Oral Presentations
Monday, 23 September 2013
Hall & Meeting Room, Kanazawa Bunka HallTime
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20:00--ONDAY  3EPTEMBERHall
Meeting Room
9:00

Arrangement for
presentation

9:30
Opening Ceremony
10:00(EVESY !WARD #EREMONY
R. S. Dybczyński

11:00
11:10

#OFFEE "REAK
PL-01
0LENARY

11:40

PL-02

M. Yamamoto
0LENARY

12:10
13:20

FKI-01

I. McKinley,UNCH 4IME
)NVITED
API-01)NVITED

13:50

FKI-02

H. Tsuruta)NVITED

API-02

H. Harada)NVITED

14:20

FKI-03

Y. Takahashi)NVITED

APO-01

14:50

FKI-04

M. Aoyama)NVITED

APO-02
APO-03

B. Grambow
15:20

Y.L. Zhao
GeneralT. M. Nakanishi
General
S.H. Jung
GeneralM. Anvia#OFFEE "REAK

15:40

FKO-01

16:00

FKO-02

16:20

FKO-03

16:40

FKO-04

17:00

FKO-05

17:20

FKO-06

17:40

FKO-07

18:00

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

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

18:50
0OSTER 3ESSION
20:00

－1－

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

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

HMA-01

50 Years of Adventures with Neutron Activation Analysis with the Special
Emphasis on Radiochemical Separations�����������������������
Laboratory of Nuclear Analytical Techniques, Institute of Nuclear Chemistry and Technology, 03-195 Warszawa,
POLANDr.dybczynski@ichtj.waw.plRadiochemical separations are the key element of

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

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

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

this area is the best reference to the heritage of George

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

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

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

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

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

determination of trace elements by RNAA, but also purely

purification and measurement of short-lived 134mCs with

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

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

years of atomic era, only non-selective radiation detectors

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

spectrometry was used for the determination of noble

available, so except of some special cases , the analysis

metals in geological materials as well as all lanthanides in

had to rely on chemical separations. Radiochemical

biological materials. The uses of INAA included inter alia

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

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

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

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

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

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

the certification of new CRMs. The idea of “definitive

intended for RNAA. First, relied on addition of inactive

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

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

radionuclide by column chromatography followed ����-ray

measurement and determination of chemical yield. Second,

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

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

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

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

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

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

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

Er2O3 as well as La in Pr6O11. Fundamental study

Guide 99:2007, definitive methods by RNAA may be

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

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

+

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

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

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

－3－

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

PL-02

Fukushima Challenges in Perspective
1

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

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

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

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

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

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

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

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

FKI-01

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

Haruo Tsuruta1, Masayuki Takigawa2, Teruyuki Nakajima1
Atmosphere and Ocean Research Institute, The University of Tokyo, Kashiwa, Chiba 277-8568, Japan
2
Japan Agency for Marine-Earth Science and Technology, Yokohama, Kanagawa 236-0001, Japan

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

131 137I.

INTRODUCTION

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

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

RESULTS AND DISCUSSION

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

－5－

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

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

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

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

2

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

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

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

－6－

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

FKI-03

Oceanic and coastal dispersion of 134Cs and 137Cs released from the TEPCO
Fukushima NPP1 accident: past, present and prediction
Michio AOYAMA1, Yasunori HAMAJIMA2
1Meteorological Research Institute, Tsukuba, 305-0052 Japan
2 Low Level Radioactivity Laboratory,Kanazawa University, Nomi, Ishikawa 923-1224, Japan
Abstract: The bulk of the anthropogenic radionuclide 137Cspresent in the oceans today was injected about five decades
ago from atmospheric nuclear weapons tests. In the North
Pacific Ocean 137Cs inventory was 290 ± 30 PBq in 1970
and it was 69 PBq just before the TEPCO Fukushima Daiichi Nuclear Power Plant (FNPP1) accident. An impact of
FNPPP1 accident to the North Pacific Ocean in terms of
inventory was estimated to be 10 – 13 PBq by atmosphericdeposition and 3.5 ± 0.7 PBq by direct discharge, therefore
the total 137Cs inventory in the North Pacific Ocean
increased by up to 20 – 23%.Fukushima released
radiocaesium already subducted in 2011/2012 winter andformed subsurface maximum at a densities of Central Mode
Water (CMW), and Subtropical Mode Water (STMW).
Key words: 137Cs, Pacific Ocean, inventory, subduction,
radioactive plumeI. INTRODUCTION
On 11 March 2011, an extraordinary earthquake ofmagnitude 9.0 centered about 130 km off the Pacific coastof Japan’s main island, at 38.3 ºN, 142.4 ºE, was followed
by a huge tsunami with waves reaching up to 40 m heightin Iwate region and about 10 m in Fukushima region. The
station blackout developed into a disaster that left three ofthe six FNPP1 reactors heavily damaged, meltdown of core,and caused radionuclides to be discharged into the air andocean[1, 2].
II. SAMPLING AND METHODS
We collected 2 litre surface seawater samples at morethan 300 stations. The samples were treated by an improved
ammonium phosphomolybdate, AMP, procedure [3, 4].
III.RESULTS
134
Cs and 137Cs activities in surface water at Hasaki, acoastal station 180 km south of the Fukushima Dai-ichi
Nuclear Power Plant (FNPP1) accident site, were observedin April to December 2011 [5]. The maximum inradiocaesium activity at Hasaki was observed in June 2011,
representing a delay of two months from the corresponding
maximum in April 2011 at FNPP1. Directly discharged
134
Cs and 137Cs were transported dominantly southward
along the coastline of north eastern Honshu, at least in May
and June 2011.
Before the FNPP1 accident, 137Cs was already exist
which was originated from the nuclear weapon tests
conducted in the late 1950s and in the early 1960s [4, 6]. In
the western North Pacific Ocean, 90Sr and 137Cs activities insurface water was 10 – 100 Bq m-3 in the late 1950s and in
the early 1960s, then it decreased gradually and the 137Cs
activity in surface water decreased to around a few Bq m-3
just before FNPP1 accident as shown in Figure 1[6, 7].

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

The 137Cs inventory in the North Pacific Ocean was 290± 30 PBq in January 1970 based on 10 º by 10 º mesh dataof the 137Cs deposition [7]. In 2003, 137Cs inventory in the
North Pacific Ocean was 86 PBq by the model study [8]and 85 PBq by the observation [9], then it decreased to 69
PBq in 2011 because due to decay [9].
The horizontal distribution of FNPP1 derived 134Cs in
the western North Pacific Ocean except just in front of the
FNPP1 site showed that the high concentration area locatedclose to the FNPP1 accident site which might have received
both atmospheric deposition – showing good consistency
with previous atmospheric transport model study [10] – anddirect discharge [2] from the FNPP1 site. During the winterbetween 2011/2012, Fukushima derived radiocaesium
subducted and formed subsurface maximum at a densities
of Central Mode Water (CMW) of which depth is about
400 meters depths and Subtropical Mode Water (STMW)
of which depth is about 150 meters depths due to cooling at
sea surface. This implies that a speed of main body ofFukushima derived radiocaesium will be decreased muchbecause of less wind driven force at subsurface layers
rather than those at surface layers which was 8 cm s-1 as
the average speed of radioactive plume at sea surface statedpreviously. [6]REFERENCES
1. Chino, M., et al., Journal of Nuclear Science and Technology, 48(7), p.
1129-1134, 2011.
2. Tsumune, D., et al., J Environ Radioact, 111, p. 100-108, 2012.
3. Hirose, K., et al., Journal of Radioanalytical and Nuclear Chemistry,
263(2), p. 349-353, 2005.
4. Aoyama, M. and K. Hirose, Radiometric determination ofanthropogenic radionuclides in seawater, in Radioactivity in theEnvironment, P.P. Pavel, Editor. 2008, Elsevier. p. 137-162.
5. Aoyama, M., et al., Geochem. J, 46, p. 321-325, 2012.
6. Aoyama, M., et al., Progress In Oceanography, 89(1-4), p. 7-16, 2011.
7. Aoyama, M., K. Hirose, and Y. Igarashi, Journal of Environmental
Monitoring, 8(4), p. 431-8, 2006.
8. Tsumune, D., et al., Progress In Oceanography, 89(1-4), p. 38-48,
2011.
9. Aoyama, M., D. Tsumune, and Y. Hamajima, Journal ofRadioanalytical and Nuclear Chemistry, p. 1-5, 2012.
10. Honda, M.C., et al., Geochem. J, 46, p. e1-e9, 2012.

－7－

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

FKI-04

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

Bernd Grambow1
SUBATECH (Ecole des Mines de Nantes, University of Nantes, IN2P3-CNRS)
4 rue Alfred Kastler, 44307 Nantes, France,
Grambow@subatech.in2p3.fr

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

－8－

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

FKO-01

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

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

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

I.

INTRODUCTION

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

Fig.1 Sampling point of the AW and PW

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

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

FKO-02

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

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

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

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

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

I.

INTRODUCTION

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

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

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

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

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

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

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

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

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

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

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

－ 11 －

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

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

FKO-04

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

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

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

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

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

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

I.

INTRODUCTION

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

III. RESULTS AND DISCUSSION

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

－ 12 －

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

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

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

2

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

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

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

I.

INTRODUCTION

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

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

REFERENCES[1]－ 13 －

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

FKO-06

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

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

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

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

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

(b)

(c)

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

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

FKO-07

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

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

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

INTRODUCTION

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

III.

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

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

Fig.1 The time dependence change of Sr-90 and Cs-137 in Hitachi[1]L.L.Smith and K.A.Orlandini. Radiochimica Acta 73,165-170(1996)－ 15 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

FKO-08$OSIMETRIC )MPLICATIONS OF THE &UKUSHIMA 2ELEASE FOR 0ACIFIC ALBACORE IN THE.ORTHERN #ALIFORNIA #URRENT
Delvan R. Neville1, A. Jason Phillips1, Kathryn A. Higley1
1

Oregon State University, Corvallis, OR; nevilled@onid.orst.edu!BSTRACT – 5SING ACTIVITY CONCENTRATIONS IN 0ACIFIC ALBACORE AT
BOTH PRE &UKUSHIMA AND POST &UKUSHIMA LEVELS THE AVERAGEANNUAL WHOLE BODY INTERNAL DOSE FOR THESE NEKTON IS ESTIMATED
-#.0  VOXELIZED PHANTOMS APPLIED FOR DETERMINATION OF
ABSORBED FRACTION !NALYZED TISSUES INCLUDE BOTH EDIBLE TISSUEVISCERA AND OTHER NON EDIBLE TISSUES+EYWORDS – #S  #S  0ACIFIC ALBACORE RADIOECOLOGY&UKUSHIMAI.

INTRODUCTION

An unfortunate result of the already devastating
earthquake and tsunami on March 11, 2011 was a release ofradionuclides from the Fukushima Daichi power generating
station. It will be several years before this release into theNorth Pacific Gyre will be carried, at diluted and decayed
activity concentrations, to the West Coast of North
America[1]. During the interim, migratory species may bepassing through the extent of this liquid plume, and feeding
throughout that range. This work intends to address thedosimetric implications for migratory Pacific albacore,
4HUNNUS ALALUNGA

elsewhere in the animal, to allow utilizing this existing
body of work for animal dosimetric estimations" 7HOLE "ODY $OSIMETRY
Absorbed fractions were calculated for activity indifferent body compartments using MCNP and a voxelized
model developed from CT & MRI of a pelagic fish.
Activity concentrations for Cs-134 and Cs-137 measured in
Pacific albacore were then used to calculate annual internal
dose to the animal for both those that exhibited trace
concentrations of Fukushima effluents and those thatremained at pre-Fukushima concentrations. The internaland external dose from naturally occurring K-40 is also
provided for comparison. Additionally, dose estimatesusing the prior "edible-only" paradigm are presented.
[1]! 3TATE OF EXISTING BODY OF KNOWLEDGE
Historically, reported activity concentrations in the
United States have almost exclusively sampled the edible
tissues. In the case of albacore, this excludes not just skin,bone and viscera, but the fatty red muscle tissue along the
belly. These were conducted at national labs, with theprimary goal of ensuring Cold War-era radionuclides
releases were not affecting food quality.
However, muscle tissue is one of the most radioresistant tissues in the body. One goal of this work is toaddress the dosimetric impact to biota by determining
concentrations for the whole body, rather than simply inedible tissue.
There is a large body of work reporting concentration
ratios for nekton in the Pacific, which is the ratio of theactivity concentration in the tissue over the activity
concentration in the water, by mass. These concentration
ratios vary wildly, as they depend on the assumption thatthe animal sampled is in equilibrium with activity in thesurrounding environment, including the complicated food
web transfer through other species. Nonetheless, they arestill widely used for determinations of the expectedconcentrations after a release until a more thoroughdetermination may be made. Another goal of this work is
to relate edible muscle concentrations to concentrations－ 16 －

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

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

API-01

ANNRI at J-PARC

1

Hideo Harada1(on behalf of ANNRI project)
Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

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

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

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

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

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

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

API-02

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

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

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

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

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

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

－ 18 －

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

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

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

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

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

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

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

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

Fig.1a macoscopic real-time RI imaging system

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

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

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

APO-02-#.0 STUDY ON THE DEVELOPMENT OF INDUSTRIAL 30%#4 IN TERMS OF A RADIATIONMEASUREMENT DESIGN AND VOID INFLUENCE IN MULTIPHASE MEDIA
Sung-Hee Jung1, Jang-Guen Park1, Jong-Bum Kim1, Jin-Ho Moon1, Chan-Hyeong Kim2

1
2

Korea Atomic Energy Research Institute, Daedeok-daero 989-111, Yuseong-gu, Daejeon, 305-353, Korea
Dept. of Nuclear Engineering, Hanyang Univ., 17 Haengdang-dong, Seongdong-gu, Seoul, 133-791, Korea!BSTRACT – 4HERE HAVE BEEN EXTENSIVE STUDIES ON THE DEVELOPMENT
OF 30%#4 3INGLE 0HOTON %MISSION #OMPUTER 4OMOGRAPHY FOR
INDUSTRIAL APPLICATIONS /WING TO ITS INTRINSIC LIMITATION ORIGINATED
FROM THE DIMENSIONS AND DENSITY OF OBJECTS IN INDUSTRIAL PROCESSUNITS IT HAS BEEN A CHALLENGING ISSUE TO GET A SPATIAL RESOLUTION
GOOD ENOUGH TO DRAW INFORMATIVE DATA FROM IT 4HIS STUDYDEMONSTRATES THE FEASIBILITY OF A RADIATION MEASUREMENT ARRAYPROPOSED FOR A GREATER REGION OF INTEREST RESULTING IN BETTER SPATIALIMAGE RESOLUTION #ONSIDERING THAT THE INDUSTRIAL PROCESS UNITSARE DESIGNED TO MIX UP DIFFERENT MATERIALS IN DIFFERENT PHASES THE
INFLUENCE OF A VOID RATIO INTO THE IMAGE QUALITY OF THE INDUSTRIAL
30%#4 WAS INVESTIGATED WITH THE -ONTE #ARLO CODE FOR A,IQUID6APOR PHASE SYSTEM+EYWORDS –)NDUSTRIAL 30%#4 2ADIOISOTOPE TRACER -ULTIPHASEFLOW INVESTIGATION 'AMMA RADIATION COLLIMATION -#.08

I.

INTRODUCTION

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

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

II. METHODS AND RESULTS! 2EDESIGN OF RADIATION COLLIMATOR CONFIGURATIONThe configurations in Fig. 1 show the conventional andnewly proposed radiation measurement arrays for an
MCNPX simulation. Besides the diverging orientation ofcollimation, the proposed array is identical to theconventional one. The cylindrical vessel is 40 cm indiameter and contains water. Radiation probes are NaI(Tl)with 1.3 cm in diameter and 2.5 cm in length. The
radioisotope is 68Ga with 511 keV of gamma radiation andthe energy window for measurement was set to r10% of it,
460-562 keV. The radioisotope was positioned at fivedifferent points, 0, 4, 8, 12, and 16 cm from the center toevaluate the precision of the reconstructed images atvarious locations.

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

" )NFLUENCE OF VOID FRACTION TO IMAGE QUALITY
Homogeneous void formation at the same layer with the
6 detectors of industrial SPECT was modeled with MCNP
code.
Table 1. NRMSE for quantitative comparison of image quality
Source68
Ga(511 keV)
137
Cs(662 keV)Counting
Method
Gross
Peak
Gross
Peak

5%
1.93
1.69
1.88
1.42

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

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

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

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

APO-03

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

Mellodee Anvia1,2 and Susan A. Brown1
ANSTO Minerals, Locked Bag 2001, Kirrawee DC, NSW 2232, Australia
2
School of Chemistry, The University of Sydney, NSW 2006, Australia

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

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

NCO-01

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

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

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

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

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

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

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

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

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

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

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

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

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

I.

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

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

INTRODUCTION

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

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

REFERENCES
[1]
[2]
[3]

－ 23 －

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

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

NCO-03The Statues of Chemical Characterization of a Spent Nuclear Fuel
Yeong-Keong Ha, Soon-Dal Park, Yang-Soon Park, Jung-Suk Kim, Kyuseok Song
Korea Atomic Energy Research Institute, 989-111 Daedeokdaero, Yuseong, Daejeon, 305-353, Korea
Abstract –The high burnup nuclear fuel requires an experimental
data to support the fuel integrity, a safety analysis, and ashielding design. At high burnups, the composition of a nuclear
fuel changes in a non-homogeneous manner throughout the radius.
We present the R&D activities being performed in KAERI for
spent fuels discharged from PWR in Korea; focused on the local
chemical properties such as ‘local burnup', 'structural changes'
and 'the distribution of retained fission gas'.

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

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I.

INTRODUCTION

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

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

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

A. Isotopic Distribution and Structural Changes

IV. CONCLUSION

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

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

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

NCO-04

Determination of 93Zr from intermediate level radioactive effluent

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

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

ICP-MS;－ 25 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

NCO-05

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

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

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

－ 26 －

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

Age Determination of a single Pu and Pu/U mixed oxide particle
Yutaka MIYAMOTO, Fumitaka ESAKA, Daisuke SUZUKI, Masaaki MAGARA
Research Group for Analytical Chemistry, Nuclear Science and Engineering Directorate
Japan Atomic Energy Agency (JAEA), Tokai, Ibaraki 319-1195, JAPAN
Abstract – Age-dating of a single Pu oxide particle and a Pu/U
mixed oxide (MOX) particle ~1 µm in diameter was demonstrated.
The particles were prepared from the U and Pu standard referencematerials for this demonstration. They were separately dissolved,
and Am, U, and Pu were chemically separated from the solution via
anion-exchange chromatography. The isotope ratios of Am and Pu
in the eluted fractions were measured using a high-resolution
inductively coupled plasma mass spectrometer (HR-ICP-MS). The
precision and accuracy of the Pu age were improved through theaddition of 243Am or 243Am-242Pu mixed spikes to the sample
solutions and by the trace chemical separation of Pu and Am. The
determined age in this work was in good agreement with the
expected age with high accuracy and precision. These results
indicate that a combination of measurement using a mass
spectrometer and chemical separation of the spiked samples
provides an effective tool for the analysis of environmental samples
collected during nuclear safeguard inspections.
Keywords – Age dating, MOX, Plutonium, Trace analysis, Ionexchange separation, Safeguards

I.

INTRODUCTION

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

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

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

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

F. Esaka et al., Talanta, 83, 569 (2010).
Y. Miyamoto et al., Radiochim. Acta, in press (2013).

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

Radiochemical measurement of 10-15 MeV proton induced fission yields for U-238
Narek Gharibyan1, Kenton J. Moody1, Thomas A. Brown2, John D. Despotopulos1, Julie M. Gostic3,
Roger A. Henderson1, Evgeny Tereshatov1, Scott J. Tumey2 and Dawn A. Shaughnessy1
1Chemical Sciences Division, Lawrence Livermore National Laboratory
Atmospheric, Earth, and Energy Division, Lawrence Livermore National Laboratory
3
Air Force Technical Applications Center, Patrick Air Force Base, Florida

2

Keywords – Fission yields, protons, fission product separation, U238I.

INTRODUCTION

The improvements in fidelity of nuclear forensic exercise
samples require the development of analytical referencematerials with the end goal of establishing a realistic exercise
sample. This is designed to test the national laboratory
analysis and data evaluation communities through a truly
coupled, end-to-end “unknown sample” exercise. The
fabrication of such a sample requires an accurate knowledgeof cross sections and fission yields for numerous reactions
that can be explored to obtain fission products and/or shortlived actinide isotopes. Due to the limited amount of nuclear
data and the large uncertainties associated with the reported
values of proton-induced fission for U-238, experiments were
performed to measure the fission mass yields and the crosssection. Radiochemical separations were established forfission products of interest in order to improve the fission
yields in comparison to those obtained from the initially
irradiated samples.

separation of wing and valley fission products. Various
chemical separation methods were developed based on thesorption behavior of the fission products on ion exchange
resins. Chemical fractions containing the fission products ofinterest were counted individually and the total fission yields
were back calculated for each sample.
III. RESULTS
The measured fission yields are based on the results
generated by the GAMANAL program [1] evaluation of the
raw gamma spectra. Fission yields for short lived fission
products, as low as t1/2=14 minutes, were acquired. An
example of a fission mass yield obtained from theseexperiments is provided in Figure 1. The measured values of
the cross sections and fission yields are relatively close to
those reported in literature [2-4].

2ELATIVE 9IELD

Abstract – The production of realistic nuclear forensics debris
requires an accurate knowledge of cross sections and fission yields
for large number of systems. Proton induced fission of U-238 was
examined for incident energies in the range of 10-15 MeV. Fission
yields were first measured directly from the irradiated materials.
The valley and wing fission products were then isolated in various
chemical fractions in order to increase the counting statistics
leading to improvements in the fission yields. In addition to the total
fission cross section and the fission mass yields for U-238, proton
based reaction cross sections on U-238 and U-235 were alsomeasured.















-ASS

II. EXPERIMENTAL

Figure 1. Fission mass yield from 11.9 MeV protons on U-238.

A stacking foil technique was employed in the irradiationof nat. U foil with 10-15 MeV protons with Y as the beam
intensity monitor. A series of irradiations were performed
using the tandem Van De Graff accelerator located at theCenter for Accelerated Mass Spectrometry at Lawrence
Livermore National Laboratory (LLNL). Irradiated samples
were transferred to the Nuclear Counting Facility on site at
LLNL for the initial counting. After sufficient data wereobtained, the uranium foils were dissolved and separated into
three fractions: one as a standard and one each for the

Acknowledgements – This work was performed under the auspicesof the U.S. Department of Energy by Lawrence Livermore National
Laboratory under contract DE-AC52-07NA27344.
[1]
[2]
[3]
[4]

－ 28 －

Gunnink, R., Niday, J.B., UCRL-51061, Vol. I (1972)
Yokoyama, A., et al., Z. Phys. A 356, 55-60 (1996)
Baba, H., et al., Z. Phys. A 356, 61-70 (1996)
Karttunen, E., et al., Nucl. Sci. Eng. 109, 350-359 (1991)

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

Effect of Interferences on Actinide and Strontium Separations in Unusual Matrices
Ralf Sudowe1, Evelyn M. Bond2, Ashlee R. Dailey1, Derek R. Mclain1, Audrey R. Roman1
1

2

University of Nevada Las Vegas, Las Vegas, Nevada 89154, USA
Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA

Abstract – Insufficient information is currently available about theeffects that the interferences present in complex matrices can haveon radiochemical separations utilizing extraction chromatography.
This poses a particular challenge for sample analysis in theaftermath of a nuclear incident involving an Improvised Nuclear
Device or a Radiological Dispersion Device. This research aims at
obtaining this information by examining the composition of common
urban materials and by investigating the influence that theirconstituents have on radioanalytical separations. To address thisissue the compositions of several different sample matrices ofinterest has been investigated. Subsequently the uptake of Sr, Pu,
Am and Cm on different commercially available resins was studied
in the presence of varying concentrations of potentially interfering
elements such as Al, K, Ca, K, Cr, Fe, Ni, Zr and Nd.
Keywords – Extraction chromatography, Actinide, Strontium,
SeparationsI.

INTRODUCTION

Most current radioanalytical methods have been developed
for the analysis of air, water, soil and bioassay samples.
While these protocols build the foundation of operational
environmental monitoring, they are not necessarily suitable
for the analysis of samples that will be encountered in theaftermath of a nuclear incident involving an improvised
nuclear device or a dirty bomb. Of particular interest for
emergency response and nuclear forensics are therefore
methods that can be applied to the analysis of steel, concrete,
melt glass, asphalt and bone samples.
Extraction
chromatographic resins have been used for radiochemical
separations for many years now, and a large body of data has
been published on the retention capabilities of many of theseresins for a large variety of elements that can be found inenvironmental samples. Little can be found, however, on theeffect that the matrix constituents found in debris samples canhave on analyte uptake. Even though it is known that theelements of interested are retained on the respective resins toa high degree, the samples analyzed will have a much more
complex composition than previously encountered. Theirbehavior might therefore potentially deviate from normal
sorption characteristics.
In particular the competition
between the potential interference and the analyte of interest
has to be studied in a systematic manner. The goal of thisstudy is to obtain information about the major and minor
constituents that are present in several sample matrices ofinterest for emergency response and to investigate theinfluence that they can have on the radiochemical
determination of several actinide elements and radiostrontium.

