEnvironmental samples (soils, plants, and so on) were
immersed in concentrated HNO3 and heated at 413 K. Afterevaporation of HNO3, diluted HNO3 was added and this wasused as the source material. Strontium was recovered fromthe samples by extraction chromatography with UTEVAresin and Sr-resin following ion-exchange chromatography
with ion-exchange resin. Concentration of recovered
strontium was analyzed with a quadrupole inductively
coupled plasma mass spectrometer, and that of 90Sr was
analyzed by �� ��������etry. Correlation between 90Sr and137
Cs was also checked. These samples were supplied for
TIMS.
Isotopic ratios of Sr were measured with a TIMS (TritonT1, Thermo Fisher Scientific). About 100 ng of strontium
was loaded on a rhenium single filament with TaO activator.
The isotopic reference material SRM987 was used as thestandard. Our analytical result of SRM987 agreed with the���������� ������ ������� �� analytical error. As a possible
source of 89Sr and 90Sr, on the other hand, 10 mg of UO2 ofnatural uranium was irradiated at the Kyoto University
Research Reactor. Similar to the environmental samples,strontium was recovered from UO2 irradiated and analyzed.
Since the amounts of 89Sr and 90Sr were much smaller thanthose of stable Sr isotopes, their mass spectra were obtainedwith a secondary electron multiplier detector. The isotopic
data obtained are discussed by conjunction with the results of� spectrometry.
[1] K. Shibata et al., J. Nucl. Sci. Technol.. 48, 1 (2011).

The purpose of the present study is to enhance the analysis
of Sr isotopes in environmental samples in Fukushima
prefecture for safety assessment about 90Sr dose. Generally,
concentration of 90Sr is determined by � spectrometry. Since
this method gives no data of stable isotopes, the thermal
ionization mass spectrometry (TIMS) was applied for high－ 206 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-12

Distribution of radioactive caesium in the North Pacific one year and a half after
the Fukushima Dai-ichi Nuclear Power Plant accident
K. Tsujita1, A. Hasegawa1, N. Harada2, T. Yamagata2, H. Nagai2, M. Aoyama3
1

Graduate School of integrated Basic Sciences, Nihon University
2
College of Humanities and Sciences, Nihon University
3
Geochemical Research Department, Meteorological Research Institute
Abstract – In stations off Fukushima, 137Cs concentration insurface seawater were 3.9±0.2 and 2.7±0.2 mBq/kg. Between
stations off Fukushima and open ocean station (K2; 47°N, 160°E),
average 137Cs concentration was 2.9±0.2 mBq/kg. From 160°E to
170°W along 47°N in the North Pacific, average 137Csconcentration was 4.9±0.2 mBq/kg. It was higher than that off
Fukushima, and 134Cs was also detected. Thus, the effects of the
Fukushima Dai-ichi Nuclear Power Plant accident were observed.
But it was not observed in Bering Sea and east of 170°W.
Keywords – Fukushima Dai-ichi Nuclear Power Plant; 137Cs;
Cs; North Pacific

134

I.

INTRODUCTION

On 11 March 2011, the accident occurred at the
Fukushima Dai-ichi Nuclear Power Plant (F1NPP) due tothe Tohoku earthquake and tsunami. A large amount of134
Cs (T1/2=2.06 y) and 137Cs (T1/2=30.07 y) were released
to the environment. The estimated total amounts of 137Cs
released from the F1NPP reactors to the atmosphere andocean were 15 [1] and 3.5±0.7 PBq [2], respectively. In thisstudy, we measured the distributions of 134Cs and 137Cs inseawater off Fukushima and in the North Pacific toinvestigate the spread of the radionuclides about a year anda half after the accident.

km south (BD-01) and 250 km east (BD-04) of F1NPP
were 1.4±0.1 and 1.3±0.1 mBq/kg, respectively. It wasalmost same as those before the accident (1.5 mBq/kg) [5].
Between off Fukushima and open ocean (47°N, 160°E,
BD-05~07), average 137Cs concentration in surface water
was 2.9±0.2 mBq/kg, still high compared to that before theaccident (1.8 mBq/kg) [6]. From 160°E to 170°W along
47°N (BD-08~14), average 137Cs concentration was 4.9±0.2
mBq/kg. It is higher than those off Fukushima. For all
stations of high 137Cs concentration, 134Cs were also
detected. In those regions the effects of the F1NPP accident
were observed. In Bering Sea and east of 170°W (BD15~17), 137Cs concentration in surface water were equal toor lower than those before the accident and 134Cs were notdetected. In those regions the effects of the F1NPP accident
were not observed.

�������
Dutch
Harbor
BD-10

BD-12

SB-1

BD-08
BD-07
BD-06

BD-15

BD-09
S1 BD-11 BD-13

Vancouver������
BD-16

BD-14

BD-05

mBq/kg
BD-17

BD-02 BD-03
BD-04
�� BD-01
Tokyo

II. EXPERIMENTAL
Seawater samples (20 L) were collected with anunderway pump and a large-volume water sampler during
the KH-12-4 cruise (23 Aug. to 3 Oct. 2012). The sample
was acidified to pH1.8 by adding concentrated nitric acid,stirred for 1 hour after adding 200 mg of stable cesium,then stirred again for 1 hour after adding 4 g of ammonium
phosphomolybdate (AMP). The sample was settled for 12hours and filtrated to collect AMP-Cs compound onto amembrane filter (0.45 �m). The AMP-Cs compound was
dried for 12 hours at 100 °C, transferred to a counting tube,
then measured 134Cs (E�=604 keV, 795 keV) and 137Cs(E�=661 keV) gamma rays using a well-type HPGe
detector.

Fig.1 The surface 137Cs concentration in the North Pacific and the KH-124 cruise track

REFERENCES
[1]

[2]
[3]
[4]
[5]
[6]

III. RESULTS AND DISCUSSION
In regions off Fukushima, 137Cs concentration in surface
water from BD-02 and 03 located 30 km east of F1NPP
were 3.9±0.2 and 2.7±0.2 mBq/kg, respectively. The 137Csconcentrations reduced by two orders of magnitude fromthose observed in MR-11-03 cruise (Apr. 2011) [3] and
KOK cruise (Jun. 2011) [4]. For distant stations about 190－ 207 －NERH (Nuclear Emergency Response Headquarters, Government ofJapan) (2011) Report of Japanese Government to the IAEA
Ministerial Conference on Nuclear Safety—The Accident at
TEPCO’s Fukushima Nuclear Power Stations.
D. Tsumune et al., J. of Environ. Radioact., 111 (2012) 100e108.
M. C. Honda et al., Geochemical J., 46 (2012) e1- e9.
N. Harada, Bachelor thesis (2011).
K. Buesseler et al., Environ. Sci. Technol., 45(2011) 9931-9935.
K. Hirose et al., Deep-Sea Res. II, 50 (2003) 2675-2700.

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

Image analysis for the study of radiocesium distribution in coniferous trees:
two years after the Fukushima Daiichi Nuclear Power Plant accident
Haruka Minowa
Radioisotope Research Facility, The Tokyo Jikei University School of Medicine
Abstract – The accident at the Fukushima Daiichi Nuclear Power
Plant in March 2011 resulted in the deposition of radioactive fallout
over wide area in eastern Japan. Environmental samples were
examined with an imaging plate to investigate the characteristics
and the behavior of fallout deposits. In the autoradiographs, socalled “hot particles” were evident in many samples. There were no
particulate contamination on new leaves which grown after theaccident. The state and adsorption amount of fallout was different
depending on the locality and the timing of sampling. The results ofthis study confirm that deposition on the leaves and the barks would
remain several years and radiocesium concentration would bedecrease with the growing of new leaves.
Keywords – radiocesium, autoradiography, coniferous treeI.

INTRODUCTION

III. RESULTS AND DISCCUSION
Autoradiographs are shown in Figure 1 and 2. Samples
were collected from Naraha-machi at Nov. 2012. It wasobserved that the fallout seemed to be granular, so-called “hotparticles”. These radioactive particles had not moved fromthe initial site of adhesion on the leaf despite repeatedexposure to rain. Particulate contaminations were distributed
only the bottom leaves spread before the accident and did notseen in the top leaves grown after the accident. This confirmsthat particulate deposition on the leaves and the barks would
remained several years and radiocesium concentration would
be decrease with the growing of new leaves.

Radioactive fallout from the March 2011 disaster at the
Fukushima Daiichi Nuclear Power Plant (NPP) spread acrossmuch of eastern Japan. Deposition of fallout on land wasaffected by rain, wind, and geographical features [1]. The
purpose of this research is to investigate the characteristics
and behavior of the fallout. Because it was early spring ineastern Japan at the time of the accident, many trees werebare of leaves except for evergreen trees include coniferous
trees. Radioactivity on the perennial leaves of coniferous
trees would be an appropriate indicator for the monitoring of
the radionuclides in the environmental system.
Fig. 1. Leaves of Juniperus chinensis from Naraha-machi at Nov. 2012.
Particulate contaminations were seem only on the bottom leaves and notseem on the top leaves.

II. SAMPLES AND METHODS
Samples were collected at Naraha-machi, Hirono-machi
and Iwaki city in Fukushima prefecture, which are locatedapproximately 20 to 50km in south or southwest side from
Fukushima Dai-ichi NPP. It was considered that the dried
deposition were more principal than the wet deposition inthese area [2]. As a typical coniferous tree, Pine trees (Pinus
thunbergii,
Pinus
densiflora),
Japanesecypress(Chamaecyparis obtusa), Japanese cedar (Cryptomeria
japonica), and Chinese juniper (Juniperus chinensis) wereselected.
Samples were flattened and covered with a wrapping filmand exposed to an imaging plate BASIII 2040 (Fujifilm Co.,Tokyo, Japan) for time periods ranging from overnight to one
week. Autoradiographs were scanned using an image
analyzer Typhoon FLA7000 (GE Healthcare Japan Co.,Tokyo, Japan).

Fig. 2. Tree barks of Chamaecypars obtusa from Naraha-machi at Nov 2012.
Heterogeneously contaminations were visible throughout on the bark.
[1][2]－ 208 －

Kinoshita et al. (2011) PNAS 108, 19526-19529
Katata et al. (2012) J. Environ. Radioact. 109, 103-113

APSORC’13 – 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-14$ISTRIBUTION OF )ODINE  IN OFF &UKUSHIMA AND THE .ORTH 0ACIFIC ONE YEAR AND A
HALF AFTER THE &UKUSHIMA $AI ICHI .UCLEAR 0OWER 0LANT ACCIDENT
A. Hasegawa1, T. Yamagata2, H. Nagai2, M. Aoyama3, H. Matsuzaki4
1

Graduate School of integrated Basic Sciences, Nihon University
2
College of Humanities and Sciences, Nihon University
3
Geochemical Research Department, Meteorological Research Institute4
School of Engineering, the University of Tokyo!BSTRACT – (IGH ) CONCENTRATIONS WERE OBSERVED IN SAMPLESFROM STATIONS OFF &UKUSHIMA "$  LOCATED  KM AWAY FROM
&UKUSHIMA $AI ICHI .UCLEAR 0OWER 0LANT &.00  )N THESE
STATIONS ) INVENTORY DOWN TO  M WATER DEPTH WAS NOTDECREASE SINCE THREE MONTH AFTER THE &.00 ACCIDENT )N ADJACENTSTATIONS OFF &UKUSHIMA "$  ) CONCENTRATIONS WEREALMOST IDENTICAL TO THOSE OBSERVED IN SEAWATER COLLECTED IN THE+UROSHIO REGION BEFORE THE &.00 ACCIDENT )N THE .ORTH 0ACIFIC
"$^ ) CONCENTRATIONS IN SURFACE SEAWATER WERE  TIMESHIGHER THAN THOSE IN THE +UROSHIO REGION+EYWORDS – )ODINE  SEAWATER &UKUSHIMA $AIITI .UCLEAR
0OWER 0LANT .ORTH 0ACIFICI.

INTRODUCTION

The Fukushima Dai-ichi Nuclear Power Plant (F1NPP)
was damaged by the great earthquake of magnitude 9.0 andthe associated tsunami on 11 March 2011. As a result,Many radionuclides such as, 134Cs (2.06 yr), 137Cs (30.2 yr),131
I (8.01 d), 129I (1.57 x 107 yr) were discharged from
F1NPP into the ocean. These nuclides were transported by
the Oyashio current and the Kuroshio current, andsupposed to spread along the Kuroshio extension. Many
data for 137Cs discharged into ocean from F1NPP inseawater has already reported[1][2] but few data for 129I
have reported[3][4].
A large amount of 129I discharged from nuclear
activities such as, weapons testing until the 1970’s, nuclear
power plant accidents, nuclear fuel reprocessing plants, into
the environment. As a result, most of 129I present in theenvironment is anthropogenic, and 129I concentrations inseawater are higher than pre-nuclear activities. Due to the
F1NPP accident, 129I concentration in seawater may
enhanced. In this study, we measure of 129I concentration inseawater, to investigate the influence of the F1NPP
accident in the North Pacific.

back-extracted into aqueous layer. Finally, silver nitride
solution was added to make silver iodide precipitation. The
129 127
I/ I ratios of samples were measured by Accelerator
Mass Spectrometry (AMS) at MALT, the University ofTokyo. All measured ratios were normalized to thestandard reference material having 129I/127I=63.6 x 10-12(SPuredue2).
III. RESULTS AND DISCUSSION
129

I concentrations in surface seawater in the Western
North Pacific (BD05~09) and Eastern North Pacific(BD11~17) were almost constant (12.7~17.1 x 106
atoms/kg). On the other hand, 129I concentrations in stations
off Fukushima were higher than those in the North Pacific.
Maximum 129I concentration 71.4 x 106 atoms/kg wasobserved at BD03 (about 30 km away from F1NPP). 129I
inventory down to 100 m water depth at BD03 was 35.3 x1011 atoms/m2, which is comparable to those observed threemonth after the F1NPP accident (KOK cruise). Therefore,
the effects of the F1NPP accident still remain in this region.
In other stations off Fukushima (BD01 and BD04), 129I
concentrations were almost identical to those observed inseawater collected in the Kuroshio region before the
F1NPP accident (KT-09-13). In the North Pacific(BD05~17), 129I concentrations were 2 times higher thanthose in the Kurosio region. It considered with high 129I
concentration seawater inflow from the Bering Sea.

6ANCOUVER
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II. EXPERIMENTAL PROCEDURE

"$
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Seawater samples (1L) were collected with an underway
pump and a large-volume water sampler during the cruiseof the R/V Hakuho-maru in 23 Aug. to 3 October 2012
(KH-12-4). The cruise track and positions of the station are
shown in Fig. 1. First, seawater samples were filteredthrough a membrane filter (0.45 Pm), them iodine carrier (I: 1 mg) were added to filtered seawater samples. Secondly,
separation of iodine from seawater samples has carried out
solvent extraction and back-extraction. The moleculariodine extracted into carbon tetrachloride (CCl4), then&IG  The KH-12-4 cruise track and sampling stations[1] http://www.mri-jma.go.jp/Topics/hotyouhi/houtyouhi_sea.html[2] P. P. Povinec et al., Biogeosciences Discuss, 10, 6377-6416, 2013[3] T. Suzuki et al., Biogeosciences Discuss, 10, 1401-1419, 2013
[4] X. Hou et al., Environ. Sci. Technol. 47, 3091-3098, 2013

－ 209 －

24-FKP-15
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Agricultural Implications for Fukushima Nuclear Accident
Tomoko M. Nakanishi
Graduate School of Agricultural and Life Sciences, The University of Tokyo
Abstract – The overview of our research projects for
Fukushima is presented including how they were
derived. Then, where the fallout was found, right after
the accident, is briefly summarized for soil, plants, trees,
etc. The time of the accident was late winter, there werehardly any plants growing except for the wheat in thefarming field. Most of the fallout was found at thesurface of soil, tree barks, etc., which were exposed tothe air at the time of the accident. The fallout found was
firmly adsorbed to anything and did not move formonths from the site when they first touched. Therefore,
the newly emerged tissue after the accident showed very
low radioactivity. The fallout contamination was not
uniform, therefore, when radiograph of contaminatedsoil or leaves were taken, fallout was shown as spots.
Generally, plants could not absorb radiocesium
adsorbed to soil. Some of the results we obtained will
be presented.

animals, fish, etc. Our activities were classified into
several groups as follows but most of them weredeveloped based on voluntary activities.
Research projects
Influence of fallout (distribution & movement)
1. crop plants and soils
2. stock raising & dairy products
3. fishery
4. environment, including wild life
5. radiation measurement & radiochemistry
6. science communication
Research sites

Keywords – Fukushima nuclear accident, research inagiriculture, research project, research site, fallout, theway of contamination
Introduction
After the accident of Fukushima Daiichi nuclear
power plant, thousands of measuring data have been
piling up, especially in the web sites of government
agencies. However, most of them are two kinds of thedata. One is the radio activities of the places, including
soil, air dust or sea water and the other is themeasurement of the foods. These are just the monitoringdata and it is difficult to find out the research data
related to agriculture, such as, how much amount ofradioactivity was found or estimated when the plants
were grown in the contaminated field or how much
radioactivity was accumulated in mountains and what
about the contamination of river water coming from themountain, etc.
Research groups
Right after the accident, about 40 academic staffs in
our Graduate School had started the research project for
Fukushima in plants, soil, animals, fish, etc. Our
activities were classified into several groups as follows
but most of them were developed based on voluntary
activities. research project for Fukushima for plants, soil,

Results & discussion
The Cs movement in soil showed that Cs is so firmly
adsorbed on soil and there was no further washout of Cs
by rain, therefore, Therefore, it was suggested that thisthin contaminated surface soil can thus be collected andburied on site, leaving the land safe to work again, as
the radionuclides are unlikely to be leached from thesoil. The downward movement of the radiocesium insoil was further monitored. The study of fruit tree
showed that Cs was transferred from bark surface tofruits and there was not any radiocesium taken up fromroots. Animals are now investigated how radiocesium is
distributed among the tissues. We have now expanded
our investigations into a long-term study that will also
cover trees and fisheries.
Reference
Agricultural Implications for Fukushima Nuclear
Accidents. Nakanishi, T.M. and Tanoi, K. ed. Springer(2013)－ 210 －

24-FKP-16
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Concentration of Radiocesium in Rice, Vegetables, and Fruits Cultivated in
Evacuation Area at Okuma Town, Fukushima
Kenji Ohse1, Kyo Kitayama1, Seiich Suenaga2, Kiyoyuki Matsumoto2, Akira Kanno1, Chika Suzuki1,
Kencho Kawatsu1, Hirofumi Tsukada1
1

Fukushima Future Center for Regional Revitalization, Fukushima University
2
Okuma Government Office

Abstract – Rice, vegetables, and fruits were cultivated in theevacuation area at Okuma town, and the radiocesium concentrationof the crop samples cultivated in contaminated and decontaminatedsoil was compared. Decrease of the concentration in every crop bydecontamination was observed. The TF of brown rice was higher
than previous reports.
Keywords – evacuation area, test cultivation, radiocesium

I.

INTRODUCTION

Okuma Town which Fukushima Daiichi nuclear power
plant locates, the whole region contaminated severely byradioactive nuclides including 134Cs and 137Cs and was
designated the evacuation area. The prospect for reactivate of
agriculture was not found in the regions. However, in order toobtain the scientific data for recultivation in the future, test
cultivations of several crops in the contaminated anddecontaminated soils and collected fruits grown in the town
were carried out. In this study, the concentration and translate
factor of radiocesium in rice, vegetables, and fruits cultivatedin the contaminated and decontaminated sites are reported.

the weighted average of the concentration for the depth of 15
cm was 31.6, 7.46, 15.4, 13.7, and 14.8 kBq kg-1,. The
concentration of radiocesium in the decontaminated uplandsoil decreased 1/4 by removing the soil of 0-15 cm depth.
However, the radiocesium concentration in decontaminatedpaddy soil was slightly decrease compared to the contaminated paddy soil because the paddy field was disturbed byanimals and radiocesium mixed in deeper before cultivation.
The radiocesium concentration in crops and their transfer
factor (TF) were shown in Table 1. The concentration ofradiocesium in every crop cultivated in the decontaminatedfield was lower than that cultivated in the contaminated field.
The concentration of radiocesium in eggplant and pumpkin of
edible part cultivated in the decontaminated field was lower
than standard limit (100 Bq kg-1). However, the TF values of
the crops cultivated in the contaminated fields were within afactor of 3 to those cultivated in the decontaminated fields.
More techniques are required to decrease the radiocesium
concentration in crops.
Table 1 Concentration and translate factor of radiocesium in crops.
Crop

contaminated field

Sampling
date

Cs-134

Cs-137decontaminated field
TF(Bq kg-1 fresh weight)

II. MATERIALS AND METHODS

Cs-134

Cs-137

TF(Bq kg-1 fresh weight)

rice plant

Test cultivation site, which had paddy and upland field,
was located about 6 km far from Fukushima Daiichi Nuclear
Power Plant. Each paddy and upland field was divided into
two parts, which was contaminated and decontaminated byremoving surface soil. Several crops including rice plant,
eggplant, green soybean, sweet potato, pumpkin, and cabbage
were cultivated in both sites. After harvest, the crops were
washed and separated in several parts. They were dried andpulverized to powder. An ancient black rice plant was also
harvested from other paddy field. Soil samples werecorrected for the depth of 30 cm, cut into sections 0-2, 2-5, 510, 10-15, 15-20, 20-25, 25-30 in depth, oven dried andsieved 2 mm mesh. 134Cs and 137Cs in the samples were
determined by germanium semiconductor detector.
III. RESULTS AND DISSCUSSION
The abundance of radiocesium in the soils at contaminatedupland, decontaminated upland, contaminated paddy,
decontaminated paddy and ancient black rice paddy field was
3680, 877, 1820, 1640, and 1070 kBq m-2, respectively and－ 211 －

brown rice 3-Oct-12
rice hull 3-Oct-12
reaf and straw 8-Aug-12
reaf and straw 3-Oct-12
ancient black ricebrown rice 3-Oct-12
rice hull 3-Oct-12
reaf and straw 22-Aug-12
reaf and straw 3-Oct-12

117
264
89.0
185

195
438
132
300

0.02030.04560.01440.0315

82.7
197
39.2
113

139
322
57.5
187

0.01620.03790.0071
0.0219

258
474
178
285

424
762
271
464

0.04610.08350.03030.0506

58.5
32.4
69.1
161

90.0
52.9
116
262

0.00470.00270.00590.0134

7.01
7.39
12.2
46.4

11.0
11.5
20.4
77.1

0.00240.00250.00440.0166

161
240
302
627

257
395
492
992

0.01320.02010.0251
0.0512

69.4
97.0
91.8
136

116
158
153
226

0.02490.03420.03290.0486

151
223
171
215

261
356
284
361

0.01300.01830.01440.0182

84.4
68.6
101
137

139
115
163
226

0.03000.02460.03540.0487

113
145
191
143

184
234
319
234

0.00940.01200.01610.0119

13.4
16.0
14.6
41.7

21.7
24.5
22.6
62.8

0.00470.00540.00500.0140

250
375

402
634

0.0206
0.0319

148
321

241
520

0.05220.1129eggplant
edible part 8-Aug-12
edible part 3-Oct-12
stalk 3-Oct-12
reaf 3-Oct-12
green soybean
bean 3-Oct-12
pod 3-Oct-12
stalk 3-Oct-12
reaf 3-Oct-12
sweet potato
edible part 3-Oct-12
coat 3-Oct-12
vine 3-Oct-12
reaf 3-Oct-12
pumpkinedible part 3-Oct-12
coat 3-Oct-12
gut 3-Oct-12
vine and reaf 3-Oct-12
cabbagehead 3-Oct-12
un-head reaf 3-Oct-12

24-FKP-17
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Isotopic U, Pu, Am and Cm signatures in environmental samples fromthe Fukusima Dai-ichi Nuclear Power Plant accident
Masayoshi Yamamoto1, Aya Sakaguchi2, Shinya Ochiai1,Takahiro Takada1, Seiya Nagao1, Peter Steier3
1

Low Level Radioactivity Laboratory, KINET, Kanazawa University, Nomi, Ishikawa 923-1224, Japan
2
Graduate School of Science, Hiroshima University, Higashi-Hiroshima, 739-8526, Japan
3
VERA-Laboratory, Faculty of Physics, University of Vienna, Währinger Str. 17, A-1090 Vienna, Austria
Abstract – Alpha-ray spectrometry and AMS measurementsof U, Pu Am and Cm isotopes isolated from black materialsof roadsides collected at areas within the 20-km exclusion
zones (Minami-Souma, Namie, Futaba and Okuma Towns)
and Iitate Village are reported. For most of the samples, lowlevels of 236U, 238Pu, 239,240Pu, 241Am, 242Cm and 243,244Cm
were successfully determined. The results provide a coherent
isotopic data set, indicating that traces of U and transuranic
nuclides were released into the environment without theirlarge fractionations, probably with forms of fine particles.
These data are also very important in order to check thevalidity of estimation of fuel compositions in the FDNPP.
Keywords – FDNPP accident, 236U, transuranic elements, blackmaterials of roadside, alpha-ray spectrometry, AMS

contaminated with extremely high levels of radionuclides
released. They seemed to be suitable for getting information
on isotopic composition of trace amount of U and transuranicelements. The samples were mainly collected from areas
within the 20-km exclusion zones (Minami-Souma, Namie,
Futaba and Okuma Towns) in Sep.- Nov., 2012. Also were
samples taken from Iitate Village heavily contaminated. The
collected samples were air-dried, and sieved through a 2-mm
mesh to remove pebbles and big plant remains, andpulverized in an agate mortar to obtain homogeneous samples.
After chemical separation of each element, Pu (238Pu and239,240Pu), 241Am and Cm (242Cm and 243,244Cm) were
determined by alpha-ray spectrometry, respectively.
Uranium-236 was determined by AMS installed at VERALaboratory, University of Vienna (Vienna, Austria).

I. INTRODUCTION

III. RESULTS AND DISCUSSION

In the Fukushima Dai-ichi Nuclear Power Plant (FDNPP)
accident which occurred in connection with the M9 Great
East Japan Earthquake and subsequent tsunami on 11 March
2011, large amounts of radionuclides, especially volatile ones
such as 131I, 134Cs and 137Cs, have been accidently released
into the environment from the FDNPP. By broadly survey ofthese nuclides and researches, whole picture about levels andspreading areas of contaminants has been becoming clear,
together with the situation of plant accident. However,information on releases of U and transuranic nuclides as
refractory elements in fuel core was extremely limited due tothe difficulties of analyzing these nuclides. In this paper, weintended to clarify a full picture about these elements released
into the environment. For this purpose, 236U, Pu isotopes(238Pu, 239Pu and 240Pu), 241Am and Cm isotopes (242Cm and
243,244Cm) were measured for roadside dust collected at the
Fukushima areas heavily contaminated. Their released levels
and isotopic compositions will be discussed, compared withthe fuel compositions in FDNPP estimated by Nishihara et al.
(2012).

The collected black materials samples were found to becontaminated with extremely high levels of 134Cs and 137Cs
over 1000 kBq/kg by the FDNPP accident. More than 100
samples from areas within the 20 km-exclusion zones were
determined for 238Pu, 239,240Pu, 241Am. 242Cm and 243,244Cm by��ray spectrometry. Furthermore, in some samples, 236U was
successfully determined by AMS.
The results provided a coherent isotopic data set as
follows: 1) traces of 239,240Pu (range: 0.0n-1.8 Bq/kg) andhigh levels of 238Pu/239,240Pu activity ratios (range; ca.1-2.7,
but mostly around 2.1-2.4) were detected; for samples
showing 238Pu/239,240Pu ratios of more than 2 ( most (or all) of
Pu detected is due to the accident); 2) 241Am/239,240Pu activity
ratios were in the range from 0.32-0.75 with the mean valueof 0.53 ± 0.12 (n=35); 3) 242Cm/243,244Cm activity ratios(decay-corrected to 11 March, 2011) were 25.1±8.9 (n=61)
on average; 4) 242Cm/239,240Pu activity ratios (decay-corrected
to 11 March, 2011) were 33.6±10.6 (n=52) on average; and5) 236U/239,240Pu activity ratios were in the range of (1.9618.4) x10-4 with the weighted mean value of 7.87x10-4 (n=12).
When these activity ratios are compared with those of fuelcompositions in the FDNPP estimated by Nishihara et al(2012) of the JAEA group, fairly good agreement was found,indicating that traces of U and transuranic nuclides, probably
with forms of fine particles, were released into theenvironment without their large fractionations.

II. MATERIAL AND METHODS
The road dusts, called "Black Materials", whose color isapparently black, are browned in a corner and/or dip ofresidential streets and roadside by wind and rain. Thesematerials are composed with fine aerosol particles, fine carcut asphalt materials, residue of lichens, soil and so on, andK. Nishihawa et al. (2012), JAEA-Data/Code, 2012-018.

－ 212 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-18

Influence of the Fukushima Daiichi nuclear disaster on the tritium concentrationin the precipitation of Kanazawa city
Yoshimune Yamada1, Kaeko Yasuike1, Toshiyuki Kawabata2, Akihiro Fujii2, Hitoshi Kakimoto2
1

2

Faculty of Pharmaceutical Sciences, Hokuriku University, Kanagawa-machi, Kanazawa, 920-1181, Japan
Ishikawa Prefectural Institute of Public Health and Environmental Science, Taiyogaoka, Kanazawa, 920-1154, Japan

Abstract – The variation in tritium concentration in the
precipitation of Kanazawa city was measured the day after the
Fukushima Daiichi nuclear disaster, which occurred on 11 March,
2011. The most interesting result in the period from March toAugust 2011 is that a secondary peak of 4.6 Bq/L was observed on
22 March after the maximum peak of 15.0 Bq/L on 16 March. This
fact suggests that a sudden release of a large amount of tritiumfrom the Fukushima Daiichi nuclear power plant occurred
between 21 March and 22 March, followed by the release from 11
March to 15 March. Another interesting result is that dramaticincreases in the tritium concentration of 131.6 Bq/L and 99.9
Bq/L were observed on 30 May and 13 June in the variation
patterns of the tritium concentration in the precipitation of
Kanazawa city. These increases may have been caused by windblowing down from the upper atmosphere during a storm. A large
amount of tritium which had been released by hydrogen
explosions from the Fukushima Daiichi nuclear reactors wasconsidered to exist in the bulk air in the upper atmosphere.

rainfall in a stainless tray of 560 mm x 405 mm, and thendistilled after the addition of KMnO4 and Na2O2 to remove
any acidic contaminants. The counting source for a liquid
scintillation spectrometer was prepared by mixing 40 mL of
distilled water with 60 mL of cooled sol-gel emulsifier-type
scintillating cocktail, ULTIMA GOLD LLT �PerkinElmer
Inc.� in a 100 mL Teflon vial. It was allowed to standunder cool, dark conditions for three days before counting
to suppress chemical luminescence. The tritium activity
was measured under temperature-stabilized conditions at
12°C using a low background liquid scintillation counter,
Aloka LB-5. The counting was carried out for at least fourcycles of 1,150 min (50 min x 23) run. The backgroundcount rate was 2.22-2.48 cpm at an efficiency of 30.030.8 %, which was determined by the external standard
channels ratio method.