II. EXPERIMENTAL
The composition of several different matrices of interest
was determined by either obtaining information fromreference materials or by performing elemental analysis on
suitable samples. Batch studies were then used to determine
the uptake of the analyte of interest on a particular resin in thepresence of varying concentrations of different alkali, earth
alkali and transition metals, as well as lanthanides. The
uptake of Sr on SR resin [1] was investigated in addition to
the uptake of Pu, Am and Cm on DGA and UTEVA resin [2,3]. Single analyte solutions were contacted with small
amounts of resin in the presence of varying concentrations of
the potential interference. Aliquots were taken and theamount of analyte remaining in solution was determinedusing either LSC measurement or gamma spectroscopy.
Simultaneously the concentration of the interfering element
after contact with the resin was measured by ICP-AES.
III. RESULTS
The compositions of several different sample matrices ofinterest, such as bone ash, steel, concrete, asphalt and melt
glass has been investigated. The uptake of Sr on Sr resin wasstudied in the presence of varying concentrations of Mg, Al,
P, K, Ca, Cr, Fe, Ni, Cu and Zr. The adsorption of Pu, Am
and Cm on DGA and UTEVA resin was studied in thepresence of varying concentrations of Fe, Zr, Mo, Sr, Tc, Cs
and Nd. The presence of several of the interferences studied
led to a significant decrease in uptake of the element ofinterest on the resin. Others appeared to have no influence.
In some cases the presence of the interference lead to anincreased adsorption of the analyte on the resin, hinting at asynergistic effect that needs to be studied in greater detail.
REFERENCES
[1]
[2]
[3]

－ 29 －

E.P. Horwitz et al, A novel strontium-selective extraction
chromatographic resin, Solvent Extraction Ion Exchange 10, 313(1992)
E.P. Horwitz et al, Novel extraction of chromatographic resins basedon tetraalkyldiglycolamides: Characterization and potential
applications, Solvent Extraction Ion Exchange 23, 319 (2005)
E.P. Horwitz et al, Separation and preconcentration of uranium from
acidic media by extraction chromatography, Analytica Chimica Acta,
266, 25 (1992)

Poster Session 1
Monday, 23 September 2013
18:50 ~ 20:00

Scientific Topics (Abbrev.)
1. Fukushima issues (FK)
2. Education in nuclear and radiochemistry (ED)
3. Nuclear forensics (NF)
4. Nuclear energy chemistry (NE)
5. Nuclear chemistry (NC)
6. Actinide chemistry (AC)
7. Environmental radiochemistry (EN)
8. Radiopharmaceutical chemistry and Nuclear medicine (RP)
9. Nuclear probes for materials science (NP)
10. Activation analysis (AA)
11. Application of nuclear and radiochemical techniques (AP)－ 115 －

23-FKP-01
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013137

Cs Accumulation Enhanced by Potassium Starvation in Lotus japonicus

Jun Furukawa1, Hiroki Noda2, Ryohei Sugita3, Keitaro Tanoi3, Tomoko M. Nakanishi3, Shinobu Satoh1
1

Faculty of Life and Environmental Sciences, University of Tsukuba
Graduate School of Life and Environmental Sciences, University of Tsukuba
3
Graduate School of Agricultural and Life Sciences, The University of Tokyo

2

Abstract – Radionuclides released from Fukushima Dai-ich Nuclear
Power Plant spread to the environment. The transfer of 137Cs fromsoil to land plants is one of the most important steps for considering
the influx of 137Cs into ecosystem. To identify the responsible genes
for 137Cs uptake and translocation in plants, we focused on the K+
transport system in the model legume, Lotus japonicus. The
dynamics of 137Cs uptake and translocation was differed between
two accessions, B-129 and MG-20, and K starvation drasticallyenhanced 137Cs uptake in B-129. The expression levels of known K+transporters were also investigated under several K conditions.
Keywords – cesium-137, potassium, accumulation, Lotus japonicus

I.

137

Cs was detected with an image analyzer (BAS) and gamma
counter, respectively.
Real-time Radioisotope Imaging
RRIS (Real-time Radioisotope Imaging System) was used
for obtaining the images of 137Cs uptake and translocation in
L.japonicus.
RRIS
is
a
non-destructive
digitalautoradiography system specialized for the use in living plantresearch [2]. The plants prepared as previous BAS
experiment were placed in RRIS and the 137Cs distribution
images were obtained for 24 h.
III. RESULTS AND DISCSSIONINTRODUCTION

After the Fukushima Dai-Ichi Nuclear Power Plant
accident, large amount of radioactive materials were released
into the environment and the major radionuclides leaking was
137
Cs. Cesium is known as an analog of potassium in the plant
nutrition and, therefore, one of the main route of 137Cs into
the ecosystem is an uptake process in land plant. Uptake andtranslocation of 137Cs is thought to be carried out by the K+
transport systems in plants [1]. However, because of thecomplexity of K+ transport system, the responsible
transporters, which transport 137Cs, were not well identified.
In this research, the identification of the K+ transport system,
which involved in the 137Cs uptake and transport, in Lotus
japonicus was attempted. L.japonicus has been proposed as amodel legume for molecular biology, and the results obtained
from L.japonicus are applicable to one of the major crops,
soybean.

As for the plants grown under normal K condition, 137Cs
in B-129 root was about twice the concentration of that in
MG-20. However, 137Cs concentration in shoot was notdiffered between two accessions. In the plants treated with -K
solution for 3 days, drastic enhancement of 137Cs uptake wasobserved in B-129 root. The increase of 137Cs translocationfrom root to shoot was observed both in B-129 and MG-20.
Because of the constant 137Cs concentration in MG-20 root,
the increase of 137Cs concentration in MG-20 shoot suggested
the high 137Cs translocation activity in MG-20 under K
starvation. Real-time 137Cs images clearly indicated the 137Cs
uptake site in root and the rapid uptake and translocation of137
Cs in B-129 (Figure 1).

II. MATERIAL AND METHODS
Plant Materials and Growth Conditions
Two L.japonicus accessions, Gifu B-129 (B-129) and
Miyakojima MG-20 (MG-20), were obtained from the
Biological Resource Center in Lotus and Glycine, Universityof Miyazaki, Japan. Seedlings were grown with continuously
aerated 1/10 strength Hoagland’s solution in a 2 L plastic
container under light- and temperature-controlled condition;light 16 h, darkness 8 h, 24oC. The solution was renewed
every 3 days. At the last 3 days before 137Cs uptake
experiment, the solutions with and without K were prepared.

Figure 1 Real-time imaging of 137Cs uptake and translocation in B-129 andMG-20 treated with -K solution for 3 days. Each panel indicates theradioactivity image obtained for every 2.4 h.

Potassium starvation promotes K uptake system, especiallyhigh affinity K+ transporter, in root [3]. Therefore, theexpression levels of known K+ transporters in L.japonicus
will be discussed.

137

Cs Uptake
Plants grown for one month were transferred to 50 mL of
1/10 strength Hoagland’s solution (without K) containing
137
CsCl and non-radioactive Cs (10 �M) for 12 h. After
harvesting shoots and roots, distribution and radioactivity of

IV. REFERENCES
[1]
[2]
[3]

－ 116 －White PJ and Broadley MR (2000) New Phytol., 147, 241-256.
Kanno S et al. (2012) Philos. Trans. R. Soc. B, 367, 1501-1508.
Wang TB et al. (1998) Plant Physiol., 118, 651-659.

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

Decontamination of the Contaminated Water on Severe Nuclear Accidents byTitanium Oxide Adsorption
Youko Takahatake1, Masahiro Nakamura1, Atsuhiro Shibata1, Kazunori Nomura1, Yoshikazu Koma1,
Yasuo Nakajima1
1

Japan Atomic Energy Agency

Abstract – In order to establish a decontamination process for contaminated water that generated in a severe nuclear power plant accident
such as the Fukushima accident, we proposed a new decontamination process. A new decontamination process is composed of codecontamination of radioactive transition metals and Cs with hexacyanoferrate(II) ion, and decontamination of radioactive metals including
Sr with titanium oxide adsorption. This study discussed the adsorptivity of a new titanium oxide and its applicability to the radioactive water
after co-decontamination of transition metals and Cs.
Keywords – Sr decontamination, titanium oxide adsorption, contaminated water of Fukushima accident

The massive amount of radioactive contaminated water
was generated in Fukushima Dai-ichi NPP. This water is
unique compared to contaminated water generated inprevious treated radioactive contaminated waters, concerning
the amount of minerals due to the utilization of seawater
during the emergency cooling of reactor cores. According to
the analysis of the water, it contains fission products (90Sr,
125
Sb and 134,137Cs), corrosion products and large amount of
non-radioactive metals. The special treatment system wasapplied to decontaminate it. If NPP accidents may be occur inthe future, the experience on this accident is utilized
effectively.
In order to minimize the amount of secondary waste fromthe water treatment system, we proposed a new
decontamination process (figure 1) for radioactive
contaminated water generated at NPP accidents. At first, thisprocess decontaminates transition metals and Cs
simultaneously by adding hexacyanoferrate(II) ion. This step
was already discussed [1]. The next step is decontaminationof Sr, Sb and remaining Co and Mn by titanium oxide
adsorption. This study discusses the adsorptivity of a newtitanium oxide and its applicability to the radioactive water
after co-decontamination of transition metals and Cs.
Titanium oxide adsorption is commonly used todecontaminate Sr and Co. One of adsorbents is “READ-Sr”,
which will be used for the treatment of low level liquid waste
at the Tokai Reprocessing Plant in Japan. An investigation of
its applicability to the decontamination of Sr from thecontaminated water containing seawater suggested thattitanium oxide adsorb other alkaline earth elements those areabundant in seawater[2]. Therefore, selectivity of Sr fromother alkaline earth elements is necessary.
We synthesized a new titanium oxide with titanium sulfate
and ammonium solution, and obtained distribution coefficient(Kd) of Sr, and separation factor (SF) between Sr and alkaline
earth elements by batch method. And then the titanium oxide
was added to the radioactive water after co-decontaminationof transition metals and Cs. This mixture was stirred for 45
minutes and filtrated with 0.1 µm membrane, and thendecontamination factor (DF) was calculated fromconcentration of each radioactive and non-radioactive
elements.
On experiment of radioactive water, Sr, Mn, Co and Sb
was successfully decontaminated, and their DFs were >16,
460, 260, 230, respectively. But Mg and Ca were adsorbed totitanium oxide; particularly Ca was adsorbed as much as Sr.
Selectivity of Sr to alkaline earth elements is important to
reduce secondary waste, so further improvement is necessary.

Figure 1. Schematic flow of a new decontamination process[1][2]

Decontamination of radioactive liquid waste with hexacyanoferrate(II),Takahatake et. al., Procedia Chemistry , 7: 610-615 (2012)
Strontium decontamination from the contaminated water by titaniumoxide adsorption, Takahatake et. al., Proceedings of International
Conference on Toward and Over the Fukushima Daiichi Accident(GLOBAL 2011), CD-ROM. (2011)

ACKNOWLEDGEMENTS
The authors would like to thank Masashi Kaneko, Kaname
Kubo and Jun Hashimoto of Fuji Sangyo KK for synthesizing
titanium oxide.

－ 117 －

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

Iodine-129 in the aquatic environment
adjacent to a spent nuclear fuel reprocessing plant, Rokkasho, Japan1

Shinji Ueda1, Hideki Kakiuchi1, Hidenao Hasegawa1
Naofumi Akata1, Hidehisa Kawamura2, Shun’ichi Hisamatsu1
Department of Radioecology, Institute for Environmental Sciences, 1-7 Rokkasho, Aomori 039-3212, Japan
2
Kyushu Environmental Evaluation Association, 1-10-1, Higashi, Fukuoka 813-0004, Japan

Abstract – The spent nuclear fuel reprocessing plant in Rokkasho,
Aomori Prefecture, Japan, has been undergoing final testing since
March 2006. Iodine-129 is one of radionuclides released into theatmosphere and the coastal water by the operation of the plant. We
measured the concentrations of 129I in various environmental
samples such as water, sediment, and aquatic biota collected in theaquatic environment adjacent to the reprocessing plant from 2005 to
2012. The concentration of 129I in the environmental samples
increased during testing of the chemical separation of dissolved fuel.
Since the end of that stage, the 129I concentration in lake water andaquatic biota samples has been rapidly decreasing, whereas theconcentration in sediment samples has remained steady.
Keywords – iodine-129, spent nuclear fuel reprocessing plant, water,
sediment, aquatic biota

I.

INTRODUCTION

Japan’s first commercial spent nuclear fuel reprocessing plant,
which is in Rokkasho, Aomori Prefecture (Fig. 1), isundergoing final testing. Since the cutting and chemical
separation using actual spent nuclear fuel started in March
2006, small amounts of radionuclides (85Kr, 3H, 129I, and 14C)
have been released into the atmosphere and the Pacific Ocean.
Iodine-129 released from the plant into the atmosphere andthe ocean enters Lake Obuchi, which is adjacent to the plant(Fig. 1), through various routes: from the ocean by tides,from river water, and from the atmosphere by deposition.
The aim of this study was to investigate the fluctuations of
129
I concentrations in water, sediment, and aquatic biota
samples collected in the aquatic environment, mainly in Lake
Obuchi, from 2005 to 2012.

II. MATERIALS AND METHODS
Water was sampled from five locations (Sts. 1–5), andsediment from two locations (Sts. 2, 3); samples fromaquatic biota (fish, seagrass, shellfish, shrimp, and plankton)
were collected from the lake in an area near the north shore(Fig. 1). The samples were analyzed for 129I with anaccelerator mass spectrometer (PRIME Lab, Purdue
University, USA).
III. RESULTS AND DISCUSSION
The concentrations of 129I in the water samples collected from
Lake Obuchi during 2006 to 2008 were approximately anorder of magnitude higher than the background level in 2005,
whereas the concentrations in the seawater samples collected
off the Rokkasho coast (St. 5) showed no increase over the
background level during the study period. The 129I
concentrations in aquatic biota samples during 2006 to 2008
were also approximately one order of magnitude higher thanthe background level. Most of the chemical separation of fuelmaterial was finished by 2008, and the rate of 129I releasefrom the plant markedly decreased thereafter. Corresponding
with the decrease in the release rate, the 129I concentrations in
the lake water and aquatic biota samples rapidly decreased
after 2008. In contrast, the 129I concentrations in the sediment
samples were stable even after the chemical separation was
finished.
The committed effective dose due to annual ingestion offoods with the maximum 129I concentration in the biota
sample in Lake Obuchi was calculated as 6.7 nSv y-1.
/UTLET OF WASTE WATER PIPELINEFROM THE REPROCESSING PLANT
 KM OFF THE COAST&UTAMATA 2IVERO.
.

5RANIUM ENRICHMENT PLANTO
3EA OF *APAN

O

0ACIFIC /CEAN

3T ,OW LEVEL RADIOACTIVE WASTEDISPOSAL AREA DISPOSAL CENTER

3T 

O

/BUCHI FISHING
PORT

3T 
M

3T 

M

O

2OKKASHO

2EPROCESSING PLANT

M

2OKKASHO #OAST

3T 

O

0ACIFIC /CEAN
O


O%

KM
O

O

O

!OMORI 0REFECTURE
O

O



 KM

,AKE /BUCHI

O









 M

WATER DEPTH

Fig. 1. Map of the sampling stations. Aquatic biota samples were collected in the hatched area.

This study was performed under a contract with the government of Aomori Prefecture, Japan.

－ 118 －

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

Specific activity and time dependence of radionuclides in soils affected by theaccident of the Fukushima Dai-ichi nuclear power plant (Part 2).
Tatsuya Shimasaki1, Yoshioki Shiraishi1, Osamu Kawahara1, Kumiko Goto1,
Masako Shimamoto1,Akihiro Kojima1 and Seiji Okada2
1

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

Abstract – The purpose of this study is to clear the specific activity
and the time dependence of the radionuclides in soils at Fukushima
prefecture and neighborhood area. We performed soil sampling forsix times at several points within 60km from FDNPP and at Tokyo
to October 30, 2012 from March 23, 2011. The concentration of 131I,
134
Cs, 136Cs, 137Cs and 129mTe were obtained, but only trace amountsof 95Nb, 110mAg and 140La were detected whitch were too low toprovide accurate concentrations. The concentration of radioactivity
on March 15, 2011 is 8234 kBq/m2 for 131I and 882 kBq/m2 for 137Cs
at Fukaya, Iitate village. Some radionuclides, such as 103Ru, and106
Ru and 140Ba, observed in the Chernobyl accident, were notmeasured in the soil samples. This is estimated that mainly noble
gasses and volantile radionuclides were released from FDNPP. For
the time dependence of 137Cs concentration in soil, it was decreased
approximately 30% in 19 months at Fukaya, Iitate village. However,at some sampling points, there was not a change at all.
Keywords – Fukushima Dai-ichi N, 137Cs, specific activity, timedependence, 134CsI.

INTRODUCTION

The Fukushima Dai-ichi Nuclear Power Plant (FDNPP)
lost all electricity due to a huge tsunami after the Richterscale magnitude 9 earthquake of March 11, 2011. The water
circulation system was severely damaged, and theradionuclides were released to the environment, specially fordays in the middle of March. The purpose of this study is toclear the specific activity and the time dependence of theradionuclides in soils at Fukushima prefecture andneighborhood area.

and 129mTe were obtained, but only trace amounts of 95Nb,
110m
Ag and 140La were detected whitch were too low toprovide accurate concentrations. Some radionuclides, such as
103
Ru, and 106Ru and 140Ba, observed in the Chernobyl
accident, were not measured in the soil samples. This isestimated that mainly noble gasses and volantile
radionuclides were released from FDNPP. The concentrationof radioactivity on March 15, 2011 is 8234±1654 kBq/m2
for 131I and 882 ± 182 kBq/m2 for 137Cs at Fukaya, Iitate
village. The highest difference was more than 100 times inFukusima. Only 137Cs from global fallout was observed in thesoil collected at kumamoto city. The ratio of the total
amounts of 137Cs in each section depth was shown in Fig.5.
Approximatery 95% of deposited 137Cs were found in theupper 3 cm of the soil. The ratio of the depth profiles did notchange at all sampling points during the measurement period.
Time dependence of radionuclides in soils
Fig.1 shows the temporal changes of 137Cs concentration
in soil at several sampling points during from March 23, 2011
to October 30, 2012. For the time dependence of 137Csconcentration in soil, it was decreased approximately 30% in
19 months at Iitate village, Fukaya district. It was decreased
approximately 20% in 15 months at Minamisouma city.
However, at some sampling points, there was not a change ofthe time dependence of 137Cs concentration at all. For theenvironment half life of the cesium-137 in the comparatively
land with a little vegetation, it was with the range for four
years from two years except a physical half life.

II. MATERIALS AND METHODS
We performed soil sampling for eight times at several
points within 60km from FDNPP and at Tokyo from March
23, 2011 to October 30, 2012. Soil samples, at 0-2, 0-3, 3-6
and 6-10 cm depths, were taken using a scraper with asampling area of 100cm2 (10cm×10cm). The second and thesubsequent sampling were carried out at 3 m intervals fromthe previous sampling points. The specific activity of samples
were measured by Ge detectors (SEIKO EG&G) and decay
corrected to March 15, 2011.
III. RESULTS AND DISCUSSION
Specific activity in soils
We were taken soil samples in Iitate village, Fukaya , on
March 23, 2011. The concentration of 131I, 134Cs, 136Cs, 137Cs－ 119 －

Fig. 1 The temporal changes of 137Cs concentration in soil at several
sampling points during from March 23, 2011 to October 30, 2012.

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

Differences between year 2011 and 2012 in Cs-137 concentration in brown rice grownin Fukushima Prefecture
Shigeto Fujimura1,2, Yuuki Sakuma1, Toshimi Yamauchi1, Kazutoshi Niitsuma1, Norio Sato3, Mutsuto
Sato1, Takashi Saito1, Kunio Yoshioka1
1

Fukushima Agricultural Technology Centre, 2 NARO Tohoku Agricultural Research Center
3
Inawashiro Town

Abstract – Brown rice was collected from ten paddy fields located infour sites in Fukushima Prefecture in year 2011 and 2012 to clear
the year difference in radiocesium concentration in brown rice.
Paddy fields with the same management including fertilization inboth years were selected. Cs-137 concentration in brown rice was in
the range of 2.8-290 Bq kg-1 in 2011 and 1.3-160 Bq kg-1 in 2012.
The concentration of Cs-137 was decreased by 40 % in the average
from year 2011 to year 2012.
Keywords – brown rice, Cs-137, paddy field, aging

I.

B. Measurement of Cs-137 concentration
The concentration of Cs-137 was determined using agermanium detector with a multichannel analyzer system.
The actual decay date was determined as October 1, 2011,using the half-life (i.e., decay constant) of the Cs-137. Brown
rice was dried for 48 h at 105 °C and dry weight wasdetermined.
III. RESULTS AND DISCUSSIONINTRODUCTIONRadionuclides was released into the environment as aconsequence of the accident at Fukushima Daiichi Nuclear
Power Plant (FNPP) that was triggered by the earthquake andsubsequent tsunami that occurred on 11 March 2011. Brown
rice (unpolished rice) produced during the 2011 growing
season was contaminated by radiocesium released from
FNPP. Concentration of radiocesium in agricultural products
is annually declined because radiocesium is fixed to sorption
site for cesium of soil. In addition, potassium and/or zeolite
was applied to farmland in Fukushima Prefecture to avoid thecontamination of radiocesium to brown rice in the year 2012.
In the results, concentrations of radiocesium in brown rice
were much lower in the year 2012 than in the year 2011. The
aim of this study is to clear the annually declined effect on
the concentration of brown rice to evaluate the effects ofpotassium and zeolite application on uptake of radiocesiumby crops.
II. MATERIALS AND METHODS

Concentration of Cs-137 in brown rice investigated in thisstudy was in the range of 2.8-290 Bq kg-1 in 2011 and 1.3160 Bq kg-1 in 2012 (Table 1). There were differences in theconcentration of Cs-137 between paddy fields in the samesite in both years. The differences between paddy fields in thesame sit would be due to the differences in exchangeable
potassium content and/or the sorption sites for cesium in soil.
The details will be published else where.
The concentration of Cs-137 in brown rice was 30-114 %in 2012 compared to those in 2011. It was increased in one often paddy fields. The concentration of Cs-137 in brown rice
was decreased by 40 % in the average from year 2011 to year
2012. It was suggested that uptake of radiocesium by rice
plant in the second year from the radiocesium contamination
is a half of that in the first year without decontamination nor
the application of potassium, zeolite and so on.
Table 1. Concentration of Cs-137 in brown rice.
Site

A. Brown rice sampled
Rice was grown in ten paddy fields in four sites (Aizu
Bange, Inawashiro Koriyma and Nihonmatsu) located in
Fukushima Prefecture during the year 2011 and 2012.
Management including fertilizer followed the conventional
practices in each site in both year except in Aizubange andInawashiro. In these two sites, potassium had not been
applied more than ten years in one paddy field and practical
fertilizer had been applied in another one. Brown rice was
sampled from the paddy fields in the year 2011 and 2012.

Concentration of Cs-137(Bq kg-1 dw)
2011
2012
Aizu Bange
1
22
10
2
3.3
2.0
Inawashiro
1
17
19
2
3.8
3.1
Koriyama
1
2.8
1.3
Nihonmatsu
1
200
160
2
290
160
3
130
50
4
61
26
5
74
22
Maximum
290
160
Minimum
2.8
1.3
Average29
16
Geometric average is shown for the concentration of Cs-137.

－ 120 －

No.

2012 / 2011
(%)
48
61
114
82
48
80
56
41
42
30
114
30
60

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

Size-distribution of airborne radioactive particles from the Fukushima Accident
H. Muramatsu1, K. Kawasumi1, T. Kondo1, and K. Matsuo2
Department of Chemistry, Faculty of Education, Shinshu University, Nishinagano, Nagano-shi, Nagano 380-8544, Japan
2
Graduate School of Education, Shinshu University, Nishinagano, Nagano-shi, Nagano 380-8544, Japan

Abstract –The particle size distribution of radioactive aerosols has
been observed using the Andersen-type classifier combined with ahigh volume air sampler. Estimated AMADs of 131I-, 134Cs- and137
Cs-aerosols were ranging from 0.56 to 0.60 �m, which werelarger than that of 7Be-aerosols, about 0.2 �m.
Keywords – particle size distribution, radioactive aerosols, airborne
radionuclide, nuclear power plant accident

INTRODUCTION
The release of radioactive materials from the Fukushima I
nuclear power plant accident brought about seroius and wide
contaminations in the area of northeastern Japan. Released
radioacive materials from the reactors would migrate asradioactive aerosols, attaching to non-radioactive aerosols
suspended in the surface air and being affected by a transportof air masses which is somewhat complex and strongly
depends on the distribution of high and low atmosphericpressure regions around the Japanese Islands. In this report,
we describe the results of radioactivity measurements in theregion far from the site where the present nuclear accident
had occurred. Especially, are shown the results obtained in
the experiment done by using a high-volume cascade
impactor to estimate the size distribution of aerosols attachedby fission products.
EXPERIMENTAL
Air samplings were carried out at the sampling station on
the roof of the building (height above ground level 12 m)
located in our university campus (36º39´N, 138º12´E).
Suspended particles attached by fission products werecollected by using the Andersen-type classifier combinedwith the high volume air sampler (Model AH-600). The
sampler is a jet cascade impactor consisting of five multi-jet
stages (including a backup stage) and a filter, verticallystacked, designed for use at a flow rate of 566 L/min, and it
can collect the particles classified into five sizes from 1.1 �m
to 7.0 �m.
RESULTS AND DISCUSSION
The sampling was carried out at the sampling station from
April 7 to April 24, during 17 days, with the flow rate of 566
L/min and the total volume of 138400 m3. Aerosol particles
were classified and collected on four glass fiber filters, andon a back-up filter for aerosols smaller than 1.1 �m indiameter. About 60% of collected activities were found on
the back-up filter, which means that the majority ofradioactivity would attached to aerosols with the diameters
less than 1.1 �m. This tendency is much more remarkable forthe case of 7Be-aerosols, which is formed through attachingby the cosmogenic radionuclide of 7Be and whose size
distributions have been measured by using the same manner
mentioned below during a couple of years.
In order to estimate a size distribution and a mean particle
diameter, we used only three data, which the particle-size
range is neatly known, that is, corresponding to particle-size
ranges of 3.3-7.0, 2.0-3.3 and 1.1-2.0 �m. Under theassumption that the particle size distribution of radioactive
aerosols in surface air is in a lognormal and unimodal
distribution, the cumulative probability was plotted against
the particle diameter, as is shown in Fig.1. Activity Median
Aerodynamic Diameter (AMAD) was estimated by the value
when the cumulative probability is 50%. Estimated AMADsof 131I-, 134Cs- and 137Cs-aerosols were ranging from 0.56 to
0.60 �m, which were larger than that of 7Be-aerosols, around0.2 �m.
99.9999

Log Normal Probability Plots

99.99

Cumulative probability

1�������������

99
90��������������

50���������������
��������������

10
1
0.01
0.00010.01

0.1
1���������������������

10

Fig.1 Probability plot for the cumulative percent as a function of aerosol
particle diameter.

According to the physical characteristics reported by
Whitby for sulfur aerosols [1], the geometric mean radii of
0.57, 0.60, and 0.56 �m for 131I-, 134Cs- and 137Cs-aerosols,
respectively, seem to belong to the accumulation mode whosemean value is (0.48 ± 0.1) �m. Beyond the difference inorigin and chemistry between cosmogenic 7Be and fission
products of 131I, 134Cs and 137Cs, what controls mean radius ofradioactive aerosols is not clarified yet. It is surely consideredthat the difference in the formation and growth of both
radioactive aerosols would be important.
[1] Whitby, K. T., Atmos. Envir. 12, 135-159 (1978).

－ 121 －

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

Long-term effects of radionuclides originating from the Fukushima nuclear power
plant accident in airborne particulate matters in Kawasaki
Ko Nakamachi1, Hirotaka Matsuno1, Teruyuki Honda1, Yoshikazu Kikawada2
1

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

2

Abstract – This study is intended to elucidate the long-term effects ofatmospheric radioactive cesium in Kawasaki City, Kanagawa. As aresult, it became clear that the radioactive cesium activity
concentration in December 2012 had decreased to about 1/105ofthat observed immediately after the Fukushima Daiichi nuclear
power plant (FDNP) accident in March 2011 and sulfate aerosols
may act as a carrier and transport radioactive cesium.
Keywords – Fukushima Daiichi nuclear power plant accident,
radioactive cesium, carrier, airborne particulate matters, Kawasaki

I.

INTRODUCTION

The FDNP accident was caused by the Great East Japan
Earthquake, which occurred on March 11, 2011. The artificial
radionuclides 131I, 134Cs, and 137Cs were detected in the Kanto
region.
In this study, we focused on 131I, 134Cs, 137Cs, and otherradionuclides contained in airborne particulate matters(APM) sampled from filters in the Atomic Energy ResearchLaboratory of Tokyo City University located in the west of
Kawasaki City, Kanagawa, which is about 250 km southsouthwest from the FDNP.
The aim of this study was to determine the time series of theradioactive decay and the atmospheric dispersion of theartificial radionucl����� ��� �-ray spectrometry. Moreover,because we have been sampling the APM continuously frombefore the FDNP accident, we can compare the results before
and after the FDNP accident.

Fig. 1. The 134Cs and 137Cs activity concentration in
December 2012 had decreased to about 1/105 of the activity
concentration observed immediately after the FDNP accident.
Sulfate aerosols can act as carriers of radioactive cesium.
Because sulfates are formed from sulfur dioxide in theatmosphere, we indirectly examined the relationship between
radioactive cesium and sulfate by comparing the activity
concentration of radioactive cesium and the sulfur dioxidelevels recorded by the Kawasaki pollution monitoring center.
The fluctuations in the radioactive cesium concentration weresimilar to the fluctuation in the sulfur dioxide concentration.
This finding suggests that sulfate acts as a carrier andtransports radioactive cesium.

Fig.1 Time series of 134Cs and 137Cs activity concentration in Kawasaki

II. METHODS

IV. CONCLUSION

After sampling the APM from the filters, we compressed thefilter into an acrylic case to measure the �-rays. A high purity
germanium semiconductor detector was used for the analysis.
The measurements were carried out for 80,000 s. The Seiko
EG&G spectrum navigator environmental analysis program
was used for nuclide analysis.
III. RESULTS AND DISCUSSION
Immediately after the accident at the FDNP in March 2011,
Nb, 97Nb, 110mAg, 129Te, 129mTe, 131I, 134Cs, and 137Cs weredetected. The activity concentrations of 131I, 134Cs, and 137Cs
immediately after the accident were 1.66, 0.61, and 0.60
Bq/m3 respectively, and the 131I/137Cs activity concentration
ratio was 2.78. The time series of the radioactive cesium
activity concentration after the FDNP accident is shown in
95(1)

Immediately after the accident at the FDNP in March
2011, 95Nb, 97Nb, 110mAg, 129Te, 129mTe, 131I, 134Cs,
and 137Cs were detected.
(2) The activity concentrations of 131I, 134Cs, and 137Cs
immediately after the FDNP accident were 1.66, 0.61,
and 0.60 Bq/m3, respectively, and the 131I/137Cs
activity concentration ratio was 2.78.
(3) The 134Cs and 137Cs activity concentration in
December 2012 had decreased to about 1/105 of theactivity concentration observed immediately after the
FDNP accident (March 2011).
(4) The fluctuation in the radioactive cesium activity
concentration was similar to the fluctuations in thesulfur dioxide concentration; therefore, sulfate
aerosols may act as a carrier and transport radioactive
cesium.

－ 122 －

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

Measurement of Iodine-129 concentration in water samples in relation with
Fukushima Daiichi Nuclear Power Plant accident
Hiroyuki Matsuzaki1, Hironori Tokuyama1, Yasuto Miyake1, Maki Honda2, Takeyasu Yamagata3,
Yasuyuki Muramatsu4
1

Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, Japan
2
Graduate School of Integrated Basic Sciences, Nihon University, Japan
3
College of Humanities and Sciences, Nihon University, Japan
4
Department of Chemistry, Gakushuin University, Japan

Abstract – Iodine-129 (129I) concentration in several water samples
were measured by means of Accelerator Mass Spectrometry anddiscussed in relation with Fukushima Daiichi Nuclear Power Plant(FDNPP) accident. 129I concentration of river waters collected Iitate
village and Minami-Soma city (North to North-west of FDNPP)
showed as high as 1.0·109 atoms/L and had not vary significantly
during period from March to October, 2012. The combination of
129 127
I/ I ratio and 127I concentration of these water samples can be
explained as mixture of fossil rain water (ground water) and therain radioactively contaminated by FDNPP accident.
Keywords – FDNPP accident, Iodine-129, Accelerator Mass
Spectrometry, tap water, environmental waterI.

INTRODUCTION

According to Fukushima Dai-ichi Nuclear Power Plant(FDNPP) accident, vast amount of radioactive nuclides
including radioactive iodine were spilled out into theenvironment. A rare isotope Iodine-129 (129I) was also widelydistributed in a very short time by the FDNPP accident. 129I
directly landing on the soil surface had been trapped in theupper layer of the soil and the depth profile should indicate
the migration and the interaction with the soil. If 129I was
trapped in the woods, it seems to take rather longer time forlanding on the ground. Either way, a certain portion of the 129I
should be moving downward and finally washed out by thegroundwater or river with a certain rate and transported into
the sea. The concentration of 129I in environmental water
samples taken from rivers and ponds are considered to reflect
the iodine transportation process by the fluvial system.

The University of Tokyo. An aliquot taken from the water
sample before adding carrier was analyzed for iodine
concentration by ICP-MS.
III. RESULTS AND DISCUSSION
129

I concentration of river waters collected Iitate village
and Minami-Soma city (North to North-west of FDNPP)
showed as high as 1.0·109 atoms/L and had not varysignificantly during period from March to October, 2012.
This concentration is quite high compared to the pre-accident
level (1-2·106 atoms/L), which was determined from theresult of measurement for tap water collected in 2006. The
combination of 129I/127I ratio and 127I concentration of thesewater samples can be explained as mixture of fossil rainwater (ground water) and the rain radioactively contaminatedby FDNPP accident (Fig. 1).

II. EXPERIMENTAL
River water samples and lake water samples werecollected from the South-west region (Abukuma area) andNorth to North-west region (Minami-Soma city and Iitate
village) during the period from April, 2011 to March, 2013.
500mL or 1 L of each water sample was served for analysis.
2mg of iodine carrier was added to water and mixed well in alittle reduced condition. Iodine was extracted by the solvent
extraction and the back extraction process and precipitated asa Silver Iodide (AgI). Collected AgI was mixed with
Niobium powder and pressed into a cathode of Accelerator
Mass Spectrometry (AMS). 129I/127I ratio was measured at
MALT (Micro Analysis Laboratory, Tandem accelerator),

Fig. 1. 129I/127I – 1/127I plots of several water samples. Lines
are the mixing lines between the end members.

Considering the accidental 129I deposition in Northwest of
FDNPP (~1.4·1014 atoms/m2) and annual precipitation rate(~1300 mm), it is figured out that no more than 1% of total
inventory is transported by the river system annually.

－ 123 －

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

Observed radioactivities and activity ratios in aerosols from April 2011 at the
Geological Survey of Japan, Tsukuba, Japan
Yutaka KANAI1

1

Geological Survey of Japan, National Institute of Advanced Industrial Science and Technology

Abstract – The aerosol monitoring was started at the GSJ, Tsukuba,from the end of March 2011 for the assessment of environmental
impact and residents' dose rate. This paper reviewed the obtained
data and the geochemical behaviors of natural and artificial
radionuclides were studied. Many artificial nuclides derived fromthe FDNPP accident as well as natural 7Be and 210Pb were observedin this study and the most of them with short half-lives became
below the detection limit in June, 2011. Several high concentration
peaks of 134Cs and 137Cs were observed after June, and around 10-4
Bq/m3 concentration was estimated as temporal background level.
After middle April 2012, it became in half level. The observed
7
134
Cs/137Cs, 136Cs/137Cs and 132Te/13 Cs activity ratios showed
relatively good attenuation corresponding to their half-lives. For
131
I and 129mTe, the activity ratios showed a decreasing trend withfluctuations. 110mAg showed a bigger attenuation rate than its halflife and 95Nb showed increasing trend. The variation of activity ratiowith time observed at the GSJ was supposed to depend on particle
size, their chemical species, the source, discharge amount, mixing
and the transportation processes of nuclides.
Keywords – Radioactivity, Aerosol, the Geological Survey of Japan,
Tsukuba, Activity ratio, Natural and artificial nuclides

I.

INTRODUCTION

A big earthquake (M. 9.0) and the subsequent tsunami
on 11 March 2011 resulted in severe damages to the
Fukushima Daiichi Nuclear Power Plant (FDNPP). All thepower supply was lost and the luck of cooling system caused
the release of a large amount of radioactive nuclides such as
131
I and 137Cs into the environment.
We started the monitoring of radionuclides in aerosols at
the Geological Survey of Japan (GSJ) in Tsukuba from theend of March, about 20 days after the FDNPP accident, forthe purpose of assessing their environmental impacts and theradiation dose for safety of the habitant. In this paper wesummarize and focus on the geochemical behavior of
artificial radionuclides as well as natural radionuclides using
their activity ratios.
II. OBSERVED RADIOACTIVITIES IN AEROSOLS
Tsukuba is located about 170 km south-southwestward
from the FDNPP. The radionuclide concentrations observedat the GSJ would be greatly dependent on those emitted fromthe FDNPP and the climate conditions, because the released
radioactive nuclides would move as a plume. 95Nb,
99
Mo/99mTc, 110mAg, 129mTe/129Te, 131I, 132Te/132I, 134Cs, 136Cs,
137
Cs, 140Ba/140La, 141Ce and 144Ce were main artificial
nuclides observed in this study and the most of them withshort half-lives became below the detection limit in June,
2011. Several high concentration peaks of 134Cs and 137Cs
were observed after June, and around 10-4 Bq/m3
concentration was estimated as temporal background level,
which is about 2 orders of magnitude higher level than that
before the accident. After middle April 2012, it became in a
half level.
III. ACTIVITY RATIOS BETWEEN NUCLIDESSupposing the nuclear reactions almost stopped at thetime of accident, activity ratio of nuclide versus 137Cs should
decrease nearly with the half-life of nuclide because that of137
Cs is by far larger. Variations of the activity ratio of 134Cs,
136
Cs, 131I, 129mTe, 132Te, 110mAg and 95Nb versus 137Cs were
examined.
The observed macroscopic 134Cs/137Cs, 136Cs/137Cs and132
Te/137Cs activity ratios showed relatively good attenuation
corresponding to their half-lives, although these nuclides
might be released from the different three reactors that might
have different activity ratios owing to the different burn-up.
As 134Cs, 136Cs and 137Cs are isotopes of the same element,
the change and large fluctuation of activity ratio duringtransport would not occur. The small fluctuation after several
months from the accident might suggest complex release andmixing of the source reactors at different situations. The
131 137
I/ Cs activity ratio in aerosol showed a decreasing trendwith a little fluctuation, and also the tendency of a little
higher concentration after 60 d. The change of composition(gas/particle), the release rate and temperature at the reactors,
transport processes and their mixing would contribute to theactivity ratios. Although 129mTe and 132Te show thedecreasing trend, the former showed rather large fluctuation
with a high value. There may be complicated processes
concerning the older and younger air masses whose132
Te/129mTe activity ratios differ from each other because ofhalf-lives. On the other hand, 110mAg showed a bigger
attenuation than that supposed from its half-life, probably
owing to its chemistry and the discharge rate. Although 95Nb
was emitted in the atmosphere together with other radioactive
nuclides in the accident, 95Nb/137Cs activity ratio showed
increasing trend with time.
It was shown that the activity ratios of artificial nuclides
observed at the GSJ might depend on their chemical species,
particle size, diversity of the source, change of discharge andthe transportation processes of nuclide. These facts would
help the better understanding of the reactor conditions in andafter the accident in addition to other information.

－ 124 －

23-FKP-10
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23-FKP-11
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Thermal Oxidation of Cesium Loaded Prussian Blue as a Precaution for Exothermic
Phase Change in Extreme Conditions
Durga Parajuli, Hisashi Tanaka, Akira Takahashi, and Tohru Kawamoto
Nanosystem Research Institute, AIST, Japan
Abstract – Cesium adsorbed Prussian blue is studied for the thermaloxidation. The TG-DTA shows exothermic phase change of micro
aggregates of nano-PB at above 270 ºC. For this reason, Cs loaded
PB was heated between 180 to 260 ºC. Heating at 180 removed only
the water. Neither the oxidation of Iron nor the removal of cyanide
is observed at this temperature. Oxidation of cyanide is observed
upon heating above 200 ºC while loaded Cs is released after heatingat >250 ºC followed by washing with water. Thermal oxidation
between 200 to 220 ºC for more than 2 h showed control on
exothermic phase change and loaded Cs is also not solubilized.
Keywords – Prussian blue, Cesium, Exothermic Phase Change

I.

INTRODUCTION

Prussian blue (PB), ferric hexacyanoferrate (Fe-HCF), is
an inorganic complex, mostly known in the history for its
peculiar Cesium (Cs) selectivity.1 In reference to the PB
parent molecule, a number of transition metal
hexacyanoferrate are synthesized and named as PB-analogues.
The PB forms an open cage structure that possesses a typicalzeolytic characteristic, an adjective typically given to any
molecule capable of trapping other ions within its latticecavities.2 Interestingly, PB, different from the common
zeolytic materials, possesses unique selectivity for the Cs-ion.
Due to this structural coincidence, PB has become theultimate Cs-trapper. From Ni-HCF for Cs in alkaline
solutions to Cu-HCF for electrochemical removal of Cs or
Fe-HCF for neutral to acidic solutions, no materials showhigh Cs selectivity, faster kinetics, and high capacity like PBanalogues. However, based on the Sax’s Dangerous
Properties of Industrial Materials some concerns were raised
regarding the stability of used HCF analogues during longterm storage.3 Cash et. al. performed extensive study on
ferrocyanide storage tanks in Hanford site (USA) for
resolving such issues.4 Their report ruled out all these
postulations. Therefore, any speculations on the long-term
storage of PB are unlikely. Even so, to ensure the post-use
safety of the PB adsorbent for assured long-term storage, we
propose the thermal oxidation of the Cs loaded adsorbent
prior to the storage.

heated at different temperature. The oxidized sample waswashed with water and analyzed for the release of loaded Cs.
ICP-MS, TG-DTA, IR, Mossbauer, etc. were used for
different analyses.
III. RESULTS AND DISCUSSION
The phase change behavior of PB was studied by taking
micro aggregates of PB nanoparticles. The TG-DTA takenwith air, Figure 1, Shows the exothermic oxidation at about
272 ºC. Therefore, Cs loaded PB was heated at 180 ºC to 250ºC. No oxidation of iron or cyanide but only water removal
was observed at 180 ºC, while the loaded Cs is released uponwashing the PB oxidized at 250 ºC. Heating above 200 ºC is
necessary to induce the oxidation. But, the process may getvigorous when heated above 250 ºC. So, optimum oxidation
temperature is above 200 ºC and below 250 ºC. Exothermic
phase change was disappeared for a sample loaded with 0.2
wt% Cs when heated at 210 ºC for 3 h. Washing this sample
after oxidation, Cs release was not observed.

Figure 1. TG-DTA of Cs adsorbed PB taken in air. 10 mg, 10 ºC/min.

References[1][2]

II. EXPERIMENTAL
As a parent molecule of number of analogues, PB itself isused for the thermal oxidation experiment. For this, PB isloaded with given amount of Cs from pure water or fly-ash
extracted solution containing Cs along with highconcentration other alkali metals, and other ions. Then it isM.T. Ganzerli Valentini, S. Meloni, V. Maxia, J Inorg. Nucl. Chem., 34,1427, 1972.
M. Ware, Prussian Blue: Artists’ Pigment and Chemist’s Sponge. J
Chem. Edu., 8,612, 2008

[3]

R. J. Lewis, Sr., "Sax's Dangerous Properties of Industrial Materials," Van
Nostrand Reinhold (1992).

[4]

R.J. Cash, J.E. Meacham, M.A. Lilga, H. Babad, Resolution of the
Hanford Site Ferrocyanide Safety Issue. Proceeding of the Waste
Management Symposium 1997.

－ 126 －

23-FKP-12

Analysis of 134Cs and 137Cs distribution in soil of Fukushima prefecture and their
specific adsorption on clay minerals
A. Maekawa1, N. Momoshima2, S. Sugihara2, R. Ohzawa1, A. Nakama1
1

Graduate School of Sciences, Kyushu University, 6-10-1, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
2
Radioisotope Center, Kyushu University, 6-10-1, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan

Keywords – Radiocesium Interception Potential, Fukushima Daiichi Nuclear Power Plant accident

137Cs activity / Bq kg-1

0

2000

4000

6000

8000

Depth / cm

0-1
1-2

April 2011

2-3
3-4
4-5

137Cs activity / Bq kg-1

0

500

1000

1500

0-1

Depth / cm

Various kinds of radionuclides were released fromthe Fukushima Daiichi Nuclear Power Plant (FDNPP)
due to the accident that occurred in March of 2011. Of
the radionuclides released from the FDNPP, 134Cs and 137Cs
are the major radionuclides of concern in radiation dose
because of large amounts in deposition on surface soil andtheir long half-lives. Cs is known to be adsorbed specificallyon clay minerals in soil. The strong affinity of clay minerals
for Cs is considered to be due to the presence of the frayededge sites (FES). Cremers et al. (1988) proposed that thestrength of the affinity can be explained by the radiocesium
interception potential (RIP), which was defined by the
product of the FES capacity and Cs-K selectivity coefficienton the FES [1]. The RIP would be usable as an index of themobility of radiocesium in soil and expected to be used to
predict the downward migration of radiocesium.
We collected surface soil samples within 60 km from the
FDNPP and analyzed spatial and temporal radiocesium
distributions with a Ge semiconductor detector. No largechange in vertical distribution pattern of radiocesium has
observed on the samples collected in April 2011 and April
2012 at the same location, suggesting strong adsorption of134
Cs and 137Cs on soil (Fig. 1). To confirm the specificadsorption of Cs on clay minerals, we divided the soil into
different particle sizes by sieving and sedimentation method
and measured the activity in each size fraction. The activity
was highest in the clay fraction (< 2 �m) and it tended todecrease as the particle size increased. The RIP
measurement was carried out based on the procedure
adopted from Wauters et al. (1996) [2]. One g of soil was
equilibrated with carrier free 137Cs in a 100 cm3 of 0.1 mol
dm-3 CaCl2 and 0.5 mmol dm-3 KCl solution. Under theabove condition the amount of Cs adsorbed on the FES is
negligibly small compared to that of K. A known amount ofcarrier-free 137Cs was used for the equilibration experimentand the activity of 137Cs in the solution was measured with a
NaI scintillation detector for the determination of the solidliquid distribution coefficient for Cs (KdCs). The RIP can becalculated from the KdCs and the K concentration in solution.
The obtained RIP value ranged 200-1500 mmol kg-1 that
seemed to be high enough to adsorb 134Cs and 137Cs derived
from the accident. The relationship between the RIP and Cs
soil depth profile will be discussed.

1-2

April 2012

2-3
3-4
4-5

Fig. 1. Vertical distribution of 137Cs in soil collected at the same location(30 km west of the FDNPP) in 2011 and 2012. The concentrations differ but
the vertical distribution pattern was similar.

[1] A. Cremers, A. Elsen, P. De Preter, A. Maes, Nature 335, 247-249(1988)[2] J. Wauters, A. Elsen, A. Cremers, A. V. Konoplev, A. A. Bulgakov, R.
N. J. Comans, Applied Geochemistry 11, 589-594 (1996)－ 127 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

23-FKP-13

Distribution of radionuclides in seabed sediments off Ibaraki coast after the
Fukushima Daiichi Nuclear Power Plant accident
1

M. Nagaoka1, H. Yokoyama1, H. Fujita1, M. Nakano1, H. Watanabe1, S. Sumiya1

Nuclear Fuel Cycle Engineering Laboratories, Japan Atomic Energy Agency, 4-33 Tokai-mura, Naka-gun, Ibaraki 3191194, Japan

Abstract – Various kinds of radionuclides were released into theatmosphere and the sea from the Fukushima Daiichi Nuclear
Power Plant of Tokyo Electric Power Co. (TEPCO) by theaccident and then reached to the neighboring prefectures.
Therefore the accident influence in Ibaraki prefecture wasinvestigated by measuring the concentrations of cesium-134,
cesium-137, strontium-90 and plutonium isotopes in seabedsediments. The values for 137Cs ranged from 6.1 to 300 Bq/kg (drywt) and the ratio of 134Cs/137Cs ranged from 0.48 to 0.77. The
highest point of 137Cs concentration was observed at thenorthernmost station and the concentration was similar to thatreported by MEXT [1].
Keywords – seabed sediments, Ibaraki coast, Fukushima Daiichi
Nuclear Power Plant accident, cesium-134, cesium-137

I.

137

Cs ranged from 6.1 to 300 Bq/kg (dry wt) and the ratio of
Cs/137Cs ranged from 0.48 to 0.77. The concentration of134
Cs and 137Cs before the accident at the sea area in thepast 10 years were < DL* and < DL* to 1.0 Bq/kg,
respectively. The highest 137Cs concentration was observedat the northernmost station near Kitaibaraki City and was
similar to that reported by MEXT [1]. The higher 137Csconcentrations were also observed along the coastal area of
Tokai-mura including the mouth of the Kuji River.
Therefore, the influence of the Kuji River on sea area
should be investigated in detail. Radioactivity
concentrations of 90Sr and plutonium isotopes are undermeasurements.
134* DL: detection limit (134Cs:1 Bq/kg, 137Cs:0.8Bq/kg)

INTRODUCTION(a)

Various kinds of radionuclides were released into theatmosphere and the sea by the Fukushima accident, andthen reached around the Tokai Reprocessing Plant (TRP)
located about 120 km south of the Fukushima Daiichi
Nuclear Power Plant. The influence of the radioactivity on
the environment should be investigated because we have
performed the routine environmental radiation monitoringaround TRP. In this research, strontium-90, cesium-134 andcesium-137 concentrations in the additional special seabedsediments were measured with plutonium isotopes (238Pu,
239+240Pu), to find out the accident influence on sea area.
Moreover, strontium-90/cesium-137 radioactivity ratio wascompared with the ratio before the accident. Finally, eachradioactivity distribution in sea area was arranged toacquire the influence of the accident.

#S �"QKG DRY�+ITAIBARAKI#ITY+UJIHA
MA

(b)

+UJI
RIVER

 "QKG DRY
 "QKG DRY
MORE THAN
 "QKG DRY
4AKAHAGI #ITY*!%!

(ITACHI #ITY

3HIN RIVER*!%!

(ITACHIKOU(ITACHINAKA
KOU

4OKAI MURA

(ITACHINAKA#ITY.AKAMINATO

Fig.1 Distribution of 137Cs concentration in seabed sediments of(a) Ibaraki coast and (b) Tokai coast

II. METHODS
From May to July in 2012, fifty-one Seabed sediments
were collected by the Smith–McIntyre sampler set on amonitoring ship. The samples were dried at 105 °C for 3
days and then packed in measurement vessels. Cesium-134
and 137Cs radioactivity concentrations were measured byhigh-purity germanium semiconductor detectors for 10,000
sec. On the other hand, Strontium-90 and plutonium
isotopes were purified by chemical separation and werethen measured by a beta gas-flow counter and a silicon
semiconductor detector, respectively.

IV. CONCLUSION
In order to identify the accident influence, distribution ofradionuclides in seabed sediments off Ibaraki coast wasinvestigated. Cesium-137 concentrations had more thanhundreds times higher than that before the Fukushima
accident. Furthermore, the Fukushima accident influence
was observed from the ratio of 134Cs/137Cs. The highest
point of 137Cs radioactivity was located at the northernmost
station.
[1]

III. RESULTS AND DISCUSSION
Distributions of 137Cs concentration in seabed sediments
at each place are shown in Fig. 1(a), (b). Radioactivities of－ 128 －

MEXT,
http://radioactivity.mext.go.jp/ja/contents/6000/5704/2
4/229_so_0710.pdf, Accessed on March 28, 2013.

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

23-FKP-14

Radiocesium Concentration Change in Tree Leaves Before and After Defoliation
1

Shigeo Uchida1, Keiko Tagami
Office of Biospheric Assessments for Waste Disposal, National Institute of Radiological Sciences

Abstract – Understanding the fate of radiocesium in a tree is ofgreat important to estimate the removal rates of radiocesium.
Defoliation is one of the important removal pathways, however,radiocesium might retranslocate from senesced leaves to othertree parts like potassium. In this study, several tree species were
measured the cesium-137 concentrations in leaves before andafter defoliation. It was found that a portion of radiocesium
retranslocate from senesced leaves to other tree tissues; thismechanism will extend radiocesium retention time in trees.
Keywords –defoliation

Cesium-137,

I.

Potassium-40,

retranslocation,

INTRODUCTION

Two years after the TEPCO’s Fukushima Daiichi
Nuclear Power Plant (FDNPP) accident, radiocesium(134+137Cs) is recognized as the only major contaminant in
the terrestrial environment. Decontamination of houses,
public places as well as some agricultural fields have beenproceeded, however, forests are difficult to clean up
because they occupies large areas in contaminated areasand countermeasures have not been established yet. Thus,
radiocesium will be recycled in natural forest ecosystems.
Under these circumstances, it is important to know the
reduction rate of radiocesium from a tree to understand thefate in forests after contamination. The most important
removal pathway is defoliation; the old leaves fell off withsome radiocesium in them so that radiocesium
concentrations could decrease with time [1]. However, as it
was found for potassium [2] retranslocate to developing
tissues or internal stores before defoliation would occur forradiocesium because both elements are in the same group.
The mechanism extends the radiocesium residence time intrees. However, there was no data on Cs retranslocationfrom senesced leaves to green leaves. In this study,
therefore, we measured concentrations of radiocesium
before and after defoliation to see whether the mechanism
was found or not.

selected leave sample was decomposed with mineral acids
and the concentrations were measured by ICP-MS (Agilent
7500a) for Cs and ICP-OES for K (Seiko Vista-Pro).
III. RESULTS AND DISCUSSION
The retranslocate percentage (Tr) is defined as follows
Tr=(Agreen-Asenesced)/Agreenx100
Where Agreen is activity concentration of green leaves ofa tree (Bq kg-1-dry) and Asenesced is activity concentration of
fallen leaves of the tree (Bq kg-1-dry). The Tr values ofSomei-yoshino cherry trees (3 samples from different tree
stands) showed 19-49% for 137Cs while 16-40% for 40K.
Deciduous tree stands tended to show radiocesiumtranslocation (Tr=0-81%) however, no clear result was
found for evergreen tree stands because direct deposition
effect on senesced leaves remained. The stable isotope
determination results for K agreed well with 40K data,
however, the data for radiocesium and stable cesium did
not agree due to the above mentioned reason. The Tr valuesof stable Cs for deciduous tree ranged 0-63%, while less Cstranslocation was found for evergreen tree stands (0-17%).
The second year results will be added and discussed at
the presentation.
Acknowledgement: This study was partially supported by
the Agency for Natural Resources and Energy, Ministry of
Economy, Trade and Industry (METI), Japan.
REFERENCES
[1]

[2]

II.