Keywords – Tritium, Fukushima Daiichi nuclear disaster,precipitation of Kanazawa city

III. RESULTS AND DISCUSSIONI.

INTRODUCTION

Tritium distribution in nature is mainly the result ofcontinuous production by cosmic rays in the upper
atmosphere and prolonged exposure from thermonuclear
bomb tests carried out during the 1950’s and early 1960’s.
The tritium concentration of the precipitation in
Ishikawa Prefecture, Japan, showed the highest annually
averaged value of 74.1 Bq/L1 in 1963, which corresponded
to the year of the maximum fallout of tritium in thenorthern hemisphere. After the maximum, it decreased year
by year for the past four or five decades, and returned tolevels lower than 1 Bq/L in 2007.
Tritium is generated by various nuclear reactions andpresents as tritiated water (HTO), tritiated hydrogen gas(HT) and other chemical forms in nuclear reactors. A large
amount of tritium was released from the Fukushima Daiichi
nuclear power plant caused by the damage of the nuclear
reactors in consequence of the Great East Japan Earthquakeon 11 March 2011. In this paper, the variations in tritium
concentration in the precipitation of Kanazawa city arereported for the period from March to August 2011. Thiswas done to determine the influence of the tritium released
into the environment by the Fukushima Daiichi nuclear
disaster on the tritium concentration in the precipitation of
Kanazawa city.
II. MATERIAL AND METHODS
The precipitation of Kanazawa city (36.52oN, 136.71oE)
Ishikawa Prefecture, Japan, was collected during every

The first rainfall in Kanazawa city after the occurrenceof the Fukushima Daiichi nuclear disaster was observed on
15 March 2011 (from 15:50) and it changed to intermittent
snow the next day. The tritium concentration in the
precipitation of Kanazawa city (36.52oN, 136.71oE)
Ishikawa Prefecture, Japan was at levels of 0.35-0.54 Bq/L
during the period from February to early March in 2011. It
began to increase following the snow of 4:10-9:00 on 16
March, and through to a maximum peak of 15.0 Bq/L after
the snow of 9:00-19:00 on 16 March. It decreased to thenormal level of 0.5 Bq/L in the rainfall of 9:00-13:30 on 21
March, and thereafter increased again rapidly to 4.6 Bq/L
in the sleet from 19:10 on 22 March to 9:00 on 23 March.
These facts suggests that a sudden release of a large amountof tritium from the Fukushima Daiichi nuclear power plant
occurred between 21 March and 22 March, followed by theaccidental or uncontrolled release of tritium from 11 March
to 15 March.
A dramatic increase in tritium concentrations of 131.6
Bq/L and 99.9 Bq/L was observed in the rainfalls of 9:3013:40 on 30 May and those from 21:30 on 13 June to 9:00
on 14 June in the variation patterns of tritium concentrationin the precipitation of Kanazawa city, although no marked
change was observed in the period from April up to the endof May. This may have been caused by the wind violently
blowing down from the upper atmosphere during a storm.
A large amount of tritium which had been released byhydrogen explosions from the Fukushima Daiichi nuclear
reactors is considered to exist in the bulk air in the upper
atmosphere.
[1]－ 213 －

Y. Yamada, K. Yasuike, K. Komura, J. Nucl. Radiochem. Sci., 6,
17-20 (2005)

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-19

Sediment transport processes in reservoir-catchment system inferred fromsediment trap observation and fallout radionuclides
1

Shinya Ochiai1, Seiya Nagao1, Masayoshi Yamamoto1, Taeko Itono2, Kenji Kashiwaya3
Low Level Radioactivity Laboratory, Institute of Nature and Environmental Technology, Kanazawa University, Japan
2
Graduate School of Natural Science & Technology, Kanazawa University, Japan
3
Institute of Nature and Environmental Technology, Kanazawa University, Japan

Abstract – Sediment trap observation of 210Pb, 137Cs, and 134Cs in
an artificial reservoir located in central Japan indicates that thedischarge rate of these radionuclides from the catchment islargely influenced by the precipitation, with high precipitation in
typhoon and snow season. The annual discharge rate of 134Cs
from the catchment is larger than that of 137Cs, suggesting that
FDNPP-derived 134Cs is concentrated at the erodible surface soil
and it is a major sediment source for the annual timescale. The
137
Cs/210Pbex activity ratio was high during rainy season andtyphoon season, corresponding to the change in 10 mm/h excess
rainfall. The soil erosion during the heavy rainfall may extend tothe high 137Cs accumulated part in the catchment where is not
erodible in the normal condition. This result suggests that heavy
rainfall affects the source of eroded sediment and the erosion
process in the catchment.
Keywords – sediment transport, sediment trap,
Fukushima Dai-ichi NPP

I.

210

Pb,

134,137

Cs,

INTRODUCTION

The sediment transport processes in the catchment areimportant to understand the landform development andmaterial transport to downstream rivers, lakes and ocean.
The fallout radionuclides 137Cs and 210Pb have been widelyused to investigate soil erosion and sediment transport
processes. 210Pb is continuously supplied on the soil
through atmospheric deposition, while the supply of 137Cs
is negligible at the present and its distribution has beenchanged by downward migration and erosion during thepast several decades. Additionally, 134Cs was newly
accumulated on the surface soil by the Fukushima Dai-ichi
Nuclear Power Plant (FDNPP) accident in 2011. The
difference in horizontal and vertical distribution of theseradionuclides in the catchment may provide the informationon the eroded sediment sources and its response toerosional forces (e.g., hydrological and geomorphologicalconditions).
This study aims to investigate the sediment transport
processes in the reservoir-catchment system based on thecontinuous sediment trap observation and these fallout
radionuclides.
II. SAMPLES AND METHOD
Study site is an artificial reservoir Takidani-ike for
agricultural irrigation located in Ishikawa Prefecture incentral Japan. Sediment trap observations have been
performed since 2000 in Takidani-ike. Deposited sediments
collected monthly using a sediment trap on the bottom wereoven dried at 110°C to obtain their dry weights andsedimentation rates. Samples collected during the period
from February 2010 to December 2011 were used for theradioactivity measurements. Soil samples were also
obtained in the catchment using a steel tube (30 cm length)
to estimate inventory of the radionuclides. The activity
concentration of 210Pb (peak energy: 46 keV), 214Pb (352keV), 137Cs (661.6 keV), and 134Cs (604.7 keV) were
determined by gamma-ray spectrometry using low
background Ge detectors. The activity of excess 210Pbex was
estimated by subtracting the activity of 214Pb from that of210
Pb.
III. RESULTS AND DISCUSSION
Sedimentation fluxes of 210Pbex and 137Cs in Takidaniike range 3.5–80 and 0.1–2.6 Bq/m2/day, respectively, andwere high during autumn and winter than in spring andsummer. 134Cs was first observed just after the FDNPP
accident and showed the similar seasonal fluctuation
ranging n.d.–0.15 Bq/m2/day. These fluctuations
correspond to the changes in precipitation, with highprecipitation in typhoon and snow season, indicating thatthe discharge of these radionuclides from the catchment islargely influenced by the precipitation.
Based on the average sedimentation flux, the annual
210
Pbex, 137Cs, and 134Cs discharge rates from the catchment
were estimated as 222, 7.1, and 0.62 Bq/m2/year,
respectively. These values correspond to 0.72, 0.25, and
4.2 %/year of the inventory of 210Pbex (31 kBq/m2), 137Cs(2.8 kBq/m2), and 134Cs (14.7 Bq/m2). The annual discharge
rate of 134Cs is much larger than that of 137Cs, suggestingthat FDNPP-derived 134Cs was accumulated at the erodible
surface soil and it is a major sediment source for the annual
timescale.
The 137Cs/210Pbex activity ratio of the trap samples
temporally changes from 0.02 to 0.045, and was highduring rainy season and typhoon season. This fluctuation
well corresponds to the change in 10 mm/h excess rainfall(total rainfall exceed 10 mm/h for each sampling interval)
reflecting the heavy rainfall events. This fluctuation may
result from the soil erosion at the high 137Cs accumulatedpart in the catchment during the heavy rainfall where is not
erodible in the normal condition. This result suggests thatheavy rainfall affects the source of eroded sediment and theerosion process in the catchment.

－ 214 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-20

Transfer of Radiocesium to Crops Cultivated in Fukushima
1

Shinji Sugihara1, Toshio Hara2, Akihiro Maekawa3, Noriyuki Momoshima1

Radioisotope Center, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Iizuka, Fukuoka 820-8555, Japan
3
Graduate School of Sciences, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
2

Abstract – Several kinds of crops were cultivated by using thecontaminated soil in the field of Fukushima Prefecture and theradioactivity of soil and crops was measured. The soil-to-crops
transfer factor of a radiocesium was calculated, and a different
value was calculated by corps and the part of crops. But the levelof the calculated value is almost equal to already reported.
Keywords – Transfer factor, Radiocesium, Crop, Fukushima Daiichi Nuclear Power Plant

I.

INTRODUCTION

A large amount of radioactive materials were discharged
into the atmosphere during the Fukushima Dai-ichi Nuclear
Power Plant accident. As a consequence, a wide region ofJapan has been contaminated by mainly radiocesium.
As part of the proof examination of the revival model
after the Fukushima nuclear disaster, several kinds of crops
were cultivated and the effect of decontamination anddesalinization of the contaminated farmland were inspected.
The soil-to-plant transfer factor (TF) of radiocesium isextremely variable among soils.
Radionuclides can reach the human body throughseveral food chains in the environment. A lot of data in thetargeted environment such as TF is necessary to evaluate
the influence on the human body.

The radioactivity of the sunflower (Helianthus annuus)
grown at the field in A area was measured similarly.
III. RESULTS AND DISCUSSION
Figure 1 shows the depth distribution of the Cs in thesoil before the ploughing of A area. Cs that deposited tosurface on the field by the Fukushima nuclear disasterremained in the surface layer after two years passed, andmost was detected within 5cm in depth. The radiation dose
rate at A area was 1.14 �Sv/h by 1m on the ground. The Cs
concentration was about 1/3 of that of A area, and the dose
rate was 0.71 �Sv/h on B area.

II. METHOD

Fig.1 Depth distribution of Cs in A area before the ploughing

The cultivation examination ground was set by twoplaces (A area: Harashita, B area: Kekaya) in Tomioka,
Fukushima Prefecture. B area had received the flood
damage of the tsunami. After the disaster, the area was left
because these areas were specified for the no-go zone
though both areas were originally rice fields. The radiation
measurement, the ploughing and the sowing were done inMay, 2013. Crops were sorghum (Sorghum bicolor), corn
(Zea mays), rapeseed (Brassica napus) and Sugar beet
(Beta vulgaris ssp). Sorghum and corn were harvested in
the middle of November, 2013 at A area. Because thecultivation period was different, the flowering of therapeseed was difficult. Only the sugar beet grew and it
harvested in December, 2013 though sorghum and corn
were fruitless on B area due to the salt damage. The
radioactivity of the soil before and after the ploughing andthe harvested crops sample was measured. The soil sample
was cut at intervals of 1cm. The samples of Crops weremade separately for the leaf, the stalk and the seed. A dry
sample was put in the U8 container, and the Cs
concentration was measured with the Ge solid state detector.

Soil-to-crop transfer factor (TF) was calculated as theratio of the radionuclide concentration in crops (Bq/kg dryweight) to its concentration in soil (Bq/kg dry weight).
Both the dry weight and the fresh weight were used as forthe numerator, and the dry weight was used here. TF
differed according to the part of the crop, and existed in therange of 0.01 to 0.1. Because TF of the seed was small, theseed might be able to use as fodder.
It will be necessary to obtain the basic data for therevival by changing the kind of the soil and crops inaddition and accumulating the vast scope of data in the
future.

－ 215 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-21

Dynamics of radiocesium in bamboo forests
after the accident of Fukushima Daiichi nuclear power plant
Tsutomu KANASASHI, Mitsutoshi UMEMURA, Yuki Sugiura , Chisato TAKENAKA
Graduate School of Bioagricultural Sciences, Nagoya University
Abstract – To understand the dynamics of radiocesium in bamboo
forests, we compared the 137Cs concentrations in one-year old
bamboo with older ones. The leaves from one-year bamboo
contained 137Cs at similar concentration to those of older
bamboos. Since bamboo shoot of 2012 also contained 137Cs,
cesium should be actively transported in bamboo body.
Keywords – bamboo, radiocesium, leaves, branch, shootI.

INTRODUCTION

The accident of Fukushima daiichi nuclear power planton 2011 caused serious problems through the deposition ofradionuclide in a large area of Fukushima prefecture.
Bamboo forests, which have been familiar to peoples as
producing area of various livelihoods like bamboo shoots,
were also contaminated with radionuclide, especially 137Cs.
The decontamination of 137Cs from bamboo forests has
been expected but supposed to be difficult because of theexistence of a large amount of subterranean stems. In orderto design an effective decontamination procedure of 137Cs
and resume the usage of bamboo forests in Fukushima, it isessential to understand the dynamics of 137Cs in bamboo
forests. We aimed to clarify the absorption and transport of137
Cs in bamboo by comparing the 137Cs concentration in
one-year old bamboo with older one.

From these data, the radioactivity at site A was almost athird of those at sites B and C. In addition, at the sites A
and B, the concentrations of 137Cs in soil layer were higher
than those in litter layer, whereas the activity of litter was
almost twice of that of soil layer at site C. Theseobservations suggested that the degree of 137Cs infiltration
into root system were different among three sites.
The concentrations of 137Cs in leaves and branches
collected at site A were shown in Fig.1. The 137Csconcentration in leaves from one-year bamboo, which
sprouted on 2011 after the accident, was not so different
from the values of leaves in the other samples (2 to 11years old bamboos), whereas the data in branch of one-year
bamboo was quite low comparing with those of the otherbamboos. Since the bamboos older than one year adsorbed
137
Cs on their surface at the accident of FNPP, thedifference of concentrations among branches with various
aged bamboo should reflect the direct deposition. On thecontrary, the similar concentrations of 137Cs in leaves of
one-year bamboo with the others might indicate the uptakeof 137Cs through root system. The same results wereobtained from the data of site B and C. The bamboo shootsprouted on 2012 also contained 137Cs at the same level asleaves.
Table 1. Acticity of Cs-137 in litter and soilat three moso forests (kBq/m2)
A
B
C

II. MATERIAL & METHODS
Bamboo samples were collected from three moso
bamboo (Phyllostachys pubescens) forests in Fukushima
prefecture during spring season of 2012. At one site (siteA), since the age of each bamboo could be defined, notonly an one-year old bamboo, which sprouted after theaccident of FNPP, but also 2,4,5,10,11-years old bamboos
were collected. At the other two sites (sites B and C),
three one-year old bamboos and three bamboos older than
one year were sampled. A bamboo shoot was alsocollected at site C. Litters and soils were collected fromthree sites.
Each bamboo was divided into stem, branch and leaves.
For the samples from site C, branch and leave samples
were prepared from top and middle parts of a stem.
Every plant samples were pulverized after drying. The
activity of 137Cs was counted by a Ge- semiconductor
detector (Seiko EG & G). Each counting was continued
until the count error becomes below 10%.
III. RESULTS & DISCUSSION

Litter

44

161

254

Soils

66

186

132

Figure 1. Concentration of 137Cs of leaves and branches in various agedbamboos

Table 1 shows the concentration of 137Cs per area inlitter and soil layers at three moso bamboo forest sites.
－ 216 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-22

Reaction Behavior of Uranium and Zirconium Oxides in Oxidative and Reductive
Conditions
Nobuaki Sato, Kohei Fukuda and Akira Kirishima
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,
2-1-1, Katahira, Aoba-ku, Sendai,980-8577, Japan

To investigate the treatment of fuel debris formed in the damaged reactors at Fukushima Daiichi NPP, study on
the reaction behavior of main constituents in the reactor is essential. The main component in the damaged
reactor is the mixture of uranium and zirconium since there are the fuel and cladding. As for the reaction
between fuel oxide and fission products in oxidative condition, the phase relation of the oxides in the U3O8 andNd2O3 system was reported [1]. Then the reaction behavior of the uranium and zirconium oxides at elevatedtemperatures in oxidative and reductive atmospheres was studied by XRD method. After the heat treatment of
the mixture of UO2 and ZrO2 with a Zr amount of 50 mol % under vacuum at elevated temperature, the UO2solid solution phase such as ZryU1-yO2+x seemed to be formed at temperatures lower than 1273 K. However,phases similar to U3O8 structure appeared in the temperature range from 1073 K to 1473 K. Over thistemperature, a new phase similar to the UO2 phase seemed to be formed showing the decomposition of U3O8
phase at high temperature. When the mixture of zirconium to uranium oxides was treated by mechanochemical
method under reducing condition , the X-ray pattern of the products showed that they were the same fluorite
structure and the lattice parameter of linearly decreased with increasing zirconium ratio. This suggests that theUO2 and ZrO2 form the solid solution from low Zr/U ratio to high one. These results were also discussed withthe phase diagram.

Keywords: Fuel debris, Uranium oxides, Zirconium, UO2 solid solution, Phase relation[1] N. Sato, G. Shinohara, A. Kirishima and O. Tochiyama, High Temp. Mat. Proc., 29 (2010) 461–468.

－ 217 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-23

Radiocesium in zooplankton in seawaters off Miyagi, Fukushima, and Ibaraki
Prefectures
1

H. Takata1, M. Kusakabe2, S. Oikawa1
Central Laboratory, Marine Ecology Research Institute2
Head Office, Marine Ecology Research Institute

Abstract – Zooplankton samples in seawaters were collected off
Miyagi, Fukushima, and Ibaraki prefectures from May 2012 toJanuary 2013. Activity concentrations of 134Cs and 137Cs inzooplankton varied from 0.1to 9.1 Bq/kg-wet weight, and from
0.1 to 12.8 Bq/kg-wet weight, and were higher in May 2012 thanin the other sampling months. We also estimated the zooplanktonto-water activity ratio of 137Cs to be 20-754 L/kg.
Keywords – zooplankton, radiocesium, concentration ratio,
Fukushima Dai-ichi nuclear power plantI.

INTRODUCTION

The East Japan earthquake and tsunami of March 11,
2011, resulted in unprecedented radioactivity releases fromthe Fukushima Dai-ichi nuclear power plant (FDNPP) to
the Northwest Pacific Ocean. Radionuclides (e.g., 134Cs (t1/2=2 y), and 137Cs (t1/2=30 y)) originated from the FDNPP
migrated horizontally (e.g., Aoyama et al., [1]); however,the vertical transport mechanisms for radiocesium in the
coastal areas off Japan are not fully understood.
Zooplankton activity such as excretion and verticalmigration can be one of candidates to play an importantrole in vertical transport of man-made radionuclides (e.g.
Fowler et al. [2]).
We report here the results from a radiochemical analysisof zooplankton for raiocesium (134Cs and 137Cs) collected in
the waters off Miyagi, Fukushima, and Ibaraki prefecturesin 2012 and 2013.

12.8 Bq/kg-wet weight for 134Cs and 137Cs, respectively
during May 2012 to January 2013 (Fig. 1). In addition,
relatively high activity concentrations of radiocesium wereobserved near off Ibaraki prefecture during May 2012
cruise, and near off Fukushima prefecture during January
2013 cruise (Fig. 1). The variation in activity
concentrations would be due to changes in activity
concentrations of radiocesium in their ambient waters.
However, there was no significant correlation between
radiocesium activity concentration in the ambient water andin the zooplankton.
Another possible reason is probably due to the differencein the composition of zooplankton at each station; however,so far it is unclear as to the relationship between planktonic
species and their 137Cs contents.
We also estimated the zooplankton-to-water activity ratioof Cs to be 20-754 L/kg; most of them are higher than theone (40 L/kg) published by the IAEA[3].
137

II. MATERIALS AND METHODS
Zooplankton were collected at seven stations during fourcruises (May 2012, Aug. 2012, Oct. 2012, and Jan. 2013) atthe depths of around 20-80 m with a large ring net (160 cm
mouth diameter, 0.5 mm mesh) during daytime by a 30-min
horizontal towing. To ensure sufficient amounts of sample
for radionuclide analyses, 2–3 hauls per station werecombined into one sample. After the collection, samples on
the mesh were transferred to plastic buckets. A small
amount of samples were preserved immediately in 5% (v/v)
formalin–seawater buffered with borax for microscopic
observation, and the rest of the sample was stored in afreezer at -20oC.
Zooplankton samples were weighed (wet weight),
ovendried (105 C), and weighed again to obtain dry weight.
The activity of radiocesium in dried samples was measured
with coaxial type Ge detectors for a few hours. The
radioactivities of 134Cs and 137Cs in the samples weredecay-corrected to the sampling date.
oIII. RESULTS AND DISCUSSION
Activity concentrations of radiocesium in zooplankton
ranged from 0.1 to 9.1 Bq/kg-wet weight, and from 0.1 toFig. 1 Activity concentrations of 137Cs in zooplankton at 7stations during
each sampling cruise.

REFFERENCES[1]

Aoyama, M., Uematsu, M., Tsumune, D., and Hamajima, Y.:
Surface pathway of radioactiveplume of TEPCO Fukushima NPP1
released 134Cs and 137Cs, Biogeosciences Discuss., 10, 265–283,
doi:10.5194/bgd-10-265-2013, 2013.
[2] Fowler, S.,W., Buat-Menard, P., Yokoyama, Y., Ballestra, S., Holm,E., and Nguyen, H.,V.: Rapid removal of Chernobyl fallout from
Mediterranean surface waters by biological activity, Nature 329, 56–
58, 1987.
[3] IAEA: Sediment distribution coefficients and concentration factors
for biota in the marine environment, Technical Report Series no. 422,
IAEA, Vienna, 1–95, 2004.
This work was part of a research project contracted from the Ministry of
Education, Culture, Sports, Science and Technology, Tokyo, Japan.

－ 218 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-FKP-24

Plutonium isotopes and 241Am in surface sediments off the coast of the Japaneseislands after the Fukushima accident
S. Oikawa1, T. Watabe2, H. Takata1, J. Misonoo2, M. Kusakabe2
1

Central Laboratory, Marine Ecology Research Institute2
Head Office, Marine Ecology Research Institute

Abstract – We determined concentrations of Pu isotopes and241
Am in surface (upper 3cm) bottom sediments collected in a sea
area along the coast of the Japanese islands after the Fukushima
Dai-ichi Nuclear Power Plant (FDNPP) accident. The
concentration in the sediments collected immediately after theaccident was at almost the same levels as those obtained before
the accident.
Keywords – plutonium; 241Am; bottom sediment; Fukushima Daiichi Nuclear Power Plant accident

I.

INTRODUCTION

As a result of the FDNPP accident on March 11, 2011, alarge amount of 131I (half-life: 8 d), 134Cs (2 y), 137Cs (30 y)and other radionuclides were released into the atmosphere.
In addition, a remarkable amount of radionuclides was also
released directly from the plant as the leakage of coolant
seawater poured into the reactor. Comprehensive survey
projects were immediately initiated after the accident forclarifying the distribution of radionuclides especially withhigh volatility such as 131I, 134Cs and 137Cs in theenvironment. However, a survey of actinides derived fromthe accident in the marine environment has been yet to be
sufficient to evaluate their impact. This paper represents theresults of a nationwide survey project to figure out theextent of the accident impact in the levels of Pu isotopes
and 241Am in the bottom sediments collected from the 15
sampling areas. And a comparison was made of the preaccident data to the post-accident ones.

clayey sediment collected in the Aomori area and thelowest of 0.42 Bq/kg-dry in the sandy sediment in the
Ehime area. Although the 241Pu was detected from somesamples having relatively high 239+240Pu concentration (ca.
>0.7 Bq/kg-dry), the 241Am was detected from all of thesediments. The 241Pu/239+240Pu activity ratio found in thesediments varied among the sites even if the sediments
collected in the same period of time and ranged from 0.75
to 1.2. The 241Am/239+240Pu activity ratio in the sediments
were nearly constant (ca. 0.6), and the 240Pu/239Pu atom
ratios were also nearly constant (ca. 0.24) throughout thenationwide sites. The concentrations of Pu isotopes and241
Am, and their ratios found even in the sediments taken in
the vicinity of the FDNPP accident have no significant
differences between prior to and after the accident. Thus,
our nationwide survey results showed that the accident at
the FDNPP did not contribute so greatly to the inventory of
Pu isotopes and 241Am even in the coastal area off
Fukushima Prefecture.

II. MATERIALS AND METHODS
The radioactivity survey project was implemented innationwide 15 sampling areas (Fig. 1). Bottom sediment
samples were collected by a box-type sampler, which
retrieves a 1600 cm2 of sediment from the ocean floor
without disturbing their surface. The upper 3 cm of thesediments were taken for analysis. Plutonium and 241Am
analysis was performed using 50 g aliquot of dried sample,
and alpha spectrometry and beta counting method was used
to measure 239+240Pu (alpha), 241Pu (beta) and 241Am (alpha).
We also used SF-ICP-MS to measure 240Pu/239Pu atom ratio.
III. RESULTS AND DISCUSSION

Fig. 1 Locations of sampling areas.
REFERENCES[1]

The activity concentrations of 239+240Pu found in thesesurface sediment samples collected in May-July 2011,
immediately after the accident ranged from 0.42 to 3.7
Bq/kg-dry, which was comparable to those reported byZheng et al. [1] and Oikawa et al. [2]. The highest 239+240Pu
activity concentration of 3.7 Bq/kg-dry was found in the[2]

Zheng, J. et al., Distribution of Pu isotopes in marine sediments in
the Pacific 30km off Fukushima after the Fukushima Daiichi nuclear
power plant accident. Geochem. J. 46, 361-369 (2012).
Oikawa, S. et al., Plutonium isotopes concentration in seawater andbottom sediment off the Pacific coast of Aomori sea area during
1991-2005. J. Environ. Radioact. 102, 302-310 (2011).

This work was a part of a research project contracted from the Ministry of
Education, Culture, Sports, Science and Technology, Tokyo, Japan.

－ 219 －

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

A theoretical study of actinide and lanthanide extraction withcarbamoylmethylphosphine oxide ligands
Cong-Zhi Wang , Jian-Hui Lan , Yu-Liang Zhao , Zhi-Fang Chai , Wei-Qun Shi*

Nuclear Energy Nano-Chemistry Group, Key Laboratory of Nuclear Analytical Techniques and Key Laboratory For
Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing
100049, China
E-mail: shiwq@ihep.ac.cn
Abstract – With the development of nuclear energy, safe disposal of
the spent nuclear fuel especially high level liquid waste (HLLW)
generated during the PUREX (Plutonium Uranium Extraction)
process has become the key factors affecting the sustainable
development of nuclear energy. The n-octyl(phenyl)-N,N-diisobutylmethylcarbamoyl phosphine oxide (CMPO) used in the so-called
TRUEX (Transuranium Extraction) process was found to possess
excellent extracting ability for actinide and lanthanide cations inacidic media.1,2 In this work, The UO22+, NpO2+, Pu4+, Am3+ andEu3+ extraction complexes with CMPO and diphenyl-N,N-diisobutyl
carbamoyl phosphine oxide (Ph2CMPO) have been investigated bydensity functional theory (DFT) in conjunction with relativistic
small-core pseudopotentials. For most extraction complexes, the
CMPO and Ph2CMPO molecules are coordinated as bidentate
chelating ligands through the carbonyl oxygen and phosphoric
oxygen atoms. The metal-ligand bonding is mainly ionic for all ofthese complexes. The neutral UO2L2(NO3)2, NpO2L2(NO3),
PuL2(NO3)4, AmL3(NO3)3 and EuL3(NO3)3 complexes are predicted
to be the most thermodynamically stable molecules according to themetal-ligand complexation reactions. As reported in the literature,3-5
the extractability of these actinides decrease in the order of Pu4+>
UO22+> Eu3+ � Am3+> NpO2+. In addition, hydration energies may
play an important role in the extractability of CMPO and Ph2CMPO
for these actinide ions. In most cases, the complexes with CMPO
and Ph2CMPO ligands have comparable metal-ligand binding
energies, i.e., the substitution of a phenyl ring for the n-octyl at thephosphoryl group of CMPO has little influence on the extraction ofthese actinides and lanthanides.

Fig. 1 Extraction complexes of UO22+, NpO2+, Pu4+, Am3+ and Eu3+ from
nitric acid solutions with CMPO
[1]
[2]
[3]
[4]
[5]

Keywords – actinide, lanthanide, extractant, relativistic quantum
chemistry－ 220 －

Horwitz, E. P.; Kalina, D. G.; Diamond, H.; Vandegrift, G. F.; Schulz,
W. W. Solvent Extr. Ion Exch. 1985, 3, 75.
Horwitz, E. P.; Kalina, D. G.; Diamond, H.; Kaplan, L.; Vandegrift, G.
F.; Leonard, R. A.; Steindler, M. J.; Schulz, W. W. DE85 010251, 1985.
Visser, A. E.; Jensen, M. P.; Laszak, I.; Nash, K. L.; Choppin G. R.;
Rogers, R. D. Inorg. Chem. 2003, 42, 2197.
Wisnubroto, D. S.; Nagasaki S.; Enokida Y.; Suzuki A. J. Nucl. Sci.
Technol. 1992, 29, 263.
Mathur, J. N.; Murali, M. S.; Natarajan P. R. Taianta 1992, 39, 493.

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

The role of microorganisms during the wet nuclear fuel storage in Slovak Republic
1

Martin Pipíška1, Lenka Tišáková2, Miroslav Horník1, Jozef Augustín1
Department of Ecochemistry and Radioecology, University of SS Cyril and Methodius, J. Herdu 2, Trnava, SK-917 01,
Slovak Republic (pipiska@ucm.sk)
2
Institute of Molecular Biology, Slovak Academy of Sciences, SK-845 51, Bratislava, Slovak Republic

Abstract
The role of short-term and long-term effects of microbialactivity on the wet disposal of spent nuclear fuel in storage
facilities is relatively discussed question. Deionized water instorage pools serves as a coolant and, at the same time, as aprotection against radiation. However, microorganisms havebeen shown to survive and grow in high levels of radiationand in highly pure water and they can tolerate both high andlow osmolarity and extreme pH and temperature values �1, 2�.
This work is focused on a characterization of bacterial
contamination in pool water of the Interim spent nuclear fuelstorage (ISFS, JAVYS Inc.) in Slovakia. The ISFS consists of
4 interconnecting pools: 3 fuel storage pools and 1 reserve
pool built from austenitic steel and permanently filled with
deionized water (Fig 1). The mean specific radioactivity of����� ������ ���� �� ��������� ���� ����×10 5 Bq/L�� ���� �� ���������
53
3.7 ×10 Bq/m . Tritium participated by the activity 1.3 ×105
Bq/m3 and contribution of radionuclides increased in theorder: 60Co < 134Cs < 3H < 137Cs. From the microbiologicalpoint of view, the pool water represents oligotrophic
environment which enables the growth of mesophilic bacteria,
where chronic radiation exerts selective pressure, alteringboth the diversity and abundance of bacteria.

the water from the bottom of the pool SP 3 and SP4 to SP6
fluctuated between 100 and 5 500 CFU/L, although
noticeable higher values were observed in August andOctober 2011 and from April to June 2012. Observed higher
values up to 250 000 CFU/L can be caused by manipulation
procedures such as filling the new fuel assemblies ormanipulation in filtration units and by the facility
reconstruction. In our primary screening 7 different bacterial
isolates from spent nuclear fuel pools were obtained. Only 4
isolates showed stable growth on DEV nutrient agar.
Subsequently, these isolates were identified by 16S rDNA as
Kocuria palustris, Micrococcus luteus, Ochrobactrum spp.
and Pseudomonas aeruginosa.
In laboratory experiments, the bioaccumulation of 137Cs
and 60Co by isolated bacteria were also studied �3�. The
maximum specific uptake of Cs+ after 48 h cultivation inmineral medium (MM) reached 7.54 ± 0.48 µmol/g dw.
(Ochrobactrum spp.), 19.6 ± 0.1 µmol/g dw. (M. luteus) and20.1 ± 2.2 µmol/g dw. (K. palustris). The maximum specificuptake of Co2+ after 24 h cultivation in MM reached 31.1 ±3.5 µmol/g dw. (Ochrobactrum spp.), 86.6 ± 12.2 µmol/g dw.
(M. luteus) and 16.9 ± 1.2 µmol/g dw. (K. palustris).
Analyzing of bacterial communities inhabiting anenvironment exposed to radiation gives opportunities to findbacterial strains with interesting properties such asradioresistance and radionuclide sequestering, able to survive
in extremely nutrient deficient environment. We found thatbacteria K. palustris, Ochrobactrum spp. and M. luteus
isolated from ISFS pool water effectively accumulate both137
Cs and 60Co under growth conditions indicating that thesebacteria affect the fate of radionuclides in pool water.
Presented results should serve also as the basis for further
studies relating to the microbial safety of wet nuclear waste
storage in Slovak Republic.
Keywords spent nuclear
bioaccumulation, 60Co, 137Cs

fuel,storagepools,

bacteria,

References
Fig. 1 Circulation system of pool water in spent nuclear fuel storage facility
at ISFS. Samples of water were collected from fixed 6 sampling points: SP1
and SP2 – near the water surfaces, SP3 – from the bottom, SP4, SP5 andSP6 – after filtration unit, after catex and anex columns, respectively.