MATERIALS AND METHODS

Eight species of deciduous trees and evergreen trees
were studied in October to November 2011, within the
grounds of our institute (NIRS), Chiba Prefecture, Japan.
Tree leaves both just after defoliated (senesced leaves) andthe green leaves still remained on the tree branches werecollected on the same sampling day. They were dried at80��� ���� �� ����� ��� ������ ��� ������� ��������� �������� �����
sample mass was 8-22 g on dry weight basis. After drying,each sample was mixed well and transferred into a plastic
bottle to measure 137Cs and 40K concentrations with a Ge
detecting system (Seiko EG&G). In order to check thestable Cs and K concentration change, a 0.1-g amount of－ 129 －

Tagami, K., Uchida, S., Ishii, N., Kagiya, S.: Translocation ofradiocesium from stems and leaves of plants and the effect onradiocesium concentrations in newly emerged plant tissues. J.
Environ. Radioactiv. 111, 65-69 (2011).
Ares, A., Gleason, S. M.: Foliar nutrient resorption in trees species.
In: New Research on Forest Ecology, Eds. Archibald K.S., pp. 1-32.
Nova Science Pub. New York (2007).

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

Distributions and Concentrations of Radionuclides in Giant Butterbur after the
Fukushima Nuclear Power Plant Accident
1

Keiko Tagami1, Shigeo Uchida1
Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences, Japan

Abstract – Distributions of radiocesium 137Cs) and radioiodine (131I)
in giant butterbur (Petasites japonicus) was studied to investigatetranslocation of these radionuclides. The concentration ratios (ondry weight basis) between petiole and leaf for the first samples (28March 2011) showed about 0.2 for both isotopes, however, the ratio
increased to ca 0.7 for 131I while that for 137Cs was ca. 0.4 by 5 May
2011. The newly emerged shoots showed the concentrations in
between.
Keywords – translocation, radioiodine, radiocesium, herbaceous
plantsI.

INTRODUCTIONRadioiodine and radiocesium released due to the
Fukushima Daiichi Nuclear Power Plant (FDNPP) accident
were deposited around Kanto Plain, mainly on 20-22 March2011 with rain [1]. Radionuclide behavior in herbaceous
plants after deposition will provide information ofradionuclide mobility and uptake from roots and throughplant surfaces after emergency situation. Previously, newly
emerged part concentrations were reported [2], however, thedistribution patterns between old plant parts, which directly
affected by deposition, and newly emerged plant part has notbeen reported yet.
In this study, we focused on giant butterbur (Petasites
japonicus), which is a herbaceous plant and had already beengrown at the time of FDNPP accident occurred. Distributionsof radioiodine and radiocesium in this plant will provide us
the fate differences between radioiodine and radiocesium
after deposition.
II. MATERIALS AND METHOD
Plant samples were collected from 28 March 2011 at NIRS,
about 210 km SSW from FDNPP. Newly emerged parts werecollected from 13 April to 5 May 2011. The sampled plantparts are shown in figure 1. Immediately after the collection,
each parts were cut and mixed well. The radioactivity
concentrations were measured with a Ge detecting system(Seiko EG&G). Concentrations of iodine-131 (131I) andcesium-137 (137Cs) in the ground were 4500 and 8300 Bq m-2
at 25 April 2011. About 200 days after the first sampling, theconcentrations of radiocesium in leaves and petiole samples
were collected again, however, due to the low concentrations,the samples were dried to reduce volume.
The samples collected between 28 March to 5 May 2011were measured in wet weight mass, thus, the concentration
was estimated to dry weight mass using the following data.

Figure 1. Schematic of giant butterbur sampling parts

III. RESULTS AND DISCUSSION
The average concentration ratios (on dry weight basis)
between petiole/leaf for 137Cs and 131I showed 0.42 (0.340.51) and 0.59 (0.40-0.76), respectively, for the samples
collected between 12 April to 5 May. The ratio for the firstsampling date were the same (ca. 0.2), thus these radionuclidetranslocation showed different increments in the petiole part.
The concentrations of 137Cs and 131I in newly emerged shoots
were between those of leaves and petioles. Compared to otherherbaceous plants, 137Cs concentration in giant butterbur
shoots was almost the same after 22 April, thus it was
assumed that the root uptake pathway became major by thattime. However, the concentration in shoots collected on 13
April was about 2.5 times higher than 22 April sample;
probably, translocation from leaf surface to newly emerged
shoots would partially affect.
Acknowledgement: This study was partially supported by the
Agency for Natural Resources and Energy, Ministry of
Economy, Trade and Industry (METI), Japan.
REFERENCES[1][2]－ 130 －

Ishii, N., Tagami, K., Takata, H. Fujita, K., Kawaguchi, I., Watanabe,Y., Uchida, S.: Deposition in Chiba Prefecture, Japan, of Fukushima
Daiichi Nuclear Power Plant Fallout. Health Phys. 104, 189-194 (2013).
Tagami, K., Uchida, S., Ishii, N., Kagiya, S.: Translocation ofradiocesium from stems and leaves of plants and the effect onradiocesium concentrations in newly emerged plant tissues. J. Environ.
Radioactiv. 111, 65-69 (2011).

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

23-FKP-16

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

23-FKP-17

Transfer of Radiocesium from Soil to Cut Flowers

1,2

Yasukazu Suzuki , Hiroyuki Munakata1, Yutaka Yajima1, Yosihiro Tooyama3, Hirokazu Suzuki1,
Hirofumi Tsukada4, Kazuyuki Inubushi2
1

Fukushima Agricultural Technology Centre, 2 Graduate School of Horticulture, Chiba University3
Ken-poku District Agriculture and Forestry Office, Fukushima, Japan , 4Fukushima University

Abstract – Concentration and transfer factor of radiocesium,
which was derived from the Fukushima Daiichi Nuclear Power
Plant Accident, from soil to cut flowers was determined. Field
experiment was performed in Gray Lowland soil located in
Fukushima Prefecture from May to October of 2011 and sevenspecies of plants, gypsophila paniculata, sunflower,
chrysanthemum, gentian, lily, dahlia and eustoma, were cultivated.
Concentration of radiocesium (134+137Cs) in the soil was 18004400 Bq kg-1 and the range of the transfer factor in the plants
was 0.008-0.066, which was within one order of magnitude.
Keywords – cut flower, Fukushima Daiichi Nuclear Power Plant,
radiocesium, transfer factor

I.

INTRODUCTION

A huge amount of radionuclide was released into theenvironment at the Fukushima Dai-ichi Nuclear Power
Plant accident. Radiocesium, which is major radionuclide,
was deposited on the soil and agricultural products were
contaminated. Radiocesium is an important radionuclide
for the assessment of radiation exposure to the public andalso need to know the contamination level of agricultural
products for the public relief. Few data available on
behavior in soil-cut flower interactions. This study was
conducted to clarify the concentration and transfer factor ofradiocesium in cut flowers.
II. MATERIALS AND METHODS
Field experiment was performed in Gray Lowland soil
located in Fukushima Prefecture from May to October of
2011. The soils was sampling of 0–15 cm depth in five
points and mixing. Seven species of cut flowers such as

gypsophila paniculata (Gypsophila paniculata), sunflower(Helianthus annuus), chrysanthemum (Dendranthemagrandiflorum), gentian (Gentian triflora.), lily (Lilium ×
formolongo), dahlia (Dahlia pinnata.) and eustoma(Eustoma grandiflorum) were cultivated in the field
experiment. Cut flowers were harvested as when flowering.
After the plants maturing, they were collected from thefields. The samples were rinsed with water, and dried at
80°C for 3 d. The dried samples were pulverized withcutter blender and compressed into plastic vials (U-8). The
soil samples were collected after harvesting the cutting
flowers, air-dried at 25°C for 10 d, and passed through a 2mm mesh sieve. The soil samples were also compressed
into the plastic vials. The radioactivity of the samples wasmeasured with a germanium semiconductor detector with amultichannel analyzer, over a period of 2,000-48,000
seconds for the plant and 1,200 seconds for the soil samples.
III.

RESULTS AND DISCUSSIO.

The concentration of radiocesium in the soil was 18004400 Bq kg-1. The concentration of radiocesium in cut
flowers was from 33 to 120 Bq kg-1 dry wt, which was 4.0
times differences between the eustoma and gypsophila
paniculata. The transfer factor of radiocesium in the sevenplant was 0.008-0.066 which was 8.3 times differences
between the eustoma and gypsophila paniculata. The
transfer factor in cut flowers was a relatively similar orderto the reported values in leafy vegetables.[1][2][1]http://www.maff.go.jp/j/press/syouan/nouan/pdf/110527-01.pdf(in Japanese)[2]http://www-pub.iaea.org/MTCD/publications/PDF/trs472_web.pdf

Table 1 Concentration and transfer factor of radiocesium in cut flowers

Cut flower

Samplingday�Bq kgGypsophila paniculata

Sunflower
Chrysanthemum
Gentian
Lily
DahliaEustoma

2011/8/18
2011/7/25
2011/8/17
2011/10/5
2011/9/5
2011/8/5
2011/8/16

Transfer factor

Radiocesium concentration
soils
Cs

134+ 137
-1

134

Cs

dry wt�

1800 ± 260
3500 ± 1100
2900 ± 310
3100 ± 170
3000 ± 350
4400 ± 880
4400 ± 450

Plants137
Cs
�Bq kg60 ± 32
39 ± 2120 ± 4.8
19 ± 4.6
32 ± 3.342 ± 3.3
13 ± 4.0

Decay correction was done from sampling day. Average ± SD (n = 3).

－ 132 －

-1

134+ 137

Cs

dry wt�64 ± 3444 ± 30
24 ± 5.923 ± 3.933 ± 7.2
48 ± 6.4
19 ± 3.7120 ± 66
84 ± 5044 ± 1142 ± 8.0
65 ± 1190 ± 8.933 ± 7.7

0.066 ± 0.028
0.024 ± 0.013
0.016 ± 0.005
0.014 ± 0.003
0.022 ± 0.003
0.021 ± 0.006
0.008 ± 0.002

23-FKP-18
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23-FKP-19
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Estimation of I-131/I-129 ratios and vertical distribution of radioiodine in soil
collected from Fukushima Prefecture
N. INAGAWA1, Y. MURAMATSU1, T. OHNO1, T. TOYAMA1, C. SATOU2, M. OUTSUKI3,
T. MATSUZAKI4
1

Gakushuin University
Fukushima Agricultural Technology Centre
3
Tohoku University
4
University of Tokyo

2

Keywords – I-131, I-129, I-131/I-129 raitos, vertical distribution ofradioiodine

I. INTRODUCTION
A severe nuclear accident occurred at Fukushima Daiichi
nuclear power plant in March 2011, resulting in the release ofenormous amounts of I-131 and Cs-137. Subsequently, soils
in Fukushima Prefecture were contaminated. Becauseradioiodine accumulates in thyroid glands in human body, it
is important to obtain data of I-131 in the environment at thetime of the accident. However, I-131 was below the detection
limit after a few months because its short half-life of 8.02
days. On the other hand, I-129 released simultaneously with
I-131 still remained in soil in Fukushima Prefecture, due to
its long half-life of 1.57 × 107 years. Therefore, we
determined I-129 in Fukushima soil samples in which I-131
concentrations were known, and calculated I-131/I-129 ratios
for radioiodine derived from the Fukushima accident.
II. EXPERIMENTALSThe soil sample collected in Fukushima Prefecture after
the accident was measured for I-131 and Cs-137 byGe-detector. Soil samples were dried and pulverized with ballmill. The powdered sample was placed in in a quartz tube andheated at 1000� to collect the evaporated iodine in alkaline
trap solution (TMAH). Stable iodine (I-127) concentrations in
the trap solution were measured by ICP-MS. Solvent
extraction was performed using remaining solution, andiodine was separated and purified. Silver nitrate was added toprecipitate AgI as a target for AMS and the I-129/I-127 ratios
were measured for about 150 samples. For the estimation of
I-129 concentrations the I-129/I-127 ratios and I-127
concentrations were used.

III. RESULTS AND DISCUSSION

The observed concentration of I-129 in soil samples
showed a wide range, (4.1×10 -5 to 6.3×10-2 Bq/kg). It isinterested to note that a good correlation was found between
the concentrations of I-131 and I-129. This finding suggests
the possibility to estimate previous I-131 levels in soil
samples through the analysis of I-129. We obtained anaverage I-131/I-129 ratio as (2.1 ± 0.7) × 107. However, due
to the variations in the data, it is possible that the ratios aredifferent according to the area.
We examined the depth distribution of I-129 and Cs-137 forinvestigating their behavior in soil. Most of the nuclides were
found to be retained in surface soil. If we compare the
distribution pattern for these two nuclides, we found that
I-129 moved deeper than Cs-137. We also examined different
soils such as wheat field, rice field and forest soils. It was
found that I-129 did not migrate deeper in rice field(uncultivated) because of its dense nature, while in wheat
field (uncultivated) I-129 penetrated deeper due to its highporosity. In case of forest soils, about 90% retained in thelayer of leaf litters.
18
131I ( ×105 Bq / kg )I-131 was released by the accident of Fukushima Daiichi Nuclear
Power Plant. However, due to its short half-life and there are notenough data for this nuclide to understand its dispersal. In this study
we determined I-129 (half-life: 1.57×107 years) in soil samples by
AMS for estimating I-131/I-129 ratios. We also studied vertical
distribution of radioiodine in soil and compared it with the profile ofradiocesium in soil.

15
12
9
6
y = 2.11×107x
R² = 0.97

3
0
0

2

4

6

8

129� ( ×10-2Bq / kg )Fig.1 Relationship between the concentration of I-129 andthat of I-131－ 134 －

23-FKP-20
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Effects of soil types on the transfer of radiocesium to plant
K. ODA1, Y. MURAMATSU1, T. OHNO1, T. KOBAYASHI2, S. FUJIMURA2
1

Gakushuin University
Fukushima Agricultural Technology Centre

2

Following the accident of Fukushima Daiichi Nuclear Power Plant,
radiocesium was detected in agricultural crops cultivated in
Fukushima Prefecture. Although the activity levels in crops
significantly decreased in second year, some crops still exceeded theguideline (100 Bq/kg). In this study we cultivate agricultural crops
using different types of soils contaminated by the accident anddiscuss the mechanisms of transfer.
Keywords – radiocesium, soil-plant transfer, agricultural crops

I. INTRODUCTION
Agricultural fields in Fukushima Prefecture were
contaminated with radiocesium released from the accident ofFukushima Daiichi Nuclear Power Plant. From a perspectiveof agricultural safety, Cs-137 (half-life 30.1 y) and Cs-134(half-life 2.06 y) are very important. Following the accident,
radiocesium was detected in many agricultural crops. Morethan 2 years after the accident, however, some crops stillshow high concentrations. The mechanisms responsible forthe transfer of radiocesium from soil to plants are poorly
understood. Therefore, we investigated radiocesium andstable element concentrations in agricultural crops grown in
different types of soils. For the purpose of our investigation,soils were collected from the contaminated fields inFukushima Prefecture. We discuss mechanisms ofradiocesium transfer with special reference to the soil
characteristics in this study.
II. EXPERIMENTALS
Cultivation experiments using soil that was contaminatedwith radiocesium were carried out in Fukushima Agricultural
Technology Centre and the radiocesium concentrations ofboth soil and plant samples were determined by a Ge-detector
at Gakushuin University. Four different types of soil
collected in Fukushima Prefecture were used in our
experiments. The plant samples used in these experiments
are: komatsuna (a leafy vegetable) and rice plants. The plants
were cultivated in Wagner pots (3 L) in a greenhouse at
Fukushima Agricultural Technology Centre. Some soils weremixed with contaminated fallen leaves or humus in order toexamine whether there is a relationship between the transferof radiocesium and the organic content of the soils. The soil
and plant samples were decomposed with acid to determine
concentrations of stable elements by ICP-MS. In addition, we
operated extraction experiments with ammonium acetate toverify whether there is any correlation between the extractible
radiocesium and the transfer factor to plants.
III.

RESULTS AND DISCUSSIONRadiocesium concentrations in both the paddy rice and thekomatsuna harvested in this study were found to be
influenced by the soil types. The highest values for transfer
coefficient were observed in agricultural crops grown inbrown forest soils, while the plants cultivated in gray lowland
soil showed the lowest values.
In order to compare soils with different radiocesium levels,
we collected them from the top layer with high radiocesium
concentrations (upper 5 cm) and from the underlying soil
with lower concentrations (5–15 cm). We cultivatedkomatsuna and found that the transfer coefficients of plants
grown in the underlying soils are greater than the transfer
coefficients of komatsuna planted in the surface soils. Thismight be related to the speciation of radiocesium in the soils.
Deeper layers may have more labile, plant-available
radiocesium, while less labile particulate-bound radiocesium
from the accident may be more common in the surface soils.
Additionally, we also noted that the transfer coefficients ofkomatsuna cultivated with the underlying soils mixed withcontaminated fallen leaves or humus are higher than thetransfer coefficients of komatsuna grown with underlying
soils alone. Therefore, we speculate that the radiocesium thatexists in organic materials is more mobile, and is
subsequently more readily taken up by plants.
As a result of the analysis of stable cesium, we found that
komatsuna absorbed more radiocesium than stable cesium. It
would seem that stable cesium exists in a less labile form andis adsorbed tightly within the soils, particularly clay minerals.
The extraction experiments show that there is no clear
relationship between transfer coefficients and the proportionof radiocesium that is extractable along with potassium using
ammonium acetate. Further research should be done anothermethodologies for extracting plant-available radiocesium
from soil.

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

23-FKP-21

Temporal distribution of plutonium isotopes in marine sediments off Fukushima
and Ibaraki after the Fukushima Dai-ichi Nuclear Power Plant accident

Wenting Bu1,2, Jian Zheng*2, Tatsuo Aono2, Shigeyoshi Otosaka3, Keiko Tagami2, Qiuju Guo1, Shigeo
Uchida2
1

School of Physics, Peking University, China
National Institute of Radiological Sciences, Japan
3
Japan Atomic Energy Agency, Japan

2

Large amounts of radionuclides were released into theatmosphere as well as discharged into the sea as aconsequence of the Fukushima Dai-ichi Nuclear Power
Plant (FDNPP) accident caused by the earthquake andsubsequent tsunami on March 11, 2011. The radionuclide
contamination in the marine environment due to the
FDNPP accident is of great public and scientific concern.
Radiocesium (137Cs and 134Cs) were detected in thesediment traps in the deep sea in Pacific Ocean one monthafter the FDNPP accident, indicating the quickincorporating of radiocesium in seawater with thesediments.[1] In the coastal area of Fukushima and Ibaraki,
spatial and temporal distributions of radiocesium in themarine sediments from June 2011 to February 2012 were
determined.[2,3] Nevertheless, information about thetemporal distribution of Pu in the sediments off Fukushima
and Ibaraki after the FDNPP accident is limited.
Plutonium isotopes derived from the FDNPP accident
have been detected in the soil and liter samples in the 20-30
km zone around the FDNPP, revealing the release of Pu
from the accident.[4] In our previous works, we determinedthe distribution of Pu isotopes in the marine sediments off
Fukushima and Ibaraki collected from April 2011 to July
2012, and observed no detectable Pu contamination fromthe FDNPP accident.[5,6] However, as no information about
the Pu isotopes in the discharged liquids from the FDNPP
accident is available to date and the release of radionuclides
from the FDNPP site continued one year after the accident,
Pu contamination in the marine sediments off Fukushimaneeds continuous investigation.[7]In this work, we determined vertical distribution of Pu
activities and Pu atom ratios (240Pu/239Pu and 241Pu/239Pu) ina sediment core collected from the coastal areas off
Fukushima in January 2013. For the analysis of Pu isotopes,
ca. 2.0 g dried sediment sample was weighted out andspiked with 1 pg 242Pu as yield monitor. The extraction of
Pu was performed in a Teflon tube with 20 mL
concentrated HNO3 on a hot plate at 180-200ºC for at least
4 h. A two-stage anion-exchange chromatographic method
was employed for the separation of Pu and for the further
purification of Pu prior to the ICP-MS analysis. Combinedwith our previous results, the temporal distribution of Pu
isotopes in marine sediments off Fukushima and Ibaraki
will be discussed to understand the source and transport of
Pu in the sediments after the FDNPP accident.

Acknowledgments This work was supported by the
Agency for Natural Resources and Energy, the Ministry of
Economy, Trade and Industry (METI), Japan, and partly
supported by the Ministry of Education, Culture, Sports,
Sciences and Technology (MEXT) (24110004), Japan.
References[1] Honda, M. C., Kawakami, H., Watanabe, S. et al., Biogeosciences
Discuss., 10, 2455-2477, 2013.
[2] Otosaka, S. and Kobayashi, T., Environ. Monit. Assess, doi:10.1007/
s 10661-012-2956-7, 2012.
[3] Kusakabe, M., Oikawa, S., Takata, H. et al., Biogeosciences Discuss.,
10, 4819-4850, 2013.
[4] Zheng, J., Tagami, K., Watanabe, Y. et al., Sci. Rep., 2: 304,
doi:10.1 038/srep00304, 2012.
[5] Zheng, J., Aono, T., Uchida, S. et al., Geochem. J., 46, 361-369,
2012.
[6] Bu, W. T., Zheng, J., Aono, T. et al., Biogeosciences Discuss., 10,643-680, 2013.
[7] Kanda, J., Biogeosciences Discuss., 10, 3577-3595, 2013.

－ 136 －

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

Evaluation of Iodine-129 mobility and deposition amount in the soil contaminated by
the Fukushima Daiichi nuclear power plant accident
Maki Honda1, Hiroyuki Matsuzaki2, Takeyasu Yamagata 3, Yoko (Sunohara)Tuchiya2, Chuichiro
Nakano2, Yuki Matsushi4, Yuji Maejima5, Hisao Nagai3
1

2

Graduate School of Integrated Basic Sciences, Nihon university, Japan
Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, Japan
3
College Humanities and Sciences, Nihon University, Japan
4
Disaster Prevention Research Institute, Kyoto University, Japan
5
National Institute for Agro-Environmental Sciences, Japan

Abstract – Iodine-129 depth profiles of 13 soil cores were analyzed
to evaluate the 129I distribution and mobility in soil. The cores were
sampled from various fields around the Fukushima Daiichi Nuclear
Power Plant (FDNPP). Four cores out of the 13 were collected fromalmost the same position in Kawauchi village crop field 20 km apartfrom FDNPP at different times between May 2011 and June 2012 toobserve the temporal variation of depth profile of 129I in soil. Clear
enhancement of the accidental origin 129I was observed but nopositive evidence of 129I migration was found. Other 9 cores werecollected from various fields including crop fields and man-madesoils within 30 km from FDNPP on June 2012. These cores showedlarge variation of depth profile of FDNPP origin 129I. The fractionof top 5 cm to the total inventory was varied from 56% to 100%.

III. RESULTS AND DISCUSSION

Keywords – FDNPP accident, Iodine-129 concentration depth
profile, crop fieldI.

well. An amount of about 0.2 or 0.5 g was mixed with V2O5 in aceramic boat and placed in a quartz tube. The sample is then heatedat 990 � under a flow of oxygen gas and water vapor. The
evaporated iodine is collected with a trap solution (2% TMAH
solution). (Here, an aliquot was separated for ICP-MS for thedetermination of the stable iodine concentration.) Iodine in thealiquot of trap solution (2-9 mL) with 2-4 mg iodine carrier ispurified by a sequential solvent extraction and back extraction and a
finally extracted as AgI precipitation. Extracted AgI was dried welland pressed into a cathode of AMS system. 129I was measured at
MALT-AMS system, The University of Tokyo.

INTRODUCTIONFDNPP accident (on 11 March, 2011) released a large amount ofradionuclide into atmosphere such as 129I (T1/2= 1.57x107 y), 131I
(T1/2= 8.01d). Subsequently it caused extensive radioactive
contamination. Among them, 131I is absolutely essential radionuclide
for the estimation of primary dose. However the data on deposition
amount and distribution pattern of 131I most contaminated area, istotally lacking because of its short half-life. Through the 129I data,
the 131I levels at the time of accident can be estimated [2]. The
accidental origin 129I has also a great potential as a geographic andoceanographic tracer [3]. Predominant source of 129I in global
environment, including Japan, before FDNPP accident have been
two large nuclear reprocessing facilities at Sellafield and La Hauge.
They have released 129I totally over 1.03 TBq (7.35x1026 atoms) [4] toatmosphere. To evaluate the distribution and the mobility of 129I, it isessential to identify 129I of FDNPP origin from that of previously
existed. From this point, crop field is ideal because soil should havebeen tilled and well mixed by farmers to the depth of around 30cm
until just before the FDNPP accident. Therefore it is speculated thatthe crop field soil had been made homogeneous, so that the direct
accumulation from the accident should be clearly observed. Thiswas confirmed by the observations that depth profiles of 127I
concentration, as well as carbon content, of these soil cores wereroughly constant.
II. EXPERIMANTAL PROCEDURE
Collected column soil was cut into 1.5 or 3 cm layers. The soil
sample were first dried by oven (80�, 48h). Then homogenized

The 129I depth profiles of four cores from Kawauchi villagecommonly showed particularly high concentration at the top mostlayer, steep exponential decrease as a depth and constant blow 10cm depth (Fig. 1). This enhancement in the top 10 cm layer can beconsidered as the direct accumulation from the FDNPP after theaccident. However no positive evidence of 129I migration was foundbecause there was only a small difference among these profiles
which can easily explained by the spatial variation of 129I deposition
amount suggested by other observation [1]. In any of the four cores,
more than 89% of FDNPP origin 129I was existed within top 5 cm
and 98% within top 10 cm. Other 9 cores showed larger variation of
depth profile of FDNPP
origin 129I. Especially thefraction of total inventory
existed within top 5 cm
were varied from 56% to100%. This large profile
variation for crop fieldand Man-made soil
should be controlled by
the soil properties such as
porosity. Sampling site
and/orshouldbecarefully chosen not tounderestimate the total
Fig. 1 Proportion of F1NPP generated 129I
deposition amount of 129I
per depth in Kawauchi village crop fieldoriginated from FDNPP.
[1]
[2]
[3]
[4]

－ 137 －

T. Ohno et al., J. Radiat. Res. 50, 325-332, 2009
S. K. Sahoo et al., Geochem. Cosmochim. Acta 63, 1927-1938, 2009
U. Rao et al., Geochem. Cosmochim. Acta 63, 1927-1938, 1999
UNSCEAR 2008, Annex C

23-FKP-23
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Vertical distribution of the Fukushima-derived radiocesium in the western North
Pacific in January and February 2011
Yuichiro Kumamoto1, Akihiko Murata1, Takeshi Kawano1, Michio Aoyama2
1

Japan Agency for Marine-Earth Science and Technology, Japan
2
Meteorological Research Institute, Japan

Abstract – The radiocesium in seawaters from surface to 800-m
depth at stations more than hundreds km away from the Fukushima
Dai-ichi nuclear power plants in the western North Pacific Ocean
were measured in January and February 2012. Activity of the
Fukushima-derived Cs-134 in the surface mixed layer (0 ~ 200-m
depth approx.) was highest (~ 20 Bq m-3) in the transition area
between the subarctic (north of 40°N approx.) and subtropicalregions (south of 35°N approx.), which was due to the directdischarge of radiocesium from the plants. In the subtropical region,
we observed Cs-134 maxima just below the mixing layer (200 ~ 300m depth approx.). The Cs-134 activities in the maxima corresponded
to those in the surface mixed layers in the transition area, which
implies that the Cs-134-rich waters in the transition area have beentransported southwardly to the subtropical region across theKuroshio Extension Current along isopycnal layers.
Keywords – Fukushima Dai-ichi nuclear power plants, radiocesium,
North Pacific OceanI.

INTRODUCTION

The massive Tohoku earthquake and consequent giant
tsunami of March 11, 2011 resulted in global releases ofradiocesium (Cs-134 and Cs-137) from the Fukushima Daiichi nuclear power plants (FDNPPs). In the North Pacific
Ocean, a large portion of Fukushima-derived radiocesium has
been settled in both through atmospheric deposition anddirect discharge of contaminated waters. The total amount of
the radiocesium derived from the direct discharge wasestimated to be about 4 PBq for Cs-137 (Kawamura et al,2011 [1]; Tsumune et al., 2012 [2]; Estournel et al., 2012[3]).
On the other hand, evaluation of the radiocesium derived
from the atmospheric deposition contains large uncertainty
mostly due to the restriction of available data in the vast
North Pacific Ocean. In particular, vertical distribution of the
Fukushima-derived radiocesium in the open ocean is hardly
known. We measured the radiocesium in seawaters fromsurface to 800-m depth at stations more than hundreds kmaway from FDNPPs in the western North Pacific Ocean in
January and February 2012.
II. METHODS

filtrated and acidified by nitric acid on board. Radiocesium inthe seawater was concentrated onto ammonium
molybdophosphate (AMP). The radiocesium in the AMP/Cs
compound was measured using a gamma-spectrometry withwell-type Ge detector. Detection limit of the radiocesium
measurement was 0.2 ~ 0.3 Bq m-3. Uncertainties for themeasurement was about 8 %. The radiocesium decay werecorrected to the sampling date.
III. RESULTS AND DISCUSSION
Before the FDNPPs accident, Cs-134 derived from thenuclear weapon tests and the Chernobyl accident was notdetected in the environment because of its short half-life(about 2 years). Therefore Cs-134 observed in the North
Pacific was derived from FDNPPs after the accident. Cs-134
was found in surface waters at all the stations from 20°N to
42°N about ten months after the disaster. Activity of Cs-134
in the surface mixed layer (0 ~ 200-m depth approx.) was
highest (~ 20 Bq m-3) in the transition area between thesubarctic (north of 40°N approx.) and subtropical regions(south of 35°N approx.). Those in the subarctic andsubtropical regions were less than 5 and 1 Bq m-3,
respectively. This meridional distribution was due to thedirect discharge of radiocesium into the transition area from
FDNPPs located at 37.4°N/ 141.0°E.
Below the surface mixed layer Cs-134 activity decreased
sharply and was not detected in deeper layers than 400-m
depth at stations in the subarctic region and transition area,
which is explained by vertical one-dimensional penetration ofradiocesium from the surface mixed layer to the deeper layers.
However, at stations in the subtropical region, south of theKuroshio Extension Current, we observed Cs-134 maxima
just below the mixing layer (200 ~ 300-m depth approx.). The
Cs-134 activities in the maxima corresponded to those in thesurface mixed layers in the transition area, which implies that
the Cs-134-rich waters in the transition area have beentransported southwardly to the subtropical region across theKuroshio Extension Current along isopycnal layers.
[1]

We conducted water sampling during a cruise of R/VMirai, Japan Agency of Marine-Earth Science andTechnology (MR11-08) along the 149°E meridional line
approximately. The seawater samples were collected into 20L cubitainers using a bucket and a conductivity-temperaturedepth rosette with Niskin water samplers. The sample were

[2]
[3]

－ 138 －

Kawamura, H., Kobayashi, T., Furuno, A., In, T., Ishikawa, Y.,
Nakayama, T., Shima, S., and Awaji, T., J. Nucl. Sci. Technol., 48,
1349–1356, 2011.
Tsumune, D., Tsubono, T., Aoyama, M., and Hirose, K., J. Environ.
Radioactiv., 111, 100–108, doi:10.1016/j.jenvrad.2011.10.007, 2012.
Estournel, C., Bosc, E., Bocquet, M., Ulses, C., Marsaleix, P., Winiarek,
V., Osvath, I., Nguyen, C., Duhaut, T., Lyard, F., Michaud, H., andAuclair, F.,J. Geophys. Res., 117, C11014, doi:10.1029/2012JC007933,
2012.

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

23-FKP-24

Effect of Application Timing of Potassium Fertilizer on Root Uptake of 137Cs in
Brown Rice
Takashi Saito1, Kazuhira Takahashi1, Tomoyuki Makino2, Hirofumi Tsukada3, 4,
Mutsuto Sato1, Kunio Yoshioka1
1

2

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

Abstract – We have already reported that potassium fertilizer iseffective to reduce radiocesium in brown rice. In this study, we
tried to find the most appropriate timing for potassium fertilizer
application during the rice cultivation period in terms of 137Csconcentrations in brown rice. The concentration of 137Cs in brownrice cultivated without application of potassium fertilizer was 32
Bq
kg-1, while that with application of basal fertilizer including
potassium was 5 Bq kg-1. The concentration of 137Cs in brown rice
was increased with the late application timing. Therefore,
application of potassium fertilizer in the early growing period
reduced the uptake of 137Cs by rice plant from contaminated soils
effectively.
Keywords –137Cs, Brown rice, Potassium fertilizer, Soil-to- brownrice transfer factor

I.

INTRODUCTION

After the accident of Fukushima Daiichi Nuclear Power
Plant, in 2011, the concentration of radiocesium in brownrice collected in some areas of Fukushima prefecture
exceeded the provisional regulation value for brown rice
(500Bq kg -1). It is reported that the concentration ofradiocesium in brown rice decreases with increasingexchangeable potassium concentrations in soil (Saito et al,2012). In terms of more positive application method ofpotassium fertilizer for reducing radioactive concentrationin rice, concentrations of 137Cs in brown rice according toapplication timing of potassium fertilizer were investigatedin the present study.

we collected soil from the vicinity of the rice plant. Afterthe soil samples were air-dried for 21 days, the soil in eachsample was properly mixed and sieved through a 2 mmsieve. Rice seeds were collected from the soil where thesoil was sampled. After threshing rice samples were passed
through a 1.80-mm sieve and grains remained on the sieve
were used for the analysis. The dried soil was compressed
into cylindrical polystyrene containers. The brown rice
samples were compressed into 0.7 L Marinelli beakers. The
concentration of 137Cs in the soil and brown rice were
measured using a Ge gamma- ray detector connected to a
multichannnel analyzer system by counting for 3600-7200s.
III. RESULTS AND DISCUSSIONSThe concentration range of 137Cs in the soils of theexperimental plot was 3262-3983 Bq kg-1. The 137Csconcentration in brown rice cultivated without potassium
fertilizer was 32 Bq kg-1, while that decreased to 5 Bq kg-1
with application of basal potassium fertilizer. On the other
hand, the 137Cs concentrations of brown rice to whichpotassium fertilizer was applied at 50, 70 and 80 d after
transplanting were 15, 23 and 36 Bq kg-1, respectively. As aresult, the concentrations of radiocesium in brown riceincreased with late application timing. These results showthat application of potassium fertilizer in the early growing
period decreases the uptake of 137Cs by rice plants fromcontaminated soils effectively.

II. MATERIALS AND METHODS
A field test was carried out in the northern part of
Fukushima Prefecture. Plowing, puddling and transplanting
were performed on April 20, May 4 and May 10, 2012,
respectively. The planting density was 17.1 hill m-2 (30×19.5 cm). The nitrogen and phosphorus fertilizer (g m-2)
were applied to each plot of paddy field in the proportion
6.0:10 (N-P2O5) on April 17, 2012. The potassium fertilizer
was applied to each plot of the field at a rate of 8.0 g m-2
before plowing, 50, 70 and 80 day after transplanting,respectively.
Rice straw had been applied to the test field every year.
The soil in the rice paddy field was classified as Gray
lowland soil. Soil samples (at the depth of 0-15cm) werecollected from each plot of experimental rice paddy field
after the cultivation of the rice plant on September 19, 2012.
In order to determine the soil-to brown rice transfer factor,

Fig.1 Concentrations of 137Cs in brown rice by differenceof application timing using potassium fertilizer[1]－ 139 －

Saito T et al : Effect of potassium application on root uptake ofradiocesium in rice, KUR Research Program for Scientific Basis of
Nuclear Safety, 165-170, 2012

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

23-FKP-25

Low levels of 134Cs and 137Cs in bottom sediments along the Japanese Archipelagoside of the Sea of Japan after the Fukushima Dai-ichi NPP accident
M. Inoue1,*, S. Ochiai1, T. Murakami1, S. Oikawa2,
M. Yamamoto1, S. Nagao1, Y. Hamajima1, H. Kofuji1, J. Misonoo2
1

Low Level Radioactivity Laboratory, Kanazawa University
Marine Ecology Research Institute2

Abstract

38.5

We examined radiocesium concentrations in bottom sediment

5

0

0
2

0
0

2

0
0
2

0
0
5
1

samples collected along the Japanese Archipelago side of the Sea

1

Latitude (degree)of Japan before/after the Fukushima Dai-ichi Nuclear Power
Plant (FDNPP) accident. Low levels of 134Cs were detected in anarea located near estuaries. This was considered to be due to theriverine discharge rather than direct radioactive depositions tosea surface.

0

0

38.0
0
2

1500

0

0

37.0

� D2
�D1

0

0
2

Niigata� Agano

River

Agano
River
ShinanoRiver
Shinano
River

138.5

139.0

0

138.0

Sea of
Japan

�Da

0

50

Fukushima Dai-ichi Nuclear Power Plant accident

0

�Db

37.5
1

Key words- radiocesium; bottom sediment; riverine discharge;

0

0
0

139.5

Longitude (degree)

Fig. 1 sampling sites for sediment samples

I. INTRODUCTION
The FDNPP accident on March 11, 2011 resulted in134

in 2011) in contrary to the sediments at other coastal areas

Cs (half-life:

along the Japanese Archipelago side which were below theCs (30.2 y) to the atmosphere and to land anddetectable limit [1]. In estuary areas, particle materials playsea surfaces over a wide region of eastern Japan. We

important roles in the transportation of radiocesium. Due tothe widespread release of large amounts of
2.06 y) and137

Cs concentrations in sediment

the existence of the thermocline, the contamination of 134Cs

samples collected in the Japanese Archipelago side of thein sediment samples in area D could not be ascribed to the

Sea of Japan in May 2011, which indicated the slightcontribution

contamination of the FDNPP-derived radiocesium in a

downward water circulation, but to the transportation of thesediment sample from site D1 (Fig. 1) [1]. In the present

reactive fraction together with particle materials. Agano

analyzed thestudy,

we134

Cs andexamined137

radiocesium

concentrations

of

of

the

solublefraction

accompanying

River and Shinano River meet around area D. Detection of

sediments in area D and clarify delivery process of134radiocesium from the FDNPP.

introduction of contaminated riverine particles from theCs in samples collected in May 2011 suggests thatestuary may lead to radiocesium contamination in thesediment samples, showing immediate transportation

II. SAMPLES and EXPERIMENTAL
We collected a total of 11 bottom sediment samples(0–3 cm depths) at four sites in Niigata offshore (D) area(within 1–2 months) of radioactive particle materials to thebottom

of

this

area.

Furtherclarification

of
134

the

(230–530 m depths) during 2010–2012 (Fig. 1). Sedimentcontamination levels and delivery patterns forsamples were freeze-dried and crushed into a powder with137

an agate mortar after washing with distilled water (5–25 g-

sediment samples, including riverine sediments. This is andry). �-Spectrometry was performed on all samples using

operation that we are currently engaged in.

Cs andCs in this area can be achieved by obtaining additional

Ge-detectors designed for low-background counting andReferences

located at the Ogoya Underground Laboratory [2].

[1] Inoue, M. et al. (2013) Appl. Radiat. Isot. (in press)

III. RESULTS and DISCUSSION
In area D,

134[2] Hamajima, Y. and Komura, K. (2004) Appl. Radiat. Isot. 61, 179-183

Cs was detected in bottom sediments

collected in 2011 and 2012 (e.g., 7.7 mBq/g-dry at site D2－ 140 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

23-NCP-01

The heavy-ion reactions 238U + 238U and 238U + 248Cm and actinide
production close to the barrier revisited
1

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

Gesellschaft für Schwerionenforschung mbH, 64291 Darmstadt, Germany
currently at Institut für Kernchemie, Johannes Gutenberg-Universität, 55099 Mainz, Germanybcurrently at Advanced Science Research Center, Japan Atomic Energy Agency, Tokai-mura,
Ibaraki 319-1195, Japanccurrently at Paul Scherrer Institut, 5232 Villigen, SwitzerlandaKeywords – Quasi-elastic and damped collisions/Sequential
fission/Total kinetic energy loss/Production of surviving heavy
actinides/Excitation functions/Survival probabilities

Recent theoretical work [1,2] has renewed interest inradiochemically determined isotope distributions inreactions of 238U projectiles with heavy targets that had
previously been published only in parts [3,4]. These data���� ������ ����������� ���� ������ ��������� ��Z) below theuranium target have been determined as a function ofincident energy in thick-target bombardments. These arecompared to predictions by a diffusion model [5] whereby
consistency with the experimental data is found in theenergy intervals 7.65 – 8.30 MeV/u and 6.06 – 7.50 MeV/u.
In the energy interval 6.06 – 6.49 MeV/u, the experimental
data are lower by a factor of 5 compared to the diffusion
model prediction indicating a threshold behaviour formassive charge and mass transfer close to the barrier. For
the intermediate energy interval, the missing mass between
the primary fragment masses deduced from the generalised
Qgg systematics including neutron pair-breaking corrections
and the centroid of the experimental isotope distributions as
a function of Z have been used to determine the average
excitation energy as a function of Z. From this, the Z
dependence of the average total kinetic-energy loss

independent of the bombarding energy indicating that thesame bins of excitation energy are responsible for the
production of these fissile isotopes. A comparison of thesurvival probabilities of the residues of equal charge andneutron transfers in the reactions of 238U projectiles witheither 238U or 248Cm targets [4] is consistent with this cutoff
as evaporation calculations assign the surviving heavy
actinides to the 3n and/or 4n evaporation channels.
[1]
[2]
[3]
[4]
[5]
[6]
[7]

T K E L has been determined. This is compared to thatmeasured in a thin-target counter experiment at 7.42
MeV/u [6,7]. For small charge transfers, the values ofT K E L of this work are typically about 30 MeV lower
than in the thin-target experiment with the difference
decreasing with increasing charge transfer developing intoeven slightly larger values in the thick-target experiment
for the largest charge transfers. This is the expectedbehaviour which is also found in a comparison of thepartial cross sections for quasi-elastic and deep-inelastic
reactions in both experiments. The cross sections forsurviving heavy actinides, e.g., 98Cf, 99Es, and 100Fm
indicate that these are produced in the low-energy tails of
the dissipated energy distributions, however, with a lowenergy cutoff on the order of 35 MeV. Excitation functions
show that identical isotope distributions are populated－ 141 －

V. Zagrebaev et al., Nucl. Phys. A787, 363c (2007)
V. Zagrebaev et al., Phys. Rev. C78, 034610 (2008)
M. Schädel et al., Phys. Rev. Lett. 41, 469 (1978)
M. Schädel et al., Phys. Rev. Lett. 48, 852 (1982)
C. Riedel et al., Z Physik A290, 385 (1979)
K.D. Hildenbrand et al., Phys. Rev. Lett. 39, 1065 (1977)
H. Freiesleben et al., Z. Physik A292, 171 (1979)

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

23-NCP-02

Mechanism of Mo-99 Adsorption and Tc-99m Elution from
Zirconium-Based Material in Mo-99/Tc-99m Generator Column Using
Neutron-Irradiated Natural Molybdenum
Rohadi Awaludin1, Adang Hardi Gunawan1, Hotman Lubis1, Sriyono1, Herlina1, Abdul Mutalib1,
Akihiro Kimura2, Kunihiko Tsuchiya2, Masakazu Tanase3, Masahiro Ishihara2
1

Center for Radioisotope and Radiopharmaceutical, National Nuclear Energy Agency of Indonesia.
rohadi_a@batan.go.id
2
Neutron Irradiation and Testing Reactor Center, Oarai Research and Development Center, Japan Atomic Energy Agency
3
Chiyoda Technol Corporation, Japan

Keywords – adsorption mechanism/Mo-99/Tc-99m radionuclide
generator/neutron-irradiated natural molybdenum

It is expected that the use of fission product Mo-99 for
Tc-99m production can be replaced by neutron-irradiatednatural molybdenum. The challenge in using neutronirradiated molybdenum is that the Mo-99 has low specificradioactivity. Zirconium-based material has a great
opportunity as an adsorbent in Mo-99/Tc-99m radionuclide
generator using neutron-irradiated natural molybdenum
since the material can adsorb molybdenum with highcapacity. However, until now, there is still no data to
explain the mechanism of Mo adsorption and Tc-99m
elution process from the material. It is very important toinvestigate the mechanism for increasing the adsorption
capacity, increasing the Tc-99m elution yield as well as
reducing the Mo-99 breakthrough in Mo-99/Tc-99m
generator using irradiated natural molybdenum. In thisstudy, the Mo-99 adsorption and Tc-99m elution
mechanism were investigated using Scanning Electron
Microscope-Energy Dispersive X-ray Spectroscopy (SEMEDS) to analyze the elemental composition of the material
surfaces before Mo adsorption, after Mo adsorption andafter Tc-99m elution using saline solution. The results werecompared with the value of adsorption capacity of thematerial to irradiated natural Mo and elution yield of Tc99m. From the changes of elemental composition in thesurface, it was found that molybdate ions were adsorbed
into the adsorbent by ion exchange with Cl- ions in thematerial. It was also revealed that Tc-99m can be eluted
from the material column in high oxidation state (99mTcO4-)
since oxidizing agent was needed in the elution process. It
was considered that in lower oxidation state the Tc-99m
easily made coordination bonds with other elements in theadsorbent.

－ 142 －

23-NCP-03
APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013�����������������������������������������������������
���������������������������������������������������������������������������������� �������������
����������������������������������������������������������������������������������������������
��������������
�����������������������������������������������������������������������������
��������������������������������������������
����������������������������� ����� ��������� �����
��������������������� �������� ���������������
�������������������� ������� ���������������

Abstract Ð We developed a new gas-filled recoil separator GARIS-II,
which consists of 5 magnets in a Q-D-Q-Q-D configuration, to study
on actinide-based fusion reaction. The solid angle of the separator
was determined to be 18.2 msr measured by a standard �-source of241
Am. Basic characteristics of the separator, such as a backgroundsuppression and transmission, was studied by using fusion products
via well-known nuclear reactions of 169Tm(40Ar,4n)205Fr and208
Pb(40Ar,3n)245Fm, respectively.
Keywords Ð gas-filled recoil ion separator, GARIS, new element,
superheavy element, SHE chemistry��������������������������������������������������������
��������������������������������������������������������������
�������������������������������������������������������
��������������������������������������������������������������
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23-NCP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Purification of Scintillation Cocktails containing the alpha emitters americium andplutonium
E. Löfström-Engdahl*, G. Skarnemark, K. El Tayara, J. Eriksson, N. Halldin, J. Halleröd, M. Malmberg,
J. Mattiasson Bjugren
Nuclear chemistry, Department of Chemical and Biological Engineering,
Chalmers University of Technology, SE 412 96 Gothenburg, Sweden*Corresponding author, elinlo@chalmers.se

ABSTRACTOne efficient way of measuring alpha emitters is by the usage ofliquid scintillation counting (LSC). A liquid sample is placed in a

scintillation cocktail. In neither the americium nor thevial containing a scintillation cocktail. The alpha particles excite

plutonium system, adverse effects of increasing the volume

electrons in the surrounding liquid, and when they are de-excitedwere detected. The products of the process are a solid fraction

photons are emitted. The photons are detected and the activity canthat can be sent to final storage and a practically non-be quantified. LSC has a high efficiency for alpha radiation and isradioactive liquid fraction that can be sent to municipal

therefore a fast and easy way for measuring alpha emitting samples.

incineration.

One drawback is that it does not differentiate very well between
alpha energies; measurements of for example curium and plutonium
simultaneously are impossible and demand other techniques.

Liquid scintillation counting, Alpha emitting waste, Co-precipitation

Another drawback is the production of a liquid alpha active waste.
In Sweden alpha radioactive waste liquids with an activity oversome kBq per waste container cannot be sent for final storage. If,
however, the activity of the liquids could be reduced by precipitationof the actinides, it would be possible to send away the liquidsamples to municipal incineration. In this work a method for apurification of alpha active scintillation cocktails was developed.
The method was first tried on a lab scale, and then scaled up. Until
today (March, 2013) more than 20 liters of scintillation liquids havesuccessfully been purified from americium and plutonium at
Chalmers University of Technology in Sweden.

The four scintillation cocktails used were Emulsifier Safe®,
Hionic-Fluor®, Ultima Gold AB® and Ultima Gold XR®. The
scintillation cocktails could all be purified from americiumwith higher yield than 95 %. The yield was kept when theliquids were mixed. Also plutonium could be precipitatedwith a yield over 95 % in all cocktails except in HionicFluor® (>55 %). However, that liquid in particular could be
purified (>95 %) by mixing it with the three other cocktails.
Up-scaling was performed to a batch size of 6-8 L of

－ 144 －

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

Formation and stability of sulfides of the superheavy elements Cn and Fl
1

N.M. Chiera1,2, R. Eichler1,2*, A. Türler 1,2

Department of Chemistry & Biochemistry, University of Berne, Freiestrasse 3, CH-3012 Berne, Switzerland
Laboratory for Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, CH-5232 Villigen, Switzerland

2

First chemistry experiments with Cn and Fl revealed a
relativistic stabilization of their elemental state leading to amuch weaker metallic interaction with gold compared to theirlighter homologues in the groups 12 and 14 of the periodic
table [1,2]. Extrapolative predictions, inwhich
thermochemical state functions were correlated mutually,
showed that Cn and Fl may form stable sulfides. However,the stability trends in group 12 and 14 are predicted to be
opposite. Hence, FlS is expected to be more stable compared
to CnS. An experimentally exceptionally favourable case forcomparative studies of Cn and Fl is the possibility of asimultaneous production of both elements in Ca-48 induced
nuclear fusion reactions with Pu-242/Pu-244 [3]. The affinityof mercury towards sulfur is well known, and the formationof HgS is thermodynamically favored [4]. Hence, thischemical system is an ideal model system to investigate thekinetics and thermodynamics of the adsorption and reactionof a volatile noble metal with sulfur surfaces. For thispurpose the method of isothermal reaction chromatography isused. Here, first results from these investigations will bepresented. Some conclusions will be drawn, which areimportant for the preparation of further chemical
investigations of Cn and Fl.
[1] R. Eichler et al., Nature 447, 72 (2007)[2] R. Eichler et al., Radiochim. Acta 98, 133 (2010)[3] Y. Oganessian, J. Phys. G: Nucl. Part. Phys, 34 (2007)[4] M. Svensson, Sci. Tot. Env. 368, 418 (2006)－ 145 －

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

Development of a Batch-Type Solid-Liquid Extraction Apparatus for Repetitive
Extraction Experiment of Element 104, Rf
Y. Kasamatsu1, T. Yokokita1, A. Kino1, K. Nakamura1, K. Toyomura1, Y. Komori1, N. Takahashi1, H.
Haba2, J. Kanaya2, M. Huang2, Y. Kudou2, T. Yoshimura3, A. Shinohara1
1

2

Graduate School of Science, Osaka University
Nishina Center for Accelerator-Based Science, RIKEN
3Radioisotope Research Center, Osaka University

Abstract – For the extraction of element 104, Rf, an automatic andrapid solid-liquid extraction apparatus by batch method was newly
developed. On-line solid-liquid extraction experiments using an
accelerator were performed in the TIOA/HCl system with 89m,gZr
and 175Hf produced in the nuclear reactions. As a result, thedistribution coefficients in equilibrium were obtained within 10 s in
7–11 M HCl. This indicates the applicability of the present
apparatus to Rf experiment.
Keywords – Solid-liquid extraction, Triisooctylamine (TIOA), Zr, Hf,
Superheavy element

Chemical properties of transactinide elements (Z �� �����
are expected to be characteristic due to strong relativistic
effects on their electronic shells. Therefore, transactinide
chemistry is very fascinating. It is, however, very difficult toperform chemical experiments of these elements because of
their short half-lives and low production rates in the nuclear
reactions. On-line chemical experiments on a “one-atom-at-atime” basis are required. In recent years, the fluoride complex
formation of Rf was successfully investigated under thecondition that chemical equilibrium is attained for its
homologues. To systematically study the complex formationof Rf, we are interested in the chloride complexation of Rf.
Purpose of the present study is to clarify the chloride
complex formation of Rf based on the extraction data inequilibrium and further to investigate time dependence of thechemical behavior of Rf for the first time. In our previous
work [1], solid-liquid extraction of Zr and Hf, thehomologues of Rf, using triisooctylamine (TIOA) from HCl
was performed by batch method. In this work, we newly
developed the automatic apparatus to perform batch-wisesolid-liquid extraction of transactinide elements rapidly andrepeatedly. On-line experiments using this apparatus wereconducted with 89m,gZr and 175Hf tracers produced at the AVF
cyclotron in RIKEN. We investigated the equilibrium time inextraction in several HCl concentrations by determining timedependences of the Kd values.
Schematic view of the solid-liquid extraction apparatus isshown in Fig. 1. Nuclear reaction products transported by thegas-jet system are deposited on the collection site of the
dissolution section and then dissolved with an aqueous
solution. The solution sample passes through two valves anda slider which moves horizontally to three positions, and thenenters a Teflon reactor containing TIOA resin, reactor 1 inFig. 1. After shaking the reactor using a vortex mixer, only

the liquid phase is pneumatically pushed out of the reactor,
and is subjected to the radiation measurement. To measure
the radioactivity on the resin, the control experiment without
the resin is performed using reactor 2. The present apparatus
is controlled by a computer through a LabVIEW system.
In the on-line experiment, 89g,mZr (T1/2 = 3.27 d, 4.18 min)and 175Hf (T1/2 = 70 d) were produced in the 89Y(p,n)89g,mZr
and 175Lu(p,n)175Hf reactions, respectively. Extraction
experiments were performed by the above operations with the
25–57 wt. % TIOA resin (2.6–3.8 mg) and 6–11 M HCl(160–23�����. Shaken time was varied to be from 10 s to 120
s. Remained Zr and Hf on the resin were eluted by washing�����������������������������������������������������3 and0.01 M HF three times. The TIOA resin was reused 3–6 times.
Each solution sample was a������� ��� �-ray spectrometry
using a Ge detector to obtain the Kd values by the equation Kd(mL/g) = [M]resin/[M]soln (M = Zr or Hf).
It was found that the Kd values are basically constant in thestudied time range, and are consistent with those obtained in
our previous batch experiment [1] in 7–11 M of HCl. This
result suggests that chemical reactions in the extraction reachthe equilibrium within 10 s for 89mZr and 175Hf under thepresent experimental conditions. It took about 35 s until theend of elution of the HCl solutions. These results suggest theapplicability of the present apparatus to Rf experiment.