Bacterial content in pool waters is kept on very low levelby extremely low concentration of solutes in deionized waterand by both the efficient water and air filtration systems.
During the monitoring from 2009 to 2012, bacterial densities
in the water samples from the surface of pools (SP1, 2) were
within the range from 50 to 4 525 CFU/L. Viable counts in[1] Wolfram JH, Dirk, WJ (1997) Biofilm development and the survival of
microorganisms in water systems of nuclear reactors and spent fuelpools. In: Wolfram JH, Rogers RD, Gaszó LG (Eds) Microbial
degradation process in radioactive waste repository and in nuclear fuelstorage areas. Dordrecht, Kluwer Academic Publishers, pp. 139-147[2] Diósi G, Telegdi J, Farkas G, Gazso LG, Bokori E (2003) Corrosion
influenced by biofilms during wet nuclear waste storage. Int Biodeterior
Biodegrad 51: 151-156[3] Tišáková L, Pipíška M, Godány A, Horník M, Vidová B, Augustín J(2013) Bioaccumulation of 137Cs and 60Co by bacteria isolated fromspent nuclear fuel pools. J Radioanal Nucl Chem 295: 737-748－ 221 －

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

Single centrifugal contactor test of a proposed group actinide extraction process forpartitioning and transmutation purposes
1

Emma Aneheim1,2, Christian Ekberg1, Giuseppe Modolo3, Andreas Wilden3

Nuclear Chemistry, Department of Chemical- and Biological Engineering, Chalmers University of Technology, SE41296
Gothenburg, Sweden
2
Targeted Alpha Therapy group, Department of Radiation Physics, Sahlgrenska Academy at Gothenburg University, SE41345
Gothenburg Sweden
3
Forschungszentrum Jülich GmbH (FZJ), Institut für Energie- und Klimaforschung, Nukleare Entsorgung und
Reaktorsicherheit (IEK-6), 52428 Jülich, Germany
Partitioning and Transmutation (P&T) is one of the future strategies
for handling of used nuclear fuel. Within P&T, compared toconventional reprocessing, not only uranium and plutonium are to
be recycled, but also the rest of the actinides present in the used fuel.
By doing this, the idea is to decrease the storage time needed for the
residual waste as well as to lower the strain on the final repository.
Group Actinide Extraction (GANEX) is a process scheme for P&T
where the actinides are extracted as a group directly from thedissolution liquor, after removal of bulk uranium. A solvent intended
for GANEX purposes, utilizing two well-known extractants (tri-butyl
phosphate and bis-triazine,bi-pyridine) in cyclohexanone has
previously been intensely investigated. The extraction system has inbatch tests been found to extract the actinides as a group and, withsome modifications, separate them from most of the fission products.
The solvent was also found to be resistant both towards strong nitricacid and irradiation up to ca 200 kGy. Due to these positive findings,
the extraction system has in this work been used in a single
centrifugal contactor test on a simulated high active raffinate
solution, spiked with radiotracers. The kinetics of the system wasfound to be relatively slow in the equipment of choice, especiallyregarding the stripping. However, it was still possible to recover
more than 87% of all actinides in one extraction step with a flowrateof 30ml/h.
Keywords – GANEX, TBP, BTBP, Centrifugal contactor－ 222 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-NEP-04

Application of Flow Analytical Methods for Determination of Radionuclides in Cooling Water
and Wastes from Nuclear Plants
Anna Bojanowska-Czajka1�������������������1, Marek Trojanowicz1
1

Institut of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, PolandI.

include determinations of such radioisotopes as
Sr, 99Tc, 226Ra or 231,240Pu and 241Am. For
design of flow-injection setups different
configurations of instrumentation can be
employed, including FIA, SIA, and also multisyringe and multi-pumping devices. Most
commonly both in environmental samples or
cooling waters from nuclear plants those isotopes
are determined in trace or ultra-trace levels,
hence, in flow systems especially efficient
preconcentration steps are developed. As themost efficient is considered extraction
chromatography, but among other methods
possible for this purpose are sorption on solid
sorbents including recently also nanostructured
materials, and precipitation or co-precipitation
processes. Those operations can be especiallyefficient in flow conditions, hence construction ofsuch monitoring systems is very advantageous formonitoring of selected radionuclides in nuclear
power reactors.
90

INTRODUCTION

Flow analytical systems can be described asmeasuring devices, in which all operations ofsample pretreatment and detection of analyte arecarried out in flowing streams. This concept ofanalytical measurements is widely employed inprocess
analysis,andforlaboratory
measurements was primarily developed forclinical analysis. In last decades these methods
have gained a lot of interest especially forenvironmental applications [1]. This is proved byvast number of research papers and developed
methods, increasing number of commerciallyavailable instruments and increasing number ofmethods, which are recognized by national andinternational authorities as standard methods.
The methodology of flow-injection
analysis (FIA), being developed since 1970-ties,
has gained numerous technical modifications
such as e.g. systems with sequential injection ofsample and reagents into a single line system(named as sequential injection analysis - SIA),
flow measurements with direct injection to thedetector sensing surface (named as batch
injection analysis – BIA), or application in flowinjection systems with a moveable solid particles,
also named as bead-injection analysis. [2].
Commonly, as major advantages of flow methodsof analysis are considered possibility of efficient
on-line methods of sample processing prior to thedetection step, and improvement of precision andefficiency compared to batch procedures. Fromthe point of view of application of flow analysis
in determination of trace level of selectedradionuclides especially valuable is possibility ofeffective on-line preconcentration of trace
analytes [3], and carrying out elemental
speciation analysis.
Flow methods are mainly developed fornon-gamma or low-energy gamma emitters withapplication for detection of individual
radioisotopes mainly �� and �-spectrometry (gasproportionalcounters,
liquid-scintillation
counters) [4]. Some developments reported so far

APSORC’13 HEADING (WITHOUT NUMBER)
[1]
[2]
[3]
[4]

M. Trojanowicz (Ed.), Advances in Flow Analysis, Wiley-VCH,
Weinheim, 2008.
M. Trojanowicz, Flow Injection Analysis. Instrumentation andApplications.
World
Scientific
Publishing,
Singapore,
2000APSORC’13 Reference
Z. Fang, Flow Injection Separation and Preconcentration, VCH,
Weinheim, 1993
Y. Fajardo, J. Avivar, L. Ferrer, E. Gomez, M. Casas, V. Cerda,
Trends Anal. Chem., 29 (2010) 1399.

Acknowledgments:
Research task No. 8 „Study of processes occurring underregular operation of water circulation systems in nuclear
power plants with suggested actions aimed at upgrade ofnuclear safety" financed by the National Research andDevelopment Centre in the framework of the strategic
research project entitled „Technologies Supporting
Development of Safe Nuclear Power Engineering”.

－ 223 －

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

Determination of low level 99Tc in the primary coolant water by ICP-MS. Analysis ofpotential interferences.
Ewelina Chajduk1, Sylwia Witman-�����1, Halina Polkowska-Motrenko1
1

Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland

Keywords – technetium-99, primary coolant water, inductively
coupled plasma mass spectrometry (ICP-MS)

Development Centre in the framework of the strategic
research project entitled „Technologies Supporting
Development of Safe Nuclear Power Engineering”.

Tc-99 is produced by the fission of U-235 and Pu-239.
Information on technetium and other fission and activation
product content in the primary coolant and at various
locations in the purification system can be of considerable
value in assessing fuel integrity and performance of
purification

systemcomponent.

Nowadays,mass

spectrometry methods are complementary to radiometrictechniques for radionuclide determination. Using inductively
coupled plasma mass spectrometry (ICP-MS) for long-lived
radionuclides

improves detection

limit

and

accuracy.

However, in accurate measurements by ICP-MS method, thecontribution of isobaric interferences from atomic- andmolecular ions created by plasma gas and/or solvent usedshould be defined and appropriate ways of their elimination
should be introduced. During the determination of Tc-99, thefollowing interferences can be taken into account: 99Ru+,64

Zn35Cl+, 98Mo1H+, 198Hg2+, 198Pt2+, 157Gd40Ar2+, 40Ar218O1H+

etc. In this work, possibility of presence isobaric inferences
has been investigated. From obtained results, it could beconcluded, that some of interference examined can berecognized as insignificant.

However, a careful chemical

separation of Tc species before the measurements, for theremoval of interfering elements, such as Ru traces, as well as
for the high recovery of Tc is necessary.
Acknowledgments:
Research task No. 8 „Study of processes occurring underregular operation of water circulation systems in nuclear
power plants with suggested actions aimed at upgrade ofnuclear safety" financed by the National Research and－ 224 －

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

Extraction of Homologous Elements of Dubnium and Seaborgium from HCl Solution
T. Yokokita1, K. Nakamura1, A. Kino1, Y. Komori1, K. Toyomura1, Y. Kasamatsu1, N. Takahashi1,
T. Yoshimura2, K. Ooe3, Y. Kudou4, K. Takamiya5, A. Shinohara1
1

Graduate School of Science, Osaka University
Radioisotope Research Center, Osaka University
3
Faculty of Science, Niigata University
4
Nishina Center for Accelerator Based Science, RIKEN
5
Research Reactor Institute, Kyoto University
2

Abstract – We aim at studying aqueous chemistry of element 105,
dubnium (Db), and element 106, seaborgium (Sg). In this work, we
carried out extraction experiments of Nb, Mo, Ta, W, and Pa which
are homologous elements of Db and Sg by batch method. These data
are significant to investigate the chemical properties of Db and Sg
and to determine the experimental conditions of these experiments.
Keywords – Hydrochloric acid, Niobium, Molybdenum, Tantalum,
Tungsten, ProtactiniumI.

INTRODUCTION

It is predicted that the chemical properties of transactinide
elements, atomic numbers Z � 104, show some difference
from periodicity in the Periodic Table due to increasingly
strong relativistic effect. These elements are produced only
by nuclear reactions with very low production rates as one
atom at a time, and their half-lives are short, �s to ca. 1 min.
Therefore, we must repeat rapid chemistry by such as
partition method and alpha-particle measurement. In thesestudies, the complex formation and chemical species of thetransactinides were investigated based on the comparison of
their chemical behaviors with those of lighter homologues
and pseud homologues. To the chemistry of element 104 (Rf),
105 (Db), and 106 (Sg), we have studied extraction
experiments of homologous of Rf, Db, and Sg. Moreover, wehave developed rapid extraction apparatuses. In thispresentation, we report on solid-liquid and liquid-liquid
extraction of Nb, Mo, Ta, W, and Pa as homologous elementsof Db and Sg in HCl solution. For Db only one result
obtained in HCl solution, so far, and Sg is expected to show
different behavior with oxidation states.
II. EXPERIMENTAL
We carried out extraction experiments using carrier-freeradiotracers of 95Nb, 99Mo, 179Ta, 181W, and 233Pa. Two kindsof macro amounts of Mo(V) samples were used; one is[MoCl5] and the other is prepared by electrochemical
reduction of Na2[MoO4] solution. Macro amounts of W(V)
was prepared by reducing Na2[WO4] containing 181W tracer
by SnCl2. Liquid-liquid extraction was performed by mixing
1–2 mL of the 0.1–11 M HCl solutions containing RI tracers
or Mo(V) or W(V) with the same volumes of Aliquat 336 inchloroform or carbon tetrachloride solutions. The mixture

was mechanically shaken at 25 °C. After centrifuging thesolution, both the phases were pipetted in separate tubes andthen subjected to �- or X-ray spectrometry. The quantity of
Mo(V) was determined by thiocyanate method. In solidliquid extraction, cation-exchange resin (DOWEXTM 50W×8)
or MCI GEL CHP20/P30 powder sorbed by Aliquat 336 and
0.5–1 mL of 0.1–11 M HCl solution containing 95Nb, 179Ta,
and 233Pa tracers was mixed. The aqueous solution was
pipetted into another tube and the sample was subjected to �or X-ray spectrometry. In all solid-liquid extraction, control
experiments without the resin were performed to determine
the radioactivities on the resin indirectly. We also carried out
solvent extraction with a flow-type extraction apparatus.
Distribution ratio (D) and distribution coefficient (Kd) were
determined from radioactivity of RI tracer or concentration of
Mo(V).
III. RESULTS AND DISCUSSION
In the results of the cation-exchange of Nb, Ta, and Pa, theKd value was in the sequence of Ta > Pa > Nb. In the liquidliquid extraction and solid-liquid extraction of the anioniccomplexes of Nb, Ta, and Pa using Aliquat 336, the D value
and Kd value were in the sequence of Pa > Nb > Ta. FromHCl concentration dependences of the Kd and D values, Nb
forms neutral and anionic complexes in 0.1–4 M and 5–11 M
HCl, respectively. The Ta forms cationic and neutral
complexes in 0.1–5 M and 6–11 M HCl, respectively. The Pa
forms cationic, neutral, and anionic complexes in 0.1–1 M,
1–3 M, and 4–11 M HCl, respectively. Based on thecomparison with these elements, we are planning toinvestigate the chloride complex formation of Db. In theliquid-liquid extraction of group-6 elements using Aliquat
336, the D values of Mo(VI) were higher than those of W(VI).
The D values of Mo(V) were higher than those of Mo(VI).
The D values of Mo(V) obtained by the reduction of Mo(VI)were in good agreement with those obtained with [MoCl5].
These results suggest that reduction behavior of Sg can beobserved by solvent extraction in Aliquat 336/HCl system. In
contrast, the D values of W(VI) and W(V) were similar toeach other. This suggests that the behavior of W(V) is similarof that of W(VI). The alternative interpretation is that W(VI)
could not be reduced or W(V) was rapidly oxidized torecover W(VI) species.

－ 225 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-NCP-02

Evaluation of Stopping Powers of Superheavy Ions in Al and U
Y. H. Chung
Department of Chemistry, Hallym University, 1 Hallymdaehak-gil, Chuncheon 200-702, Korea
yhchung@hallym.ac.kr
Electronic and nuclear stopping powers of superheavy ionswith Z>120 in Al and U were estimated in the energy rangeof 0.01-0.20 MeV/u. In the previous study [1], thecorresponding stopping powers of a superheavy ion with
Z=120 and A=300 in several media were estimated using
stopping powers of ions with 6�Z�92 obtained from SRIM[2]. Results were compared with those deduced from
Northcliffe and Schilling’s stopping-power tables [3]. In
the lower energy regime the contribution of nuclear
stopping powers is substantially significant in both media
while it is not negligible even in the higher energy regime.
[1] Y. H. Chung, Int. J. Mod. Phys. E 19, 1117 (2010).
[2] http://www.srim.org.
[3] L. C. Northcliffe and R. F. Schilling, Nuclear Data Tables A 7, 233(1970).

－ 226 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-NCP-03

Separation of tungsten from LEU fission-produced 99Mo solution to improve
technological performance in both the processes of 99Mo and 99mTc generator
production
Van So Le1 , Cong Duc Nguyen2
1

Medisotec, NSW, Australia
ChoRay Hospital , HCM, Vietnam

2

I. INTRODUCTION99
Mo is a parent nuclide of the 99mTc radioisotope generator
which is used in diagnostic imaging procedures in nuclear
medicine world-wide. The 99Mo production is mainly basedon the 235U fission using HEU and/or LEU targets and on
the 98Mo (n, �� 99Mo reaction. The conversion of present
HEU-based technology to those using LEU requires a 5-6
fold increase in total uranium target weight. Consequently,
LEU target possibly contains approximately five times
more W contaminant than HEU target, assuming the same
purity of the both types of the targets. The large amount of
W is seriously challenging the performance of both theprocessing of 99Mo stock solution and the 99mTc generator
production. So the development of the method of W
separation from LEU-produced 99Mo solution should be
addressed.
II. METHODS
A 99Mo/188W-spiked simulator of the fission 99Mo solution
containing (0.05 mg Mo + 0.06 mg W) per mL and thecontaminant ions was used for W/Mo separation method
development. The element composition of the simulator
solution is mimicked based on an elemental analysis resultof a real 99Mo solution sample which is obtained from thechemical processing steps in which a base-dissolutionprocessed 99Mo solution of LEU (20% 235U) target ispassed through anion exchange (AG-1 X8 and AGMP) andChelex resin columns to remove the majority of fission
products.
Kd values of molybdate and tungstate ions adsorption
on the acidic alumina in the above mentioned simulator
solution of variable acidity were first studied as describedin the literature [1]. The separation process was thenperformed using a chromatographic column of 1.0 g acidic
alumina sorbent, on which a given amount of the simulator
solution was loaded. The elution of 99Mo-molybdate ions

was performed by sulphuric and/or nitric acid solutions
with an acidity optimised based on the Kd measurement
results. Tungstate ions were then striped out of the column
with 5 mL 1.0 M NH4OH solution. The elution fractions of
5 mL were collected and their 99Mo/188W radioactivity wasmeasured using an Ortec gamma-ray spectrometer coupledwith HpGe detector.
III. RESULTS
The Kd values versus acidity of H2SO4 solutions and theelution profile of 99Mo/W separation are shown in Fig.1
and Fig. 2, respectively. Based on the obtained results it isstated that the separation of 99Mo from W contaminant canbe effectively performed using a small acidic alumina
column and H2SO4 eluant. This process can beconveniently integrated with the base-dissolution
technology process of LEU target-based 99Mo production.
This additional alumina column separation step, following
the step of AG-1 X8/AGMP anion exchange and Chelex
resin column separation, is proposed to eliminate or reduce
W contaminant content from 99Mo solution. A typicaldesign of a chromatographic column loaded with 5-10 gacidic alumina and the elution of 99Mo with 50-70 mL 4 M
H2SO4 solution can be effectively used to remove morethan 80% W contaminant content (~ 100 mg W) from a3665 Ci activity (E.O.B) 99Mo solution (~ 70 mg Mo)
produced using 18.4 g 235U LEU target neutron-activatedfor 120 hours in the OPAL reactor. The 99Mo recovery
yield is >96 %.
REFERENCE[1] Le, VS, Morcos N. (2008) New SPE column packing material:
Retention assessment method and its application for the radionuclide
chromatographic separation, J Radioanal nucl Chem, 277: 651-661－ 227 －

24-NCP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effecting Separation of Fission Products from the Actinides By Direct Reaction with
Diketones
Daniel B. Rego, Paul M. Forster, Kenneth R. Czerwinski
University of Nevada, Las Vegas

Abstract – The use of diketone ligands, such as
hexafluoroacetylacetone (Hhfac) and tetramethylheptandione(Htmhd), can react in solvent -free and solvent-minimal routes toeffect separation fission products from uranium matrices without
any pre-preparation of the isotopes in question, and provides a pathto drastically simplify the separations process and limits thepotential for contamination and waste formation due to extensive
handling, while increasing the rapidity of separation and isolation oftarget elements. In particular, the reactivity cesium, barium,
strontium, silver, and lead [1] with Hhfac can allow for rapid
separations from uranium matrices such as oxide mixtures, in somecases in a matter of minutes.
Keywords – Fission Products, Uranium, Cesium, Strontium,
Volatility, Separations.

I.

INTRODUCTION

Current radioelement separations necessitate the dissolutionof solids in either an acidic aqueous solution or a molten salt.
The resulting solutions must be manipulated through a variety
of means to achieve the desired separation.
These
manipulations can involve a complex set of conditions (e.g.,the UREX+ suite of separations). Volatile dikeotones, suchashexafluoroacetylacetone(Hhfac)andtetramethylheptandione (Htmhd), have been used to react
with, and isolate with crystalline purity, fission products [2,3]and actinides [4,5] such as uranium (figure 1) and neptunium.

Ball and stick diagram of UO2(hfac)2(H2O).
Initial studies have focused on characterizing thecoordination with the diketone ligands. The use ofcoordinating ethers to help break up matrices in order tomaximize volatility has been examined and can increase thevolatility and separatability of species from uranium
matrices: For example, cesium hexafluroacetylacetonate
forms an extended polymeric structure with extensive Cs-O
and Cs-F coordination; in contrast, the use of diglyme or 18crown-6 reduces this extensive cross-coordination
significantly.

Direct separation of reactive species from uranium containingoxide mixtures has been demonstrated. The additional abilityof exploiting differences in volatility of these diketone
complexes themselves serves as a secondary method ofseparating the isotopes in question with limited handling andprocessing. [6] The flexibility of this system can allow for
customization to fit specific scenarios and situations. Single
solvent extraction from solid material, or volatilization oftreated solid samples, are utilizable routes. An additionalroute is that these metal complexes are often used as metal
vapor deposition precursors. [7] Thus, a pure metal could beobtained directly from vapor phase volatile complexes
formed directly in the reaction mixture from the oxides andvaporous ligands in situ, which would allow for the potential
combination of separations with metal formation in a single
step.

[1] (a) Evans, W. J.; Rego, D. B.; Ziller, J. W. Polyhedron 2006, 25, 26912697. (b) Malandrino, G.; Nigro, R. L.; Rossi, P.; Dapporto, P.; Fragalá, I. L.
Inorg. Chim. Acta 2004, 357, 3927. (c) Rego, D. B. Lanthanide Reduction
Chemistry of the LnZ3/M and LnZ2Z�/M Systems and Related Coordination
Chemistry Dissertation, University of California, Irvine, 2007.
[2] (a) Evans, W. J.; Giarikos, D. G.; Johnston, M. A.; Greci, M. A.; Ziller, J.
W. J. Chem. Soc., Dalton Trans. 2002, 520-526. (b) Fragalà, L.; Maladrino,G.; Benelli, C.; Castelli Chem. Mater. 1998, 10, 3434. (c) Fragalà, L.
Maladrino, G.; Incontro, O.; Castelli, F. Chem. Mater, 1996, 8, 1292.
[3] (a) Krisyuk, V.V.; Sysoev, S. V.; Fedotova, N. E.; Igumenov, I. K.;
Grigorieva, N. V. Thermochim. Acta 1997, 307, 107-115. (b) Drake, S. R.;
Hursthouse, M. B.; Abdul Malik, K. M.; Miller, S. A. S. Inorg. Chem. 1993,
32, 4653-4657. (c) Darr, J. A.; Poliakoff, M.; Blake, A. J.; Li, W.-S. Inorg.
Chem. 1998, 37, 5491-5496. (d) Strasser, A.; Vogler, A. Inorg. Chem. Comm.
2004, 7, 528-530. (e) Azad Malik, M.; O’Biren, P.; Motevalli, M.; Jomes, A.
C.; Leedham, T. Polyhedron 1999, 18, 1641-1646. (f) Fenton, D. E.;
Newman, R. J. Chem. Soc., Dalton Trans. 1974, 655-657. (g) Cotton, F. A.;
Holm, R. H. J. Am. Chem. Soc. 1960, 82, 2979-2983.
[4] (a) Nikitenko, S. I.; Moisy, Ph.; Tcharushnikova, I. A.; Blanc, P.; Madic,
C. Ultrasonics Sonochemistry, 2000, 7, 177-182. (b) Danford, M. D.; Burns,
J. H.; Higgins, C. E.; Stokely, J. R., Jr.; Baldwin, W. H. Inorg. Chem. 1970,
9, 1953-1955. (c) Morris, M. L.; Moshier, R. W.; Sievers, R. E. Inorg. Chem.
1962, 1, 411-412.
[5] (a) Giarikos, D.G. Dissertation. University of California, Irvine, 2003. (b)Yamamura, T.; Shiokawa, Y.; Yamana, H.; Moriyama, H. Electochim. Acta
2002, 48, 43-50. (c) Kramer, G. M.; Dines, M. B.; Kaldor, A.; Hall, R.;
McClure, D. Inorg. Chem. 1981, 20, 1421-1426. (d) Kramer, G. M.; Dines,
M. B.; Hall, R. B.; Kaldor, A.; Jacobson, A. J.; Scanlon, J. C. Inorg. Chem.
1980, 19, 1340-1347.
[6] Sedai, B.; Heeg, M. J.; Winter, C. H. Organometallics, 2009, 28, 10321038.
[7] Lin, W., Warren, T.H., Nuzzo, R.G., and Girolami, G.S.: J. Am. Chem.
Soc., 115 (24), 11644–11645 (1993).

－ 228 －

24-NCP-05
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013-UONIC !TOM &ORMATION BY -UON 4RANSFER 0ROCESS IN #(  #(##L -IXTURES

M. Inagaki1, K. Fujihara1, G. Yoshida1, K. Ninomiya1, Y. Kasamatsu1, A. Shinohara1, M. K. Kubo2,
W. Higemoto3, Y. Miyake4, T. Miura5
1
Graduate School of Science, Osaka University
Colleage of Liberal Arts, International Christian University
3
Advanced Science Research Center, Japan Atomic Energy Agency
4
Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK)5
Radiation Science Center, High Energy Accelerator Research Organization (KEK)
2!BSTRACT – .EGATIVE MUON TRANSFER PROCESS IN THE MIXTURES OF #( #( ##L WAS STUDIED 4HE MUONIC #L 8 RAY STRUCTURE OF #(##L MIXTURE SAMPLE WAS SIMILAR TO THAT OF PURE ##L SAMPLE(OWEVER THE MUONIC #L 8 RAY STRUCTURE OF #( ##L MIXTURESAMPLE WAS DIFFERENT FROM THAT OF PURE ##L SAMPLE 4HIS RESULT CAN
BE EXPLAINED BY ASSUMING THAT THE NUMBER OF MUONS TRANSFERRED TO
CHLORINE ATOMS IN #( ##L MIXTURE SAMPLE IS SMALLER THAN THATIN #( ##L MIXTURE SAMPLE 4HIS FACT SUGGESTS THAT THE MUON
TRANSFER RATE FOR CARBON ATOMS OF #( IS HIGHER THAN THAT FOR
CARBON ATOMS OF #(+EYWORDS – -UONIC !TOM %XOTIC !TOM -UON 4RANSFER -UONIC 8RAYI.

INTRODUCTION

A muonic hydrogen is one of the simplest exotic atom thatconsists of a muon and a proton. The charge of a proton isstrongly shielded by a muon in the muonic hydrogen because
the mass of a muon is 206 times larger than that of anelectron. The muonic hydrogen can diffuse in the substancelike a neutron and transfer the muon to the other heavier
atoms. This process is known as muon transfer process. The
transfer process occurs also in the case of a pionic hydrogen,which consists of a pion and a proton.
It is reported that the structure of molecule affects theformation or transfer process of the exotic atom. This effect iscalled as chemical effect. In the previous study on piontransfer process, we investigated the chemical effect in
mixtures of C6H6 / C6H12 + CCl4. The pion transfer rate forcarbon atoms of C6H6 is twice higher than that for C6H12 [1].
In this study, we examined the chemical effect on the muontransfer in the same sample system.

III. RESULTS AND DISCUSSION
The experimental muonic Cl X-ray structure (muonic Xray intensity ratios) in pure CCl4, C6H12 + CCl4 (33%)
mixture and C6H6 + CCl4 (33%) mixture samples are shownin Fig. 1.
The relative intensity of Cl (5–3) / Cl (4–3) and Cl (4–2) /Cl (3–2) in C6H12 + CCl4 mixture sample was smaller thanthat in pure CCl4 sample. The difference indicates that initialstate (principal and angular momentum quantum number) of
the muon captured by chlorine atoms in C6H12 + CCl4
mixture sample is different from that in pure CCl4 sample.
Because the muon transfer occurs in C6H12 + CCl4 mixture
sample while no muon transfer in pure CCl4 sample, it seems
that the muon transfer process changes the initial state of themuon captured by chlorine atoms in C6H12 + CCl4 sample. On
the other hand, although the muon transfer also occurs in
C6H6 + CCl4 sample, the muonic X-ray structure of that was
similar to pure CCl4 sample. This can be explained byassuming that the number of muons transferred to chlorine
atoms in C6H6 + CCl4 sample is smaller than that in C6H12 +CCl4 sample. This fact suggests that the muon transfer rate
for carbon atoms of C6H6 is higher than that for carbon atomsof C6H12. Despite using different particle, this result is
consistent with the previous study for pion transfer in thesame sample system [1].

II. EXPERIMENTAL
The muon irradiation experiments were performed at the
MUSE D2 beam line of Materials and Life Science
Experimental Facility in Japan Proton Accelerator ResearchComplex (J-PARC). We selected the following samples formeasurement; C6H6 + CCl4 (33%) mixture, C6H6 + CCl4 (3%)
mixture, C6H12 + CCl4 (33%) mixture, C6H12 + CCl4 (3%)
mixture, pure C6H6, pure C6H12, and pure CCl4. Muonic Xrays, which are emitted after formation of muonic atoms,
were measured by Ge detectors.

Fig. 1. Muonic chlorine X-ray structure. Cl (n–n′) means muonic Cl X-ray
emitted with muon deexcitation from principal quantum number n to n′.
[1]－ 229 －

A. Shinohara ET AL, Hyperfine Interact. , 301 (1997).

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-NCP-06

Research for Fusion Reaction Mechanisms with Deformed Nuclei
S. Ueno1, K. Toda1, A. Asano1, N. Takahashi2, Y. Kasamatsu2, T. Yokokita2, A. Yokoyama3,
1

Graduate School of Natural Science and Technology, Kanazawa Univ.
2
Graduate School of Science, Osaka Univ.
3
Institute of Science and Engineering, Kanazawa Univ.

Abstract – In order to better understand the reaction on the fusion
reaction, we have focused on the deformation of the nuclei. We
have researched for the fusion reactions of 169Tm+16O [1],169
Tm+20Ne, and 165Ho+20Ne [2]. The cross sections for fusion
were compared between systems of different entrance channels.
The results are consistent with the idea that the degree of
deformation makes an effect on the rising edge of excitation
functions near the Coulomb barrier.
Keywords – Fusion reaction/ Excitation function/ Deformed
nucleusI.

INTRODUCTION

Heavy ion fusion reaction is often used in the synthesisof heavy elements recently. For the synthesis of transactinides, evaporation residues cross section is very small
compared to fission. Briefly, it is important to understandthe reaction mechanism and to know the conditions for
efficient synthesis.
We have focused on the deformation of nuclei. In thisstudy, in order to study the effect of the degree of nuclear
deformation on the fusion reaction, we have researched forthe fusion reactions of 169Tm+16O [1], 169Tm+20Ne, and165
Ho+20Ne [2]. Figure 1 shows deformed nuclei in a
spheroid model and Table 1 shows the degree of nuclear
deformation of 20Ne, 16O, 169Tm and 165Ho based on themodel. In 169Tm+20Ne and 165Ho+20Ne systems, the target
nucleus 165Ho is more deformed than 169Tm. In 169Tm+16O
and 169Tm+20Ne systems, the projectile nucleus 16O isspherical, while 20Ne is deformed. Both systems of169
Tm+16O and 159Ho+20Ne form the same compound
nucleus, 185Ir*.

a

a

b

Osaka University. The targets were prepared byelectrodeposition with standard solution on an Al foil of 2.7
mg/cm2 thickness. For instance, the 169Tm content was 4.55.1 mg/cm2 in thickness. In order to achieve experiments ofwide energy range in a single irradiation, energy
degradation technique was used. In the present experimentusing two stacks with four targets each, each target wasirradiated at a different energy below 155 MeV in
169
Tm+20Ne system. Typical beam intensity was 1 particle�A. The activities produced in each target were assayedusing a high resolution HPGe detector. Excitation function
was made from the measured activities.
III. RESULTS AND DISCUSSION
The evaporation residues detected, for instance, in
Tm+20Ne system were 185Pt, 183�185Ir, 181,182Os and 181Re.
Figure 2 shows the excitation function for fusion reactionof 169Tm+20Ne, 169Tm+16O [1] and 165Ho+20Ne [2]compared with the theoretical calculations using code
HIVAP taking into consideration degree of deformation of
nucleus. In order to compare the systems between different
entrance channels, let the value obtained by subtracting the
Coulomb barrier [3] from the incident energy, (Ecm�Bc),
be the horizontal axis in the figure. Comparing 169Tm+16O,
169
Tm+20Ne and 159Ho+20N systems, more deformed systemof 159Ho+20Ne induced fusion reaction from lower incident
energy. Comparing 169Tm+20Ne and 165Ho+20Ne systems,
starting points for fusion reaction were nearly the same.
The trends were reproduced by HIVAP calculation.
169b

Figure1 Deformation of nucleus
Table1 Degree of deformation of relevant nuclei
20

a/b

Ne

16

0.75

1.00

O

169

Tm

0.95

165

Figure2 Excitation function of 169Tm+20Ne (�), 169Tm+16O (�) [1]and 165Ho+20Ne (�) [2] compared to theoretical values of each system

Ho

1.16

[1]
[2]
[3]

II. EXPERIMENTAL
The bombardment for synthesis was carried out using
O and 20Ne beam supplied from the AVF cyclotron
facility at Research Center for Nuclear Physics (RCNP),
16－ 230 －

A. Asano, master thesis of Kanazawa Univ. (2010)
K. Toda, master thesis of Kanazawa Univ. (2013)
R. Bass, Nuclear Reactions with Heavy Ions, Springer-Verlag, NewYork (1980)

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-NCP-07

Extraction behavior of Nb and Ta in HF solutions with tributyl phosphate
M. Murakami1,2, S. Tsuto1, K. Ooe1, H. Haba2, J. Kanaya2, S. Goto1, and H. Kudo1
Department of Chemistry, Faculty of Science, Niigata University, Niigata 950-2181, Japan
2
Nishina Center for Accelerator-Based Science, RIKEN, Saitama 351-0198, Japan

Abstract – Extrtaction behavior of carrier-free Nb and Ta withtributyl phosphate (TBP) from HF solutions was studied by abatch method. Tantalum is extracted well to an organic phase,
while Nb is left in an aqueous phase at 0.053�1.0 M HF
concentrations. The similar extraction trends of Nb and Ta areshown in the solid phase extraction using a TBP resin. The
extraction equilibria in the solid phase extraction are attained
within �10 s.
Keywords – niobium, tantalum, extraction, tributyl phosphateI.

INTRODUCTION

In the synthesis experiment of an element 115,
chemically separated 27-h spontaneously fissioning nuclide
was assigned to 268Db which is the descendant of 288115[1,2]. To clarify this 27-h nuclide is actually Db, further
chemical investigations are needed for both of known
nuclides of dubnium, 262Db (T1/2 = 34 s), and 27-h
spontaneously fissioning nuclide.
Tributyl phosphate (TBP) is one of the most effective
extractants used for industrial separation of Nb and Ta [3].
In this work, solvent extraction behavior of Nb and Ta with
TBP was first studied by a batch method. Solid phaseextraction with a TBP resin was also performed to examine
the feasibility of this resin to an automated rapid reversedphase chromatography apparatus for 262Db.