Fig. 1 Schematic view of the solid-liquid extraction apparatus[1]－ 146 －

A. Kino et al., 4th International Conference on the Chemistry andPhysics of the Transactinide Elements, Sochi, Russia, 5-11 Sep. (2011).

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

23-NCP-07

Coprecipitation of Zr, Hf, and Th with Sm Hydroxide for Chemical Study of Rf
K. Toyomura1, Y. Kasamatsu1, N. Shiohara1, T. Yokokita1, Y. Komori1, K. Nakamura1,
N. Takahashi1, T. Yoshimura2, H. Haba3, Y. Kudou3, H. Kikunaga4, T. Ohtsuki4, K. Takamiya5,
T. Mitsugashira6, and A. Shinohara1
1

Graduate School of Science, Osaka University

2

Radioisotope Research Center, Osaka University
3

Nishina Center for Accelerator-Based Science

4

Research Center for Electron Photon Science, Tohoku University
5

Research Reactor Institute, Kyoto University

6

International Research Center for Nuclear Materials Science, Institute for Material Research, Tohoku University

Abstract – The purpose of our study is to perform hydroxide
coprecipitation experiments of element 104, rutherfordium (Rf), toinvestigate its complex formation with hydroxide ions. In thiswork, we investigated the hydroxide coprecipitation behaviors of
the group-4 homologues Zr and Hf, and the pseudo homologue Th
in aqueous NH3 and NaOH solutions by coprecipitation methodwith Samarium (Sm) hydroxide. In addition, we developed thesemiautomatic and rapid suction filtration apparatus for
repetitive experiment of Rf, and tested its performance by on-line
experiments of Zr and Hf using an accelerator.
Keywords – Superheavy elements, Rutherfordium, CoprecipitationI.

INTRODUCTION

Elements with the atomic numbers Z � 104 are calledsuperheavy elements (SHEs). They have short half-lives
and are produced only by nuclear reaction with anaccelerator. Therefore, much repetition of rapid
experiments targeting one atom is required. This is why it
is difficult to perform experiments of SHEs, and theirchemical properties are hardly elucidated. So far, chemical
properties of SHEs have been studied mainly bychromatographic methods. Experiments of SHEs in morevarious chemical systems should be performed to study
their chemical properties in more detail. We have beendeveloping a new method to investigate chemical
properties of SHEs.
The purpose of our study is to perform coprecipitation
experiments of element 104, rutherfordium (Rf), toinvestigate its complex formation with hydroxide ions by
the coprecipitation method with samarium (Sm) hydroxide.
By this method [1], we can prepare a precipitate sample
which has good energy resolution in � spectroscopy in a
few min. Therefore, this method is expected to be
applicable to SHE chemistry that requires rapid operations.
In this work, we investigated the hydroxide coprecipitation
behaviors of the group-4 homologues Zr and Hf, and thepseudo homologue Th with Sm in aqueous NH3 and NaOH
solutions with various concentrations. In addition, wedeveloped a semiautomatic and rapid suction filtration
apparatus for repetitive experiments of Rf and tested its
performance by on-line experiments of Zr and Hf using an
accelerator.

II. EXPERIMENTS AND RESULTS
The Sm standard solution (1 M HNO3) with the volume of
20 �L containing 20 �g of Sm was added into the HClsolution containing 88Zr, 175Hf, and 228Th radiotracers. The
solution was stirred and then the basic solution (dilute andconcentrated aqueous NH3, and 0.1–12 M NaOH solutions)
was added. The solution was stirred for 10 s or 10 min. The
solution containing the precipitate was filtrated by suction
with a polypropylene membrane filter. The filtrate wascollected in a vial. Both the precipitate and filtrate weredried on the heater at 100°C. The precipitate, filtrate, andbeaker used were subjected to � and � spectrometry. The
precipitation yields of Zr, Hf, and Th were determined fromeach radioactivity. Above experiments were performedchanging conditions such as solution volume and filter sticksize to determine suitable conditions for Rf experiment.
The precipitation behaviors of Zr, Hf, and Th without Sm
were investigated using macro amounts of Zr, Hf, and Th
samples in the same conditions to coprecipitation
experiments with radioactive tracers.
As a result, the coprecipitation yields of Zr and Hf werelower as concentration of the hydroxide ions increases. On
the other hand, the precipitation yields of Th wereapproximately 100% under all conditions. We observed
clear differences in precipitation yields among theseelements, suggesting that it is possible to investigate thestability of complex formation with hydroxide ions by thismethod. Because precipitation yields of the samples stirred
for 10 s and 10 min were almost the same, it was found thatprecipitate is rapidly formed within 10 s. We were able toprepare a precipitate sample of Th with good energy
resolution in � spectrometry. These results are preferred in
Rf experiment. In the presentation, we will also report thedevelopment of the semiautomatic apparatus and results of
the on-line experiments using an accelerator, and propose
suitable conditions for Rf experiment.
[1]－ 147 －

H. Kikunaga et al.: Appl. Radiat. Isot. 67, 539 (2008).

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

23-NCP-08

Development of modified epoxy paint films to reduce the volatile iodine source
term in the containments of LWRs during severe nuclear accidentsaSabrina Tietzea
PhD student, Severe Nuclear Accident Chemistry, Nuclear Chemistry Department, Department of Chemical andBiological Engineering, Chalmers University of Technology, Göteborg, Sweden, sabrina.tietze@chalmers.se

During a severe nuclear accident in a light water
reactor (LWR) significant amounts of iodine will be
released from damaged UO2 fuel into the containment.
Primarily released cesium iodide aerosols and elemental
iodine will partly dissolve in steam or the containment
water pools. The remaining gaseous species can undergo
complex reactions with released radiolysis- (e.g. ozone)
and pyrolysis products such as volatile short chainedorganics released from e.g. cable plastics to form under theconditions of a severe nuclear accident (high temperatures,
high radiation field) a series of different volatile iodine
species. While inorganic iodine oxide aerosols (IOx) arerather water soluble and are likely to deposit on metal
surfaces, organic iodides such as methyl- and ethyl iodide
are less reactive with metal surfaces and more hydrophobic
and thus are more likely to remain in gaseous phase.
While gaseous elemental iodine can be sufficiently trappedwith the currently used charcoal-, spray- and wet-scrubber
filter systems, the used filter materials are less selective fororganic iodides. Thus, both in case of a venting of thecontainment and in case of a failure of the containment
these highly volatile species are more likely to be released
into the environment and cause harm to the public. In caseof a Fukushima like containment pressure increase in a
nuclear power plant which is not equipped with an external
wet-scrubber filter system through which the vented air canbe filtered, significant amounts of both volatile inorganicand organic iodine species will be released into theenvironment.
In modern nuclear power plants bisphenol-A based
epoxy paints are commonly used as coatings within thecontainment. These aromatic rich paints withstand higher
radiation doses and thus they are expected to contribute lessto the formation of highly volatile organic iodides such as
methyl iodide than formerly used (partly) oil based paintfilms.
Experimental studies at Chalmers University ofTechnology on Teknopox Aqua VA epoxy paint, which isrecently used in Swedish and Finish nuclear power plants,
have shown that the paint can chemisorb significant
amounts of both inorganic- and organic iodine species. The
chemisorbed iodine will be partly washed out in steam or
can be revapourised under the increased temperature andgamma irradiation field during a severe nuclear accident.
Attempts are made at Chalmers University ofTechnology to develop a modified epoxy paint to increase
the retention of gaseous iodine species already inside thecontainment. For this purpose different organic andinorganic, irradiation stable, water insoluble and for
different iodine species reactive additives are tested using
e.g. a Co-60 gamma irradiator with a dose rate of 14 kGy/h.

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

23-NCP-09

New insights into the formation and stability of
Molybdenum carbonyl compounds
1

I. Usoltsev1,2, Wang Yang3, R. Eichler1,2, A. Türler1,2, Qin Zhi3

Department of Chemistry & Biochemistry, University of Berne, Freiestrasse 3, CH-3012 Berne, Switzerland;Laboratory for Radiochemistry and Environmental Chemistry, Paul Scherrer Institute, CH-5232 Villigen, Switzerland;
3
Institute of Modern Physics Lanzhou; Chinese Academy of Sciences, 509 Nanchang Road, CN-730000 Lanzhou, China
2

The “Ms. Piggy” 252Cf spontaneous fission (SF) source
installed at the University of Bern allows for production ofdifferent transition metal fission products with a wide
variety of half-lives. Volatile metal carbonyl compounds
were formed in situ and transported by flushing pure CO or
CO mixed with inert gas (N2, Ar, He) through the recoilchamber of this source at a flow rate of 1 l/min [1]. Thus,
these compounds are available outside of the source forradiochemical experiments. Our work focuses on thedecomposition or thermal stability of the formed complexes.
Therefore, the carbonyl complexes are transported trough a
decomposition column held at variable temperatures
between 25°C and 800°C. The surviving complexes aretrapped in a charcoal filter, which was monitored by a
HPGe gamma-ray detector. The fused silica decompositioncolumn (1 m, 4 mm i.d.) covered by selected stationary
surface materials was heated up within a steel cladding tube
by means of a resistance furnace. By performing a gamma
spectrometric measurement of the charcoal trap
decomposition curves for carbonyl complexes wereobtained. We will discuss here the results obtained for104
Mo. Several different surface materials were examined:
quartz, silver, gold, palladium, and PFA-Teflon®.
Formation and decomposition of the complexes has beenstudied also in dependence on the CO concentration and on
the inert gas used to dilute the CO. Thus, decomposition
curves were obtained for different isotopes and different
carrier gas mixtures, which allowed for determination of apseudo-reaction order on carbon monoxide in the metal
carbonyl formation. For the first time formation of nitrogencontaining carbonyl complexes with the neutral transition
metal atom Mo was observed. It was also shown that thebeta decay of the Mo central atom in the carbonyl complex
does not lead to the formation of volatile compounds of thedaughter nuclide Tc. Obtained results are discussed in thelight of upcoming decomposition studies of transactinide
carbonyl complexes.
[1]

Even J. et al: Inorg. Chem. 51, 6431 (2012).

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

23-NCP-10

Adsorption behavior of super-heavy elements (Z ������
on metal and inert surfaces
1

J. Anton1, T. Jacob1, V. Pershina2
Institut für Elektrochemie, Universität Ulm, Albert-Einstein-Allee 47, D-89069 Ulm, Germany
2
Gesellschaft für Schwerionenforschung, Planckstr 1, D-64291 Darmstadt, Germany

Investigation of chemical and physical properties of theheaviest elements (those beyond Lr) is a hot topic since
several decades. In this time period, many new elements
were discovered and after a proper characterization wereadded to the Periodic Table of the elements. The main
problem of such investigations, however, is the rather shorthalf-life of these elements, which requires the developmentof innovative experimental techniques. Nowadays theresearch focusses on the chemical properties of the element
114. So far, two gas chromatography experiments to study
the interaction strength of element 114 with a gold surface
have been performed with conflicting results. One
experiment [1] reported a weak interaction of element 114
with a gold surface, leading to adsorption only at very low
temperatures of approximately -90°C, while in the second
experiment [2] adsorption on gold has been observed at theroom temperature, indicating a much stronger bond
between element 114 and gold. To resolve this conflict,further experiments on chemical properties of the element
114 will be performed at GSI and PSI/JINR in the next two
years. For theoretical studies, standard quantummechanical packages that treat a system mostly non- or
only scalar-relativistically are not satisfactory: Due torather significant relativistic effects on the electron shells of
the heaviest elements a fully-relativistic four-component
description is required.
Recently, we have studied the adsorption behavior ofelements 112, Cn, and 114 and their lighter homologues Hgand Pb, respectively, on gold surfaces [3] by using acluster-approach [4]. We found that Hg/Cn and Pb/114
prefer different adsorption sites. Also, the adsorptionenergies of elements 112 and 114 are related to those of
their lighter homologues in a different way. Thus, Eb(Cn) is
only slightly (0.1-0.2 eV) lower than Eb(Hg), while Eb(114)
is much lower (1.4 eV) than Eb(Pb). This is due to the fact,that in element 112 both the relativistically stabilized 7s
and destabilized 6d AOs take part in the binding, while forelement 114 binding is mostly determined by the
relativistically stabilized 7p1/2 orbital. In contrast to Pb,
where 6p3/2 strongly contributes to the surface bond, the
7p3/2 participate much less due to its large relativistic
destabilization (the spin-orbit splitting between 7p1/2 and7p372 is about 3.5 eV). Furthermore, binding of element 114
to gold is similar to that of Cn, however, about 0.2 eVstronger. Our predicted sequence in the Eb values is Cn <Hg < E114 << Pb. Thus, we predicted that in thethermochromatography experiments, element 114 will
adsorb right at the beginning of the chromatography
column with the hot end of 35°C, at the position of Hg.
This prediction was recently confirmed experimentally [2].

In this talk we will present theoretical results on
adsorption energies and distances of the elements from 112
to 114 and their homologues on metal (gold) and inert(SiO2) surfaces.
Acknowledgment – J.A. gratefully acknowledges the support by
the Deutsche Forschungsgemeinschaft (DFG) and BMBF
[1]
[2]
[3]
[4]

－ 150 －

R. Eichler et al. Radiochim. Acta, 98, 133 (2010).
A. Yakushev, NUSTAR-SHE-11, GSI Scientic Report 2009.
V. Pershina, J. Anton, and T. Jacob, J.Chem. Phys., 131, 084713(2009).
J. Anton, B. Fricke, E. Engel, Phys. Rev. A69, 012505 (2004).

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201323-ACP-01

Structural studies of the Eu(III) and U(VI) interactions with pentapeptides
A. Jeanson1, J. Roques1, S. Safi1, E. Simoni1, D. Aitken2
1

IPN - Université Paris Sud, 91406 Orsay Cedex, France
ICMMO - Université Paris Sud, 91406 Orsay Cedex, France2

It is of great importance to assess the mechanisms
governing radionuclide impact on the environment(particularly the biosphere) and to unravel the molecular
processes underlying actinide transport and deposition intissues. But most data available on the interaction ofactinides with biological systems are based on
physiological or biokinetic measurements, with scarce
information on the microscopic factors such as structure of
the actinide coordination site within biological molecules(proteins, peptides...). These structural data are essential tounderstand structure, function and affinity interdependence,
which governs the organ deposition of such elements. In
this paper, we will present first results on the complexationof trivalent and hexavalent metals (in a first step, Eu3+ wasused as a surrogate to Am3+ and UO22+ represented the VI
oxydation state) with peptides containing various,
biologically relevant, geometrical constraints. The
pentapeptide sequences contain sequential differences thatinduce conformational change, but relatively close enoughso one parameter was varied at a time. We used the three
DGDGD, ADPDA and DPDPD peptides, since they are
differentiated by the number of proline (P) residues, thatinduce different angular strains. Both experimental(EXAFS, micro-calorimetry, laser fluorescence, ATRFTIR) and theoretical (DFT methodology) approaches havebeen performed in order to determine the structure of theobtained complexes and the consequences on their stability.

－ 151 －

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

Solubility of Amorphous UO2 and NpO2 in Nitrate Media
Containing Platinum Catalyst
1

Akira Kitamura1, Satoko Shimoda2

Japan Atomic Energy Agency, Tokai, Ibaraki 319-1194, Japan
Mitsubishi Materials Corporation, Naka, Ibaraki 311-0102, Japan

2

CONCENTRATION MOL DM  

NO 0T #&
WITH 0T #&NO 0T �M 

WITH 0T �M
NO 0T K$A
WITH 0T K$A

 
 
 

$,

 
 

 

 
 
 
 
;.A./=INI MOL DM 





Fig. 1 – Solubility of UO2(am) as a function of NaNO3 concentration
with/without platinum black 

CONCENTRATION MOL DM 

Significant amount of nitrate salts are contained in a groupof TRU wastes which may be disposed under deep
underground together with high-level radioactive waste.
Nitrate may oxidize redox-sensitive elements, e.g., uranium
and neptunium. Although it was found that no effects ofnitrate on solubility of amorphous neptunium(IV) dioxide(NpO2(am)) was observed under anoxic conditions [1], it isstill concerned that some catalysts may promote redox
reactions between nitrate and elements reduced. Therefore,solubility of NpO2(am) was investigated under nitrate media
containing platinum catalyst. Similar experimental study wasapplied to amorphous uranium(IV) dioxide (UO2(am)) tocompare results with those for NpO2(am).
An oversaturation method was applied to prepare theUO2(am) and NpO2(am) using stock solutions of uranium(VI)and neptunium(V), respectively, with addition of the reducing
agent sodium dithionite (Na2S2O4). After removing thesolution containing Na2S2O4 and washing several times,
various concentration of sodium nitrate (NaNO3) solution
was added to UO2(am) and NpO2(am). A porous platinum
black powder was added to some samples as a catalyst. The
pH of solution was adjusted around 9, and no adjustment ofredox potential was carried out. After contacting from 2
weeks to 5 months, an aliquot of sample solution was pickedup, centrifuged (CF), filtered with 0.45 �m membrane, andfiltered with molecular weight cut-off of 104. All theexperimental procedures were performed in an argon-filled
glove box to avoid contamination of oxygen gas.
The obtained solubility values of UO2(am) and NpO2(am)as a function of NaNO3 concentration are shown in Figs. 1
and 2, respectively. Due to no dependences of nitrateconcentrations on solubility of UO2(am) and NpO2(am)containing platinum black powder, no redox effects of
NaNO3 on their solubility were found. On the other hand, it
was found that the obtained solubility values of UO2(am) andNpO2(am) containing porous platinum black powder werelarger than those without porous platinum black powder.
Considering with large difference of solubility by filtration
types, aqueous uranium and neptunium species may form
colloidal species in lower NaNO3 concentrations and bephysically absorbed into porous platinum black powder inhigher NaNO3 concentrations.
It was found that the oxidation state of uranium solid was
4 even after the solubility experiment using X-ray
diffractometry. According to thermodynamic calculations,the oxidation state of neptunium solid can also be 4.

NO 0T #&
WITH 0T #&NO 0T �M

WITH 0T �M
NO 0T K$A
WITH 0T K$A

 

 

 
$,
 
 

 

 
 
 
 
;.A./=INI MOL DM 





Fig. 2 – Solubility of NpO2(am) as a function of NaNO3 concentration
with/without platinum black[1]

M. Mihara et al., Proc. ASME 13th Intl. Conf. on Environmental
Remediation and Radioactive Waste Management (ICEM2010),
October 2010, Tsukuba, Japan, Paper No. ICEM2010-40040 (2010).

This work was performed in the project “TRU waste disposal
technology – Combined development of nitrate salt removal
technology and an assessment system for the impact of nitrateon the co-locational disposal of TRU waste and HLW” in FY
2012 funded by the Ministry of Economy, Trade and Industryof Japan.

－ 152 －

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

Apparent formation constants of actinide complexes with humic substances
determined by solvent extraction
Takayuki Sasaki1, Yury M. Kulyako2, Katharina Müller3, Taishi Kobayashi1,
Maxim Samsonov2, Boris F. Myasoedov2
1 Department of Nuclear Engineering, Kyoto University, Kyoto daigaku-Katsura, Nishikyo, Kyoto 615-8540, Japan
2
V.I. Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Kosygin str. 19, Moscow, Russia
Helmholtz-Zentrum Dresden-Rossendorf e.V., Institute of Resource Ecology, 510119, D-01314 Dresden, Germany

Abstract – Apparent formation constants of Pu(IV) with two kinds ofhumic substances (HSs) were determined in 0.1M NaClO4 at 25 �Cusing a back-solvent extraction method. The effect of solution
conditions, such as the pH, the initial metal and HS concentrations,and the ionic strength, on the formation constants was investigated.
The obtained data were compared with the other actinide series.
Keywords – Humic substances / Actinides / Apparent formation
constant / Solvent extraction

Organic substances may greatly affect the speciation andsolubility of tetravalent actinides in groundwater, dependingon the complex formation constants, pH, the ionic strength,
the organic ligand-to-metal concentration ratio, and so on. In
order to estimate how these parameters influence the apparent
solubility, reliable thermodynamic data on the interaction oftetravalent actinide ions with counter anions in aqueous
solutions are required in the safety assessment of geologicaldisposal. In the present study, we investigate the formation
constants of Pu(IV) with typical HSs in groundwater.
The formation constants were determined using thesolvent extraction method which was conducted in a similarmanner as described in a previous study [1,2]. The organic
phase of xylene containing thenoyltrifluoroacetone (HTTA)
without further purification and the aqueous phase containing
Pu at a pHc ~3 were placed in a polypropylene tube andshaken by hand for several minutes. The concentration ofPuIV(TTA)4 complexes extracted into the organic phase wasca. 10-6�-9 M, while the hydrophilic polymer/colloidal species
and species with other oxidation states such as PuIII,V(TTA)x
could not be co-extracted under the present condition. Soon
after, the organic phase was isolated and brought into contact
with fresh aqueous phases containing HS of pHc 4 to 8, andionic strength I = 0.1 M (NaClO4). In this back-extraction,
two kinds of humic acids were used. One is the purified
Aldrich humic acid (ALHA). The other is the Elliott soil
humic acid (1S102H, the International Humic SubstanceSociety) abbreviated to SHA. Back-extraction was performed
using a mechanical shaker at 25 ± 1 °C, and the pHc and Ehvalues were measured.
The Eh values were stable at around +0.5–+0.6V (vs.SHE)
throughout the measurement period at the examined pH
values. The predominant species of plutonium was tetravalentstate as discussed in ref. [1]. The concentration in both phases
was determined by alpha spectrometry (5.16MeV). Though
the recovery ratio for Pu was approximately 50% due tostrong adsorption of Pu on the polypropylene vessel wall, theratio was not dependent on the shaking time. Hence, thepresence of the adsorbed Pu was ignored in the analysis.
The apparent formation constant is expressed by thebinary or ternary complex, depending on the definition of thespecies.

�app,q �[M(OH) q L],
[M 4� ][OH]q [R � ]where q=0 or 1 is assumed in the present study. From thedifference of the distribution ratio between the presence (D)and absence (D0) of HSs,log ��
�

D0

� p
� q
� �
�
� � log � 1 � � � OH,p [OH ] � � app,q [OH ] [R ] ��D���
1 � � � OH,p [OH � ] p��

For A = 1 + � ßOH,p[OH]p,log D � log D0 � log( A � � app,q [OH � ]q [R � ]) � log A

where the �OH,p values at a given ionic strength calculated
from specific ion interaction theory (SIT). In Figure, thelog�app values for tetravalent Pu are higher than those for Th
due to an effect of actinide contraction.
30

log�app3

25

Pu(IV) SHA

20

Pu ALHA

15

Th ALHA, SHA

10
Np(V) ALHA, SHA

5
-7

-6

-5

-4
logCR�

-3-2

Fig. Comparison of the log�app (I=0.1 (NaClO4) and 25ºC) values for Pu– and
Th–OH–HS (as q=1) ternary complexes at pH 4 [1] and Np-HS binary
complexes at pH 6 [2] as a function of CR.
[1] T. Sasaki, S. Aoyama, H. Yoshida, Y.M. Kulyako, M. Samsonov, T.
Kobayashi, I. Takagi, B.F. Myasoedov, H. Moriyama, Radiochim. Acta, 100,
737-745 (2012).
[2] K. Müller, T. Sasaki, Radiochim. Acta, 101, 1-6 (2013).

－ 153 －

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

The solubility of Np(IV) under alkaline and anoxic conditions
Göran Källvenius1, Stefan Allard2, Christian Ekberg2
1

2

AB SVAFO, SE-611 23 Nyköping, Sweden
Chalmers University of Technology, Nuclear Chemistry, SE-41296 Göteborg, Sweden

The solubility of Np(IV) has been studied under alkaline (10 < pH< 14) and reducing conditions. Previously the solubility of Np(IV)has been studied under acidic and near neutral conditions, with justa few studies in the range of 11 < pH < 13. In these studies theanalysis technique used was liquid scintillation counting on 237Np,
resulting in a detection limit of about 10-8 M. The results from thesestudies have indicated solubility around or below this limit resulting
in a high degree of uncertainty. Another problem with the previous
studies is that they have been made on the amorphous hydroushydroxide which may not be a uniquely defined phase. This study
was initiated to test if the alkaline solubility of NpO2(c) would bewithin the detection limit using ICP-MS technique.
Experiments on Np(IV) in the form of NpO2(c) were performed in(Na+, OH-, ClO4-) media at 8 different pH values in the range of 10
to 14 and an ionic strength of 2 M. In trying to achieve reducing
conditions hydrogen atmosphere was used, and Pt(s) catalyst added
to the solutions. The neptunium concentration was determined using
ICP-MS technique thereby lowering the detection limit to between
10-12 and 10-11 M. In most of the studied pH region the solubility ofNp(IV) was found to be below the detection limit. However, at two
pH values, 10.4 and 13.5 the Np(IV) concentration was found to beat least 3·10-10 and 3·10-11 M respectively.
Np(IV), solubility, LSC, ICP-MS, detection limit－ 154 －

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

Separation of Am and Cm by Using TODGA and DOODA(C8) Adsorbents with
Hydrophilic Ligand-Nitric Acid Solution

1

Shigekazu Usuda1, Kei Yamanishi1, Hitoshi Mimura1, Yuji Sasaki2, Akira Kirishima3, Nobuaki Sato3,
Yuichi Niibori1

Department of Quantum Science and Energy Engineering, Graduate School of Engineering, Tohoku University
Research Group for Aqueous Separation Chemistry, Japan Atomic Energy Agency
3
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University
2

Abstract – Extraction chromatographic separation of Am and Cm
was studied by using TODGA and DOODA(8) adsorbents and nitricacid eluents containing hydrophilic ligands, DOODA(C2) and
TEDGA, respectively, in order to produce a synergistic effect inmutual separation properties.
Keywords – Chromatographic Separation of Am and Cm, TODGA
and DOODA(C8) Adsorbents, Hydrophilic Ligands

For an improved partitioning of high level radioactive
waste containing trivalent minor actinides (MA: Am, Cm)[1,2], extraction chromatographic separation of Am and Cm
was studied by using porous silica/polymer support (SiO2-P
particles), into which two lipophilic diamide-type extractants,
tridentate ligands TODGA (N,N,N’,N’-tetraoctyl-1,3oxapentane-1,5-diamide) and tetradentate ligands DOODA(8)(N,N,N’,N’-tetraoctyl-3,6-dioxaoctane-1,8-diamide)
wereimpregnated (TODGA and DOODA(C8) adsorbents,
respectively). For the TODGA and DOODA(C8) adsorbents,
nitric acid eluents containing hydrophilic ligands,
DOODA(C2) (N,N,N',N'-tetraethyl-3,6-dioxaoctanediamide)
and
TEDGA
(N,N,N',N'-tetraethyl-diglycolamide),
respectively, were selected as masking agents in order toproduce a synergistic effect in mutual separation of trivalentlanthanides (Ln) and/or MA.
Mutual separation properties of Ln were preliminarily
investigated in both separation systems by batch and column
methods, especially paying attention of separation between
Nd and Sm. In nitric acid solution, the uptake of Ln onto the
TODGA and DOODA(C8) adsorbents increased with nitricacid concentration. While the distribution coefficient (Kd)values of Ln for the TODGA adsorbent increased with atomic
number of Ln, those for the DOODA(C8) adsorbent
decreased with atomic number of Ln [3]. In nitric acidsolution containing hydrophilic ligands, the Kd (Ln) values
onto the TODGA and DOODA(C8) adsorbents decreased
with concentration of DOODA(C2) and TEDGA ligands [4].
Relative separation factors (SF) of Ln (Nd~Tb) for the
TODGA/DOODA(C2) system were almost the same degreeirrespective of DOODA(C2) concentration, but those for the
DOODA(C8)/TEDGA system were enlarged in lower
TEDGA concentration. Consequently satisfactory eluent
concentration of hydrophilic extractant and nitric acidconcentration for each adsorbent was determined to be 0.05

M DOODA(C2)-0.1 M nitric acid eluent for TODGA
adsorbent and 0.005 M TEDGA-3 M nitric acid eluent for
DOODA(C8) adsorbent. Chromatographic separations of Ln(Nd~Tb) by both systems were effectively performed (SF(Nd/Sm): 4.2 for the TODGA system and 2.7 for the
DOODA(C8) system and peak resolution (R) of Nd/Sm: 2.5
for the TODGA system and 2 for the DOODA(C8) system).
In this presentation, separation of MA(III) in both systems
was demonstrated using not only Am-241 and Cm-243 but
also Eu-152 for comparison between MA and Ln
adsorbabilities. In the TODGA system, SF (Am/Cm) was
considerably large (4.2), but chromatographic development
was not sufficient and R (Am/Cm) was ca. 0.9 since the Kd(Am) value was unexpectedly small (0.7~0.8). In the
DOODA(C8) system, SF (Am/Cm) was not so large (2.3) andR (Am/Cm) was ca. 1.2 because of adequate developed
elution. It seems that the DOODA(C8) system is better than
the TODGA system for practical use from a viewpoint of 3 M
nitric acid eluent. On the other hand, the latter was superior to
the former from an angle of mutual separation of Ln (Nd~Gd).
In near future, the optimum elution condition will be searched
for more effective separation of MA in pursuit of higher peak
resolution between Am and Cm (R�1.5).
A part of this study is the result of “Development ofmutual separation technology of minor actinides by the novelhydrophilic and lipophilic diamide compounds” entrusted to“Japan Atomic Energy Agency” by the Ministry of Education,
Culture, Sports, Science and Technology of Japan.
[1]

[2]

[3]

[4]

－ 155 －

Y. Sasaki, Y. Kitatsuji, Y. Tsubata, Y. Sugo, Y. Morita, “Separatiion of
Am, Cm and lanthanides by solvent extraction with hydrophilic andlipophilic organic ligands,” Solvent Extraction Research andDevelopment, Japan, 18, p.93-101 (2011).
Y. Sasaki, Y. Kitatsuji, Y. Sugo, Y. Tsubata, T. Kimura and Y. Morita,“Actinides extractability trends for multidentate diamides andphosphine oxides”, Solvent Extraction Research and Development,
Japan, 19, p.51-61 (2012).
K. Yamanishi, H. Mimura, S. Usuda, Y. Sasaki, Y. Morita,“Adsorption properties of lanthanoids for SiO2-polymer adsorbents
impregnated with extractants”, Extended Abstracts of IEX 2012 (TheInternational Ion Exchange Conference, 19-21 September 2012,
Queens’ College, University of Cambridge, UK).
K. Yamanishi, H. Mimura, S. Usuda, Y. Sasaki, Y. Morita, “Separationof lanthanoids by SiO2-P adsorbent impregnated with extractants”,
Proceedings of WM2013 Conference (The annual Waste Management
Symposia, 24-28 February, 2013, Phoenix, Arizona USA).

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

Growth of uranyl hydroxide nanowires and nanotubes with electrodeposition method
Lin Wang, Li-Yong Yuan, Zhi-Fang Chai, and Wei-Qun Shi*
Key Laboratory of Nuclear Analysis Techniques, Institute of High Energy Physics, Chinese Academy of Sciences
Email: shiwq@ihep.ac.cn
Abstract –Actinides nanomaterials have great potential applications
in fabrication of novel nuclear fuel and spent fuel reprocessing in
advanced nuclear energy system. [1-2] However, the relative researchso far still lacks systematic investigation on the synthetic methods
for actinides nanomaterials. In this work, we use track-etchedmembranes as hard templates to synthesize uranium based
nanomaterials with novel structures by electrodeposition method.
Through electrochemical behavior investigations and subsequent
product characterizations such as energy dispersive spectrometer(EDS), fourier transform infrared spectroscopy (FTIR), the chemicalcomposition of deposition products have been confirmed as theuranyl hydroxide. More importantly, accurate control ofmorphology and structures (nanowires and nanotubes) could beachieved by carefully adjusting the growth parameters such as
deposition time and deposition current density. It was found that thepreferred morphology of electrodeposition products is nanowire
when a low current density was applied, whereas nanotubes could
be formed only under conditions of high current density and theshort deposition time. The mechanism for the formation of
nanowires in track-etched membranes is based on the precipitationof uranyl hydroxide from uranyl nitrate solution, according to theprevious researches about obtaining nanostructures of hydroxides
from nitrate salt solutions. [3-4] And we have concluded that theformation of nanotubes is attributed to the hydrogen bubbles
generated by water electrolysis under the condition of over-potential
electro-reduction. The conveying of hydrogen bubbles plays the roleof dynamic template which can prevent the complete filling of uranylhydroxide in the channels. Additionally, we transform the chemicalcomposition of deposition products from uranyl hydroxide totriuranium octoxide by calcining them at 500 and 800 degree
centigrade, respectively, and SEM results show the morphologies ofnanowires and nanotubes are maintained very well. Our work
provides new idea for synthesizing one-dimension uranium based
nanomaterials. Further investigations are needed to unveil the sizeand shape effect on the physical and chemical properties of thesenanowires and nanotubes, and to demonstrate their potential
applications.

Figure 1. Growth of uranyl hydroxide nanowires/nanotubes withelectrodeposition method. Top left, scheme of electrodeposition system; top
right, result of elemental analysis for nano-structured products; down left,
SEM images of uranyl hydroxide nanowires with diameters of 400 nm; down
middle, SEM image of uranyl hydroxide nanowires with diameters of 50 nm;
down right, SEM images of uranyl hydroxide nanotubes.

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

Keywords – uranium based nanomaterials, uranyl hydroxide,
electrodeposition, track-etched membranes, template method,
nanowires, nanotubes.

－ 156 －

T. E. Albrecht-Schmitt, Angewandte Chemie-International Edition,
2005, 44, 4836-4838.
P. C. Burns, K. A. Kubatko, G. Sigmon, et al., Angewandte ChemieInternational Edition, 2005, 44, 2135-2139.
L. Gonzalez-Rovira, J. M. Sanchez-Amaya, M. Lopez-Haro, et al.,Nanotechnology, 2008, 19, 495305.
D. Z. Zheng, J. Y. Shi, X. H. Lu, et al., CrystEngComm, 2010, 12,4066-4070.

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

Adsorption Behavior of Neptunium Ions on Pyridine Resinin Hydrochloric Acid Solutions
Yu Tachibana1, Yusuke Tomobuchi1, Masafumi Inaki1, Yuki Yamazaki1, Tatsuya Suzuki1,
Tomoo Yamamura2
1

Department of Nuclear System Engineering, Nagaoka University of Technology,
2
Institute of Material Research, Tohoku Univeristy

Abstract - The adsorption behavior of neptunium ions on pyridine
resin in hydrochloric acid solutions has been studied at room
temperature. Neptunium has many kinds of valence states of ions;mainly tetravalent, pentavalent, and heptavalent ions. We controlled
the neptunium valence states and confirmed the valence states inhydrochloric acid solution by a UV-vis. spectrometry. The
adsorption study on the neptunium ions which has the confirmed
valence states, using pyridine resin was studied by batch-wise
experiments. The distribution coefficients of neptunium on pyridine
resin in hydrochloric acid solution were obtained.

Adsorption behavior was investigated by batch-wise
experiments at room temperature. The neptunium with thecontrolled valences in a hydrochloric solution was added tothe hydrochloric acid solution of adjusted concentrations. 0.1
g of pyridine resin was added to 1.0 mL of a neptunium
solution. Adsorptions of neptunium ions on pyridine resin
were evaluated by comparison of activity of neptunium
before and after adding the pyridine resin.
III. RESULTS

Keywords – neptunium, pyridine resin, nuclear fuel reprocessing

The noble nuclear reprocessing process based on
chromatography in hydrochloric acid solutions has beendeveloped [1]. This pyridine resin is used as the adsorption
medium. In our previous works, the adsorption behavior ofmany elements was investigated, and the reprocessing
process with nuclide separation system has been proposedfrom these results [2]. However we have not obtained theadsorption behavior of neptunium ions on pyridine resin inhydrochloric acid solution. It is well known that theneptunium has many valance states in solution. Thus, we
controlled the valence states of neptunium, and obtained theadsorption behavior of each valence state of neptunium.

We confirmed the methods of neptunium valence control.
Distribution coefficients of neptunium with each controlledvalence in hydrochloric acid solutions were obtained.
Distribution coefficients of heptavalent neptunium are shownin Fig. 1. In this experiment, the neptunium-239 obtained by
milking of americium-244 decay was used. The gamma-ray
spectrometry was used for measurement of neptunium
activity. We found that the heptavalent neptunium is strongly
adsorbed on pyridine resin in higher concentratedhydrochloric acid solution, and this behavior is similar to
heptavalent uranium.

$ISTIRBUTION COEFFICIENT

I. INTRODUCTION

II. EXPERIMENTAL
1. Confirmation of valance states of neptunium
An ultraviolet-visible absorption photospectrometry(Lambda750, Perkin Elmer) was used for confirmation ofvalence states of neptunium. The wavelength of absorption
peaks used for confirmation of Np(IV), Np(V), and Np(VI)species are about 750 and 960 nm, 980 nm, and 1230 nm,
respectively.
Neptunium we used was confirmed to consist of pentavalentand heptavalent ions in original solution. In addition, we also
confirmed that the neptunium can be controlled to be
heptavalent by twice treatments of evaporation to dryness
with the concentrated nitric acid solution and the perchloric
acid solution. Tetravalent condition was confirmed to be able
to be obtained by adding 0.5 M of hydroxylaminehydrochloride to the original solution. It was confirmed that
Np(V) species are able to be obtained by adding peroxide toNp(VI) solution.
2. Adsorption experiments

























(#L  MOL,Fig. 1 Distribution coefficients of heptavalent neptunium on pyridine resin inhydrochloric acid solution.

REFERENCES[1][2]－ 157 －

S. Koyama, et al ., J. Nucl. Sci & Technol. 43 (2006) 681.
T. Suzuki, et al., Prog. Nucl. Energy. 50 (2008) 476.
T. Suzuki, et al., Energy Procedia 7 (2011) 421., etc.

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201323-ACP-08

A method for 237Np determination with liquid scintillation counting in theexperiment of neptunium sorption onto bentonite
LI Ping, LIU Zhi, GUO Zhijun, WU Wangsuo*
Radiochemistry Laboratory, School of Nuclear Science and Technology, Lanzhou University, Lanzhou 730000, Chinabackground counting rate (cpm)





Background Sample
Mixed Sample



























measurement at a PSA-level=38.
[1] Thakur P, Mulholland G P. Determination of 237Np in environmental
and nuclear samples: A review of the analytical method [J]. Appl Radiat
Isotopes, 2012, 70: 1747-1778.
[2] Aupiais J, Dacheux N, Thomas A C, Matton S. Study of neptunium
measurement by alpha liquid scintillation with ��������������-���������� [J].
Anal Chim Acta. 1999, 398: 205-218.








Fig. 2 Influence of bentonite on LSC

sample counting rate (cpm)





m (tracer) /g




















m/V=0.2g/L pH=2.0
m/V=1.0g/L pH=2.0
m/V=1.0g/L pH=8.8
m/V=10.0g/L pH=8.5

Counting rate (cpm)

Among various analytical methods developed andused for the determination of neptunium (alpha
spectroscopy, Neutron Activation Analysis (NAA), High����������� �-Spectroscopy (HRGS), Inductively Coupled
Plasma Mass Spectrometry (ICP–MS), luminescencemethod and Liquid Scintillation Counting (LSC) etc.), The
Liquid Scintillation Counting (LSC) method does not
require extensive sample preparation and is very sensitive
for alpha-decaying radionuclides such as 237Np[1].
However, direct determination of 237��� ����� ���� �-active
daughter 233Pa is difficult.
In this study, a new method was developed for thedetermination of 237Np with liquid scintillation counting(LSC), ���� ���� ��������������� ��� �������� ���� ����� ����function of pulse shape analysis (PSA) without a pure ���������� ��� �� ����� �� �������. Before we use the PSA
technique to discriminate ���, an approach was developed
to set the optimum PSA by measuring a ������������������
sample and a background sample. The mathematic
treatment of neptunium peak indicated that at the selected
PSA-level (38), we detected ~86% of the total �emission[2]. It is suitable for the sample determination in
the sorption experiments at this PSA-level with LSC.
Moreover, we confirmed that, at m/V(bentonite) = 0~10g/L
the suspension in sample did not influence LSC
determination obviously. Thus, we could detect 237Np
samples containing bentonite suspension directly with LSC
by setting PSA-level=38.



PSA-level

Fig.1 Count rate of a mixed sample and abackground sample as a function of the PSA-levelused.

－ 158 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa,Japan, 22-27September 201323-ACP-09

Determination of Stability Constants for the Thorium Iminodiacetic acid
Complexes
D. Rama Mohana Rao, R. M. Sawant, B. S. Tomar.
Radioanalytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085

INTRODUCTION
The complexation of actinides with various naturally
present and anthropogenic organic ligands plays a vital rolein understanding their speciation and migration in theenvironment. Thermodynamics of complexation ofactinides with various organic and inorganic ligands havebeen reported in the literature. To know the binding natureand the effect of hetero atom present in the ligand on
complexation with actinides, we initiated the study todetermine the thermodynamic parameters for complexationof actinide ions with carboxylates containing hetero atom
like nitrogen, sulphur, etc. As a part of this study, in thepresent paper the stability constants for the complexation ofthorium with iminodiacetic acid have been reported. The
complexation of thorium with iminodiacetic acid have also
been reported in the literature [1] which show the formationof MLH and ML complexes whereas in our study wedetermined for the completely deprotonated ligand metal
complexes ML and ML2.
EXPERIMENTAL
The details on the preparation and standardization ofTh(IV) solution was given elsewhere [2]. The iminodiacetic
acid (IDA) was procured from sigma Aldrich and was usedas such. Carbonate free NaOH was used for the electrodecalibration. Potassium hydrogen phthalate as a primary
standard has been used to standardize the NaOH. The
ligand solution was prepared by adding known amount ofstandardized NaOH to iminodiacetic acid solution. The
acidic metal ion solution was titrated with the ligand
solution to determine the stability constants of the Th(IV) –Iminodiacetate complexes. The data collection was stopped
before the appearance of turbidity and the collected data
was analyzed by Hyperquad software.
RESULTS AND DISCUSSION
There is always a competition from H+ during thecomplexation of metal with a ligand containing dissociable
proton. Therefore, in order to determine the stability
constants of the metal ligand complexes, knowledge of the
protonation constants is essential. The protonation
constants of iminodiacetate ion were taken from ourprevious experiment results [3]. During the titration ofacidic metal ion solution with the buffered ligand solution,
following reaction can occur in the reaction vessel.

Th 4� � nL2� � ThL(n4�2 n ) �The overall stability constant for the complex formed bythorium can be given by� MLn �[ThL( 4�n ) � ][Th 4� ][ L2� ]nFigure:1 shows the speciation diagram for thecomplexation of thorium with iminodiacetic acid alongwith the fitted data of pH. Under the experimental
conditions, ML and ML2 complexes are observed
predominantly �����������������������������������������areshown in the table 1. The log � for the complex ML wascomparable with literature value ����� �� ������� [1]. The
higher values of ������indicate the role of chelation in thesecomplexes. Studies on the coordination structure in thesecomplexes are in progress.
Free Metal



ML2
Obs pH

Cal pH

ML% Formation Relative to M

Keywords:Thorium, Iminaodiacetic acid, stability constantsH � � L2� � HL�
H � � HL� � H 2 L




pH

Abstract: Potentiometric method of determining the stability
constants was employed to study the complexation of thorium withiminodiacetic acid. All the stability constant values have been
determined at temperature of 298 K and in 1 M NaClO4 medium.
The f������������������������������������������������������������
literature for ML2 complex. Under our experimental conditions
1:1 and 1:2 complexes are found to be formed and no partially
protonated ligand metal complexes such as MLH, ML2H wereobserved. The d������������������������������������2 complexes
are 10.78 ± 0.03 and 19.81 ± 0.07 respectively.
















Volume of IDA/cm3



Figure:1 Speciation diagram of complexation of thorium withiminodiacetic acid along with the fitted data of both calculated andobserved pH. ([Th] = 3*10-3 M, [H] = 0.0890 M and [IDA] = 0.2997 M,[H] = 0.2987 M, initial volume = 25 cm3, I = 1 M NaClO4, T = 298 K).
Table: 1 stability constants of thorium complexes with IDA ([Th] = 3*10-3
M, [H] = 0.0890 M and [IDA] = 0.2997 M, [H] = 0.2987 M, initial volume= 25 cm3, I = 1 M NaClO4, T = 298 K)
S.No.
Reaction
�����
2
Th
+ IDA
������������������
10.78± 0.033Th+ 2 IDA�����������������2]
19.81± 0.07

Reference





－ 159 －

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0OTENTIOMETRYv .5#!2  'OVT -ODEL 3CIENCE #OLLEGE
! 2 $ 5NIVERSITY *ABALPUR - 0 &EBRUARY  APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201325-ACP-03

Time-resolved laser fluorescence spectroscopy combined with parallel factor
analysis: a robust speciation technique for UO22+
Takumi Saito1, Noboru Aoyagi2, Takaumi Kimura2

1

Nuclear Professional School, School of Engineering, The University of Tokyo
2
Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

Speciation is a key issue for the fate of actinides and fission
products in natural environments. Time-resolved laser
fluorescence spectroscopy (TRLFS) is a popular speciation
technique for fluorescent metal ions and can be further extended
by combining multivariate data reduction methods such asparallel factor analysis (PARAFAC). This study demonstrates theapplicability of TRLFS combined with PARAFAC for the
speciation of UO22+ in solution as well as on mineral surface.
Uranium, time-resolved laser spectroscopy,
speciation, adsorption, complexation

I.

PARAFAC,INTRODUCTION

Chemical speciation governs the reactivity andmigration of radionuclides released from nuclear waste
disposal or an accident of a nuclear power plant inenvironments. Various analytical techniques are used forthis purpose. Preferably, such speciation techniques shallpossess all of the following capabilities: (i) discriminationof species by their different chemical and/or physicalproperties, (ii) quantification, and (iiii) structural
determination of the species. Time-resolved laser
fluorescence spectroscopy (TRLFS) is a particularspeciation technique for fluorescent actinide ions such as
UO22+ and Cm3+. The above three characteristics are wellbalanced in TRLFS; the discrimination and quantificationof species can be achieved, based on their
excitation/emission spectra and decay lifetimes; theconcentrations of the species are proportional to theirfluorescence intensities. The favorable characteristics of
TRLFS as a speciation technique largely rely on theinherent multi-dimensional nature of its data, which makes
the combination of multivariate statistics method suitable
for the data reduction. Parallel factor analysis (PARAFAC)
is a multi-model factor analytic method, which can only beapplied for data having more than three dimensions. It has
been shown that combining TLRFS with PARAFAC
provides robust speciation capability for the speciation of
Eu3+, a chemical homologues of the trivalent actinide ions[1-3]. In this study, the applicability of TRLFS-PARAFAC
for the speciation of UO22+ is firstly demonstrated.
II. EXPERIMENTAL

different concentrations of UO22+. The entire data set ineach series was processed by PARAFAC, using the N-way
toolbox for MATLAB®[4].
III.

RESULTS AND DISCUSSION

Three species were found for the complexation of UO22+
with H2SiO4 at pH 4, exhibiting the characteristic
fluorescence spectra (Figure 1) and decay curves. The
fluorescence intensity profiles, which approximated theconcentration profiles of the species as a function of the
H2SiO4 concentration, were used to determine the stability
constants of the complexation.
Three surface species of UO22+ on gibbsite wereobtained from the TRLFS data set by applying PARAFAC.
Based on the fluorescence spectra, decay lifetimes, and thedependence of the intensity profiles on pH and the UO22+
concentration, these species likely corresponded to mononuclear surface complexes with and without hydrolysis anda multi-nuclear surface complex.
IV.

CONCLUSION

It was shown that the combination of TRLFS with
PARAFAC was capable of discriminating the contributionof multiple species of UO22+. The obtained spectra, decay
curves, and intensity profiles were invaluable to understandand model the underlying speciation both in solution andon mineral surface.

Figure 1. Fluorescence spectra of the three UO22+ species with H4SiO4obtained from a series of TRLFS spectra by PARARAC.

A set of the time-resolved fluorescence spectra of UO22+
complexed with orthosilicate (H2SiO4) or adsorbed on�����������-Al(OH)3) surface were obtained with a TRLFS
system equipped with the forth harmonics of Nd:YAG laser.
The complexation of UO22+ with H2SiO4 was studied as afunction of the H2SiO4 concentration at different pH; theadsorption of UO22+ on gibbsite as a function of pH at the

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

－ 160 －

Saito, T., et al., Environ. Sci. Technol. 2010, 44, 5055–5060.
Ishida, K. et al., J. Colloid Interface Sci. 2012, 374, 258–266.
Lukman, S., et al., Geochim. Cosmochim. Acta 2012, 88, 199–215.
Andersson, C. and Bro, R., Chemometr. Intell. Lab. 2000, 52, 1–4.

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

Determination of 55Fe and 89,90Sr in liquid samples using Sr and/or Pb resins for themutual separation of Fe and Sr
Marijana Nodilo, ���������������, Željko Grahek
Division for marine and environmental research, Rudjer Bo��������������������������������Croatia
Abstract. The determination of 55Fe and strontium isotopes iscomplicated and time-consuming, especially the determination of
89,90
Sr. In the last decade, a number of methods have been developed
for radioactive strontium isolation and determination in various
types of samples. On the other hand, only few methods for 55Fe
determination are developed, mainly in liquid radioactive waste
samples. Since strontium isotopes are highly radiotoxic fission
products (especially 90Sr with long half-life), they are an interesting
subject for various investigations, from their distribution andbehavior in natural systems to the influences on the human health. In
distinction from strontium isotopes, 55Fe is an activation product,
low energetic emitter with approximately 2.74 year half-life. As
such, it is not as interesting as strontium, but environmental
concerns prompted the responsible institutions in the radiologicalmonitoring program to include 55Fe determinations in theirprocedures. In almost all published methods, isolation anddetermination of 89,90Sr and 55Fe are separated. Therefore, the aim of
the paper is to present a method for the isolation of 55Fe and 89,90Srfrom liquid sample in one step by using Sr and/or Pb resin andmixture of nitric and hydrochloric acid, because Fe and Sr can bebound on Sr resin from mixture of HNO3+HCl as shown earlier.1
Namely, Sr and Pb resins were primarily developed as Sr, Pb
specific resins which enable very efficient separation of Sr and Pb
from other elements as well as for their mutual separation. The main
focus in the literature was directed on their application in thedetermination of 89,90Sr and 210Pb in different kinds of samples,2,3
while determination of 55Fe was not in focus from above mentioned
reason. Therefore, it will be shown how Fe and Sr can be bound andmutually separated (and from many other elements) on Sr and Pb
resin column. It will be shown that binding strength and selectivity
on both resins depend on concentration of HCl and HNO3. Bychanging the eluent composition, separation of Fe from Sr, as well
as Pb from Fe and Sr ions, can be achieved on both resins. Based onthese results, methodology for rapid determination which involves,binding of Fe and Sr on the column from the mixture of HNO3+HCl,elution of Sr with HCl, Fe with H2O and detection on LSC is created.
It will be shown that 55Fe and 89,90Sr can be easily separated on bothresins from different types of samples with almost same efficiency.
Methodology is tested by determination of 55Fe and 89,90Sr in
proficiency testing samples and radioactive waste samples andobtained results will be presented and discussed in detail.