III. RESULTS AND DISCUSSION
Figure 1 shows the dependence of the D values of Nb
and Ta on the initial HF concentration ([HF]ini) with 1.8 M
TBP — 1,2-dichloroethane solution as an organic phase.
Tantalum was extracted well at the [HF]ini of 0.053 to 1.0
M, while Nb was left in an aqueous phase.
The number of TBP molecules combined with the Nb
and Ta compounds was examined by varying the TBP
concentration at the constant [HF]ini. The number of
combined TBP molecules was found to be 3 for Ta at[HF]ini � 2.7 M. This agrees with the results in Refs. [3,4].
Although the number of TBP molecules combined with the
Nb compound is reported as 3 [3], our results show that the
number is 2 independently of [HF]ini. This results show that
Nb and Ta are extracted with different chemical forms.
Using the 48 wt-% TBP resin, the dependence of the
distribution coefficients of Ta on [HF]ini was similar to thatof the D values in the liquid-liquid solvent extraction.
Niobium was not extracted at � 10 M. The time required
for the extraction equilibrium was less than 12 s for both of
Nb and Ta. This indicates that the present extraction system
could be applicable to an on-line experiment with the shortlived 262Db.


II. EXPERIMENTAL
95g


179

The radiotracers Nb (T1/2 = 34.991 d) and Ta (T1/2 =1.82 y) were produced in the bombardments of 14-MeV
proton beam supplied by the RIKEN AVF cyclotron onnat
Zr and natHf target foils, respectively.
In the experiment of the solvent extraction, 1 mL of HF
solution containing 95gNb and 179Ta tracers were shaken
with 1 mL of TBP—1,2-dichloroethane solution for 180 min
at 25�C. After centrifugation, 700 �L of each phase wastransferred to an polypropylene tube separately, and thensubjected to �- and X-ray measurements with a Ge detector.
The distribution ratios (D) of Nb and Ta were deduced
from the observed radioactivities.
The solid phase extraction was performed withfollowing procedures. TBP resin was prepared byadsorbing TBP on a support material (MCI GELCHP20/P30, Mitsubishi Chemical Co.) [4]. A portion of 20
to 30 mg of the TBP resin was shaken with 400 �L of HF
solution containing 95gNb and 179Ta tracers for 6 s to 60 min.
After filtration, 200 �L aliquot was transferred to apolypropylene tube. The distribution coefficients of Nb andTa were calculated with the observed radioactivities and theweight of the used resin.

$ISTRIBUTION RATIO

1



 
 
  


 

 



;(&= IN

Fig. 1. Distribution ratios of Nb and Ta.
[1]
[2]
[3]
[4]
[5]

－ 231 －

S. N. Dmitriev et al., Mendeleev Commun. 15, 1 (2005).
N. J. Stoyer et al., Nucl. Phys. A 787, 388c (2007).
Z. Zhu and C. Y. Cheng, Hydrometallurgy 107, 1 (2011).
H.Haba et al., Radiochim. Acta 95, 1 (2007).
S. Nishimura et al., Trans. JIM 5, 79 (1964).

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-NCP-08

�������������������������������������-32P] LABELLEDADENOSIN TRIPHOSPHATE
Wira Y Rahman1*, Endang Sarmini1, Herlina1, Triyanto1, Rien Ritawidya1, Abdul
Mutalib1 and Santi Nurbaiti2
1

Center for Radioisotope and Radiopharmaceuticals (PRR) - BATAN)
Biochemistry Research Division, faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl.
Ganesha 10 Bandung, Indonesia, 40132*Tel/fax : (6221)7563141, email: wira@batan.go.id2

ABSTRACT
Adenosine triphosphate-��������� ����� �-32�� ��-32P]-ATP) has been widely used in the biotechnology
research, usually as a tracer to study aspects of physiological and pathological processes. In order tosupport biotechnology research in Indonesia, a process for producti��������-32P]-ATP in accordancewith a more simple glycolysis enzymatic reaction utilizing glyceraldehid 3-phosphate dehydrogenase,3-phosphoglyceryc phosphokinase and lactate dehydrogenase has been conducted. DLglyceraldehydde 3-phosphate, Adenosine Diphosphate (ADP) and H332PO4 was used as precursors
for this reaction. Purification of ��-32P]-ATP was performed by using DEAE-Sephadex column
chromatography. The results showed that �������������� ������� ��� ��-32P]-ATP was 99,49% withradioactivity was 1,175 mCi for 20 minutes enzymatic reaction. The result suggested that thismodification method can be used for producing ��-32P]-ATP to support the provision of radiolabeled
nucleotide for biotechnology research in Indonesia.
Key words : labeled nucleotide ��-32P]-ATP, synthesis, enzymatic reaction, DEAE-Sephadex column
chromatography－ 232 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-NCP-09

Production of 88Nb and 170Ta for chemical studies of element 105 Db using the
GARIS gas-jet system
M. Huang,1 M. Asai,2 H. Haba,1 D. Kaji,1 J. Kanaya,1 Y. Kasamatsu,3 H. Kikunaga,4 Y. Kikutani,3 Y.
Komori,3 H. Kudo,5 Y. Kudou,1 K. Morimoto,1 K. Morita,1 M. Murakami,5 K. Nakamura,3 K. Ozeki,1
R. Sakai,1 A. Shinohara,3 T. Sumita,1 K. Tanaka,1 A. Toyoshima,2 K. Tsukada,2 Y. Wakabayashi1 andA. Yoneda2
1

Nishina Center for Accelerator-Based Science, RIKEN
2Advanced Science Research Center, JAEA
3
Graduate School of Science, Osaka University
4
Research Center for Electron Photon Science, Tohoku University
5
Department of Chemistry, Niigata University

Keywords – superheavy element chemistry, Nb, Ta, Db, GARIS,
gas-jet method, recoil transfer chamber

We plan to study chemical properties of element 105,
Db, produced in the 248Cm(19F,5n)262Db reaction using thegas-jet transport system coupled to the RIKEN gas-filled
recoil ion separator, GARIS1). It is important to perform Db
chemistry together with Ta and Nb under identicalconditions to find different chemical behavior among thehomologues. In this work, we tried to produce isotopes of170
Ta (T1/2 = 6.76 min) and 88Nb (T1/2 = 14.55 min) in thenat
Gd(19F, xn)170Ta and natGe(19F, xn)88Nb reactions,
respectively, using the GARIS gas-jet system.
A 106.4-MeV 19F9+ beam was extracted from the
RIKEN linear accelerator. A natGe target of 0.29 mg/cm2
thickness was prepared by vacuum evaporation onto a 0.89
mg/cm2 Ti backing foil, while a natGd2O3 target of 0.34
mg/cm2 was prepared by electro-deposition on a 0.87
mg/cm2 Ti foil. The two arc-shaped Ge targets and two
Gd2O3 were mounted together with four 0.95 mg/cm2 Ti
blank foils on a rotating wheel of 100-mm diameter, which
was rotated at 1000 rpm. The beam energy was 103 MeV in
the middle of the target and the typical intensity was�������������� �� ��������� �� �����. The working He
pressure of GARIS was 33 Pa. At the focal plane of GARIS,a recoil transfer chamber (RTC) of 100-mm inner diameterand 0~100-mm adjustable depth was installed. Evaporation
residues separated with GARIS were passed through a 0.5��� ������ ������� thermalized in RTC, and weretransported by the He/KCl-aerosol-gas-jet system to achemistry laboratory. The He flow rate was 2.0 L/min, andthe inner pressure of RTC was 47 kPa. After collection of
the aerosols on a glass filter (ADVANTEC GB-100R) for 1
and 3 min for 170Ta and 88Nb, respectively, the filters were
subjec���� ��� �-ray spectrometry using a Ge detector. The
magnetic setting of GARIS was varied in the magnetic
rigidity (B����������������–1.80 Tm for 170Ta and 0.850–

0.979 Tm for 88Nb. In the GARIS separation of 88Nb at low
B�� �������� ���� ����� ���������� ����� ��wer charge statesbroke the thin Mylar foil of RTC. Thus, we installed a
retractable Al shutter of 2-mm thickness and 30×100-mm2
size at the focal plane to protect the Mylar foil from theundesired beam particles. The gas-jet efficiencies are very
sensitive to the depth of RTC and recoil ranges of theevaporation residues in RTC. To effectively collect 88Nb
atoms in RTC, a 3-���Al degrader foil was used to reduce
their recoil ranges before entering the RTC.
The 221.2-keV and 671.2-���� �-rays are useful forchemical studies of 170Ta and 88Nb, respectively. Yield
distributions of 170Ta and 88Nb related to B�� ���� ����������
in Fig. 1. The optimal B�� �� 1.64±0.01 and 0.936±0.001
Tm were determined for 170Ta and 88Nb, respectively.
Under the optimal B� and with the 100-mm depth RTC, theproduction yields of 170Ta and 88Nb in the chemistrylaboratory were evaluated to be 8.65±0.56 and 0.61±0.02k������� ������ �-min and 3-min aerosol collection,
respectively. The gas-jet efficiency of 88Nb was 41±2%,while that of 170Ta was 77±3%.
104

Yield (arb. unit)

Abstract – We developed a production technology forradioisotopes of Ta and Nb for chemical studies of element 105,
Db, using the RIKEN gas-filled recoil ion separator � GARIS.
Isotopes of 170Ta and 88Nb produced via the natGd(19F, xn)170Ta
and natGe(19F, xn)88Nb reactions, respectively, were successfully
extracted by the gas-jet method to a chemistry laboratory after
physical separation by GARIS.

103
170

Ta
Nb

88

102
0.8

0.9

1.0

1.5

1.6

B� (Tm)

1.7

1.8

1.9

Fig.1. Yields of 170Ta and 88Nb as a function of ��.

[1]－ 233 －

H. Haba et al.: Chem. Lett. 38, 426 (2009).

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-NCP-10

Half-life measurement of 7Be in several materials
T. Ohtsuki
Research Center for Electron Photon Science, Tohoku University
1-2-1, Mikamine, Taihaku, Sendai, 982-0826, Japan

Abstract – The formation of atom-doped C60 and C70 etc. has
been investigated by using several types of radionuclides
produced by nuclear reactions. From the trace of theradioactivities after high performance liquid chromatography(HPLC), it was found that formation of endohedral fullerenes of
Be atom is possible by a recoil process following the nuclear
reaction. The decay rate of 7Be electron capture (EC) was
measured in C� 0 and Be metal with a reference method. The
half-lives of 7Be endohedral C70 and 7Be in Be metal (Bemetal(7Be)) were found to be 52.45±0.04 and 53.25±0.04 days,
respectively. This amounts to a 1.5% difference in the EC-decay
half-life between 7Be@C70 and Be metal(7Be). The results are areflection of the different electron wave-functions in nuclear site
for 7Be inside C70 compared to when 7Be is in a Be metal. The
further theoretical interpretation is needed for these experimental
results.
Keywords – Electron Capture Decay, Beryllium-7, Half-life

I.

INTRODUCTION

A long-standing challenge has been to establish thedegree to which manipulation of the environmental factors
can in practice change nuclear decay rates in experiments
to determine the decay rate of 7Be compounds. In addition,
there have been several observations of variations in thehalf-life with host metals, chemical forms, and pressure.
From the early data, the half-life of 7Be as a function ofdifferent chemical forms and/or host materials have been
limited almost to within 0.2%. In recent studies, however,large variations have been observed as a function ofdifferent chemical forms and pressures. Therefore, aprecise measurement is still needed to obtain the absolutedecay rate in different circumstances.
After the discovery of C60 and the subsequent successful
production of several kinds of fullerenes, endohedral
fullerenes which have one or more atoms inside the C60, C70,

cages etc. currently have attracted great interest. If theirmass production becomes possible, they would have many
interesting applications such as stable molecular devices in
nano-meter scales and/or as functionalized materials inmany fields. We have examined the formation ofendohedral fullerenes by a nuclear recoil implantation ofseveral foreign atoms following nuclear reactions[1,2]. We
found that the 7Be atom can be endohedrally doped tocreate the 7Be endohedral fullerenes.
Because of the unique chemical form of fullerenes and/or
several factors contributing to give rise to this environment;
many �-electrons of C60(C70), and special dynamic motions
inside C60(C70) etc., the electron contact density on the 7Be
nuclei can be affected significantly by the electron
environment of C60(C70). Therefore, it is intriguing to�
measure the half-life of the 7Be inside C60(C70); “how does
the EC decay rate in 7Be change inside the C60(C70) cage
relative to other situations?”
So far, we compared the half-life of 7Be when it isencapsulated in a C60 cage to that of 7Be in Be metal as areference. We found a surprisingly shorter half-life of 7Be
inside C60[3,4]. This fact implied that the 7Be atoms arelocated in a unique environment inside C60 cage.
Furthermore, in order to see the size effect of fullerenes, wedemonstrate the change of decay rete of 7Be in 7Be@C70
and in Be metal [Be metal(7Be)]. The decay rate of 7Be
electron capture (EC) was measured in C�0 and Be metal
with a reference method. The half-lives of 7Be endohedral
C70 and 7Be in Be metal (Be metal(7Be)) were found to be
52.45±0.04 and 53.25±0.04 days, respectively.
[1] T. Ohtsuki et al., Physical Review Letters 77 (1996) 3522.
[2] T. Ohtsuki et al., Physical Review Letters, 81 (1998) 967-970.
[3] T. Ohtsuki et al., Physical Review Letters 93 (2004) 112501.
[4] T. Ohtsuki et al., Physical Review Letters 98 (2007) 252501－ 234 －

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

Verification of anticlockwise gyre in the semi-closed water area of Lake Nakaumi,
southwest Japan, by using 224Ra/228Ra activity ratios
Ritsuo Nomura1,* Mutsuo Inoue2, Hisaki Kofuji3 and Shota Ikeda1

1

Foraminiferal Laboratory, Faculty of Education, Shimane University, Matsue 690-8504 Japan
Institute of Nature and Environmental Technology, Kanazawa University, Wake, Nomi, Ishikawa 923-1224 Japan3
Mutsu Marine Laboratory, Japan Marine Science Foundation, Minato, Mutsu, Aomori, 035-0064 Japan
2

Abstract –The Honjyo area in Lake Nakaumi is a semi-closed brackish waterarea where some mixing of up-flowing marine water and downflowing lake water take place. A large-scale gyre that caused by theresidual circulation was once indicated by a temporal algal
blooming that spread over the semi-closed Honjyo area in brackish
Lake Nakaumi. In order to verify this type of water circulation, we
examined 224Ra (t1/2=3.66 d)/228Ra (t1/2=5.75 y) activity ratios ofboth upper and lower waters that differentiated by a well-developed
halocline. The 224Ra/228Ra ratios in the upper water were lowest in
the central area, suggesting the formation of anticlockwise gyre. The
ratios in the lower water were rather uniform, but a basin-wide
anticlockwise flow of water is also indicated. The 224Ra/228Ra ratio
is clearly effective to trace the water flow for both the deep andsurface waters.
Keywords – 224Ra/228Ra ratio, Water flow, Lake Nakaumi

I.

INTRODUCTION

Estuarine biota has been critically influenced by anincreased eutrophication in Japan. The environmental andbiological interaction is complicate, but the water charactersand the dynamic water movement are major factor tounderstand the total environment of estuarine water.
The Honjyo area, occupying ~20 % of Lake Nakaumi, wasclosed for 28 years. This closed area is now partly opened
and permitted the exchange of marine water and lake water
through the opened slit [1]. After the closed area opened, theoriginal massive low salinity water changed to form a density
stratification of bottom and surface waters. In order to clarify
the deep and surface water dynamics, we analyzed
224
Ra/228Ra ratio of both deep and surface waters tounderstand the water residence time and the circulation ofwater.

keV), respectively. �����������-ray counting time for 224Ra and228
Ra was 18,000 seconds and the second counting time was
85,000 seconds. Owing to the short half-life of 224Ra, first �ray counting for 224Ra was conducted between 3-5 days after
the sampling.
II. RESULTS AND DISCUSSION
Both the upper and lower waters in the Honjyo area show
lower 224Ra/228Ra ratio, compared to that in the Sakai Channel.
The ratios of the upper water show the range between 0.020.15, and those of the lower water are 0.08-0.20. These ratios
are similar to the ratio of the Nakaumi water. It is noted thatthe 224Ra/228Ra ratio of the upper water shows regional
difference, which is higher in western and northern sides,
while the central and eastern sides are lower. The 224Ra/228Ra
ratios of lower water are characterized by similar ratios,
excepting the place near the Ohmisaki slit.
In 2010, algae blooming spread over the surface of the
Honjyo area, showed a large-scaled anticlockwise gyre in thearea. Our reconstructed surface water flow, using 224Ra/228Ra
ratios, is similar to the large-scale anticlockwise gyre shownby the algae powder. The 224Ra/228Ra ratios in the lower water
are rather uniformly distributed, but the lower water may
form a large-scale anticlockwise flow over the basin.
133°8´

133°10´

133°9´

133°11´

133°12´

133°13´

35°32´

0.12
0.15
M.S.

35°31´

0.02
0.11

0.21

0.05

Honjyo area

0.08

35°30´

A. Methods of study

0.09

Ten sampling locations were set in and out of the Honjyo
area (Fig. 1). We used Mn-fiber to collect Ra from lake water(40-60 L) prefiltered with a polypropylene filter cartridge (~1L/min; 0.5 �m median pore size). Mn-fiber was dried andthen ashed within 24 hours. Ash powder was completely
sealed in the styrene bottle.
�-Spectrometry was performed using a coaxial-type Gedetector. The 224Ra and 228Ra activities were evaluated fromthe �-ray peaks of 212Pb (235 keV) and 228Ac (338 and 911

35°29´

0.13

Lake Nakaumi

O.S.

0.10

Water flow

M.S. Moriyama Slit
O.S. Ohmisaki Slit

Figure 1. Distribution of 224Ra/228Ra ratios in the Honjyo area and the
supposed flow of upper water.
[1]－ 235 －

Nomura, R. et al., 2013. Opening of the closed water area andconsequent changes of 228Ra/ 226Ra activity ratios in coastal lagoon
Lake Nakaumi, Southwest Japan. Applied Radiation and Isotopes. DOI:
10.1016/j.apradiso.2013.03.069

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

Effect of hydroxylated fullerene on U(VI) Adsorption onto oxidized multi-walledcarbon nanotubes
Jing WANG1, Zhan LI2, Peng LIU1, Wei QI1, Juanjuan BI1, Wangsuo WU1*
1 Radiochemistry Laboratory, School of Nuclear Science and Technology, Lanzhou University, Lanzhou 73000, China
2 Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 73000, China
Abstract –Herein, hydroxylated fullerene (C60(OH)n) was chosen as
the third phase to investigate its impact on U(VI) adsorption onto
carbon nanotubes. The results showed that the drastic effect of
C60(OH)n on U(VI) adsorption of oMWCNTs was not significant at
low concentration of C60(OH)n, whereas a negative effect wasobserved at higher concentration. The adsorption of U(VI) onto
oMWCNTs was enhanced with increasing pH values at pH < 6, but
decreased after pH reached 6. The main mechanism may be theadsorbed Cu(II) on oMWCNTs is "squeezed" down to the solution
by the adsorption of C60(OH)n onto oMWCNTs. The double sorption
site model was applied to simulate the adsorption isotherms of
U(VI) in the presence of C60(OH)n and fitted the experimental datawell. This provides reference for studying the interactions between
carbon nanomaterials and radionuclide in various conditions of
natural environment. Meanwhile, it also brings theoretical basis forstudying the biological safety problems caused by multi-component
environment pollution.
Keywords –Effect, Hydroxylated fullerene, U(VI) adsorption,
Oxidized multi-walled carbon nanotubes

I.

� ��

�

�

m/V����-1)
1
0.5
0.25
0.1

�� ���
267.26-4148.21-10.97-7.72

DSSM modelk�b� ��-165.72-773.414246.26
12867.49
104.89127.13185.38
55.43
�� �

R2
0.94850.97390.97570.9457INTRODUCTION

Carbon nanotubes has potential application in the disposal of
nuclear fuel reprocessing, due to the large specific surface
area, the surface is easy to be modified, resistant to heat andradiation. As far as we known, the study concerning themechanism for radionuclide selective adsorption on a varietyof carbon nanomaterials in the ternary system was sparse.
However, it is difficult to achieve the adsorption contributionof each carbon nanomaterial when they are all chosen as
adsorbent in the experiment. Two different water-soluble
carbon nanomaterial must be selected as the adsorbent toresolve this problem.
�oMWCNTs and the nature and species of U(VI); k represents
the rate constant.
Table 1 Parameters of double adsorption site model*

�% = �� + � × � ������� �

Fig. 1 Effect of C60(OH)n on U(VI) adsorption onto
oMWCNTs as a function of pH, m/V =0.5 g/L, T = 25±1 ºC,
I=0.01 mol/L NaNO3, C[UO22+]initial =1.12×10-4 mol/L.

(1)

Where Co (mg/L) is the initial concentration of U(VI)before adsorption; Cs (mg/g) for the equilibrium
concentration of U(VI) in the solid phase after adsorption;
Ce (mg/L) is the equilibrium concentration of U(VI) in theliquid phase; Cf (mg/L) is definited as the initialconcentration of C60(OH)n; b is the parameter forcharacterization the adsorption of C60(OH)n, it depends on
the species and surface character of C60(OH)n and thenature of oMWCNTs; C1 and C2 are the performanceparameters for the sorption characterization of oMWCNTs,
these parameters depend on the surface character ofFig. 2 Effect of oMWCNTs dosage on U(VI) adsorption onto
oMWCNTs as a function of C60(OH)n initial concentrations,
pH=7.00±0.10, I=0.01 mol/L NaNO3, T = 25±1 ºC,C[UO22+]initial =1.12×10-4 mol/L.
�

Corresponding author: Wangsuo Wu,
Tel & Fax:+8609318913594,
E-mail:wuws@lzu.edu.cn(W.Wu).

－ 236 －

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

Corrosion of Copper in Water and Colloid Formation under Intense Radiation Field
Kotaro Bessho1, Yuichi Oki2, Naoya Akimune3, Hiroshi Matsumura1, Kazuyoshi Masumoto1,
Shun Sekimoto2, Naoyuki Osada4, Norikazu Kinoshita5, Hideaki Monjushiro1, Seiichi Shibata2
1

Radiation Science Center, High Energy Accelerator Research Organization (KEK),
Research Reactor Institute, Kyoto University (KURRI), 3 Graduate School of Engineering, Kyoto University,
4
Graduate School of Engineering, Tohoku University, 5 Institute of Technology, Shimizu Corporation

III. RESULTS AND DISCUSSION
Figure 1 shows soluble and size-separated colloidal
concentrations of Cu in water without irradiation or after the

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Irradiation experiments were carried out at the 60Co �-ray
irradiation facility or the electron linear accelerator (eLINAC) at the Research Reactor Institute, Kyoto University(KURRI). Cu vessels (Inside:19� X 75 mm) filled with purewater (26 ml) were irradiated by �-rays from 60Co source, orbremsstrahlung and neutrons generated by a 30 MeV electron
beam striking a Ta target assembly. At the 60Co �-ray
irradiation facility, samples were irradiated by �-ray with thedose rates of 2.9 kGy/h or 21 kGy/h for 2 to 240 h. At the eLINAC facility, irradiation experiments were carried out withseveral beam-current conditions, and the irradiation times
were varied between 2 to 24 h.
After the irradiations, water samples in the Cu containers
were collected and filtrated with four kinds of ultrafiltration(UF) units for particle size separation. Estimated pore sizes of
the UF units were 200 nm, 16 nm, 7 nm, and 3 nm. Elemental
concentrations of Cu in each UF filtrate and original samples
before UF were determined by ICP-AES analyses.

#U PPMII. EXPERIMENTS#U PPMAt high-energy accelerator facilities, colloid formation incooling water is an important subject for radiation
management at high-energy accelerator facilities, because thepresence of colloidal species complicates the behavior ofradionuclides in the cooling water systems [1]. It’s possiblethat intense radiation field inside accelerator facilities affects
the corrosion of metal components and formation of metalrelated colloid in the cooling water. Effects of radiation on
corrosion of copper and formation of copper-related colloid
in water were studied.

#U PPMINTRODUCTION#U PPMI.

#U PPM

Keywords – Radiation effect, Corrosion, Colloid

irradiation at the �-ray irradiation facility or the e-LINAC
facility. The results for the LINAC experiments wereobtained at the downstream (0-deg) sample position, where
flux of neutrons can be neglected compared to flux ofbremsstrahlung. The results demonstrate that irradiation ofhigh-energy photons (�-ray or bremsstrahlung) clearly affects
the elution of Cu into water and formation of Cu-related
colloid / particle in water phase.
Concentration of soluble Cu species increased with photon
intensity. Formation of colloidal species was also noticeable
at intense photon environment. Furthermore, qualitativeevaluations using water-quality test kits clarified that H2O2
and O3 were generated in water by irradiating �-ray orbremsstrahlung. These results imply that high-energy photons
produce active species, such as H2O2, O3 and OH radicals, inwater. These active species may affect various processes,
such as corrosion of Cu materials, transfer of Cu species into
water as a soluble species or colloidal species, and growth ofcolloidal species in water phase.
Time dependence of size-profiles for Cu species formed atconstant dose rates imply that dissolution of Cu materials inwater and formation of Cu-related colloid occurring in
intense radiation environments progress in the time scale ofseveral hours to hundreds hours.

#U PPM

Abstract – Radiation effects on corrosion of copper in water andcolloid formation were investigated. Irradiation experiments using
60
Co �-ray irradiation facility and electron LINAC demonstrated
that high-energy photons promote corrosion and elution of copper
into water and formation of copper-related colloids / particles inwater phase.

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Figure 1 Soluble (0-3 nm) and colloidal concentrations (3-7, 7-16, 16-200nm) of Cu in water without irradiation, after the irradiation at Co-60 �-ray
irradiation facility, and after the irradiation at electron LINAC. Irradiation
time : 2.0 h, 12 h
[1]

－ 237 －

K. Bessho et al., Eleventh Meeting of the Task-Force on Shielding
Aspects of Accelerators, Targets and Irradiation Facilities (2012)

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

24-ENP-04

Study on Unattached Fraction of Radon Progeny and its Environmental Influence
Factors
1

Lu GUO1, Lei ZHANG2, Qiuju GUO1
State Key Laboratory of Nuclear Physics and Technology, Peking University, Beijing 100871,China
2
Solid Dosimetric Detector and Method Laboratory, Beijing 102205, China

Abstract – The exposure of radon and its progeny contributes
more than half of the natural radiation exposure received by the
public. The unattached fraction of radon progeny is an importantparameter in radiation dose estimation through dosimetric
process; however, not so much data has been reported. For abetter understanding on temporal variation and its environmental
influence factors of the unattached fraction of radon progeny, aseries of field measurements were performed periodically by
adopting a new developed integrating monitor for measuring
unattached fraction of radon progeny, and an instrument formeasuring aerosol concentration in both indoor and outdoor
environments.
It was shown by the measurement results that the ranges ofunattached fraction of radon progeny in indoor and outdoor
environments all over the year were 8.4%�16.5% and9.4%�28.2%, respectively. Seasonal and diurnal variations of theunattached fraction of radon progeny were also analyzed. It
comes to the conclusion that during the winter season theunattached fraction of radon progeny is stable in indoor
environment because of the little change on aerosol concentration�
temperature and humidity indoor in Beijing area, while on theother hand, it changes a lot in outdoor environment due to thegreat undulation of atmospheric factors, and the average of theunattached fraction of radon progeny is higher in outdoor
environments than that of indoors. While in summer, theunattached fraction of radon progeny in indoor environment wasclose to the values of outdoor environment, and both of them hadlower average than that in winter.
Keywords – radon;
conversation factor

unattachedfraction;aerosol;dose－ 238 －

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

Preliminary Study on Measuring Radon Progeny Concentration Using Alpha/Beta
Spectroscopic Method

1

Abdumomin Kadir1, Lei Zhang2, Qiuju Guo1, and Juncheng Liang3
State Key Laboratory of Nuclear Physics and Technology, School of Physics, Peking University, Beijing, 100871, China
2
Solid Dosimetric Detector and Method Laboratory, Beijing, 102205, China
3
Ionizing Radiation and Medical Science, National Institute of Metrology, Beijing, 100013, China

Abstract – The accurate measurement of radon progeny
concentration is essential for dose evaluation of radon exposure.
Alpha/beta spectroscopic methods have great advantage comparing
with traditional total counting methods as well as alpha-spectrum
methods. This work introduces a radon progeny measurement
method using alpha/beta spectroscopy. Sample 10 min with unit flowrate (1 L/min), 1 min delay and then record the alpha/beta
spectroscopy at 3 min internals for 30 min, the uncertainty of thismethod is 9.3% in a typical indoor environment (CRn=40 Bq/m3,
F=0.4). Experiment comparison results confirm that this method
could greatly improve the measurement precision of radon progeny
concentration.
Keywords – radon progeny; spectroscopic method; least-squarecalculation; accurate measurement;－ 239 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

24-ENP-06

The Measurement Comparability of 134Cs and 137Cs in Foodstuff Samples in Japan- Result of Inter-Laboratory Experiment for Certification of Certified Reference
Material
Tsutomu Miura1, Yoshitaka Minai2, Shoji Hirai3, Hiroshi Iwamoto4, Chushiro Yonezawa5, Yoshinobu
Uematsu6, Akira Okada7�Masami Shibukawa8�Koichi Chiba1�Kiyoshi Kitamura9�Takahiro
Yamada10�Kazutoshi Kakita11�Isao Kojima11
1

National Metrology Institute of Japan, AIST, 2 Musashi University, 3Tokyo City University, 4Environmental Technology
Service Co, Ltd., 5Japan Institute of International Affairs, 6Japan Accreditation Board, 7TERM, 8Saitama University, 9Japan
Chemical Analysis Center, 10Japan Radioisotope Association, 11The Japan Society for Analytical Chemistry

Abstract – The measurement comparability of 134Cs and 137Cs infoodstuff samples in Japan was evaluated based on the interlaboratory experiment for certification of certified referencematerial (CRM) for environmental radioactivity analysis.
Keywords – measurement comparability, certified referencematerial, Environmental radioactivity, 134Cs, 137Cs, interlaboratory experiment method, Uncertainty

I.

INTRODUCTION

Following the mega earthquake, tsunami, and theaccident at the Fukushima No.1 nuclear power plant on
March 11, 2011, a massive amount of radioisotopes werereleased in the environment. This situation required urgent
measurements of radioactive isotopes in foodstuff samples
for human health. The CRM is essential to accurate andprecise measurement of radioisotopes in the samples. The
Japan Society of Analytical Chemistry was developed thecertified reference material of brown rice (JSAC0731 andJSAC0732) and bovine muscle flakes (JSAC0751 andJSAC0752) for measuring radioactive isotopes of 134Cs and137
Cs support by Grant-in-aid Japan Science andTechnology Agency. The certification of the 134Cs, 137Cs
and 40K in candidate CRM of brown rice and bovine
muscle for environmental radioactivity analysis was
performed by the inter-laboratory experiment method.
Twelve laboratories, including the research institutes, JCSS
(Japan Calibration Service System) accredited calibration
labs, universities, and industrial testing labs in Japan
participated in the inter-laboratory experiment forcertification. The certified values and associated expanded
uncertainties (k=2) of 134Cs, 137Cs, and 40K in brown rice
CRM were 141 Bq kg-1 ± 9 Bq kg-1, 210 Bq kg-1 ± 13 Bq
kg-1�and 75 Bq kg-1 ± 7 Bq kg-1, respectively [1]. And also,
the certified values and associated expanded uncertainties(k=2) of 134Cs, 137Cs, and 40K in bovine muscle CRM were174 Bq kg-1 ± 12 Bq kg-1, 297 Bq kg-1 ±20 Bq kg-1�and
276 Bq kg-1 ± 46 Bq kg-1, respectively [2].
In this paper, we present a measurement comparability of134
Cs and 137Cs in foodstuff samples in Japan resulting fromthat of the inter-laboratory experiments.

Instruments and methods
All participants of the inter-laboratory experiments
measured 134Cs, 137Cs, and 40K in the candidate CRM using
the Ge semiconductor detector.
Results and discussions
The example of the results of inter-laboratory experiments
is shown in Fig.1. In that case, the z-score of the allreported values ranged from -3 to 3, the all data were used
for calculation of the certified value.

Fig.1 The result of inter-laboratory experiment of 134Cs in JSAC
0731 brown rice CRM.

Acknowledgement
Our deepest appreciation goes to participants the interlaboratory experiment for certification of CRMs.
APSORC’13 HEADING (WITHOUT NUMBER)[1][2]－ 240 －

Certificate of JSAC 0731, 0732 Brown rice certified referencematerialforenvironmental
radioactivity,
www.jsac.or.jp/srm/CRMJSAC0731.
Certificate of JSAC 0751, 0752 Bovine muscle flakes certified
referencematerialforenvironmental
radioactivity
www.jsac.or.jp/srm/CRMJSAC0751.

24-ENP-07
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Synthesis and Characterization of Volatile Technetium Compound
Bradley C. Childs1, Frederic Poineau2, Ken R. Czerwinski2
1

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

Abstract – Technetium-99 is an important fission (T1/2= 2.13.105 y)
product of the nuclear industry. Technetium in its highest oxidation
state (VII) is highly mobile and can represent a threat to theenvironment [1]. There are over 55 million gallons of high level
mixed waste located at the Hanford site. Waste tanks at the Hanfordsite contain Tc that could potentially leak, and in the context ofmanagement of technetium, a glass waste form was proposed tocounteract the issue [2]. In the process of synthesizing melt glass
between the temperatures of 600 °C and 1100 °C, volatiletechnetium compounds were observed in the reaction tube. These
compounds displayed characteristic colors based upon the reaction
environments of either breathing air or nitrogen gas. A breathing
air atmosphere produces a red compound that adheres to the wallsof the reaction tube. An atmosphere of nitrogen gas produces awhite compound that was observed on the walls of the reaction tube.

B. Additional Synthetic Routes
One way to determine the exact species being volatilized
is to observe the technetium compound being used in thebatch synthesis material. NaTcO4 will also be observed
without adding it to the batch material to see if volatile
species are still produced in the same manner. Other
pertechnetate salts will be observed as well with and without
the batch material.

Keywords – Technetium, Red, Volatile,I.

INTRODUCTION

A study of how technetium behaves as a waste-form andthe speciation that correlates with the waste-form has
garnered much attention. One of the proposed methods tocreate a waste-form was vitrification. The main issue withvitrication is dealing with volatile products that form in theprocess of manufacturing the glass from vitrification. The
temperatures that are reached allow for radioactive
compounds to become airborne and can present a problem
when trying to retain all of the radioactive material. As it
pertains to technetium, Tc2O7 boils at 311 °C and TcO2 boils
at temperatures above 900 °C which is problematic because
melting temperatures exceed the boiling points of thosecompounds very easily [3]. Most speciation studies go into
how the glass is formed, but the focus of the study at hand is
to look at the volatilized species.

Fig.1: Volatile Red CompoundFig.2: Volatile White Compound

REFERENCES

A. Vitrification Process
The process that was used to produce volatile species
involves making glass material. Melt glass formers based on
the LAWE4H batch composition were used while loading 1%
technetium by mass to this mixture by way of sodium
pertechnetate (NaTcO4) [4]. A temperature range between
600 °C and 1100 °C will be used to produce the material.
Two different environments will be created while producing
volatile species. The first of which will be breathing air.
Under these conditions we expect to see a red volatile species(Fig.1). The second environment will be nitrogen gas. It is
expected that a white volatile species will be observed fromthis synthesis (Fig.2).

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

－ 241 －

Y. Liu, J. Terry and S. Jurisson, Radiochim. Acta, 2007, 95, 717–725
W.W. Lukens et al., Dissimilar behavior of technetium and rhenium inborosilicate waste glass as determined by X-ray absorption
spectroscopy. Chem. Mater. 19, (2007) 55-56.
J.G. Darab and P.A. Smith Chem. Mater. 1996, 8, 1004-1021.
DM-100 Melter Testing to Support LAW Glass Formulation
Correlation Development,” K. Abel and J. Westsik, WTP Test
Specification, 24590-WTP-TSP RT-04-0004, Rev. 0, 1/12/05.

24-ENP-08
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Time Variation of Concentrations of Radioactive Cesium-134, 137 and Iodine-129 in
the Ohori River, Chiba Prefecture, Japan
Nao Shibayama1, Keisuke Sueki2, Kimikazu Sasa 2,3, Yukihiko Satou1, Tsutomu Takahashi3,
Masumi Matsumura3, Hiroyuki Matsuzaki4, Michio Murakami5, Rey Yamashita6, Mahua Saha6,
Hideshige Takada6, Yukio Koibuchi7, Soulichan Lamxay7, Taikan Oki8
1

Graduate School of Pure and Applied Sciences, Univ. of Tsukuba
2Faculty of Pure and Applied Sciences, Univ. of Tsukuba
3
Research Facility Center for Science and Technology, Univ. of Tsukuba
4
MALT, The Univ. of Tokyo
5“Wisdom of Water”(Suntory), The Univ. of Tokyo
6
Tokyo Univ. of Agri. & Tech.
7
Graduate School of Frontier Sciences, The Univ. of Tokyo
8
Insitute of Industrial Science, The Univ. of Tokyo
Abstract
Radioactive nuclides emitted from the Fukushima Dai-ichi
nuclear power plant were observed for the long term in Ohori River,
Chiba Prefecture, Japan. In this presentation, we report time
variation of concentrations of 134Cs, 137Cs and 129I in the suspended
soils (SS) and dissolved matter (DM) from the flow of the river were
measured. The concentrations of radioactive cesium 134 and 137 in
SS were gradually decreasing in long term observation and risingon the rainy day. The DM/SS ratios of 137Cs were almost constantover time. In the DM, the 129I data showed strong correlation withcesium data.
Keywords
Cesium-134, 137 ; Iodine-129 ; time variation ; river waterI.

INTRODUCTIONRadioactive cesium and iodine emitted from the
Fukushima Dai-ichi nuclear power plant were detected fromenvironmental water, reflecting an aspect of dynamics ofthese radioactive nuclides in the environment. In themetropolitan area, comparatively high concentration ofradioactive cesium isotopes were detected from sediment of
Ohori River in Chiba Prefecture[1]. In this work, the long-term
variations of the concentrations of the radioactive cesium andiodine in the suspended soils (SS) and dissolved matter (DM)were measured for Ohori River, and the trend of nuclides was
discussed.
II.

III.

RESULTS AND DISCUSSION

Time variations of concentration of radioactive cesium in
the SS of Ohori River are shown in Fig.1. The average
concentrations of radioactive cesium were gradually
decreasing in long term observation. The concentration ofradioactive nuclides in the SS sampled by Auto-Sampler wastreated as average for a certain period. The momentary
concentrations of radionuclides in the SS were obtained fromthe river water sampled every two or three weeks. In mostpoints, the momentary concentration was lower than the
average concentration, but a few points which corrected inrainy differed from the tendency due to rain fall. The DM/SS
ratios of 137Cs were almost constant, which may consideredas the equilibrium constant of cesium between SS and DM. In
the DM, the 129I data showed strong correlation with cesium
data. The iodine data, however, is insufficient.

METHODSThe SS samples of two or three weeks are collected by the
SS Auto-Sampler[2] which installed at the middle of river near
the Showa-bridge, and the river water samples are collected
every two or three weeks in the same place from May, 2012
at Ohori River. The river water was filtrated. The SS was
defined as residue of 0.7 �m filter and the DM was defined as
the component passing through the 0.2 �m filter. The
concentrations of 134Cs and 137Cs were determined from the �ray spectrum obtained by HPGe detectors. 129I in the river
was investigated about the same samples by AMS at MALT,The Univ. of Tokyo[3].

Fig.1. Time variation of concentration of radioactive cesium in SS of Ohori
River. Solid line and dashed line show the average concentration of 137Cs
and 134Cs, respectively. Square points and triangular points show momentary
concentrations of 137Cs and 134Cs, respectively.

REFERENCES
[1]
[2]
[3]

－ 242 －

Ministry of Environment, 2011,
http://www.env.go.jp/jishin/monitoring/result_pw111222-1.pdf
Phillips et al. (2000) Hydrol. Process. 14, 2589-2602.
H. Matsuzaki et al., Nucl. Instr. and Meth. B, 259, 2007, 721–726.

24-ENP-09

Ra isotopes in Na-Cl type groundwater in Japan
1

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

Low Level Radioactivity Laboratory, Institute of Nature and Environmental Technology, Kanazawa University, Wake, Nomi,
Ishikawa 923-1224, Japana
Department of Radiation Protection, Nuclear Science Research Institute, Japan Atomic Energy Agency, Tokai-mura, Ibaraki
319-1195, Japan.

Abstract – Radium isotopes (226Ra and 228Ra) were measured for
Na-Cl type groundwater samples collected from Hokkaido, Aomori,
Akita and Yamagata Prefectures in Japan. The 226Ra contents variedin the wide range from 9 - 5000 mBq kg-1 and their values wereroughly correlated to the total dissolved solid (TDS). Activity ratiosof 228Ra/226Ra in groundwater ranged from 0.3 – 4.2 and most ofthem clustered around those of 232Th/238U of common rocks in Japan.
These observations agreed well with the previous results from
Ishikawa, Toyama and Niigata Prefectures, and overall indicatedthat Ra was mainly transported into the groundwater by �-recoil
process and its concentration in groundwater was constrained byadsorption-desorption reaction depending on salinity.
Keywords – Ra isotopes, Na-Cl type groundwater, �-recoil,adsorption-desorption reaction

I.

INTRODUCTION

Radium isotopes (226Ra (T1/2=1600 y) and 228Ra (T1/2=
5.75 y)) in groundwater have been investigated worldwide
from the various viewpoints such as geochemical interest andradiation protection. Activities of Ra isotopes in groundwater
vary widely, and anomalously high 226Ra contents over
several tens of Bq kg-1 have been found in saline waters andbrines.
In Japan, Ra isotopes in groundwater have been
investigated mainly in relation to the radioactive hot spring,and groundwaters with high 226Ra concentration over 1 Bq
kg-1 have been found at hot springs such as Arima and
Masutomi. Since these hot springs are commonly originatedfrom granite areas where have relatively high U contents, it
was considered that such higher 226Ra in water was attributed
to the U in granite. Recently, Na-Cl type groundwaters withintermediate salinity (ca.1-36‰) have been obtained from thedeep wells with the development of more sophisticateddrilling techniques. We have studied the distribution of Ra
isotope concentrations in these Na-Cl type groundwatersfrom coastal area and sedimentary basin in Ishikawa, Toyama
and Niigata Prefectures facing to the Japan Sea of Central
Japan, and found that some of them contained relatively high226
Ra over 1 Bq kg-1 even in coastal areas and sedimentarybasin.
Authors are interested in clarifying the geochemicalmechanism of such high 226Ra occurrence, and expanded
research to groundwater at Hokkaido and Tohoku Districts(Aomori, Akita and Yamagata Prefectures). In this study, we
report the Ra contents in Na-Cl type groundwaters from theseareas. Constraining factors which Ra content becomes higher
in groundwater will be mainly discussed, including the results
obtained previously from other areas such as Ishikawa,Toyama and Niigata Prefectures.
II. MATERIAL AND METHODSNa-Cl type groundwater samples were collected from thecoastal area and sedimentary basin in Hokkaido, Aomori,
Akita and Yamagata Prefectures in Japan. Radium isotopes
were co-precipitated with BaSO4, and their activities were
determined by �-ray spectrometry.
III. RESULTS AND DISCUSSION
Activities of 226Ra in groundwater from Hokkaido, Aomori,
Akita and Yamagata Prefectures were observed in the wide
range from 9 - 5000 mBq kg-1. These 226Ra activities ingroundwater samples showed an increasing tendency withincreasing total dissolved solid (TDS) (Fig. 1). Activity ratiosof 228Ra/226Ra of them varied from 0.3 – 4.2, and most ofthem clustered around 0.5 - 2. These ratios were nearly
similar to those of 232Th/238U of common rocks in Japan.
These observations agreed well with the previous results from
Ishikawa, Toyama and Niigata Prefectures.
Ra isotopes are supplied into groundwater by someprocesses: 1) decay of dissolved parent nuclides (Th isconsidered as insoluble element); 2) weathering and/or
dissolution of aquifer rock; 3) �-recoil at water-rockinterface; and 4) desorption reaction at water-rock interface.
Results both relationships between 226Ra and TDS andactivity ratios of 228Ra/226Ra in groundwater samples obtained
here indicated that Ra was mainly ejected into thegroundwater by �-recoil process and its Ra was constrainedby adsorption-desorption reaction depending on salinity.

－ 243 －

Fig. 1 Relationship between 226Ra-TDS in groundwater

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

24-ENP-10

A new method to estimate 210Po/210Pb activity ratio in atmospheric aerosol byalpha spectrometry
1

2

N. Momoshima1, S. Nishio2, K. Hibino2, S. Sugihara1

Radioisotope Center, Kyushu University, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Graduate School of Science and Technology, Kumamoto University, Kurokami, Kumamoto 860-8555, Japan

Keywords – aerosol, 210Po 210Pb activity ratio, alpha spectrometry
Various kinds of radionuclides are observed in
the atmosphere, among them radon and its daughter
nuclides attached to aerosol are most abandon andthe daughter nuclides finally decay to 210 Pb within a
few hours. The formed 210 Pb (22.3 y) decays to 210 Bi(5 d) followed by 210 Po (138 d). The half life of210
Po is rather long compared to the removal processfunctioning to atmospheric aerosols; therefore
210
Po/ 210 Pb activity ratio as well as 210 Bi/ 210 Pb
activity ratio is usable to estimate residence time ofaerosol in the atmosphere.
The growth curves of 210 Po from 210 Pb in aerosol
are shown in Fig.1 as a function of initial210
Po/ 210 Pb activity ratios. The growth patterndiffers depending upon the initial 210 Po/ 210 Pb
activity ratio. The initial activity ratio varies in theenvironment due to additional input of 210 Po toatmosphere from such as volcanic release, fireburning of vegetation etc. Atmospheric migration ofsoil dusts increases the initial activity ratio because
of secular radioactive equilibrium in soil. Under thegeneralenvironmental
circumstances
major
radionuclide in aerosol would be 210 Pb and then,210
Po is considered to be the main alpha particle
emitted from aerosol. If we measure a growth of210

Po activity with time and compared with growth
pattern shown in Fig. 1, we can estimate the210
Po/ 210 Pb activity ratio of the aerosol samples.
The theoretical calculation of 210 Pb- 210 Bi- 210 Po
equilibrium suggests that 210 Po/ 210 Pb slightly
depends on initial 210 Bi/ 210 Pb activity ratio. The
measurement time of a few days would be necessary
for alpha spectrometry to obtain statistically
acceptable counts. Then, the 210 Po growth patterndependent on the initial 210 Bi/ 210 Pb activity ratio
would be obscure. However, the proposed method is
simple and no chemical separation is necessary.
The growth of 210 Po activity in the aerosol
collected on a membrane filter and measured several
times with a silicon surface barrier detector of analpha spectrometer is shown in Fig. 2 as an example.
The growth pattern is analyzed under theassumption that the initial 210 Bi/ 210 Pb activity ratio
is 0.6, which would be the representative value inthe general environment [1]. The least square fitting
was carried out to obtain the initial 210 Pb and 210 Po
counts. The measurements were done at theidentical geometrical configuration between thedetector and the sample, and in a series ofmeasurements the same detector of the same alpha
spectrometer system was used.
[1] Rangarajan, C., J. Environ. Radioactivity, 15, 193-206(1992�

Fig. 1 Theoretical change in 210Po/210Pb activity ratiowith time at different initial 210Po/210Pb activity ratio.

Fig. 2 Counts of 210Po measured with the alpha
spectrometer for the aerosol collected on a membranefilter and the theoretical counts obtained by least square
fitting.

－ 244 －

24-ENP-11
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Sedimentary environment inferred from sedimentation rates by210

Pb and 137Cs

and their inventories in Mutsu Bay, Japan
Kazuhito Hamataka1, Seiya Nagao1, Michio Kato2, Isao Kudo3, Masayoshi Yamamoto1
1

Low Level Radioactivity Laboratory, KINET, Kanazawa University, Ishikawa 923-1224, Japan
2
Graduate School of Science, Kanazawa University, Kanazawa, Ishikawa 920-1192, Japan
3
Graduate School of Fisheries Sciences, Hokkaido University, Sapporo 060-0808, Japan

Abstract –Fourteen sediment cores were collected from Mutsu Bay,
Aomori in Japan, and excess 210Pb and 137Cs were measured
�-spectrometrically. The spatial distributions of sedimentation rates
by 210Pbex and 137Cs and their inventories were studied in order toclarify whole pictures about the sedimentary environment of Mutsu
Bay. Excessively post-depositional mixing (up to a depth of 10-15cm) of surface sediments by bioturbation was observed on the210
Pbex depth profiles in cores from the offshore areas. The
sedimentation rates calculated varied in the wide range from 0.04 to
0.2 g/cm2/y. The sedimentation rates using 137Cs method could not
be applied. Apart from the 210Pbex inventories from the nearshorearea, the responding inventories (17-30 kBq/m2) from the offshore
area were higher than the reported value of ca.15 kBq/m2 in thesurrounding soils, indicating that the sediment focusing due to theinner current etc., to the deeper area from the surroundingnearshore area, affects the sediment accumulation in the offshorearea.
Keywords –Mutsu Bay, Aomori, sedimentation rate, inventory, 210Pb,
Cs, sedimentary environment

137

I.

Measurements of 210Pb and 137Cs: The samples were then sieved
through a 2-mm mesh to remove pebbles and fragments of shell, andpulverized in an agate mortar to obtain homogeneous samples.
An aliquot of 5-10 g of sample was packed into a plastic vessel andstored for more than 3 weeks. The 210Pb, 226Ra (from daughter
nuclide 214Pb) and 137Cs were measured by a low–background �-ray
spectrometer with a high pure Ge detector (planar or well type).
The
spectrometerwascalibrated
withstandards
preparedbytheNew
Brunswick Laboratory (NBL)
reference materials No. 42-1
(4.04%
uranium),andanalytical
grade
KCl.
Unsupported 210Pb activity(210Pbex) was calculated fromthe difference between the total
210
Pb and the 226Ra (from 214Bi)
contents.
Fig. 1 Sampling sites in Mutsu Bay
III. RESULTS AND DISCUSSIONINTRODUCTION

Semi-enclosed bay is sensitive to human activity and change ofnatural environment, and these directly and strongly impact in its
sedimentary environment.
Mutsu Bay (surface area of 1580 km2, average depth of 34 m, andmaximum depth of 75 m), which is located in the north of Honshu inJapan, is indirectly connected with the open sea by a narrow channel
through which seawater flows in and out the bay. The east floor of
Mutsu Bay is relatively flat and shallow (40 m deep on average).
The coastal areas are excessively populated and extensive scallop
farming has been popularly practiced since 1970s. The present–day,
death of scallop due to overcrowded cultivation and generation of
red tides by declining water quality are going on, and muds aremarkedly accumulating in the offshore areas (Minoura et al. (1992)).
We have been interested in clarifying whole pictures about such
sedimentary environment of Mutsu Bay, investigating the sediment
rates by using radioactive 210Pb and 137Cs and their inventories in
sediments.
II. MATERIAL AND METHODSCore sampling: The core sediment samples were collected duringcruises in May and August 2011, and June and September 2012. A
small gravity corer (3.5 or 8.0 cm in diameter) was used to collectsurface sediments (20-40 cm long) at 14 locations (Fig. 1). The
obtained cores were immediately cut every 1 cm from top along thecore, and after taking them to laboratory the samples were freezedried.

To date, activity measurements of 210Pb and 137Cs were finishedfor cores from St.1 to St.10. Overall, the sediments (Sts. Sts. 2-4 and6-8) from the offshore area were mostly mud, while sand andcoarser sediments, with their low mud contents, are restricted to thenearshore area. Surface mixed layers (up to a depth of 10-15 cm)
were observed on the 210Pbex depth profiles from the offshore area,
evidencing the excessively post-depositional mixing of surface
sediments by bioturbation and so on. For other sites, 210Pbex
concentrations declined more or less exponentially with depth.
Sedimentation rates calculated for these cores varied in the wide
range from 0.04 to 0.2 g/cm2/y. Sedimentation rates using 137Cs
method could not be applied. A generally increasing trend in
sedimentation rate after the late 1970s, when correspond to the rapid
increase of scallop-production activity, was clearly observed at St.10.
Excess 210Pb and 137Cs inventories were calculated as the sum of210
Pbex and 137Cs through a sediment core, respectively. The 210Pbex
inventories ranged from 7-30 kBq/m2. Apart from the values (7-9kBq/m2) from the nearshore areas, the responding inventories (1730 kBq/m2) for cores (Sts. 2-4 and 6-8) from the offshore areas were
somewhat higher than the reported value of ca.15 kBq/m2 estimatedfor the surrounding soils, indicating that the sediment focusing due
to the inner current etc., to the deeper area from the surroundingnearshore area, affects the sediment accumulation in the offshore
area. The 137Cs inventories (0.08-0.14 kBq/m2) were clearly lower
than its inventories (around 3 kBq/m2) in the surrounding soils.
Further works are going on organic contents and grain-size of
sediments.
K. Minoura et al. (1992), Marine Geology, 103, 487-502.

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

24-ENP-12

Distribution of radiocarbon in Japanese agricultural soils
Nobuyoshi Ishii, Keiko Tagami, Shigeo Uchida
Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences
Abstract – Distributions of C-14 in solid, liquid, and gas phases
were determined by batch sorption tests using 142 Japanese
agricultural soil samples. The agricultural soils used wereclassified into “paddy” and “upland” soils. Each of the soil
samples was suspended in deionized water containing [1, 2-C-14]
sodium acetate and shake-incubated for 7 days. After the
incubation, the distributions of C-14 in solid, liquid and gas
phases were approximately 35%, 5% and 60% of the spiked C-14,
respectively. These results suggested that if the C-14 of acetate
migrated from a TRU repository site to agricultural soils, most of
the C-14 would be released into the air and the rest would be
distributed in the soil solid phase. The distribution of C-14 in gas
phase was lower for upland soils than for paddy soils..
Keywords – TRU waste, Radiocarbon, Distribution, Agricultural
soils

I.

INTRODUCTION

Transuranic (TRU) waste is generated during theoperation and dismantling of reprocessing facilities andmixed oxide (MOX) fuel fabrication facilities, and thewaste contains radionuclides that have long half-lives. The
dominant nuclides contributing to the dose from TRU
waste are C-14 and I-129 [1]. These radionuclides,
therefore, are very important in safety assessments forgeological repositories of TRU waste.
C-14 could be released from a geological repository
over a timescale of several thousand years. Because there
is little information regarding reliable migration andrealistic transport models, the possible migration of C-14
from a TRU repository site to the biosphere throughgroundwater presents some concern. It is, therefore,
required to clarify the behavior of C-14 in the environment
due to the reduction of exposure to C-14.
In general the environmental behavior of chemicals is
influenced by various factors such as land use, soil type,temperature, pH, oxidative conditions and so on. The
behavior of C-14 may differ between paddy and uplandsoils. In this study, distribution of C-14 for both Japanese
paddy and uplands was determined and compared. The
relationships among the distribution of C-14 and selectedsoil properties were discussed.

For batch culture experiments, 0.5-g of air-dried soil
sample was soaked with a 5-mL of the radioactive solution.
The culture was shake-incubated at 25���������������������
dark. After the incubation, the C-14 activities of the culture
were determined to estimate the distribution of C-14 insolid, liquid and gas phases by measuring C-14 in solid,
liquid phase with a liquid scintillation counter.
III. RESULTS AND DISCUSSION
Distribution of C-14 in solid, liquid and gas phases were
determined on day 7 of incubation. The mean values of
those distributions were 59.1 ± 8.6% in as phase, 35.4 ±
7.7% in solid phase, and 5.5 ± 5.4% in liquid phase. For
each phase, a positive excess kurtosis was found (2.7 forsolid, 7.1 for liquid and 4.2 for gas), and the interquartile
range, which is the difference between the third and firstquartiles, was less than 10%. Results of these statisticalanalyses mean that the distribution of C-14 in each phase
had small variation ranges for Japanese agricultural soils.
It should, however, note that there were big differences
between the two extreme values for each phase. These
values were far from the average and thus must be paid
attention in safety assessments for geological repositories
of TRU waste.
Distribution in liquid phase was correlated positively
with pH of the culture solution. Similar results were foundin our previous study [3].
Significant differences in the distribution of C-14
between paddy and upland soils were found for all phases.
Distributions in solid and liquid phases were higher for the
upland soils than for paddy soils, but, on the other hand,
distribution in gas phase was lower for upland soils than forpaddy soils. The difference in distribution in liquid phase
may be explained by pH of the solution because pH of theupland samples was significantly higher than that of the
paddy samples.
This work was supported by the Agency for Natural
Resources and Energy, the Ministry of Economy, Tradeand Industry (METI), Japan.
REFERENCES

II. MATERIALS AND METHODS
A total of 142 agricultural soils (63 paddy soils and 79
upland soils) were collected throughout Japan. The soil
samples were dried at room temperature, and then passed
through a 2 mm mesh sieve to obtain fine particles.
[1,2-C-14] sodium acetate was used as the chemical
form of C-14. This solution was diluted with deionizedwater to a specific activity of 1.8 kBq mL-1 and was filtersterilized to remove microorganisms [2]. The specificactivity corresponded to 4.2 x 10-1 nmol mL-1.

[1]

[2]
[3]

－ 246 －

JAEA, FEPC, Second progress report on research and development
for TRU waste disposal in Japan –Repository design, safetyassessment and means of implementation in the generic phase-,
JAEA-Review 2007-010, FEPC TRU-TR2-2007-01(2007).
N. Ishii, S. Uchida, “Bacteria contributing to behaviour ofradiocarbon in sodium acetate,” Radiat. Prot. Dosimetry. 146, 151154 (2011).
N. Ishii, H. Koiso, H. Takeda, S. Uchida, “Partitioning of 14C into
solid, liquid and gas phases for various paddy soils in Japan,” J. Nucl.
Sci. Technol., 47, 238-243 (2010).

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

Lateral distributions of 228Th/228Ra and 228Ra/226Ra ratios
in surface waters of the Sea of Japan and their physical implications
Y. Furusawa1, M. Inoue1, S. Nagao1, M. Yamamoto1, Y. Hamajima1, H. Kofuji1, K. Yoshida1
Y. Nakano1, K. Fujimoto2, A. Morimoto3, T. Takikawa4, Y. Isoda5
1

2

Low Level Radioactivity Laboratory, Kanazawa University
Fisheries Research Agency, National Research Institute of Fisheries Science3
Hydrospheric Atmospheric Research Center, Nagoya University
4
National Fisheries University
5
Graduate School of Fisheries Sciences, Hokkaido University

Abstract –We examined 228Th/228Ra and 228Ra/226Ra ratios in surface watersfrom the Sea of Japan by low background �-spectrometry. Theselateral distributions clarified the aspects of physical movement ofgeochemical species on surface.
Keywords –228
Th/228Ra ratio, 228Ra/226Ra ratio, Sea of JapanI.

INTRODUCTIONof the Kuroshio water in the Honshu Island side. On the other
hand, 228Th/228Ra ratio of waters on the transect A exhibited
gradual decrease (<0.01 to 0.12) from south to north,dominantly reflecting a higher flux of biogenic particles in
shelf water [5]. In this study, we examined the lateral
distributions of 228Th/228Ra ratio as well as 228Ra/226Ra ratioon surface of the Sea of Japan and clarify the circulation
patterns of particles and water masses. This is an operationthat we are currently engaged in, by obtaining additionalsurface water samples.

Many researchers have studied the flow pattern of the
Tsushima Warm Current (TWC), a major feature of the flow
patterns in the Sea of Japan, using various techniques [1].
However, the origin and characteristics of the circulation
pattern of the TWC have not yet been well clarified becauseof the markedly complicated seasonal variation in thecirculation. The seasonal variation in the 228Ra/226Ra ratio
recorded for the surface waters of the Sea of Japan isconsidered to be mainly controlled by the remarkable changes
in the mixing ratio of the 228Ra-poor Kuroshio (228Ra/226Ra =0.2) and the 228Ra-rich continental shelf waters (228Ra/226Ra =3.5) within the East China Sea (ECS) [2]. Activity of particlereactive 228Th (half-life, 1.91 y) in seawater is governed bybiogenic particle behavior, and therefore the combination of
228
Th and 228Ra activities (228Th/228Ra ratio) in seawater
samples is useful for the study of scavenging processes in the
Sea of Japan.
II. METHOD AND SAMPLING SITE
We collected 165 surface water samples (20 L) during
the research expeditions of T/V Oshoro Maru, R/Vs Mizuho
Maru, Tansei Maru, Soyo Maru, and Tenyo Maru (Fig. 1).
Low-background �-spectrometry was performed on thesamples using Ge-detectors at the Ogoya Underground
Laboratory in Japan [3, 4].
III. RESULTS AND DISCUSSION
Along the Tsushima Strait, the 228Ra/226Ra ratio ofsamples on the transect A gradually increased from south tonorth (from 0.8 to 2.3). On the transect B, the 228Ra/226Ra
ratio of coastal-side waters (0.6-0.8) was lower than that ofoffshore-side waters (1.2). This reflects a higher mixing ratio

Fig. 1. Sample locations for seawater

References[1] Hase et al. (1999) J. Oceanogr. 55, 217-234[2] Nozaki et al. (1989) Geophys. Res. Lett. 16, 1297-1300[3] Y. Nakano et al. (2008) J. Oceanogr. 64, 713-717[4] Y. Hamajima & K. Komura (2004) Appl. Radiat. Isot. 61, 179-183[5] M. Inoue et al. (2012) Geochem. J. 46, 311-320－ 247 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

24-ENP-14

Vertical profiles of 228Ra and 226Ra activities in the Sea of Japan and theirimplications for water circulation
1

M. Inoue1, M. Minakawa2,*, K. Yoshida1, Y. Nakano1, H. Kofuji1,
S. Nagao1, M. Yamamoto1, Y. Hamajima1

Low Level Radioactivity Laboratory, Kanazawa University
Fisheries Research Agency, National Research Institute of Fisheries Science*present address; National Research Institute of Aquaculture

2

II. SAMPLES and EXPERIMENTAL

AbstractBy employing low-background �-spectrometry combined

We analyzed a total of seawater samples collectedwith minimal radiochemical processing, we examined verticalin water columns in the Sea of Japan for 226Ra and 228Ra.

profiles of 226Ra (t1/2 = 1600 y) and 228Ra (5.75 y) activities in

Low-background �-spectrometry was performed using

water columns in the Sea of Japan. The results indicate

well-type Ge-detectors, which are located at the Ogoya

continuous delivery of 228Ra to the Deep Proper Water (DPW),

Underground Laboratory, Japan [2]. Detailed explanations

and clarify aspects of the transport of 226Ra and 228Ra by waterof these experimental procedures were presented elsewherecirculation.

[3]. �-Peaks for 228Ra measurement (228Ac; 338 and 911keV) on a blank sample, which was performed our

Keywords- 226Ra, 228Ra, Deep Proper Water, residence time, low-

experimental procedures on 50 L of distilled water, were“not detected” level. Therefore, we corrected only least Ra-

background �-spectrometrycontaminated Ba-reagent blank, which accounted for <1%
228

Ra for our water samples.

I. INTRODUCTION
The Sea of Japan is surrounded by the EurasianIII. RESULTS and DISCUSSION

continent and the Japanese Archipelago, and is connectedto the Pacific and other marginal seas by the very shallow

In the Japan Basin, the 226Ra activity of the water

Tsushima, Tsugaru, and Soya Straits (<~150 m of depth).

samples gradually increased from surface to the DPW (1.5-

Therefore, the deep water, so-called the Proper Water of

2.3 mBq/L). The 228Ra activity of the water exhibited steep

the Sea of Japan, has no influx from a surrounding sea,

gradients with depth from the surface to the Upper Proper

indicating unique vertical water circulation [1]. 226Ra and

Water

228

Ra of seawater have been used as powerful tracer forcontinuously delivered to the DPW by the active water

studying the migration of water masses. However, standard

circulation before it radioactively decays. The results(1.8-0.2

mBq/L),

andshort-lived

228

Ra

is

Ra of deep seawater

indicate continuous delivery of 228Ra to the DPW, andusually required very large volumes (hundreds to thousands

clarify aspects of the transport of 226Ra and 228Ra by waterof liters) because of its low activity and previously reported

circulation. The residence time of the DPW is calculated todata are not sufficient to allow investigating the details of

be about 100 y.

�-spectrometry for measuring

228

the vertical distribution of 228Ra in oceans. In the present
study, we analyzed seawater samples from the Japan Basin,Acknowledgements
We thank the researchers, captain, and crew of R/V

Yamato Basin, and Tsushima Basin within the Sea of Japan,
for 226Ra and 228Ra.

Soyo Maru for their assistance during sampling.
References[1] Gamo, T. and Horibe, Y. (1983) J. Oceanogr. Soc. Jpn 39, 220-230:[2] Hamajima, Y. and Komura, K. (2004) Appl. Radiat. Isot. 61, 179-183:[3] Nakano, Y. et al. (2008) J. Oceanogr. 64, 713-717.

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

24-ENP-15

Induced radioactivity in air and water at medical accelerators
K. Masumoto1, K. Takahashi1, H. Nakamura1, A. Toyoda1, K. Iijima1, K. Kosako2, K. Oishi2, F.
Nobuhara3
1

High Energy Accelerator Research Organization (KEK)2
Shimizu Co.
3
Tokyo Nuclear Service Co

Abstract – %'%!  ! #   (%# $   '&% % %       # %#!  #%!# %$ %   
##%! %%'%*!   ($!$#' %
$!%# % !'!) #  (%#$"$(#$!
!#* "#!%! $  &#!  %
##%!  !$ ($  * % % $! %# "!  % ! # ! %!#  ! % # $" #! % !' !)     %'%$(# *!$#' %% ! "#!%!   #!  ##%!  % %'%*! % (%# ($!&  %! 
BCPVU  L#RtDN BOE TFWFSBM L#RtDN  #$"%'* #! %* *$$!% &%'%* (%#      (#%%
Keywords – Activation, Air, Water, Medical accelerator

I.

INTRODUCTION

Accelerators have been widely used in medical
applications, especially in cancer treatment. Electron linear
accelerators have been used in hospitals for the X-ray
irradiation of diseased organs. Particle accelerators havealso been used in recent times as a powerful tool for cancer
therapy. In this work, we investigated the activation of air
and water in treatment rooms in hospitals for radiation
safety management. In the case of photonuclear reaction,
several positron emitting radioisotopes such as 15O and 13N
can be produced by the bremsstrahlung at higher than 15
MeV in air. In case of hadron irradiation, many
radioisotopes might be produced by high-energy particles.
In this work, we measured the induced activity in air andwater caused by the electron and hadron accelerators
employed for medical use, in order to determine whether
the concentration of radioactivity was below regulated
levels.

(1) Air: The air in a glove box of 250L was irradiated andsampled with a vacuum ionization chamber formeasurement. An aerosol was also collected on a HEPA
filter by an air sampler.
(2) Water: After irradiation, dose rate of water surface wasmonitored using a NaI(Tl) survey meter and the gammaray spectrum was measured using a LaBr3(Ce)scintillation spectrometer.
III. RESULTS AND DISCUSSION
At the 15 MeV irradiation of bremsstrahlung, theactivity of 13N was 0.87 Bq•cm-3 at the end of theirradiation. As the activity of 13N was also detected on thefilter paper, NOx fomation was presumed. Activity of water
could not be detected.
In case of 250 MeV proton irradiation, activities of 15O,
13
N, and 11C were found to be 1.9, 0.6, and 0.6 Bq•cm-3 at
the end of irradiation in air sampled from the glove box.
The activity of 13N was also detected on the filter paper. By
the decay curve analysis of water activity obtained from thesurface dose rate of the polyethylene tank, activities of 14O,
15
O, 13N, and 11C were found to be 91000, 12000, 1100, and
190 Bq•cm-3 at the end of irradiation, respectively.
In case of carbon irradiation, we performed irradiationof air for two times and fitted the decay curve for 14O, 15O,
13
N, 11C, and 41Ar. Average activities of 14O, 15O, 13N, 11C,
and 41Ar were 0.8, 1.1, 0.08, 0.09, and 0.006 Bq•cm-3 at theend of irradiation. By the decay curve analysis of water
activity obtained from the surface dose rate of thepolyethylene tank, activities of 14O, 15O, 13N, and 11C were
found to be 2100, 2000, 100 and 180 Bq•cm-3 at the end of
irradiation, respectively.

II. EXPERIMENTAL

IV. CONCLUSION

A. Activation of air and water(1) Electron accelerator:10 and 15MeV irradiations for 10
min were performed by Varian Clinac 2100C and Clinac
iX, respectively. Doses were 40 and 60 Gy at theisocenter, respectively.
(2) Proton accelerator: 200 MeV proton beam wasirradiated for 3.25 min on an area of 0.15 m × 0.15 m,
and 10 Gy at the isocenter.
(3) Heavy ion accelerator: Carbon beams of 400
MeV/nucleon was irradiated for 2 min on an area of 0.15
m × 0.15 m, and 10 Gy at the isocenter.
B. Activity measurement

In case of 10 MeV irradiation, we could not detect theresidual activity in air and water. In the case of 15 MeV
irradiation, we observed 13N in the air sampled from theglove box irradiated in front of the beam exit window andon the filter collected by the air samplers in the irradiation
room and the maze. In the case of 250 MeV proton
activation and 400 MeV/u carbon irradiation, activation of
air was not excessively high and the induced activity wascomparable to that induced by 15 MeV irradiation for theelectron accelerator. But induced activity of water was
extremely high. The main radionuclides detected were 13N
and 11C, 10 min after irradiation with protons and 11C, 20
min after irradiation with carbon－ 249 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

24-ENP-16

Radioactivity determination of 14C and 3H in solid waste samples by liquid
scintillation counter
Jong-Myoung Lim1*, Mun-Ja Kang1, Kun-Ho Chung1, Chang-Jong Kim1, Geun-Sik Choi1
1

Environmental Radioactivity Assessment Team, Korea Atomic Energy Research Institute989-111 Deadeok-daero, Yuseong-gu, Daejeon, 305-353, Korea

Abstract –This study reports the comprehensive efforts made toevaluate the analytical procedure for 3H and 14C in solid sample.
The sludge samples from National Physical Laboratory (NPL)
proficiency program (Environmental Radioactivity Proficiency
Test Exercise 2012) were combusted by high temperature furnace
and analyzed in LSC. The various performance tests of analyticalmethod were conducted with standard solutions. The detection
limit and uncertainty of the method were also evaluated in detail.
Major factors of standard uncertainty were grouped into counting
error, sample homogeneity, and efficiency calibration. Finally,
sensitivity tests of these major factors were performed.
Keywords – tritium, 14C, radioactivity, combusting, sludge,

As an attempt to reduce social costs and apprehension
arising from the radioactivity in environments, an accurate
and rapid assessment of radioactivity is highly desirable.
Nuclear wastes (e.g., sludge, activated carbon, oils, resins,etc.) have been consistently generated by actions to preventthe emission of radioactive pollutants from nuclear sites.
To decide a proper disposal option of these nuclear wastes,
we need an analytical method that can determine theradioactivity of 3H and 14C which exists in very low levels.
The 3H in the water (tritiated water; HTO) is major
chemical form in the environment. Through the natural orindustrial process with organic compounds, tritium is easily
converted into organic bound tritium (OBT). The HTO
form is easily lost at a temperature around 120°C, whereas
the strongly-bounded tritium with the form of non-HTO
requires high temperature of a few hundred degrees incentigrade for complete extraction. The 14C decays into 14N
through beta decay(Emax=156 kev). The main
anthropogenic origin of 14C is thermal neutron activation of
14
N in the nuclear reactor by a neutron capture reaction
14
N(n,p)14C. For extraction of 14C which exist in lattice
structure, it requires also high temperature to oxidize 14CO2
gas.
Radioactivity of 3H and 14C in waste water sludge has
been determined by the following combustion method. The
sludge samples were combusted in a purpose-designed
tubular high temperature furnace (Raddec Pyrolyser
TrioTM) which consist of six quartz tubes with the length of
1.5 m and the diameter of 1.5 cm. The combusting
temperature was controlled stepwise up to 800°C. The 3H
and 14C were trapped in 0.1 M HNO3 and carbon absorbersolution (Carbo-Sorb® E, Perkin Elmer), respectively. The
measuring of the radioactivity was carried out in LSC(Walac 1220 Quantulus, Perkin Elmer).
This study reports the comprehensive efforts made toevaluate the analytical procedure for 3H and 14C in solid

sample. The sludge samples from National PhysicalLaboratory (NPL) proficiency program (Environmental
Radioactivity Proficiency Test Exercise 2012) were
combusted by high temperature furnace and analyzed in
LSC. The various performance tests of analytical method
were conducted with standard solutions. In order toevaluate dynamic range of the method, real samples withspiking 3H and 14C standard solution were analyzed.
Duplicated samples (n=6) were analyzed to see therepeatability of this method. The results showed that
relative standard deviations for 3H and 14C are about 11%
and 2.9%, respectively. The activity concentrations werecompared statistically with the assigned values. The
deviation between the two values for 3H and 14C are about
14.5% and 5.7%, respectively. The detection limit anduncertainty of the method were also evaluated in detail.
Major factors of standard uncertainty were grouped into
counting error, sample homogeneity, and efficiency
calibration. Finally, sensitivity tests of these major factors
were performed.
Table 1. Uncertainty budget of the analytical procedure for solid sample
Uncertainty factor

3

H

14

Counting error
Sample homogeneity
Lab control standard
Efficiency calibration
Overall process

0.53
5.3
2.0
5.0
3.0

2.15
1.1
2.0
5.0
3.0

Combined uncertainty

8.1

6.6

Measured values

66.7

2.0

Uncertainty(k=1)

5.3

0.1

Standard
uncertainty

[1]
[2]

Unit

%

Bq/g

Kim, H.R., Kang, M.J., Choi, G.S. An experiment on theradioactivity characteristics of the tritium contaminated metal sample,
Annals of Nuclear Energy, 2011. 1074- 1077.
Hou, X., Roos, P. Critical comparison of radiometric and mass
spectrometric methods for the determination of radionuclides inenvironmental, biological and nuclear waste samples. Analytica
chimica Acta , 2008. 105-139.

*Corresponding author. E-mail: jmlim@kaeri.re.kr－ 250 －

H

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

Mössbauer Study of Iron Carbide Nanoparticles Produced by Sonochemical
Synthesis
1

Department of Chemistry, Tokyo University of Science
Department of Engineering Science, The University of Electro-Communications, 3RIKEN

Abstract – Iron carbide nanoparticles were synthesized byultrasonic irradiation of iron pentacarbonyl or ferrocene indiphenylmethane. Mössbauer spectra of the as-prepared particles
measured at room-temperature and 6 K indicated only one doublet.
The particles were annealed at 600 °C under argon for 2 h, and the
Mössbauer spectrum measured at room-temperature consisted of
Fe3C, �-Fe, and a paramagnetic component.
Keywords – Sonochemistry, Iron carbide, Iron pentacarbonyl,
Ferrocene, Nanoparticles

I. INTRODUCTION
Iron carbide nanoparticles of various compositions havebeen studied extensively due to their magnetic properties.
Recently, Fe/Fe3C nanoparticles were synthesized bysonicating iron pentacarbonyl Fe(CO)5 in diphenylmethaneand subsequent annealing [1]. But the mechanism of thesonochemical reaction and the effect of annealing are yet to
be investigated. In this study, we performed sonolysis of
Fe(CO)5 in diphenylmethane and both the as-preparednanoparticles and the particles after annealing were measured.
The similar experiments were performed using ferrocene
FeCp2 in order to investigate the difference of the products
depended on precursors.
II.

EXPERIMENT

0.1mol of Fe(CO)5 in diphenylmethane was irradiatedusing a high intensity ultrasonic horn (Ti-horn, 20 kHz) underargon flow for 1 h. 15 mmol of FeCp2 in diphenylmethane
was also sonicated under argon flow for 6 h. After thesonication, the products were centrifuged, washed withhexane and dried in vacuum. The product was annealed underargon flow for 2 h. The product was investigated by
Mössbauer spectroscopy, X-ray diffraction (XRD), andtransmission electron microscope (TEM).
III. RESULTS AND DISCUSSION
Nanoparticles were produced by sonolysis of Fe(CO)5 in
diphenylmethane. Mössbauer spectra were measured at 293 K
and 7 K, and there observed only one doublet; � = 0.35 mm/s,
�Eq = 0.94 mm/s at 293 K and � = 0.48 mm/s, �Eq = 0.94mm/s at 7 K. Thus, the product was a paramagnetic
compound. The XRD patterns with broad peaks and the TEM
images showed that the nanoparticles were amorphous. Then,the sample were annealed at 300 °C, also the Mössbauer

spectrum exhibited a doublet (� = 0.35 mm/s, �Eq = 0.88mm/s) at 293 K. However, Mössbauer spectrum measured at
6 K of the sample consisted of two sextets (� = 0.45 mm/s, H= 491 kOe and � = 0.42 mm/s, H = 428 kOe) and a doublet (�= 0.41 mm/s, �Eq = 1.12 mm/s). The some of the XRD
patterns of the sample corresponded to those of Fe3O4. It waspresumed that the particles after annealing consisted of
Fe/O/C. Room-temperature Mössbauer spectrum of thesample annealed at 700 °C showed only one sextet (� = 0.35mm/s, H = 511 kOe) which was assigned to �-Fe2O3.
Next, nanoparticles were produced by sonolysis of FeCp2
in diphenylmethane in order to eliminate the effects ofoxygen in the sample. Mössbauer spectra measured at room
temperature showed a doublet (� = 0.36 mm/s, �Eq = 0.94mm/s) (Fig.1a) while the spectrum measured at 6 K also
showed one doublet (� = 0.44 mm/s, �Eq = 0.98 mm/s).
However, Mössbauer spectrum of the sample after annealing
at 600 °C showed two sextets and a doublet (Fig.1b). The
sextets were assigned to cementite Fe3C (� = 0.20 mm/s, H =211 kOe) and �-Fe (� = 0.02 mm/s, H = 333 kOe). Iron
oxides were not found in the sample produced from FeCp2.
IV. CONCLUSION
Nanoparticles produced by ultrasonic irradiation ofFe(CO)5 in diphenylmethane consisted of Fe/O/C, whereas
the nanoparticles produced by sonolysis of FeCp2 in
diphenylmethane did not contain oxygen. As-preparedparticles were paramagnetic amorphous, and the particles
with magnetic nature were produced after annealing. FeCp2 is
an adequate starting material to produce iron carbide particles.
100.0

Fig.1 Room-temperaturemössbauer spectra of (a)as-prepared nanoparticles
produced by sonolysis of
FeCp2 in diphenylmethaneand (b) the sample after
annealing at 600 °C underargon flow for 2 h.

99.5

99.0

Relative velocity (%)

2

R. Miyatani1, Y. Yamada1, Y. Kobayashi2,3

98.5

100.0
99.5
99.0
98.5
98.0
97.5
-10

-5

0

5

10

Velocity (mm/s)[1]－ 252 －

S. I. Nikitenko, Yu. Koltypin, I. Felner, I. Yeshurun, A. I. Shames, J. Z.
Jiang, V. Markovich, G. Gorodetsky, and A. Gedanken, J.Phys. Chem.
B. 108, 7620-7626 (2004)

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

24-NPP-02-33"!5%2 345$9 /& )2/. &,5/2)$% &),-3 02/$5#%$ "9 05,3%$,!3%2 $%0/3)4)/.
1

K. Shiga1, Y. Yamada1, Y. Kobayashi2,3Department of Chemistry, Tokyo University of Science
Department of Engineering Science, The University of Electro-Communications, 3RIKEN

2!BSTRACT – )RON FLUORIDE THIN FILMS WERE PRODUCED BY A REACTION OF
LASER EVAPORATED IRON ATOMS WITH SULFUR HEXAFLUORIDE GAS 4HE
COMPOSITION OF THIN FILMS CHANGED VARYING A PRESSURE OF AMBIENT
3& GAS &E& WAS OBTAINED AT A HIGH PRESSURE WHILE &E& WAS
OBTAINED AT A LOW PRESSURE )T WAS ALSO DEMONSTRATED THAT THE
CRYSTALLINE SIZE OF &E& IN THE FILM WAS CONTROLLED BY THE SUBSTRATETEMPERATURE WHILE 0,$
+EYWORDS – )RON FLUORIDE-SSBAUER SPECTROSCOPY

I.

&ILM

0ULSED LASER DEPOSITIONINTRODUCTION

Pulsed laser deposition PLD in an ambient gas is a very
useful method to produce compound films controlling thecompositions [1-4]. In this study, we performed PLD of Fe
metal in SF6 atmosphere to produce iron fluoride films
deposited onto Al substrates, and their structures andcompositions were investigated. While SF6 is known as aninert gas, it decomposes to produce F atoms in a plasma
plume produced by the laser ablation followed by a
production of iron fluorides.

measured at 298 K (Fig. 2a) showed a sextet (G = 0.49mm/s, +L = 395 kOe) of FeF3 as well as an unassigned
doublet (G = 0.46 mm/s, '%Q = 1.71 mm/s). The crystal
growth on the substrate surface was enhanced by increasing
the substrate temperature while deposition to show the
sextet at 298 K. SEM images of the films revealed that thefilm produced at 873 K had rugged surface because of thecrystal growth, whereas the film produced at 293 K had asmooth surface. Similar experiment was performed at a low
pressure 1 Pa of SF6, and the Mössbauer spectra measured
at room temperature (Fig. 2b) showed a doublet (G = 1.39mm/s, '%Q = 2.76 mm/s) of FeF2. The assignments of thefilms were also confirmed by the XRD patterns. The
composition of the films clearly depended on the ambientSF6 pressures.
IV. CONCLUSION
PLD of Fe in SF6 gas produced FeF3 or FeF2 films. The
crystalline size in the film was controlled by the substratetemperature while deposition. Composition of films wascontrolled by the pressure of ambient gas.

II. EXPERIMENTAL

III. RESULTS AND DISCUSSION
PLD of Fe onto Al substrate at 298 K was performed in a
SF6 ambient gas of 5 Pa to produce an iron fluoride film.
The Mössbauer spectrum of the film was measured at 298
K (Fig. 1a) and only one doublet (G = 0.49 mm/s, '%Q =0.58 mm/s) was observed. When the same sample wasmeasured at 6 K (Fig. 1b), Mössbauer spectrum changed toshow a sextet (G = 0.59 mm/s, +L = 561 kOe) which was
assigned to FeF3. It was considered that the crystalline sizeof FeF3 in the film was very small showing thesuperparamagnetic nature at a high temperature. The XRD
pattern of the sample showed broad lines, and it was also
confirmed that the film consisted of small crystalline. Next,
PLD of Fe in SF6 of 5 Pa onto the Al substrate at 873 K
was performed. The Mössbauer spectrum of the film

Relative Intensity (%)

100.0
Relative Intensiy (%)

A block of Fe metal in a vessel filled with pure SF6 gas
was irradiated using Nd: YAG laser (523 nm, 85 mJ/pulse,
10 Hz) for 110000 pulses, and the laser-evaporated Fe
atoms were deposited onto an Al substrate. The SF6
atmosphere was maintained at a desired pressure between 1
and 5 Pa, and the Al substrate was kept at desired
temperature between 298 and 873 K using a heater. The
synthesized iron fluoride films were investigated by
Mössbauer spectroscopy, powder X-ray diffraction (XRD),
and scanning electron microscopy (SEM).

(a)

98.0

100.0

100.0
5 Pa

99.5
100.0

1 Pa

97.0
(b)

99.0

-10 -50

510Velocity (mm/s)

Fig.1 Mössbauer spectra of an iron
fluoride film produced by PLD onto
an Al substrate at 298 K in 5 Pa of
SF6 ambient gas. The film wasmeasured at (a) 298 K and (b) 6 K.

-10 -50

5Fig.2 Room-temperature
Mössbauer spectra of iron fluoride
thin films produced by PLD onto
an Al substrate at 873 K.
The pressures of SF6 are indicatedin the figure.

[1] D. Yokoyama, K. Namiki, H. Fukasawa, J. Miyazaki, K. Nomura, Y.
Yamada, J. Radioanal. Nucl. Chem., 272, (2007) 631[2] Y. Yamada, H. Yoshida, K. Kouno, J. Phys.: Conf. Ser. 217, 012096(2010)[3] Y. Yamada, H. Yoshida, Y. Kobayashi, Hyper. Int. 198, (2010) 55[4] R. Usui, Y. Yamada, Y. Kobayashi, Hyper. Int.  (2012) 13－ 253 －

10

Velocity (mm/s)

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

Iron sulfide particles synthesized in liquid phase
R. Shimizu1, Y. Yamada1, Y. Kobayashi2,3Department of Chemistry, Tokyo University of Science2
Department of Engineering Science, The University of Electro-Communications, 3RIKEN
1

Abstract – Iron sulfide particles were prepared by a polyol method
using ferrocene as a precursor. The composition of the particles
changed varying a mixture ratio of 1,2-hexadecanediol and 1octadecanethiol. Iron (III) sulfide (Fe2S3) which has not been
available in normal conditions was obtained.
Keywords – Iron (III) sulfide, Particles, Mössbauer spectroscopy,
polyol method

I. INTRODUCTION
Generally, iron sulfide is stable having divalent iron Fe(II),and few Fe(III) sulfides have been reported. As the iron (III)sulfide have been appeared in an amorphous form, and thus,
the existence has been the subject of discussion. Mössbauer
spectra of Fe(III) sulfide (Fe2S3) was reported in a literature[1], but the crystal structure was not clear. An unstable phase
could be stabilized in a form of small particles. In this study,
we synthesized iron sulfide particles using a polyol method,
and their Mössbauer spectra were measured.
II.

the samples produced under the conditions with HD (Fig. 2bd). Mössbauer parameters of the doublets had the similarvalues of iron (III) sulfide (Fe2S3) reported in the literature[1].
XRD patterns of the samples were shown in Fig. 3, and theyields of FeS, Fe1-xS and �-Fe were in good agreement withthe results obtained by the Mössbauer spectra. Besides thesewell assigned XRD patterns, unassigned XRD patterns wereobserved. The peaks marked ‘X’ in Fig. 3 may correspond to
Fe2S3 with a long-range periodic structure which wereobserved for the first time.
IV.

Iron sulfide particles were prepared by the polyol method.
Iron(III) sulfide (Fe2S3) particles having a long-range periodic
structure were found. The Mössbauer spectra of Fe2S3
showed that it was paramagnetic.

EXPERIMENTAL

A mixture of ferrocene (2 mmol), oleylamine (30 mL), 1,2hexadecanediol (HD), and 1-octadecanethiol (OT) (varying
the mixture ratio of HD / OT = 0 mmol / 8 mmol, 8 mmol / 2mmol, 8 mmol / 4 mmol, 8 mmol / 8 mmol) was heated toreflux for 2 h at 320 °C under a flow of argon. Particles were
washed three times with ethanol and hexane after air cooling.
The synthesized iron sulfide particles were investigated by
Mössbauer spectroscopy, powder X-ray diffraction (XRD),
and scanning electron microscopy (SEM).
III.

CONCLUSION

Fig. 1. SEM images of the iron sulfide
particles synthesized with the molar ratio of
HD / OT (a) 0/ 8 and (b) 8 / 4.

RESULTS AND DISCUSSION

Fig. 1 shows SEM images of iron sulfide particles. Particle
size changed dramatically by a presence of polyol: theparticles produced without HD were ~ 1 �m (Fig. 1a),whereas the particle produced with HD were 100 ~ 200 nm(Fig. 1b).
Fig. 2 shows the Mössbauer spectra measured at room
temperature of iron sulfide particles obtained in various
mixture ratio of HD / OT. The particles produced without HD
were assigned to Fe1-xS (pyrrotite) (Fig. 2a). When the small
amount of OT (2 mmol) was added, two sets of sextet wereobserved, which were assigned to FeS (troilite) and �-Fe (Fig.
2d). Two sets of doublet (� = 0.38 mm/s, �Eq = 0.73 mm/s
and � = 0.44 mm/s, �Eq = 0.47 mm/s) were observed in all

Fig. 2. Room-temperature
Mössbauer spectra of the ironsulfide particles synthesized in a
mixture of HD / OT = (a) 0 / 8,(b) 8 / 8, (c) 8 / 4, and (d) 8 / 2.
[1]

－ 254 －

Fig. 3. XRD patterns of the ironsulfide particles synthesized in a
mixture of HD / OT (a) 0 / 8, (b) 8/ 8, (c) 8 / 4, and (d) 8 / 2.
(�) FeS or Fe1-xS, (�) �-Fe, (×)
unidentified peaks

A. H. Stiller, B. Jack MaCormick, P. Russell, P. A. Montano, J. Am.
Chem. Soc. 100, 2553-2554 (1978)

24-NPP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Mössbauer and XRD studies of NiCuZn ferrites By Sol-Gel auto-combustion
1

Chenglong Lei1, Qing Lin1,2*, Haifu Huang3, Hui Zhang1, Yun He1

College of Physics and Technology, Guangxi Normal University, Guilin 541004, China
Department of Information Technology, Hainan Medical College, Haikou 571101, China
3
Nanjing National Laboratory of Microstructures and Jiangsu Provincial Laboratory for NanoTechnology,,Department of
Physics, Nanjing University, Nanjing 210093, Chinae-mail:hy@gxnu.edu.cn
2

Abstract:
The Ni0.6Cu0.2Zn0.2CexFe2-xO4 ferrites�0�x���85� have been
prepared by Sol-Gel auto-combustion method and we haveinvestigated the effect of impurity CeO2 phase to the microstructureand hyperfine magnetic field in spinel ferrite. The results of XRD
patterns confirm the average crystallite size of samples decreases
with Ce3+ substitution increasing and the lattice parameters vary as afunction of x content. 57Fe Mössbuaer spectra at room temperature
for all samples confirm the [Fe3+- O2--Fe3+] super exchangeinteraction decrease due to cerium substitution. For low temperatureauto-combustion samples it reveals one normal sextet line and one
doublet line x�����������������������-resolved ferromagnetic order.
Lattice defects are determined and Mössbuaer spectrums vary frommagnetic sextet to relaxation doublet at x�����������������������
CeO2 phase. In contrast, the Mössbuaer spectra for the samples
sintered at 800�/3h detect the secondary phase� -Fe2O3 where thecation distribution occurs and it collapses to paramagnetic
doublet(x����������3+ substitution has its maximum limit values ofsuper exchange interaction and high sintering temperature will affectthis interaction.
Keywords: NiCuZn ferrite, Rare earth, Cerium substitution,
Mössbuaer, XRD

I.

Fig.4 and Fig.5 show the Mössbauer spectra (RT) of
Ni0.6Cu0.2Zn0.2CexFe2-xO4 nanocrystalline ferrites measured atroom temperatures , respectively.

RESULTS AND DISCUSSION

We have successfully prepared ferrite system Ce3+ doped
Ni0.6Cu0.2Zn0.2Fe2O4 by Sol-Gel auto-combustion method.
The XRD patterns of ferrite as-brunt and sintered at 800�/3h
powders are shown in Fig.1-3, respectively.

The lattice parameter changes as a function of the cerium
substitution. The Mössbauer spectra (RT) results illustratethat only after low temperature auto-combustion the samples
exhibit ferromagnetism and a super para-magnetism.
[1]
[2]
[3]

－ 255 －

Aphesteguy, J.C., et al., Characterization of nanosized spinel ferrite
powders synthesized by coprecipitation and autocombustion method.
Journal of Alloys and Compounds, 2010. 495(2): p. 509-512.
Nedkov, I., R.E. Vandenberghe, and A. Zaleski, Surface magnetic
disorder in nanostructured Ni0.5Zn0.5Fe2O4 particles. Journal ofMagnetism and Magnetic Materials, 2010. 322(18): p. 2732-2736.
S.I.Moussa, R.R.Sheha, E.A.Saad, N.A.Tadros, Synthesis andcharacterization of magnetic nano-material for removal of Eu3+ ionsfrom aqueous solutions, Journal of Radioanalytical and Nuclear
Chemistry, 2013. 295: 929–935.

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

24-NPP-05

Thermal Stability of Locally-Associated Al and In Impurities in Zinc Oxide
1

S. Komatsuda1, W. Sato1,2, and Y. Ohkubo3
Graduate School of Natural Science and Technology, Kanazawa University
2
Institute of Science and Engineering, Kanazawa University
3
Research Reactor Institute, Kyoto University

Abstract – Local structures in 100 ppm Al-doped ZnO were
investigated by means of the time-differential perturbed angularcorrelation method. From distinct perturbation patterns obtained
for the samples annealed in different conditions, we found that the111
In, which is strongly associated with Al ions in ZnO, gradually
breaks the interaction and occupies the defect-free substitutional
Zn site in high-temperature vacuum.
Keywords – Al-doped ZnO, electric field gradient, In-111,
perturbed angular correlationI.

INTRODUCTION

Zinc Oxide (ZnO) doped with group 13 elements (Al,Ga, In) as impurity donors is expected to be applied tofunctional devices as n-type semiconductors. For apractical use of ZnO as a conduction-controlling device, it
is of great importance to study the physical and chemical
states of the dilute impurity ions in ZnO. The timedifferential perturbed angular correlation method (TDPAC)
is very suited for that purpose because it can directly
provide atomic-level information of impurity atoms. In ourprevious TDPAC studies, we found that Al ions and 111In
probe doped in ZnO can form local associations even at
extremely dilute concentrations[1]. In this work, we haveinvestigated the stability of the interaction between Al and
In impurities in various conditions.

perturbed by the outer surrounding field. This spectrum
shows that 100 ppm Al and 100 ppt 111In are locallyassociated in ZnO matrix, suggesting that there is a strong
attractive force between Al and In in ZnO[1]. Figure 1(b)and 1(c) show TDPAC spectra obtained for the samples
annealed in vacuum at 1023 K and 1173 K respectively, for
24 h after the probe was doped. For the spectrum in Fig.
1(b), two different components appearing in the spectra for
the Fig. 1(a) and undoped ZnO[2] were observed. The
component appearing in the spectrum for undoped ZnO has
become more visible in Fig.1 (c). These observations
imply that in high-temperature vacuum, the probe resides
solely at the substitutional Zn site being independent of the
field produced by Al ions. Showing TDPAC spectra of thesamples annealed in various conditions, we discuss thestability of locally-associated Al and In impurities doped in
ZnO.

-0.2
-0.15

(a)

-0.1
-0.05
0
0.05
-0.15

R (t)

II. EXPERIMENTS
For the synthesis of 100 ppm Al-doped ZnO,
stoichiometric amounts of Al(NO3)3 � 9H2O and ZnO
powder were mixed in ethanol. The suspension was heatedto evaporate the ethanol until dryness. The powders werepressed into disks and sintered in air at 1273 K for 3 h. For
TDPAC measurements, commercially available 111In
solution was added in droplets onto each of the sintereddisks at the concentration of 100 ppt. The disks again
underwent heat treatment in air at 1373 K for 2 h. Then thedisk samples were ground into powder, and sealed in aquartz tube in vacuum respectively.
The samples
underwent further heat treatment in vacuum at 1023 K and
1173 K for 24 h. The TDPAC measurements were carriedout for the 171-245 keV cascade � rays of 111Cd(�111In)
probe with the intermediate state of I = 5/2 having a halflife of 85.0 ns.

(b)

-0.1
-0.05
0
0.05

-0.15

(c)

-0.1
-0.05
0
0.05
0

50

100

150

200

Time (ns)

250

300

Fig.1 Room temperature TDPAC spectra ofCd(�111In) embedded in 100 ppm Al-doped
ZnO annealed (a) in air at 1373K, (b) in vacuum at1023 K, and (c) in vacuum at 1173K.

111

III. RESULTS[1]

Figure 1(a) shows a TDPAC spectrum obtained for the
sample heat-treated in air. The directional anisotropy, R(t),is plotted as a function of the time interval between the
cascade �-ray emissions, t, during which the probe is[2]－ 256 －

S. Komatsuda, W. Sato, S. Kawata, and Y. Ohkubo, J. Phys. Soc.
Jpn. 80, (2011) 095001.
W. Sato, Y. Itsuki, S. Morimoto, H. Susuki, S. Nasu, A. Shinohara,
and Y. Ohkubo, Phys. Rev. B 78 (2008) 045319.

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

24-NPP-06

Structure and Antimony-121 Mössbauer Spectra of Hypervalent Antimony
Compounds with an Antimony–Gold Bond in Equatorial Position
Masashi Takahashi, Asumi Sato, Shiro Matsukawa
Department of Chemistry, Toho University
Funabashi, Chiba 274-8510 Japan
Abstract – Hypervalent antimony compounds having Sb–Au bondin equatorial position are studied. [Rf2SbAu(PPh3)2] (Rf =C6H4C(CF3)2O–) has a short Sb–Au bond (2.6813 Å). 121Sb
Mössbauer spectrum of [Rf2SbAu(SMe2)] indicates a large
electron density along the Sb–Au bond. These results suggests a
dative interaction of the gold fragments to hypervalent antimony
atom.
Keywords –Mössbauer Spectroscopy, Hypervalent Compound,
Dative Bond, Antimony, GoldI.

three coordinated gold atom. The antimony atom adopts
trigonal bipyramidal geometry as expected. The Sb–Au
length (2.6813 Å) is shorter than that of (1) (2.7086 Å).
The Sb–O and Sb–C lengths are slightly longer than thoseof 2. The O–Sb–O and C–Sb–C angle is almost the same tothose of 2. These results suggest the high electron density
along the equatorial Sb–Au bond due to the strong electron
donation from gold atom. Two phosphine ligands at gold
atom should afford the electron density to Sb atom
effectively and might stabilize the Sb–Au bond.

INTRODUCTION

Since the first report on the ruthenaboratrane, in which
the boron atom at the pivot position of a tripodal ligand
acts as the Lewis acid [1] , unconventional metal to ligand
donation (M��) attracts keen interests. Although theinvestigations are mostly carried out using the electron
deficient borane ligands such as RnB(C6H4PR’2)3–n, theheavier main group elements such as phosphorus, antimony,silicon and tin can be used as the Lewis acidic point
because these elements accept the electron pair to form
hypervalent compounds. Indeed quite recently Wade andGabbai have demonstrated such M�� interactions using[(C6H4PPh2)3 SbAuI] (1) [2]. On the other hand we havealready suggested that the existence of electron flow fromorganometallic fragment to antimony atom in thehypervalent antimony compounds Rf2SbMCpLn [M = Fe,
Ru, Cr, Mo, W; L = CO, PPh3 etc; Rf = C6H4C(CF3)2O–](2) using 121Sb Mössbauer spectroscopy. [3] These results
inspired us to extend our investigation to the Au fragments.
II. EXPERIMENTAL
material: Rf2SbAuL (L = SMe2, PPh3) were prepared by
the reaction of [Rf2Sb]– with AuLCl using a modified
method for [Rf2SbFeCpLn]. The compounds werecharacterized using 1H, 19F and 31P NMR.
Structural determination: X-ray diffraction data werecollected on a SMART APEX (Bruker) at 150 K. Data
were processed as routine.
121
Sb Mössbauer spectrum: Mössbauer spectrum wasmeasured at 20 K using a Ca121SnO3 source on a
Mössbauer measurement system from Wissel (MDU-1200,
DFG-1200, MVC-450, CMCA-550). The spectrum wasanalyzed using a MossWin software. The value of theisomer shift was given relative to InSb.

Figure 1 Crystal Structure of [Rf2Sb–Au(PPh3)2] Sb–O = 2.1095, 2.1237;
Sb–C = 2.123, 2.123 Å; O–Sb–O = 161.75; C–Sb–O = 107.10°.

Fig. 2 shows the Mössbauer spectra of [Rf2SbAu(SMe2)](3). As expected 3 has a large negative quadrupole coupling
constant (–23.91 mm s–1) and a large asymmetry parameter(0.67). The isomer shift value (2.63 mm s–1) is anintermediate value between typical Sb(V) and Sb(III)complexes.
The Mössbauer
parametersindicateconsiderable electron density is present along the Sb–Au
bond, suggesting a strong electron donation of gold atom.

Figure 2 121Sb Mössbauer spectrum of [Rf2SbAu(SMe2)] at 20 K.

III. RESULTS AND DISCUSSION
The reaction product with AuCl(PPh3)2 was confirmed
to be [Rf2SbAu(PPh3)2] (Fig. 1), which has unexpectedly a

[1]
[2]
[3]

－ 257 －

Hill, A. F. et al. Angew. Chem. Int. Ed. 1999, 38, 2759.
Wade, C. R.; Gabbai, F. P. Angew. Chem. Int. Ed. 2011, 50, 7369.
Takahashi, M. et al. Z. Naturforsch. 2001, 57a, 631.

24-NPP-07
APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013��������������� �������������������������������������������
Jun Miyazaki1, Takashi Nagatomo2, Yoshio Kobayashi3, 4, Michael K. Kubo5, Yasuhiro Yamada6,
Mototsugu Mihara7, Wataru Sato8, Kazuya Mae5, Shinji Sato9, Atsushi Kitagawa9
1

College of Industrial Technology, Nihon University
J-PARC Center, High Energy Accelerator Research Organization
3
Department of Engineering Science, The University of Electro-Communications
4
RIKEN Nishina Center for Accelerator-Based Science, RIKEN
5The Division of Arts and Sciences, International Christian University
6
Department of Chemistry, Tokyo University of Science7
Department of Physics, Osaka University
8
Institute of Science and Engineering, Kanazawa University
9
Department of Accelerator and Medical Physics, National Institute of Radiological Sciences
2

Keywords Ð In-beam Mšssbauer Spectroscopy, �-decay of
Lithium hydride, DFT Calculations

I.

Mn,

57

INTRODUCTION

In-beam Mšssbauer spectroscopy is a powerful technique
to obtain the direct information on exotic chemical or
physical state of the nuclear probe that was implanted into thesample such as metal or inorganic solid. Lithium hydride(LiH) is an ionic solid having the rock salt type crystal
structure in which one Li+ cation is surrounded by six Hanions. In our previous study1, we reported the in-beam
Mšssbauer spectra of 57Mn implanted into LiH from room
temperature to over 800 K. In this study, we report the
spectra under room temperature and discus the local structureof 57Mn/57Fe implanted into LiH.
II. EXPERIMENTAL
The measurements were performed using Heavy Ion
Medical Accelerator in Chiba (HIMAC) at National Instituteof Radiological Science (NIRS) in Chiba, Japan. 57Mn beam
(E =~ 260A MeV) was produced from the projectile fragmentprocess of nuclear collisions between 58Fe ions (500A MeV,
� 1 � 106 particles per beam) and 9Be nuclei in a 27 mm thickproduction target. The beam pulse was generated every 3.3 swith a ~300 ms duration and with 1 � 106 particles/pulse.
The energy of the 57Mn nuclei was adjusted using energy
degraders to stop the ions at an appropriated depth in thesample. The polycrystalline LiH (Wako Pure Chemical) was
mounted on a cold finger or BN heater in a vacuum chamberin order to control the sample temperature from 11 K to over800 K. A parallel-plate avalanche counter (PPAC) was
employed as a detector. The anti-coincidence method thatuses a plastic scintillation detector to detect and rejectextraneous �-rays was employed to obtain high-quality inbeam Mšssbauer spectra with improved S/N ratios.
III. RESULTS AND DISCUSSION
In-beam Mšssbauer spectra of 57Mn/57Fe implanted into
LiH at 11, 274, 294 K were shown in Fig. 1. Obtained
spectra were fitted with some single lines and doublet lines.
In the spectra at 3 temperatures, the single line peaks of S (IS= -0.54 mm/s) and SÕ (IS = 0.07 mm/s) were observed. As
compared with the result from DFT calculations, S is
assigned to be in 57Fe at the substitutional Li site and SÕ is
assigned to be in 57Fe at the stubstitutional H site in LiH
crystal. Symmetrical doublet peaks of D1 (IS = -0.59 mm/s,
�EQ = 0.57 mm/s) and DÕ (IS = -0.03 mm/s, �EQ = 0.58mm/s) were also observed, and new doublet peak of D2 (IS =-0.60 mm/s, �EQ = 2.34 mm/s) was observed at 11K (Fig.1c).
In the result from DFT calculations, doublet peaks are
assigned to be in 57Fe at the substitutional Li or H site with aneighboring atom deficiency. The temperature dependenceof the relative intensities in this study suggests that the latticedefects recover with an increase temperature.

��������������������

Abstract Ð We report the in-beam Mšssbauer Spectra of 57Mn
implanted into polycrystalline LiH at under room temperature. As
compared with the result of DFT calculations, 57Fe atoms were
implanted into Li or H substitutional site in LiH crystal. With anincrease the sample temperature, we could observe the decrease oflattice defects.

S
D1

�
�
�
�
�
�
�
�
�
�
�
�
�

SÕ

��������
DÕ

D2

��

��

��������

���������������������������

�

Fig.1 In-beam Mšssbauer spectra of 57Mn implanted into LiH[1]－ 258 －

T. Nagatomo et al., Hyperfine Interact, ���, 125-128 (2012)

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

24-NPP-08

Evaluation of Vacancy-Type Defects in ZnO
by the Positron Annihilation Lifetime Spectroscopy
R. Ono1, T. Togimitsu1, and W. Sato1,2

1

Graduate School of Natural Science and Technology, Kanazawa University
2
Institute of Science and Engineering, Kanazawa University

Abstract – Annealing-temperature dependence of the formation ofvacancy-type defects in ZnO has been studied by means of thepositron annihilation lifetime spectroscopy. It was found that the
lifetime does not drastically change for ZnO samples annealed at
the temperature range below 600 � , whereas annealingtemperature dependence of the lifetime was observed above 600�,showing the minimum value at 1000�.
Keywords – positron annihilation lifetime spectroscopy, ZnO,
annealing effect, vacancy, grain boundaryI.

INTRODUCTION

Zinc oxide (ZnO) is an intrinsic n-type semiconductor
having optoelectronic properties. Because vacancy-type
defects brought about in the formation process of ZnO is
known to affect the intrinsic properties, for futureapplications, it is important to understand various behaviors
of defects in ZnO such as generation, recovery,
agglomeration and diffusion. For the evaluation of theirvacancy-type defects, positron annihilation lifetime
spectroscopy (PALS) is one of the most powerful methods
and we have applied this spectroscopy to part of our studies
on local structures of ZnO. In the present study, we
examined annealing-temperature dependence of positron
lifetime to evaluate the concentration and size of vacancytype defects formed in ZnO.

originate from self absorption in the source materials, andComponent 3 corresponds to positron annihilations in the
ZnO samples. The lifetime of Component 3 is the averageof those in the bulk and defects in ZnO samples. It is
obvious from the slopes of the decay curves of Component
3 that the lifetime of positrons in ZnO annealed at 1000�
is shorter than that for 600�. The short lifetime can be
explained as a result of the recovery of vacancy-type
defects. Particle growth arising from the heat treatment
may be another cause of the lifetime shortening because theamount of vacancy-like defects present in grain boundaries
is considered to become less by the phenomenon. The
positron lifetime, to the contrary, increases in ZnO samples
annealed at temperatures above 1000�. The reason for theincrease has not been understood yet. For the total
understanding of the defect formation process, further dataacquisition at other sample-preparation conditions is now
underway.

II. EXPERIMENTS
Polycrystalline ZnO powders (purity 99.99%) werepressed into pellets at 75 MPa. They were annealed in air atdifferent temperatures ranging from 200 to 1200� for 2h.
A 22Na (as in NaCl) positron source covered with Kapton
film was sandwiched with the sample disks. Positronannihilation lifetime was measured with a conventional
circuit at room temperature. BaF2 scintillators were used forthe detection of 1275- and 511-keV � rays.
III. RESULTS

Fig.1 PALS spectra for ZnO pellets annealed (a) at 600� and (b) at
1000�.

It was found from the PALS measurements that the
lifetime does not drastically change for ZnO samples
annealed at the temperature range between 200 to 600�.
However, obvious temperature dependence was seen for
those annealed at higher temperatures. In Fig.1 is shown
the PALS spectra obtained for the ZnO samples annealed(a) at 600� and (b) at 1000�. The spectra reproduced by
the lines named A are made up of three different decay
components as numbered 1-3. Components 1 and 2－ 259 －

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

Determination of ultratrace-levels of 99Tc using ICP-QMS in the low level radioactive
waste samples
Te-Yen Su, Tsuey-Lin Tsai, Hsin-Chieh Wu, Lee-Chung Men
Chemistry Division, Institute of Nuclear Energy Research, Longtan, Taoyuan 32546, Taiwan, R.O.C.
Abstract –A rapid, accurate and less labor intensive approach wasdeveloped to determine 99Tc in the low level radioactive wastes(LLW). Only 0.1 g of solid radwastes was firstly dissolved using
microwave digestion and then the specific TEVA resin was used forchemical separation to remove most of the matrices piror toinductively coupled plasma- quadrupole mass spectrometry (ICPQMS) measurement. The minimum detectable activity (MDA) of
ICP-QMS for the determination of 99Tc in LLW samples was 8.5
mBq g-1 (13.6 pg g-1), which was comparable to that of doublefocusing magnetic sector field inductively coupled plasma mass
spectrometry (ICP-SFMS), 5.3 mBq g-1. The sensitivity of the ICPQMS method for the determination of 99Tc was much superior tothat of the alternative radiochemical methods (e.g., liquid
scintillation analyzer; LSA) when accounting for the dataacquisition time for identical, low-concentration samples.
Approximately 88 % of the chemical recovery was achieved and thisdeveloped technique was successfully applied to LLW samples for99
Tc measurement within 5 minutes.
Keywords –99Tc; inductively coupled plasma-quadrupole mass
spectrometry (ICP-QMS); low level radioactive wastes (LLW)－ 260 －

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

Development of an Automatic Prompt Gamma-ray Activation Analysis System
1

Takahito OSAWA1
Neutron Imaging and Quantum Beam Analysis Group, Quantum Beam Science Directorate,
Japan Atomic Energy Agency (JAEA),

Abstract – An automatic prompt gamma-ray activation analysis
system was developed and installed at the Japan Research Reactor
No. 3 Modified (JRR-3M). The main control software, referred to as
AutoPGA, was developed using LabVIEW 2011 and the hand-madeprogram can control all functions of the analytical system. The coreof the new system is an automatic sample exchanger andmeasurement system with several additional automatic control
functions integrated into the system. Up to fourteen samples can be
automatically measured by the system.
Keywords – Prompt gamma-ray analysis; Automatic analysis;
Revolute robot; LabVIEW

Prompt gamma-ray analysis (PGA) using a neutron beam
generated by a nuclear reactor is a convenient andnondestructive elemental analytical technique. PGA can be
widely used in various science and technology fields [e.g. 1],
because the analytical methods have high sensitivity forcertain specific light elements.
The PGA system at the JRR-3M at the Japan Atomic
Energy Agency (JAEA) was constructed in 1992 [2].
Although the system using cold and thermal neutron beams
achieved a very low gamma-ray background level, it was
outdated because no improvements had been made since its
construction. In this study, an automatic system for PGA wasdeveloped in order to update the old analytical system andimprove its measurement efficiency.
The new automatic PGA system is mainly composed of
two computers (PC1 and PC2), four programs, a six-axis
vertical revolute joint robot (Mitsubishi RV-3SD, Fig.1), anddata acquisition devices. Although the inside of the shielding
body is not changed most of the devices and systems on theoutside of the shielding body are completely improved in thiswork. The core of the new system is an automatic sample
exchanging and measurement system, and several automatic
control functions: such as helium flow control, neutron flux
recording, internet functions, and machine vision, have been
integrated into the system.
In the system, fourteen samples hung on the center ofTeflon frames with Teflon strings that can be placed onto asample stand. Each sample frame is selected and introduced
into a Teflon sample box using a revolute joint robot.
Opening and closing of the loading hatch is enabled withcompressed air and air bulbs that are controlled using a
digital output module. A physical interlock on the loading
hatch that synchronizes with the neutron beam shutter isoperated by a single-pole single-throw relay, and the relay
can also control the opening and closing of the neutron beam
shutter.

Fig.1 A revolute joint robot of the automatic PGA system

A robot sequence program written in MELFA BASIC V
was designed by the author. The AutoPGA program isinstalled in PC1 and controls the entire series of automatic
analytical operations. When the user clicks the start button
AutoPGA starts the servomechanism of the robot and initiates
the sequence program. It then closes the neutron beam shutter,releases the interlock, and opens the loading hatch. When themachine vision system judges that the lid is not placed in thecorrect position, the sequence program stops working. The
robot begins operating, and the Teflon lid on the Teflon
sample box is removed and placed on a lid stand. The robot
selects the sample frame and introduces it into the sample box
and then places the lid on the sample box. The loading hatch
is closed, the neutron shutter is opened, and the measurement
is begun. An existing measurement program (SEIKO EG&G
Spectrum Navigator) is installed in PC2 and is used for themeasurements. In the automatic analysis, a batch processing
mode is utilized that calls a communication program (PGATalk created by the author) after each measurement. PGATalk sends a signal to PC1 via TCP, and AutoPGA
recognizes the completion of the gamma-ray recording andbegins to exchange the sample. When the sample exchange iscomplete, AutoPGA sends a signal to PC2 and PGA-Talk is
automatically shut down. Spectrum Navigator then begins themeasurement of the next sample.
[1][2]－ 261 －

T. Osawa, Y. Hatsukawa, P. W. U. Appel, H. Matsue, Nucl. Instrum.
Meth. Phys. Res. B 269 (2011), pp. 717-720.
C. Yonezawa, A.K.H. Wood, M. Hoshi, Y. Ito and E. Tachikawa, Nucl.
Instr. and Meth. A 329 (1993), pp. 207-216.

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

Concentration of Heavy Metal Elements in Chinese Medicine by INAA
S. Ishihara1, E. Furuta2, N. Iwasaki1, Y. Yoshihara3, R.Okumura4, Y.Iinuma4
1

Ochanomizu University, Facility of Sciences
Ochanomizu University, Graduate School of Humanities and Sciences3
Ochanomizu University, Facility of Human Life and Environmental Sciences
4
Kyoto University, Research Reactor Institute2

Abstract – An instrumental neutron activation analysis of Chinese
medicines and medicinal herbs was performed, in which they havepossibilities to contain toxic elements. By the preliminary
experiments, there were some medicines that arsenic and mercury
were included by observing gamma-ray spectroscopy with neutron
irradiation. The Chinese medicine can be purchased through theInternet easily; however, it is considered that some regulations may
be necessary.
Keywords – Chinese medicine, Arsenic, Mercury, INAAI.

INTRODUCTION

III. RESULTS
Table shows the results of 4 elements in the samples fromroute-1. Among 12 kinds of Chinese medicines, 6 kinds ofthem included As, and 5 kinds of them included Hg. On theother hand, these 4 elements were not included in 2 of them.
Other elements detected were sodium, potassium, calcium,
scandium, iron, manganese, lanthanum, and selenium andthese elements were included a few ten ppm except for
calcium of a few thousand ppm.
Table

Chinese medicine is used all over the world because of its
safer image than Western pharmaceutical products. It is
possible to purchase everywhere through the Internet.
However, a few reports mentioned some of them included
some kinds of toxic elements like arsenic (As), lead (Pb),mercury (Hg) and cadmium (Cd) [1]. Chinese medicines andmedicinal herbs may be taken in continuously for a long term.
So, if they include some toxic elements, it develops a healthproblem. Therefore, many kinds of Chinese medicines andmedicinal herbs which can be purchased in an Asian area
were analyzed by neutron activation at the KUR for the
purpose of clarifying the actual situation. The preliminary
experimental results were shown in the presentation.

Sample�����
Niuhuang Jiedu Pian���
Fluit, Lonicera�����Shiquan Dabu Wan�����
Tenma Shouwu Pian���
Cannabis sativa
��� (Musk)
Liu Shen Wan
����
Weiqitong Pian�����
Hou –Hashi
�����
Muxiang Shunqi Wan
�����
Rehmannia glutinosa

II. EXPERIMANTAL
Many kinds of Chinese medicine and medicinal herbs
were purchased from 5 routes to analyze the heavy metalelements; 1. 12 kinds of Chinese medicines were sold with aprescription by a hospital doctor in China; they were not soldto public in a market, 2. 8 kinds of Chinese medicines werebought through the Internet from China, 3. 11 kinds ofChinese medicines were bought at a market of Korea, 4. 47
kinds of medicinal herbs were bought at a market of Vietnam,
and 5. 25 kinds of Chinese medicines were bought at a
medical corner of a super market in Japan; they were
produced in Japan. Each of them was enclosed almost 100
mg in a double polyethylene bag. The standard samples usedwere JA-2 and JR-2 of rock standard. The samples were put
in capsules with standards and irradiated 5MW × 10 min or
1MW × 30 min at KUR. After cooling among 5 days, thecapsules were opened to take out samples, each sample was
enclosed in a new polyethylene bag, and then started
measurement of medium and long half-life radionuclides.

Four elements concentrations in 10 Chinese
medicines (ppm)

IV.

51

Cr

60

Co

76

As

203

Hg

7.1%
8.0

1.1

3.3

1.6
1.8

1.7
1.9
47

76

1.8

6.7%

6.7%

14

3.8

2.8
1.4

4.9
1.6

CONCLUSION

Some of Chinese medicines included high concentrationof toxic elements such as As and Hg. It is considered that aregulation how to sell or a limitation of the purchase method
is necessary.
[1]－ 262 －

Agilent Technologies; www.agilent.com/chem/jp

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

24-AAP-04

Application of instrumental neutron activation analysis to assess dietary intake ofselenium in Korean adults from meat and eggs
Jong-Hwa Moon1, Sun-Ha Kim1, Yong-Sam Chung1, Ok-Hee Lee2

1

Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon, 305-353, Korea
Dept of Food Science and Nutrition, Yongin University, 470, Samga-dong, Cheoin-Gu, Yongin, 449-714, Korea

2

Abstract – Selenium is a key constituent of enzyme in glutathione
peroxidase, which is effective in decreasing various types ofoxidative stress, Thus, the adequacy of selenium intake is very
important in decreasing the risks of various degenerating diseases
such as cardiovascular disease, or certain cancers. Lately, theintake of animal foods is increasing among Koreans owing to a
dietary transition toward a western style. This study was
conducted to measure the selenium content in meat and eggs, andthen assessed the selenium intake from these foods. Forty
frequently eaten items among meat and eggs were analyzed using
an Instrumental Neutron Activation Analysis. The selenium
content in 100g of raw meat and eggs ranged from 8.1ug to
50.9ug. In particular, 100g of beef contained 12.4ug to 50.9ug ofselenium; pork, 11.2ug to 22.6ug chicken, 10.2ug to 13.7ug andeggs, 28.6ug to 43.0ug. Thus, beef viscera and chicken eggs
contain the highest amounts of selenium among these groups.
100g of Pork belly, the most frequently eaten meat type among
Koreans, contains 14.6ug of selenium. An evaluation of dietary
selenium intake shows that the total selenium supply from meats
and eggs was 28.4ug/day and 27.5 ug/day in adult men andwomen, respectively. These are over one-half of the Korean
RNI(Recommended Daily Intake) of 55ug/day.
Keywords–Instrumental Neutron Activation Analysis, Selenium,
Meat and Eggs, Dietary Intake

I.

INTRODUCTION

As the biological activity of food selenium in humans isdependent, sometimes to a very large degree, on the source
and chemical form of the selenium consumed, an increased
intake of animal food can facilitate meats and eggs asimportant sources for selenium intake in Koreans.
Considering these points, an evaluation of selenium intake
in Koreans from animal foods is very important. This study
was conducted to analyze the selenium contents in meats
and eggs, and to assess the consumption pattern ofselenium in Koreans from these animal foods.

III. RESULTS
The selenium contents in the different parts of beef wereranged from 12.4ug to 50.9ug in 100g of the edible portions,where the highest value was shown with beef liver. The
selenium contents in raw Korean pork ranged from 11.2ug
to 22.6ug in 100g of food, showing a difference according
to the pork region. Pork belly, the most frequently eatenmeat among Koreans, contained selenium at an amount of
14.6ug at 100g. The raw chicken contained selenium with arange of 10.2ug to 13.7ug in 100g, showing only a small
difference by the chicken part. The selenium contents in thefrequently eaten eggs were in the range of 28.6ug 43.0ug
for 100g. Eggs were distinct in that they contained thehighest amount of selenium among the meats with a rangeof 38.9ug to 43.0ug for chicken eggs, and of 28.6ug for thequail egg per 100g of eggs. The processed pork products
contained selenium in a range of 8.8 - 14.9 ug for 100g,
which is lower than the raw unprepared pork meat. Amongthe pork products, Pyeonuk and pork hocks, cooked pork
products, showed selenium contents of 19.4 and 21.1ug for
100g, respectively. The prepared chicken, mostly from fast
food eateries, contained selenium in a range of 7.4 to
11.5ug for 100g. An evaluation of dietary selenium intake
shows that the total selenium supply from meat and eggs
was 28.4ug/day and 27.5ug/day in adult men and women,
respectively. These are over one-half of the Korean RNI(Recommended Daily Intake) of 55ug/day.
ACKNOWLEDGEMENT
This work was carried out under the Nuclear Researchand Development Program of the Korean Ministry of
Education, Science, and Technology.
REFERENCES

II. EXPERIMENTAL
The number of meat items used in the selenium analysis
was 13 items for raw beef, 8 items for raw pork, 3 items for
raw chicken, 4 items for raw eggs, and 12 items for theprocessed meat products, respectively. Most of the foods
were bought between September 2009 and February 2010.
All domestically produced and imported meats and eggs ina raw or processed state were purchased from markets witha nationwide network around Seoul and Keunggido. The
meat sample was ground using a blender with a titanium
blade, and freeze-dried in a lyophilizer at various times of
24 - 96 hours. The analysis of selenium was performed byinstrumental neutron activation analysis using the
HANARO research reactor.

[1]
[2]

－ 263 －J Rotruck JT, Pope AL, Ganther HE, Swanson AB, Hafeman DG,
Hoekstra WG. Selenium: biochemical role as a component ofglutathione peroxidase. Science 1973, 179:588-90.
The Korean Nutrition Society, Dietary Reference Intake for Koreans,
Seoul, 2010, p 481-97.

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

%VALUATION OF (YPOXIA AT $REDGED 4RENCHES IN 4OKYO "AY BY $ETERMINATION OF
2EDOX 3ENSITIVE %LEMENTS IN THE 3EDIMENTS
T. Yamagata1, K. Shozugawa1, R. Okumura2, K. Takamiya2, M. Matsuo1
1

Graduate School of Arts and Sciences, The Univ. of Tokyo
2
Research Reactor Institute, Kyoto Univ.

!BSTRACT – 3EDIMENT SAMPLES WERE COLLECTED FROM 4OKYO "AY AND
THE CONCENTRATIONS OF SOME ELEMENTS WERE DETERMINED BY
INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS ).!! 4HOUGH HYPOXIA
HAS BEEN OBSERVED IN DREDGED TRENCHES IT IS SUGGESTED THAT UPPERLAYERS OF THE SEDIMENTS ARE MORE OXIDATIVE THAN LOWER LAYERS+EYWORDS – (YPOXIA 3EDIMENT IN 4OKYO "AY )NSTRUMENTAL NEUTRONACTIVATION ANALYSIS ).!!

I.

out depending on half-lives of elements. For analysis of U,
samples were irradiated for 20 min at 1 MW or 4 min at 5
MW, and then gamma-ray was measured for 1200 seconds(live time) by Ge detector after 3 days cooling. Regarding Th
and Ce, samples were irradiated for 20 min at 1 MW or 4 min
at 5 MW, and the measurement time of gamma-ray was for
9000 seconds (live time) after 3 weeks cooling.
III. RESULTS AND DISCUSSIONINTRODUCTION

Hypoxia is water mass contained little dissolved oxygen(DO) (< 2 ml of O2 / liter) [1], which is known as dead zone
in coastal sea. At the seabed in Tokyo Bay, large-scale
dredging operations had been done in 1970s. In particular, thedredged trenches off Makuhari have the maximum area anddepth. In dredged trenches severe hypoxia has been observedin annual summer seasons, and the hypoxia has disappearedin winter. But the influence of dredged trenches on hypoxia is
not revealed yet. Therefore, it is important to estimate theinterannual variations of hypoxia by analyzing sediments.
To evaluate the sedimentary environment such as redox
conditions, the method using the Th/U-Ce/U plot based on
the data obtained by INAA was reported by Honda et al [2].
It is very useful because the correlation coefficient between
the Th/U and Ce/U ratios is high, but it hasn’t been used forevaluating the sedimentary environment at dredged trenches,
where the conditions are unique. In this study, sediment cores
were collected from the Makuhari dredged trenches in Tokyo
Bay. Concentrations of U, Th, and Ce in the sediments wereanalyzed by INAA. And then the sedimentary environment is
discussed in connection with the depth profiles of theelements and the Th/U-Ce/U plot.

The DO in the seawater at dredged trenches and referencesite (non-dredged area) indicated the similar vertical
distribution at each station. From the depth of 8 m, the DO
decreased suddenly. And below the depth of 10 m, the water
became anoxic in dredged trenches. It turned out that strong
hypoxia has developed at the dredged trenches.
From the depth profiles in dredged trenches, the Th/U andCe/U ratios are higher in the upper layers than in the lower
layers. It is said that the concentrations of Th and Ce in
sediments increase when condition of seawater is oxidative.
On the other hand, the concentration of U increases whencondition is reductive. It is considered that the sedimentary
environment of the upper layers is more oxidative than thelower layers.
Figure shows the Th/U-Ce/U plots of the sediments. The
correlation coefficient between the Th/U and Ce/U ratios ishigh enough. Therefore, this method is also useful forevaluating the hypoxia at dredged trenches, in which theenvironment changes drastically on each summer and winterseason.

II. EXPERIMENTAL
The sediment samples were collected at dredged trenches(water depth 25.5 m and 18.9 m) and reference site (nondredged seabed, water depth 10.7 m) off Makuhari in Tokyo
Bay on August 2012. Sediments were collected by a coresampler at each point. Water quality data were also obtainedby a multichannel water quality meter and an oxidationreduction potentiometer. All cores were cut in the verticaldirection at 0.6 – 3.0 cm intervals after freezing.
Approximately 30 mg of freeze-dried sediments were
packed in double polyethylene film bags. All samples were
irradiated at the pneumatic tube, Kyoto University Reactor(KUR). Two types of gamma-ray measurement were carried

Fig. Th/U-Ce/U plots of the sediments collected from Tokyo Bay[1][2]－ 264 －

R. J. Diaz and R. Rosenberg, Science, 321, 926-929 (2008).
T. Honda and K. Kimura, Bull. Soc. Sea Water Sci., Japan, 57, 166-180(2003) (in Japanese).

24-AAP-06
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Determination of ultra trace amounts of Mn in iron meteorites by preconcentration
neutron activation analysis
1

Y. Tanaka1, Y. Arai1, T. Imamura1, Y. Oura1

Department of Chemistry, Tokyo Metropolitan University

I.

INTRODUCTION

Meteorites contain cosmogenic nuclides produced by anuclear reaction with cosmic rays. Cosmogenic nuclides areuseful for determination of exposure and terrestrial ages. In
general, only radionuclides and noble gas stable-isotopes canbe detected as cosmogenic nuclides. Although it is difficult to
detect cosmogenic stable nuclides in stony meteorites, somecosmogenic stable nuclides could be detected in ironmeteorites, which consist of mainly an iron–nickel alloy,
since iron meteorites have little geochemical lithophileelements. Among such stable nuclides we focus on Mn.
Natural Mn is a monoisotopic (55Mn) element. But ironmeteorites have also a cosmogenic radioisotope, 53Mn, which
has longest half life among detectable cosmogenic
radionuclides. One of practical methods for determination of53
Mn is a preconcentration neutron activation analysis(preNAA) using 53Mn(n, �)54Mn reaction. We suggested that55
Mn content should be required for determination of ultra
trace 53Mn in iron meteorites by preNAA because ofcorrection of 55Mn(n, 2n)54Mn. But accurate concentration iniron meteorites is rarely reported. Almost 53Mn in ironmeteorites is extrapolated to be comsogenic by 45Sc contents[1]. If accurate 55Mn concentration can be determined, 55Mn53
Mn system for exposure age will be also established. And
estimation of original 55Mn concentration is interesting forconsidering a differentiation of planets. Determination of55
Mn in iron meteorites by NAA is well known to beinterfered by 56Fe(n, p)56Mn reaction. Therefore, the removalof iron prior to irradiation or irradiation at a channel withhigh Cd ratio is required. Thus we tried to determine 55Mn
concentration in iron meteorites by preNAA using wellthermalized neutrons.
II. EXPERIMENTAL
Using radiotracers, a chemical procedure using an ionexchange method was developed for separation of Mn fromiron meteorites based on one by Fujimoto and Shimura [2].
After dissolution of a sample in 2 M HF, the HF solution was
loaded on a cation exchange resin. Adsorbed Mn was eluted
by 8M HCl, and then Mn in HCl - 2-propanol solution was
purified by an anion exchange method. This procedure wasapplied to Japan steel standard samples and Gibeon ironmeteorites followed by irradiation of separated Mn fraction
for 4 hours at the thermal column pneumatic transport system(Tc-Pn) and for 1 hour at Pn-2 in Kyoto University Research
Reactor (KUR). In addition, sensitivity of 55Mn(n, �)56Mn andcontribution of 56Fe(n, p)56Mn at Tc-Pn in KUR and at PN-3
in the Japan Research Reactor-3 (JRR-3), Japan Atomic
Energy Agency were evaluated by using Mn standard and Ti
plate, respectively.
III. RESULT AND DISCUSSIONIn Mn fraction irradiated for 1 h at Pn-2, no 59Fe and 60Co
was observed. Our chemical procedure removed > 99.99% of
Fe and Co and > 99.5% of Ni, Ir and Cr, and overall
procedure blank of Mn was about 30 ng. Determined Mnconcentration in steel standards (JSS003-5 and JSS001-5) and
Gibeon meteorites are shown in Table 1. Low determination
values in Run-1 were guessed to be caused by low chemicalyield. In Run-2 a chemical yield was estimated to be 91% anddetermined concentrations on Mn in steel standards wereconsistent with certified values. It is concluded that down to
30 ppb of Mn can be determined by our method.
Sensitivities of Mn were 930 cps/�g and 2400 cps/�g for 4
h irradiation at Tc-Pn and 20 min irradiation at Pn-3,
respectively. And contributions of (n, p) reaction werecorresponding 16 ngMn/gFe and 97 ngMn/gFe for Tc-Pn and
PN-3, respectively. Since Fe was sufficiently removed,
contribution of 56Fe(n, p) reaction was more than 150 times
smaller than the present procedure blank. A detection limit of
Mn by preNAA was 30 ppb, assuming that a half of induced56
Mn is resulted by a blank. Even INAA using Tc-Pn candetermine such concentration of Mn. Reducing a procedureblank is highly required for lower detection limit.
TABLE 1: Result of Mn content
Sample

Unit

INAA*

JSS003-5
JSS001-5
Gibeon

ppm
ppb
ppb

24.9 ± 0.2
36.1 ± 2.2

preNAA
run1
run2
19.8 ± 0.4 26.0 ± 0.3
27.5 ± 2.2
273 ± 9415 ± 7

CertifiedValue
27 ± 130 ± 10*Corrected for (n, p) reaction.
[1][2]－ 265 －Oura et al., Proc. Radiochim. Acta 1.383 (2011).
K. Fujimoto and M. Shimura, Bunseki Kagaku 50, 175 (2001).

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

24-AAP-07

Instrumental photon activation analysis of geological and cosmochemical samples
Naoki Shirai1, Shun Sekimoto2, Mitsuru Ebihara1
1

Tokyo Metropolitan University
Kyoto University Research Reactor Institute

2

I.

INTRODUCTION

Bulk chemical compositions for terrestrial andcosmochemical materials are significantly important toelucidate the formation, evolution processes andmagmatism of planetary bodies. Compared to geologicalsamples, cosmochemical samples pose several severe
requirements to their analytical methods for chemicalcompositions. High sensitivity and accuracy for as many aselements as possible are required for analytical methods
applied to such samples because of the limitation of sample
amounts usable for analysis. Non-destructive analysis formany elements is equally favorable. Nuclear analyticalmethods represented by prompt gamma-ray analysis (PGA),
instrumental neutron activation analysis (INAA) andinstrumental photon activation analysis (IPAA) meetalmost all these requirements. Among these nuclear
analytical methods, INAA has been commonly used as ananalytical tool in comomochemistry for a long time, while
PGA and IPAA have not been very often applied tocosmochemical samples.
In PAA, (�,n) reaction is used for determination ofelemental abundances which is an opposite reaction ((n,��)reaction) used in INAA. Thus, IPAA could determine
elemental abundances which cannot or hardly be
determined by INAA. Ebihara et al. [1] examined thesuitability of PAA by analyzing cosmochemical samples(chondrites) and concluded that PAA is as effective as
NAA for analyzing chondritic meteorites. Usually samples
are irradiated by using 30 MeV electrons in IPAA.
However, corrections of interferences caused by secondary
nuclear reactions such as (�,p) and (�,pn) are necessary.
Although the sensitivity obtained by activation with 20
MeV electrons are suppressed compared to the activation
with 30 MeV electrons, activation with 20 MeV electrons
reduces the degree of such interferences. In this study, we
performed IPAA by using a linear electron accelerator at
Kyoto University Research Reactor Institute (KURRI) andcompared the results obtained the activation with 20 MeV
with those for activation with 30 MeV.
II. EXPERIMENTAL
In this study, four Geological Survey Japan standards
materials (JA-2, JB-3, JR-1 and JG-1) were analyzed. In
addition to these terrestrial geological samples, the Allendemeteorite was analyzed as a cosmochemical samples. Eachsamples was taken into a sample container (9 mm�) madeof highly Al foil (Al: 99.5 %, Niraco Co., Ltd). In addition
to rock samples, chemical reagents were irradiated tocorrect the spectral interferences. Five to ten samples werestacked, among which thin foil disks (9 mm�) of Au wereplaced for as monitoring the intensity of photon. Samples ina block were put in a quartz tube. Irradiations were
performed by using a linear electron accelerator at KURRI.
Electrons were accelerated by the linear accelerator toabout 20 and 30 MeV. After irradiation (about 30 hrs),
samples were taken into new Al foil and measured for
gamma rays several times with different cooling intervals at
KURRI and the Laboratory of Radioisotopes, Tokyo
Metropolitan University. Elemental abundances were
determined by comparison method by using JB-1.
III. RESULTS AND DISCUSSION
Table 1 shows the interfering reactions and theircontributions to nuclides produced by corresponding
reactions for activation with 20 MeV and 30 MeV electrons.
As shown in Table 1, significant contributions frominterfering reactions were found in activation with 30 MeV
electrons. Thus, determinations of Cr, Co and Mn
abundances need the correction of corresponding
interferences. As expected, contributions from interfering
reactions with 20 MeV electrons were lower than those inactivation with 30 MeV electrons.
A total of 17 elements (Ca, Sc, Ti, Cr, Mn, Fe, Co, Ni, Zn,
As, Rb, Y, Zr, Nb, Cs, Ba and Ce) were determined ingeological reference standard materials and the Allendemeteorite. Our Cr and Mn values obtained from activation
with 30 MeV electrons were different from literature values.
Improper corrections of the interfering reactions were
responsible for these differences. In contrast, our Cr andMn values obtained from activation with 20 MeV electrons
were in good agreement with literature values. For otherelements, there were no differences between the two sets ofour values obtained from the activations with 20 and 30
MeV electrons, which were consistent with literature values.
Table 1. Interfering reaction and correction rate for interference.
Element
Reaction used forInterfering
Correction rateinterfereddetermination
reaction
30 MeV
20 MeV52
56
Cr
0.036 mgCr/gFe
Cr(�,n)51Cr
Fe(�,�n)51Cr
59
60
Co
3.7 mgCo/gNi
0.88 mgCo/gNi
Co(�,n)58Co
Ni(�,pn)58Co
55
56
Mn
6.2 mgMn/gFe
0.1 mgMn/gFe
Mn(�,n)54Mn
Fe(�,pn)54Mn

Reference: [1] Ebihara M. et al. (2000) J. Radioanal. Nucl.
Chem., 244 (3), 491-496.

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

24-AAP-08

Monte Carlo Calculation of Chloride Diffusion in Concrete

1

A. A. Naqvi1, Khateeb-ur-Rehman1, M. Maslehuddin2, O.S.B. Al-Amoudi3 and M. Raashid1

Department of Physics, 2Center for Engineering Research, and 3Department of Civil and Environmental Engineering
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia

Abstract – Coefficient of chloride diffusion is calculated byapplying the Fick’s second law of diffusion to a chloride
concentration profile. Then from the signal strength for various
chlorine gamma-ray energies was then calculated at the detector.
of the portable D-D neutron generator based PGNAA setup.

An excellent agreement was noted between the reported results ofthe calculations for the 252Cf neutron source-based portable
PGNAA setup and the D-D portable neutron generator based
PGNAA setup developed by the authors.

Keywords –Coefficient of chloride diffusion ; Fick’s second lawof diffusion; DD based Portable neutron generator based PGNAA
setup; detector chloride signal strength calculationI.

INTRODUCTION

Corrosion of reinforcing steel is mainly caused due to thechloride ions. These ions either diffuse to the steel surface
from the service environment or they are contributed by the
mixture ingredients. The penetration of chloride ions fromthe service environment is a diffusion controlled process[1]. Consequently, the coefficient of chloride diffusion is
calculated by applying the Fick’s second law of diffusion toa chloride concentration profile. A prompt gamma-ray
neutron activation (PGNAA) setup has been designed
utilizing a portable neutron generator by the authors [2].
The setup, which mainly consists of a D-D portable neutron
source along with its moderator placed side by side with ashielded gamma-ray detector, allows the determination ofchloride concentration in a concrete structure from one side.
The D-D portable PGNAA setup has been modeled for thedetermination of chlorine concentration at various depths
using a MCNP simulation code following the proceduredescribed elsewhere [1] for a 252Cf neutron source based
PGNAA setup.

In the reported study, the chloride diffusion profile wasmodeled for several values of diffusion coefficients as afunction of time. These chloride concentrations are thenutilized as an input to the MCNP based model [1]. The
signal strength for various chlorine gamma-ray energies
was then calculated at the detector. An excellent agreement
was noted between the reported results of the calculations
for the 252Cf neutron source-based portable PGNAA setup[1] and the D-D portable neutron generator based PGNAA
setup developed by the authors[1]
Livingston, R.A., Al-Sheikhly, M., Mohamed, A.B.
“Numerical simulation of the PGNA signal from chlorine diffusion
gradients in concrete,” Applied Radiation and Isotopes, Vol. 68 (2010), pp.
679–682.
[2]
Naqvi, A. A., Kalakada, Z., Al-Matouq, F.A., Maslehuddin, M.
and Al-Amoudi, O.S.B., “Chlorine detection in fly ash concrete using a
Portable Neutron Generator,” Applied Radiation and Isotopes, Vol.
70(2012), pp.1671-4.

.

－ 267 －

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

Catalysis Induced by Radiation in Fatty Acids Adsorbed on Clay Minerals
1

A. Negron-Mendoza1*, S. Ramos-Bernal1, M. Colin-Garcia2 and F.G. Mosqueira3
Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, UNAM. A.P. 70-543, México, D.F. 04510,
México.
Instituto de Geología, Universidad Nacional Autonoma de Mexico, México, D.F. 04510, México
3
Dirección General de Divulgación de la Ciencia, Universidad Nacional Autonoma de Mexico, D.F. 04510, México

Abstract – We have studied the behavior of small fatty anddicarboxylic acids adsorbed in sodium-montmorillonite and exposed
to gamma radiation. It is observed that the radiation-induced
decomposition of the clay-acid system goes along a definitive path(oxidation) rather than following several modes of simultaneous
decomposition, as in the case of the radiolysis without the clay. Thispreferential synthesis promotes the formation of a hydrocarbon
compound with one carbon atom less than the parent compound
Keywords –Decarboxylation reaction, carboxylic acids, gamma
radiation, montmorillonite, 14CO2I.

INTRODUCTION

The adsorption of certain organic compounds by clays
gives rise to the transformation of the adsorbate by the actionof clays. These kinds of reactions play an important role inmany natural and industrial processes. In the context of oil
and gas exploration, for example, the source and trap of
petroleum hydrocarbons frequently are clay-rich rocks. Claywater based muds are also seen as environmental friendly
alternatives to toxic oil-based fluids [1].
In this perspective, several investigators [2, 3] havestudied the thermal decomposition of fatty acids in thepresence of clay minerals. The differences found by several
workers for the distribution patterns of hydrocarbons may becaused largely by thermal alteration. In addition, radioactive
bombardment alters these sediments. It is an important
subject that has not been extensively studied.
The modification by ionizing radiation of the activity ofheterogeneous catalysis is a relatively new problem inradiation chemistry. The sensitization of radiation-chemical
reactions by solid surfaces may increase the catalytic activityof the clay. The aim of this paper is to study the radiationinduced decomposition of carboxylic acids adsorbed in a clay
mineral as an example of heterogeneous radiation catalysis
that can be correlated to natural and industrial processes.
II.

the clay were prepared. The addition of the clay into thesolution was in an oxygen-free bag, with continues agitation.
(3) For gas analysis, 0.1 g of the clay was evacuated for one
hour and 1 mL of the solution was added, in an oxygen-freebag. The samples were in special glass tubes with a stopcockthat was connected to a Toepler pump. We used blanks tocorrect the yield of gas samples. Some runs were made with
14-carbon label acetic acid (CH314COOH) to show that theCO2 obtained was from the target acid. 14CO2 was measured
by a scintillation technique. The irradiations were carried out
in a high intensity gamma source of 60Co (Gammabeam 651
PT). The radiation doses were from 46. kGy to 300 kGy
III.

RESULTS AND REMARKSThe irradiation of aqueous carboxylic acid produced many
compounds, for example for acetic acid, the total yield of
polycarboxylic acids was 22% and for succinic acid wasabout 35%. The principal feature of these series of radiolysis
experiments was the production of the dimer of the acid, as
the principal way of decomposition of the target compound,but many other acids were formed. For example, in theradiolysis of acetic acid (CH3CO2H), the main product was
succinic acid (CH2CO2H)2, the dimeric product. The
formation of CO2 from the decarboxylation reaction was only
7%. The decomposition of the target compound increased asa function of the dose.
The radiolysis performed in presence of clay decreased
considerably the number of formed products. For example, in
acetic acid, the production of polycarboxylic acids was 4.8 %and the formation of carbon dioxide increased to 81 %.
The main result obtained shows that the radiolysis of thesystem clay-acid goes along a defined path rather thanshowing various pathways of decomposition. The main
pathway was the decarboxylation of the target compound
rather than condensation/dimerization reactions.
ACKNOLEDGEMENTS

MATERIALS AND METHODSThe experimental part is divided in two stages: (1)Radiolysis of aqueous solutions of the carboxylic acids, (2)Study of heterogeneous radiolysis of the water-carboxylic
acid-clay system(1) Aqueous solutions of carboxylic acids (0.1 mol L-1),
oxygen free, prepared in a glass syringe (acetic, succinic,aconitic); (2) Aqueous solutions of acids containing 0.3 g ofThis work was supported by PAPIIT Grant No. IN110513 and the
CONACyT Grant No. 168579/11.

REFERENCES
[1]
[2]
[3]

－ 268 －

Skipper, N. Hannon, A., and Buchanan, P. ISIS Experimental Report,
Rutherford Appleton Laboratory, RB 1205 (2001).
Eisma, E. and Jurg, W.J. in G. Eglinton and M.J. Murphy (Editors)
Organic Geochemistry, Springer Verlag, New York, (1969).
Simoyama, A. and Johns, W.D., Nature, 232, 14 (1971).

24-APP-02
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�－ 269 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-APP-03

Radiation synthesis and cesium removal of cellulose microspherebased hybrid adsorbent
Long Zhao1*, Yanliang Chen1, Yuezhou wei1
1School of Nuclear Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China*Corresponding author: Fax: (+86) 213420-7654; E-mail address: ryuuchou@sjtu.edu.cn
Abstract –A novel cellulose-based hybrid adsorbent was
successfully prepared by radiation-induced grafting of glycidyl
methacrylate (GMA) onto the surface of cellulose microspheres,
followed by epoxy ring-opening reaction to introduce ammonium
12-molybdo phosphate (AMP). The characterization of theobtained adsorbent was investigated in detail. To evaluate theadsorption performance of the novel adsorbent, batch and column
mode adsorption experiment against cesium (Cs) was conducted.
Keywords –radiation grafting; ammonium12-molybdophosphate;
cellulose microsphere; cesium; adsorption

I.

INTRODUCTION

It is well known that the leakage and spread of 137Cs
generated from the accident of atomic power plant such as
Fukushima nuclear disaster can affect human health, andlead to severe environmental problem [1-2]. Several
techniques have been employed for treating Cs containing
aqueous solutions, which include adsorption, reverse
osmosis, extraction and precipitation. Among thesemethods, adsorption has the advantages on high efficiency,
easy handling, availability of different adsorbents and costeffectiveness.
Ammonium 12-molybdophosphate (AMP), which showshigh selectivity toward Cs ion, can act as one of the mostpromising adsorbent materials for this purpose. [3]. However,
AMP is still not employed on a large scale because of its
fine powder form which hinders simple column operation.
To overcome this disadvantage, in this study, we proposeda novel hybrid adsorbent which could be easily prepared byradiation grafting. In current work, AMP can be introduced
onto glycidyl methacrylate (GMA) grafted cellulose
microsphere surface through epoxy ring-opening reaction.
The whole preparation procedures are rather simple.
To evaluate the adsorption performance of the novel
adsorbent, batch and column mode adsorption experiments
by using a nonradioactive Cs solution will be conducted.
In this report, the synthesis conditions and adsorption
properties of the novel adsorbent prepared by radiation
grafting are introduced in detail.

eligible solvent and then grafted polymers were dried in
vacuum. Thereafter, the grafted cellulose microsphere with
GMA having epoxy groups was reacted with AMP in aturbid liquid state at 80oC for 18h. The resulting adsorbent
was washed with water and dried in vacuum and kept for
further use. The structure of the resulting adsorbent was
confirmed by micro-FTIR spectra, TG and XPS analysis.
The batch adsorption of Cs has been investigated as afunction of contact time, pH, Cs and NaCl concentration. A
column-mode adsorption test was carried out using 15mlvolume column at a flow rate of space velocity 10h-1 forinitial Cs of 5 mg L-1 at pH5.4. The concentration of Cs
was measured by atomic absorption spectrophotometer(AAS) and Inductively Coupled Plasma Mass Spectrometer(ICP-MS).
It was found that adsorption equilibrium could beachieved within 30 min for initial Cs of 5 mg L-1. It isbelieved that the functional groups concentrated in surface
result in such quick adsorption. Cs uptake of adsorbent
depends on solution pH, with a maximum Cs uptake at pH
5.4. The adsorption kinetics was well described by thepseudo-second order model equation, and the adsorption
isotherm was better fitted by the Langmuir mode. Fig.1.
showed the breakthrough curves of column adsorption
experiment. The breakthrough curve indicated that the Cs
adsorption amount at the breakthrough point was 0.75gCs/L-adsorbent, and the Cs can be completely removed till
the flux reached roughly 150 bed volumes.

Fig.1. Breakthrough curves of adsorbent.

II. EXPERIMENTAL AND RESULTS
Adsorbent was prepared by pre-irradiation grafting
polymerization. Initially, trunk polymer was sealed inpolyethylene bags purged with nitrogen gas. The sample
bags were irradiated by EB generated from an accelerator,
at a voltage of 750 keV and a dose rate of 10 kGy per passunder the cooling of dry-ice. After getting rid of oxygen bynitrogen flow, monomer solution was injected into thesample bags. The grafting reaction was then performed in awater bath at desired temperature and reaction time. The
homopolymer and unreacted monomer were removed by

Lastly, it was found that 80% adsorption capacity canbe kept even though the adsorbent was exposed to
1000kGy �-irradiation. These results suggested thatobtained adsorbent could be used to removal Cs fromwastewater.
REFERENCES
[1]
[2]
[3]

－ 270 －

IAEA Technical Report Series, No. 356 (1993).
K. Takeshita and T. Ogata, J. Ion Exchange.23,1 (2012).
W. Faubel and S. A. Ali, Radiochim. Acta, 40, 49 (1986).

24-APP-04

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

Study about separation mechanism of endohedral metallofullerenes with
Lewis acid
K. Chiba1, T. Hamano1, E. Takeuchi1, K. Akiyama1, S. Kubuki1, and H. Shinohara2
1

Department of Chemistry, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
2

Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
separated by PTFE membrane filter (pore diameter is

Keywords – Metallofullerene, Lewis acid, Separation

INTRODUCTION

0.2 �m, Millex, Merck Millipore). The EMFs

Recently, a method for the separation andremaining on the filter were washed by water andpurification of endohedral metallofullerenes (EMFs)

acetone. After that, DCB was passed through thewith Lewis acid was reported[1]. It is found that EMFs

filter to recover the EMFs. The gamma-ray emitted

in fullerene crude extract are selectively oxidized

from 141Ce in the samples was measured for thewith Lewis acid and separated with especially highdetermination of separation efficiency by germanium

yield (>99 %) by the liquid Lewis acid such as TiCl4

semiconductor detector (GMX25, SEIKO EG&G).

I.

and SnCl4. On the other hand, the method using solid

AlCl3/CB was also added to purified La@C82

Lewis acids like AlCl3 needs long time for the

DCB solutions and their vis-NIR absorption spectra

separation compared to liquid Lewis acid and thewere measured (UV-3600, SHIMADZU) in order toseparation efficiency is decreased to around 40 % forinvestigate the electronic states of the EMF.
III. RESULTS AND DISCUSSION

the same reaction time. Based on the previous study,
it is presumed that homogeneous diffusion of Lewis

In comparison of the radioactivity of 141Ce atacid in crude extract solution lead to the efficient

before / after separation, the efficiency with AlCl3/CBinteraction between EMFs and Lewis acid.

was determined as about 40 %. This is corresponding

In this session, we will report the effect ofto that with solid AlCl3. It suggests that the separation

diffusion of AlCl3 to the separation and the detail ofefficiency is not much affected by homogeneous

separation mechanism of EMFs.

diffusion of Lewis acid.

II.

In the vis-NIR spectra of the mixed solution of

EXPERIMENTAL

Soot containing La EMFs were produced by arc

La@C82 and AlCl3/CB, two characteristic absorption

rods

bands at 1000, 1400 nm of La@C82 were disappeared(La:C=1:130). The produced soot were dissolved to

but new band was raised at 1300 nm after 5 min of

1,2,4,-trichlorobenzene (TCB), and then refluxed foradding AlCl3/CB. This result indicate that neutral

12 hours. The TCB solution including crude extracts

La@C82 is immediately oxidized by the addition ofof fullerenes was filtered and evaporated to dryness.

Lewis acid and cationic species of La@C82 isAfter that, the crude extracts were re-dissolved to

produced within 5 minute.

discharge

methodwith

La/Co-dichlorobenzene (DCB). EMFs ofcomposite

141

Detail of the mechanism of separation will beCe, which are

known to behave as with La EMFs, were added to

discussed in the session.

these solutions as a radioactive tracer. Chlorobenzene
solution of AlCl3 (AlCl3/CB) was added to the crude[1]

extract. These mixed solutions were stirred and then

－ 271 －

K. Akiyama et al., J. Am. Chem. Soc., 134, 9762-9767,(2012).

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-APP-05

CRYSTAL STRUCTURE AND SPIN STATE OF MIXED-CRYSTALS OF
Fe(NCS)x(NCBH3)2-x(bpp)2 (bpp = 1,3-BIS(4-PYRIDYL)PROPANE)
Haruka Dote1, Hiroki Yasuhara1, Satoru Nakashima2
1

Graduate School of Science, Hiroshima University
Natural Science Center for Basic Research and Development (N-BARD), Hiroshima University

2

Abstract

New mixed crystals, Fe(NCS)x(NCBH3)(2-x)(bpp)2 weresynthesized. 57Fe Mössbauer spectroscopy showed that theratio of low-spin state in the Fe(NCBH3)2 unit changed
with the change of x. The results revealed that the highspin site of Fe(NCS)2 unit affects the spin state ofFe(NCBH3)2 unit.
Keywords

Mössbauer spectroscopy, mixed crystals, spin-crossover,assembled complexes
I.

INTRODUCTION

Self-assembled coordination polymers containing
transition metal ions and organic bridging ligands haveattracted intensive interests because of their potential
abilities for selective inclusion and transformation of ionsand molecules.1) It is possible to construct various
structures for porous assembled iron complexes bridged bybis(4–pyridyl) type ligand. We have studied iron complexes
bridged by 1,3–bis(4–pyridyl)propane (bpp), which has
three methylenes, by using single crystal X–ray diffraction
analysis,
Mössbauer
spectroscopy,
and
SQUID
measurements. Fe(NCX)2(bpp)2 (X = S, Se, and BH3) had a
2D interpenetrated structure and the NCBH3 complex
showed a spin–crossover phenomenon.2) We alsosynthesized Fe(NCX)2(bpp)2· 2(benzene) (X = S, Se, and
BH3). They had a 1D structure and were in temperatureindependent Fe� high-spin state. Both 2D interpenetrated
and 1D structures were converted to each other bydesorption and adsorption of benzene molecules.3) Recently,
we discussed the spin state of the mixed crystals with zincor cobalt ion both in the 2D interpenetrated and 1D
structures for the assembled complexes bridged by bpp.4) In
the present study, we discussed the structure of the mixed
crystals of iron with NCS and NCBH3 for the assembled
complexes bridged by bpp, and then we discussed the spinstate of the mixed crystals.
�. Results and Discussions

We carried out single crystal X-ray diffraction analysis of
By
comparing
Fe(NCS)1.8(NCBH3)0.2(bpp)2.
Fe(NCS)1.8(NCBH3)0.2(bpp)2 with Fe(NCS)2(bpp)2, andFe(NCBH3)2bpp2, we found that the structure is similar toFe(NCS)2(bpp)2 but has shorter b-axis and longer c-axis.
The result is consistent with the result of powder X-ray
diffraction.
We measured Mössbauer spectra of the present mixed
crystals. All the spectra consist of Fe(NCS)2 unit andFe(NCBH3)2 unit. Fig. 1 shows that ratio of NCBH3 andfraction of low spin in mixed anion crystal. The result
reveals that the ratio of low-spin state in the Fe(NCBH3)2
unit changed with the change of x and revealed the highspin site of Fe(NCS)2 unit affects the spin state ofFe(NCBH3)2 unit. The results suggest the chemical pressure
effect, in which Fe(NCS)2 unit next to Fe(NCBH3)2 unit
makes Fe(NCBH3)2 unit to become high spin from low spin
at low temperature.
�. ConclusionWesynthesized
new
mixed
anion
crystals,
Fe(NCS)x(NCBH3)(2-x)(bpp)2. 57Fe Mössbauer spectroscopy
showed that the high-spin site of Fe(NCS)2 unit affects thespin state of Fe(NCBH3)2 unit.

Fig 1. Ratio of NCBH3 and fraction of low spin in mixed anion crystal

Elemental analysis of Fe(NCS)X(NCBH3)2-X(bpp)2 showedthat x is 0.25, 0.65, 0.95, 1.15, 1.1, 1.25, 1.4, 1.7, 1.8, and1.9, when the preparation ratio of x is 0.2, 0.4, 0.6, 0.8, 1,
1.1, 1.2, 1.4, 1.6,and 1.8, respectively. This reveals that theobtained crystals show a trend that the ratio of NCS
increases compared with the preparation ratio. All themixed crystals showed the similar powder X-ray diffraction
patterns, and the (002) diffractions of the mixed crystals are
not the superposition of those from Fe(NCS)2(bpp)2 andFe(NCBH3)2(bpp)2. The (002) diffractions are shifted tohigher degree by increasing ratio of NCS.

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

－ 272 －

B. Moulton, M. J. Zaworotko, Chem Rev., 101 (2001) 1629
M. Atsuchi, H. Higashikawa, Y. Yoshida, S. Nakashima, and K.
Inoue, Chem. Lett., 36 (2007) 1064.
M. Atsuchi, K. Inoue, and S. Nakashima, Inorg. Chim. Acta, 370(2011) 82
S. Nakashima, T. Dote, M. Atsuchi, and K. Inoue, J. Phys., C217,
01035 (2010).

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-APP-06

Analysis of Fragments of a Roman Mask using Mössbauer spectroscopy
Paulo de Souza1,2, G. Klingelhöfer3, P Gütlich3, M. Egg4
1

University of Tasmania, Hobart TAS 7001 Australia
Commonwealth Scientific and Industrial Research Organisation, Hobart TAS 7001 Australia
3
Johannes Gutenberg-Universität Mainz D-55128 Germany
4
Römisch-Germanisches Zentralmuseum, Mainz D-55116 Germany

2

Abstract – A fragmented roman mask was found in excavations
at ”Villa von Allmend”, Saarland, Germany. The mask is made ofiron, covered externally by bronze. Such objects were used in war
games during the height Roman times. During the excavations
around the mask other metallic objects were also found. Someclearly belong to the mask, such as the left ear (Figure 1, top left),among other fragments that cannot be associated with the mask
without further investigation. Some of these fragments were
investigated using backscattering Mössbauer spectroscopy. The
objective was to determine whether the fragment was a piece ofthe roman mask or was part of another object laying in the
excavated area, and shed additional light on the manufacturing
process of the mask itself.
The current communication discusses the results of the analysis offragments from this roman mask using the miniaturised
Mössbauer spectrometer (MIMOS II). This instrument wasdeveloped by Dr. Klingelhöfer’s research group in Mainz forspace exploration [1] and was successfully used onboard NASA’s
Mars Exploration Rovers [2]. Thanks to MIMOS II portability,
robustness, low-power consumption and relative good radiation
shielding, in situ characterization became possible. Theseadvantages of MIMOS II were explored in a number of outdoor
applications [3, and references therein]. In archaeology the
instrument has been applied in the analysis of rock paintings [3]and on a greek Vase [4].
On this roman mask, the results yield the understanding of theprovenance of fragments and were used to guide the process of its
restoration. The Mössbauer spectra on pieces that clearly belong
to the mas show the presence of many iron oxides including
wüstite (FeO1-x). Wüstite has been interpreted as the indication of
production of ‘brand patina’ on the surface of the object. This
oxide phase could be produced by fast cooling under reducing
atmosphere (e.g., putting the hot metal in a bath of animal fat).
Patina was a surface treatment used by romans to improve
resistance to corrosion and for aesthetics purposes. Therefore, theabsence of wüstite would imply in a possible mismatch with theoriginal mask.

Fig. 1. Room temperature Mössbauer spectra of some of the studied
metallic fragments. On the top, the left ear of the mask; on the bottom, anunidentified fragment (probably from the metallic box where it wasplaced), and on the left, the final appearance of the reconstructed mask.

REFERENCES
[1]

[2]

[3]

Keywords – Mössbauer spectroscopy, archaeology.
[4]－ 273 －

G. Klingelhöfer, R. V. Morris, B. Bernhardt, D. Rodionov, P. A. de
Souza, S. W. Squyres, J. Foh, E. Kankeleit, R. Gellert, C. Schröder,S. Linkin, E. Evlanov, B. Zubkov, O. Prilutski (2003) The Athena
MIMOS II Mössbauer Spectrometer Investigation. Journal ofGeophysical Research, v. 108, No. E12, 8067. doi:
10.1029/2003JE002138.
G. Klingelhöfer, R. V. Morris, B. Bernhardt, C. Schröder, D.
Rodionov, P. A. de Souza, A. Yen, R. Gellert, E. N. Evlanov, B.
Zubkov, J. Foh, U. Bonnes, E. Kankeleit, P. Gutlich, D. W. Ming, F.
Renz, T. Wdowiak, S. W. Squyres, R. E. Arvidson (2004) Jarosite
and Hematite at Meridiani Planum from Opportunity's Mössbauer
Spectrometer.
Science,
306,1740-1745.
doi:
10.1126/science.1104653.
C. Schröder, G. Klingelhöfer, R. V. Morris, B. Bernhardt, M.
Blumers, I. Fleischer, D. S. Rodionov, J. Gironés López, P. A. de
Souza (2010) Field-portable Mössbauer Spectroscopy on Earth, theMoon, Mars, and Beyond, Geochemistry: Exploration,
Environment, Analysis, 11 (2011) 2, 129-143. doi: 10.1144/14677873/09-IAGS-018.
P. A. de Souza, B. Bernhardt, G. Klingelhöfer, P. Gütlich (2003)
Surface Analysis in Archaeology Using the Miniaturized Mössbauer
Spectrometer MIMOS II. Hyperfine Interactions, v. 151, 125-130.
doi: 10.1023/A:1025444209059.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201324-APP-07

Synthesis of 14C labeled C60 with higher specific activity
1

T. Tadai1, K. Akiyama1, H. Aoshima2, R. Ibuki2, S. Kubuki1
Department of Chemistry, Tokyo Metropolitan University, Hachioji, 192-0397, Japan
2
Vitamin C60 BioResearch Corporation, Chuo-ku, Tokyo 103-0028, Japan

Keywords Keywords – 14C-labeled C60

I.
INTRODUCTION
Recently, Fullerenes and their derivatives have been
attracted to the medical and cosmetics fields. However,there are some problems for the application of fullerenes,
such as nano toxicity. To overcome these problems, further
study about drug disposition is required. As one of the mostuseful technique, the radioactive tracer method using 14Clabeled C60 is applicable for this purpose. Synthesis of 14Clabeled C60 has been reported so far [1, 2]. However,synthesis of 14C-labeled C60 with higher specificradioactivity is desired for the detail study. In this session,
we will report the development of synthesis and theproperties of produced 14C-labeled C60 such as specificradioactivity.
II. EXPERIMENTAL
Ba14CO3 (0.2 mmol, 57 mCi/mmol) was mixed with PbCl2
and AgCl and then put into the electric furnace for heating
at 450 oC to produce labeled CO2 under He gas flow. The
produced CO2 gas was stored in the plastic bag, and thenintroduced to the Et2O solution of 2-lithiofuran to produce
the furoic acid. The produced furoic acid was reduced with
LiAlH4 in THF solution to obtain the labeled furfuryl
alcohol. This alcohol was condensed by the evaporator, andthen dissolved into o-dichlorobenzene (o-DCB). For thepolymerization of this alcohol, p-toluenesulfonic acid wasadded into this o-DCB solution. The polymer solution wasadsorbed on a porous carbon rod (PC5060G, Tokai Carbon

Inc.) and dried at 200 oC under He gas stream for 1 hour.
After that, carbon rod was set into fullerene generator andsintered by the electric resistance heating method. The
resulting 14C-impregnated graphite electrode was thenemployed as an anode for the arc discharge for the fullerene
production. The soot containing 14C-labeled C60 wererecovered from the generator as a CS2 solution and thenfiltered to remove the insoluble substances. The 14C-labeled
C60 was purified from these filtered crude fullerenes by
HPLC (Buckyprep, Nakarai tesque Inc.). Their total weightand specific radioactivity were determined by UV/vis
absorption and liquid scintillation counter (LSC).
III. RESULTS AND DISCUSSION
The yield of 14C was estimated from the radioactivity in
Ba14CO3 and in obtained C60, and found to be 0.73 %. Thisis about 3 times larger than that of previously reported
value [1]. As the results of UV/vis absorption measurement,
the total weight of purified C60 is found to be about 3 mg.
The specific radioactivity of these C60 estimated from theradioactivity determined by the results of LSC
measurement and total weight of C60, were found to be 18.4
mCi/mmol. Enrichment of 14C for this sample was about
14
C: 12C = 1: 200. This value is the highest among that ofprevious reports and indicate that the most enriched 14Clabeled C60 is produced by our method.
[1] W. A. Scrivens, et al., J.Am.Chem.Soc.,116, 4517-4518, 1994.
[2] S. R. Wilson, et al., Fullerene Sci. & Technol., 4, 43-48, 1996.

－ 274 －

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