Table 1. Distribution coefficients of elements on Pb resin
Kd [mLg-1]

Pb

resin

Sr

Mn

Fe

Ni

Pb

-

-

-

-

322
218

4 M HCl
6 M HCl
6 M HCl + 1 M HNO3

58,91

-

220
442
796

-

68,7
8,94
3,54

6 M HCl + 3 M HNO3

101,12

-

210

-

-

6 M HCl + 5 M HNO3

105,66

-

102,5

-

-

5 M HNO3

108,42

-

-

-

>399

0,5 M HCl
2 M HCl

Figure 1. Distribution coefficients of elements in mixture of 6M HCl and
HNO3 on Sr resin

Keywords: Sr and Pb resin, Iron-55, Strontium-89, 90, separation

Figure 2. Separation of Sr and Fe from other elements on Pb resin column[1][2]－ 161 －

��� �������� ��� ����������� ��� �������� ��� ���������� �����������
separation of Fe and Sr from liquid samples by using Sr resin and rapid
determination of 55Fe and 89,90Sr. Appl. Radiat. Isot. In press
Horwitz E.P., Dietz M, Chiarzia R, Novel Strontium-Selective
Extraction Chromatographic Resin. Solvent Extraction & Ion Exchange,
10 (1992) 313-336.

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

Implementation of Dry Cow Dung Powder for Biosorption of 90Sr(II) from SimulatedRadioactive Waste
Roshan P. Khilnani, Hemlata K. Bagla
Department of Nuclear and Radiochemistry, K. C. College, Mumbai – 20, India.
Abstract – 90Sr is one of the major fission product found in the radioactive waste. The anthropogenic activities such as nuclear weapon
testing, reprocessing of liquid spent fuel etc. are major sources of 90Sr in our environment. Some of the well-established processes such as
chemical precipitation, membrane process, liquid extraction and ion exchange have been applied as a tool for the removal of this metal ion.
All the above methods are not considered to be greener due to some of their shortcomings such as incomplete metal ion removal, highrequirement of energy and reagents, generation of toxic sludge or other waste materials which in turn require further treatments for theircautious disposal. The present investigation entails the biosorption studies of 90Sr(II) from simulated radioactive waste employing dry cow
dung powder (DCP) as an indigenous, inexpensive and, eco-friendly material without any pre or post treatments. As DCP is easily available,
it is superior to other processed natural adsorbent considering their cost, time and energy efficiency. The Batch experiments were conductedemploying 90Sr as a radiotracer and the effect of process parameters such as pH, temperature, amount of resin, time of equilibration,
agitation speed and distribution co-efficient have been studied for simulated reactor and reprocessing waste with and without carrier. The
efficiency of adsorption was found to be more than 70%. The prime amenity of using DCP over other biosorbents is that it doesnot require
any degree of physical and chemical enhacement for optimization of the method and inturn adds to the economy of entire adsorption process.
Thus use of DCP manifests the principles of Green Chemistry and proves to be an eco-friendly alternative for the remediation of radiotoxic
90
Sr(II).
Keywords – Biosorption, Strontium, Dry cow dung powder, Simulated radioactive waste－ 162 －

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

Application of Simplified Desorption Method to Sorption Study: (1) Sorption ofAmericium (III) on Bentonite and Its Major Components
1

Naofumi Kozai1, Toshihiko Ohnuki1
Japan Atomic Energy Agency, Tokai, Ibaraki, 319-1195 Japan

Abstract – To elucidate the sorption behavior of americium on
bentonite, which is a mixture of montmorillonite clay, quartz and soon, simplified desorption experiments were applied to the solid
phases collected after the sorption experiments. Almost 100% of
Am was sorbed on bentonite and montmorillonite at pH from 2 to 8.
A fraction of the Am sorbed on the solid phases was desorbed bytwice treatment with a 1M KCl aqueous solution, and the residual
Am was completely desorbed by twice treatment with a 1M HClaqueous solution. The desorption behaviors of Am from bentonite
and montmorillonite were very similar to each other andsymmetrical at pH 7. Most of the Am sorbed below pH 7 wasdesorbed with 1M KCl solutions and that above pH 7 was notdesorbed with 1M KCl but with 1M HCl solutions. The trend in the
KCl-desorbable fraction vs. pH is very similar to the abundance
ratio of cationic Am species (Am3+) and so is the trend in the KClnondesorbable fraction to that of the hydrolyzed species of Am.
Keywords – Americium, sorption, desorption, pH, montmorillonite,bentonite, quartzI.

product from this bentonite. An Am (III) nitrate stock
solution was diluted with 0.01 M NaClO4 to yield a working-10
solution having an Am concentration of about 5x10 M.
For the sorption experiments, the initial pH of the Am
solution was adjusted over a range of 1.8 to 10. A weighed3
amount (0.06 g) of sold phases was soaked in 6 cm aliquotsoof the Am solution and stored at 20 C. This solid-solution
mixture was agitated once a day. After 10 days, asupernatant was collected by centrifugation.
Desorption experiments were conducted in two steps.
3
First, 6 cm of 1 M KCl solution was added to the solid
phases collected after the sorption experiments. After 2 days,
the KCl solution was separated by centrifugation. Second,
desorption with a 1 M HCl solution was undertaken in thesame way as the desorption with a 1 M KCl solution. The
desorption with each solution was carried out twice toconfirm complete desorption of Am.
III. RESULTS AND DISCUSSIONINTRODUCTION

Sorption is one of the key mechanisms to control thesubsurface environmental behavior of the radionuclides. It is
known that sorption behavior of elements on solid phases
may vary depending on the concentration of the element [1].
Thus, for the environmental study, it is desirable to examine
sorption behaviors at tracer concentrations (nanomolar orless). To date it is however impossible to apply any
instrument analysis except radiation measurements to theanalysis of the tracer level radionuclides on solid phases.
To analyze the tracer level neptunium sorbed on clays, a
simplified desorption method sequentially using two kinds ofdesorption agent solutions was effective [2]. This paper
applies the desorption method to the sorption study of Am on
bentonite and discuss the sorption and Am species. Bentonite
is a clay found ubiquitously in soil environment. Its main
component is montmorillonite, and minor components arecalcite, dolomite, quartz, pyrite, cristobalite, zeolite, etc.
Owing to high cation exchange capacity of montmorillonite,bentonite clay plays a very important role for migration ofradionuclides in the subsurface environment.
II. EXPERIMENTAL
Tsukinuno montmorillonite (Kunipia F®, Kunimine
Industries Co. Ltd.) was used after the montmorillonite was+converted to homoionic Na forms (Na-montmorillonite).
Tsukinuno bentonite (Kunigel V1®, Kunimine Industries Co.
Ltd.) was used with no pretreatment. Kunipia F is a purified

In the examined final pH range (2 – 8), almost 100% of
Am was sorbed on bentonite and montmorillonite. All of the
Am sorbed on bentonite and montmorillonite were desorbedby the two step desorption procedures. The desorption
behaviors of Am from bentonite and montmorillonite werevery similar to each other. Most of the Am sorbed below pH
5 was desorbed by the twice treatment with 1M KCl solutions.
The KCl-desorbable fraction of Am sharply decreased withincreasing pH above pH 5 and most of the Am sorbed above
pH 7 was not desorbed with 1M KCl solution but with 1M
HCl solution. The trend in the KCl-desorbable fraction vs. pH
is very similar to the abundance ratio of cationic Am species(Am3+) and so is the trend in the KCl-undesorbable fraction
to that of the hydrolyzed species of Am. It is intuitively
understand that the Am desorbable from the bentonite with
KCl solution is the Am sorbed on the montmorillonite
fraction in the bentonite.
This paper further discuss the sorption behavior of Am on
bentonite with the result of blank experiments to examine thesorption on the reaction vessels and with that of sorption anddesorption experiments on quartz, which is the second major
mineral in the bentonite.
[1][2]－ 163 －

Ohnuki T et al., J. Nucl. Sci. Technol., in press.
Kozai N et al., Radiochimica Acta, 75, 149-158 (1996).

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

Effect of aging on availability of iodine in grassland soil collected in Rokkasho, Japan
Akira Takeda, Hirofumi Tsukada, Yuichi Takaku, Shun’ichi Hisamatsu
Department of Radioecology, Institute for Environmental Sciences
Abstract – In the laboratory, we investigated the time-dependentchanges in the availability of I in soil over the course of 23 months.
Stable I was added as iodide or iodate to a soil sample collectedfrom a grassland area in Rokkasho, Japan. Whether I was added as
iodide or iodate, its water solubility, and soil-to-grass transfer
factor decreased drastically over the course of 4 months after
addition and then slightly decreased thereafter.
Keywords – iodate, iodide, radioiodine, soil-to-plant transfer

I.

INTRODUCTION

The first commercial nuclear fuel reprocessing facility inJapan, located in Rokkasho, Aomori Prefecture, isundergoing its final testing using actual spent nuclear fuel.
Iodine-129 (half-life, 1.6 × 107 y) is discharged from thefacility, and the radiation dose to the public resulting fromdischarge of this radionuclide must be assessed. Some of the129
I discharged to the atmosphere is deposited on the land
surface and retained in surface soil. The mobility of I in soil
is expected to decrease with time after its deposition, andinvestigation of the time-dependent changes in I mobility insoil is necessary for the better prediction of long-term I
behavior in the surface soil environment. We conducted alaboratory study of the changes in the water solubility andphytoavailability of trace I added to soil collected from
Rokkasho.
II. MATERIALS AND METHODS
A soil sample was collected from the surface of a pasture
field in Rokkasho, Japan. Aliquots (200 g) of the dried soil
sample were placed in plastic pots, and a solution of NaI or
NaIO3 was added to the soil in each pot at a concentration of
20 mg-I kg-1-soil. The pots were stored in an artificial climate
chamber for about 23 months. The water content of the soil
was adjusted to 60% of its maximum water-holding capacity
every 2 weeks. The soil in the pots was stirred every 4 weeks.
As controls, pots of soil without added I were treated thesame way.
Soil samples were collected from the pots at 0, 2, 9, 29, 64,
113, 204, 372, and 687 d after addition of the I solution. The
soil samples were extracted with deionized water, at a 1:10
w/v ratio of soil to water, for 1 h at 20°C. The supernatants
were separated from the soil by means of high-speed
centrifugation and then filtered through a 0.22-��-pore
membrane filter.
Orchardgrass (Dactylis glomerata) was cultivated in thepots 2–29 d, 37–64 d, 86–113 d, 117–204 d, 345–372 d, and
660–687 d after the addition of I. The cultivation experiments

were carried out in triplicate for each time period. Twenty
germinated seeds were sown in each pot. The water content
of the soil was adjusted with deionized water to 60% of
maximum water-holding capacity of the soil three times aweek during the cultivation period. The aboveground parts ofthe plants were sampled at 28 d after sowing. The plant
samples were freeze-dried and finely ground. Iodine in theplant samples was extracted with tetramethyl ammoniumhydroxide at 60ºC overnight. The concentrations of I in thesoil and plant extracts were determined by inductively
coupled plasma mass spectrometry. Concentrations of added I
in the soil extract and plant were calculated by subtracting the
I concentrations in the control samples, to which I had notbeen added.
III. RESULTS AND DISCUSSION
The water-solubility of I in the soil decreased with timeafter its addition. Soon after addition, 98% of the I added as
iodide and 54% of the I added as iodate were extracted withwater. In contrast, the extraction yield of the added I at 113 dafter addition was 2%, and no difference was observed
between the chemical forms of the added I. The extraction
yield of the added I was nearly constant thereafter, and was
1.5% at 687 d after the addition.
The concentration of added I in the orchardgrass plants
was relatively lower in the later stage compared to soon after
addition of I to the soil. The soil-to-plant transfer factor,
which is defined as (concentration of added I in theaboveground part of the plant)/(concentration of added I in
the soil) (mg kg-1 dry plant)/(mg kg-1 dry soil), decreased withtime after the addition: from 0.80 to 0.042 for the soil withadded iodide, and 1.3 to 0.041 for the soil with added iodate
over the course of the experiment (Fig. 1). The decreasing
trend was similar to that for the water extractability from thesoil.

Fig. 1 Time-dependence of soil-to-plant transfer factor of I after its addition
to the soil. Error bars indicate standard deviations (n = 3). Orchardgrass wascultivated for 28 d in each pot experiment. The plotted transfer factors arevalues for the end of each cultivation period.
This study was performed under a contract with the government of Aomori
Prefecture, Japan.

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

23-ENP-05

Study on 14C spatial distribution around Qinshan nuclear power plant in China
1

2

Zhongtang Wang1, Dan Hu2, Qiuju Guo1

State Key Laboratory of Nuclear Physics and Technology, Peking University Beijing 100871,China.
Radiation Monitoring Technical Center of Ministry of Environmental Protection, Hangzhou 310012, China

Abstract –To understand the spatial distribution of 14C discharged
by Qinshan nuclear power plant (NPP), where two heavy water
reactors (Plant III) are on commercial operation, bothexperimental investigation and model prediction (Gaussian plumemodel) were carried out by this work. Twenty one moss samples
were collected in five different wind directions near Qinshan NPP,
and analyzed by accelerator mass spectrometry (AMS). The 14C
specific activities in moss samples ranged from 265.6 to 233.0
Bq/kg C (the background is 233.8 ±1.1 Bq/kg C), decreasing withincreased distance from the stacks of Plant III. Simulation of 14C
spatial distribution in air was calculated by using a Gaussian
plume model, which was based on monthly meteorological data,
14
C discharge record, local dispersion parameter and otherparameters. A good fit was found between the predicted andmeasured values, indicating that the spatial distribution of 14C
follows a Gaussian model. It can be concluded furthermore, thatthe influence of the Hill Qinshan (located at W of Plant III, 170
meters high) on 14C’s distribution is quite limited at this site compared to meteorological influences.
Key words: Qinshan NPP; 14C; Gaussian plume model－ 165 －

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

Atmospheric deposition of radionuclides (7Be, 210Pb, 134Cs, 137Cs, and 40K) during
2000–2012 at Rokkasho, Japan, and impact of the Fukushima Dai-ichi Nuclear
Power Plant accident
Naofumi Akata1, Hidenao Hasegawa1, Hitoshi Kawabata1, Hideki Kakiuchi1, Yuki Chikuchi2
Nagayoshi Shima3, Toshitaka Suzuki4, Shun’ichi Hisamatsu1
Institute for Environmental Sciences
2
Aomori JGC PLANTECH
3
Fukushima University
4
Yamagata University

Keywords – atmospheric deposition, Rokkasho Village, Fukushima
Dai-ichi Nuclear Power Plant accident

I.

INTRODUCTION

Natural and anthropogenic radionuclides are useful tracers
for studying processes in the atmospheric environment.
Atmospheric deposition of radionuclides has been measured
at many sites for geochemical studies and radiation protection.
We have been measuring atmospheric deposition ofradionuclides in the village of Rokkasho, Aomori Prefecture,
Japan, since 2000 [1, 2]. In this study, we report the impact of
the accident at the Fukushima Dai-ichi Nuclear Power Plant(FDNPP) on the atmospheric deposition of radiocesium(134Cs and 137Cs) in Rokkasho.
II. EXPERIMENTAL
Atmospheric deposition samples were collected on theroof of a building at the Institute for Environmental Sciencesin Rokkasho (40° 57� N, 141° 21� E), approximately 13 m
above ground level. Bulk atmospheric deposition samples
were collected biweekly in a polyethylene basin from March
2000 until March 2006, and samples were collected monthly
after April 2006. Each sample was passed through a Powdex
resin (Ecodyne Co., USA) column to separate ionicradioactive species and particulates from the sample. The
homogenized resin was dried and packed into a plastic casefor �-ray spectrometry. The concentrations of �-ray-emitting
radionuclides, including 7Be, 210Pb, 137Cs, and 40K, in thesample were measured with a low-energy photon
spectrometer with a Ge detector. After the accident at the
FDNPP, 134Cs concentrations were also measured.

III. RESULTS AND DISCUSSION
Annual deposition of 137Cs from 2001 to 2010 ranged from0.04 to 0.69 Bq m-2 with a mean value of 0.21 Bq m-2. We
have already reported that recent background 137Cs deposition
was affected by Asian dust [1]. On 11 March 2011, large
amounts of radiocesium were released into the atmospherefrom the accident at the FDNPP. After the accident, monthly
radiocesium deposition increased, reaching a maximum in
April 2011. Thereafter, monthly 137Cs deposition decreased
rapidly until September 2011 (apparent half-time ~0.8 month)and more gradually (half-time ~0.7 y) from September 2011
until December 2012. Annual deposition of 137Cs was 86.9
Bq m-2 in 2011 and 1.89 Bq m-2 in 2012. Monthly 137Cs
deposition has dropped almost to the pre-accident level,although 134Cs is still detectable.
#S AND #S DEPOSITION "Q M  MONTH 

Abstract – Radionuclides, including radiocesium (134Cs and 137Cs),
were measured in atmospheric deposition samples collected in
Rokkasho, Aomori, Japan, from 2000 to 2012. After the accident at
the Fukushima Dai-ichi Nuclear Power Plant, radiocesium
deposition rapidly increased and reached a maximum in April 2011.
Since then, monthly radiocesium deposition has gradually decreased.
Monthly 137Cs deposition has almost reached pre-accident levels,
although 134Cs is still being detected.

1%  #S
 #S

% 

% 

% 

% 

% 








9EAR







Fig. 1 Monthly atmospheric deposition of 137Cs and 134Cs in Rokkasho

REFERENCES
[1]

[2]

Akata, N., Hasegawa, H., Kawabata, H., Chikuchi, Y., Sato, T.,
Ohtsuka, Y., Kondo, K. and Hisamatsu, S. (2007) Deposition of 137Cs
in Rokkasho, Japan and its relation to Asian dust, Journal ofEnvironmental Radioactivity, 95, 1-9.
Akata, N., Kawabata, H., Hasegawa, H., Sato, T., Chikuchi, Y., Kondo,
K., Hisamatsu, S. and Inaba, J. (2008) Total deposition velocities andscavenging ratios of 7Be and 210Pb at Rokkasho, Japan, Journal ofRadioanalytical and Nuclear Chemistry, 277, 347-355.

This study was performed under a contract with the government of Aomori Prefecture, Japan.

－ 166 －

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

Effect of Aging on Water Extractability of Radioactive Iodine and Cesium from Soil
Hirofumi Tsukada, Akira Takeda, Shunichi Hisamatsu
Department of Radioecology, Institute for Environmental Sciences
Abstract – Water extractabilities of radioactive 125I and 137Cs fromsoil were determined by tracer experiments. Career free 125I (iodide
or iodate) or 137Cs was spiked to soil samples, which were thenstored in an artificial climate chamber where a wetting-and-drying
treatment was repeated. Extraction yield of 125I at 4 h after spiking
with iodide was higher than that with iodate, and then both yields
decreased with aging independent of the chemical forms. Chemical
form of 125I in the water extracts at 29 d was predominantly iodide,regardless of whether the spiked form was iodide or iodate. Water
extraction yield of 137Cs immediately decreased after spiking in thesoil, which was 0.015 at 4 h, and then less than 0.001 at 320 d after
spiking.
Keywords – radioactive
extractability, aging

I.

125

I, iodide, iodate,137

Cs, water

INTRODUCTION

Aging of radionuclides in soils after deposition can play animportant role in the change of the physicochemical form,
which is an important factor in determining the fate ofradionuclides in the environment. Radioactive iodine andcesium were the major radionuclides released from the
Fukushima Daiichi Nuclear Power Plants after the accident inMarch 2011. Water extractable forms in soil make up themost mobile fraction, which can migrate and be taken up by
plants. In the present study, water extractabilities ofradioactive 125I (iodide and iodate) and 137Cs were determinedat different elapsed time intervals.

min. Chemical forms of 125I in the water extracts were also
determined at 2 and 29 d after spiking by using an anion
exchange disk (3M, Empore Anion-SR®). Radioactivity ofthe extract and disk samples were measured with NaI(Tl)detectors.
III. RESULTS AND DISCUSSION
Water extraction yield of 125I at 4 h after spiking withiodide was 0.87, which was higher than that with iodate(0.33), and both yields after spiking decreased to 0.033-0.034
at 320 d independent of the spiking chemical forms (Fig. 1).
Content of 125IO3- in the water extract at 2 d after spiking withiodate was 28%, and that it decreased to 1% at 29 d. Iodine125 in the water extract at 2 and 29 d after spiking withiodide existed as 125I-. This suggests that the chemical form of125
I in the water extracts was predominantly iodide excluding
the time just after spiking, regardless of whether the spiking
form was iodide or iodate.
Water extraction yield of 137Cs in the soil immediately
decreased after spiking, from 0.015 at 4 h to 0.0075 at 30 d.
After that, the yield was gradually decreased from 0.0012 at
120 d to less than 0.001 at 320 d, and was 0.00050 at 1110 d
after spiking. It is well known that radioactive Cs is strongly
fixed in clays, and that its mobility is limited.
The results show that transferability of radioactive iodine
and cesium in soil immediately decreases in early stage after
deposition.

II. MATERIALS AND METHODS
Volcanic ash soil (Andosol), which is a typical upland soil
in Japan, was collected from the surface of a grassland in
Aomori Prefecture (40°52’23”N, 141°16’57”E). The soil wasdried at 50°C and passed through a 2 mm sieve. Career free125
I (iodide or iodate) or 137Cs of 10 kBq was spiked to 1 g ofsoil sample. Iodate solution was prepared by the oxidation ofiodide solution by adding bromine water. The samples werestored in an artificial climate chamber (17°C, 60% relative
humidity, 30 klx, 12 h of daylight), and wetting-and-drying
treatments were repeated by adding 1 ml of deionized water
every 2 weeks. The soil samples were extracted with
deionized water for 1 h at room temperature with a 1:10 ratioof soil weight to extract. The samples were extracted from 4 h
to 320 d after spiking for 125I, and 4 h to 1110 d for 137Cs. The
extracts were filtered through a 0.22 �m pore membrane filter(Millipore, Steriflip®) after centrifugation at 10,000 rpm for 5

Fig. 1 Time dependecy of water extractabilities of 125I (iodide and iodate)and 137Cs from soil. Error bars indicate one standard deviation (n=3).
This study was performed under a contract with the government of Aomori
Prefecture, Japan.

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

23-ENP-08"ACKGROUND INTERNAL DOSE RATES OF EARTHWORM AND ARTHROPOD SPECIES IN THE FORESTS
OF !OMORI *APAN
Yoshihito Ohtsuka, Yuichi Takaku, Shun’ichi Hisamatsu
Department of Radioecology, Institute for Environmental Sciences!BSTRACT – 7E MEASURED NATURALLY OCCURRING RADIONUCLIDES INSAMPLES FROM AN EARTHWORM SPECIES AND  ARTHROPOD SPECIESCOLLECTED IN CONIFEROUS FORESTS IN 2OKKASHO !OMORI *APAN TOASSESS BACKGROUND INTERNAL RADIATION DOSE RATES 4HE RATES WERECALCULATED FROM THE MEASURED CONCENTRATIONS OF THE RADIONUCLIDESAND DOSE COEFFICIENTS FROM THE LITERATURE 4HE MEAN INTERNAL DOSE
RATE OF COMPOSITE EARTHWORM SAMPLES WAS  P'Y H  WHEREASTHE MEAN DOSE RATES OF THE ARTHROPOD SAMPLES RANGED FROM  N'Y
H  TO  P'Y H  0OLONIUM  WAS THE RADIONUCLIDE WITH THE
HIGHEST CONTRIBUTION TO THE INTERNAL DOSE RATE FOR ALL THE SPECIESEXCEPT THE LONGHORN BEETLE+EYWORDS – NON HUMAN SPECIES BACKGROUND RADIATION NATURALLYOCCURRING RADIONUCLIDES FOREST ECOSYSTEMI.

INTRODUCTION

Protection of the environment from radiation andassessing effects of radiation on nonhuman species havebeen discussed by international organizations such as theInternational Commission on Radiological Protection [1].
Many researchers have reported concentrations of artificial
radionuclides in animals living in terrestrial environments
contaminated by the nuclear accidents at Chernobyl and
Fukushima [e.g., 2, 3]. However, few studies havecompared background radiation doses with artificial
radionuclide doses.
In this study, samples of an earthworm species and 11
arthropod species were collected in coniferous forests
around the nuclear fuel reprocessing plant currently underconstruction in Rokkasho, Aomori, Japan, and the internal
background dose rates of natural radionuclides were
determined.

concentration in the samples of all the arthropods, except
for a millipede and a Japanese ground beetle. The mean210
Po concentration in the earthworm samples was 0.10 Bq
g-1-wet, and the mean 210Po concentrations in thearthropods varied widely, from 0.0042 Bq g-1-wet in a
longhorn beetle to 0.24 Bq g-1-wet in a millipede.
The internal dose rates were calculated by using themeasured concentrations of 210Pb, 210Po, 232Th, 238U, and40
K, and the dose coefficients for the earthworm and thewoodlouse reported by the Framework for Assessment ofEnvironmental Impact [4]; the dose coefficients for the
woodlouse were applied to all the arthropods. The meaninternal dose rate for the earthworm was calculated to be
0.35 PGy h-1, approximately 90% of which was due to210
Po. The dose rates for the arthropods ranged from 36
nGy h-1 to 0.79 PGy h-1, with the actual value depending
mainly on the 210Po concentration. The contribution of210
Po to the dose rate of the arthropods varied from 36% to95%.

II. MATERIALS AND METHODSOne species of earthworm and 11 species of arthropods
were collected monthly in coniferous forests in Rokkasho
from June to October 2008; the animals were collected withfalling traps buried in the ground in four areas (Fig. 1).
After being washed with pure water, the animals were
freeze-dried. For each animal species, a composite sample
was prepared from the dried animals for each sampling siteand each collection month. The composite samples wereanalyzed for 210Po, 210Pb, 238U, 232Th, 40K, and 87Rb by J-ray
and D-ray spectrometry, and ICP-AES and ICP-MS.

Fig. 1 Sampling areas for earthworms and arthropods,
along with the distribution of coniferous forests in
Rokkasho, Aomori, Japan.
This study was performed under a contact with thegovernment of Aomori Prefecture, Japan.
REFERENCES[1]

III. RESULTS AND DISCUSSION
Polonium-210 was the natural radionuclide with thehighest concentration in the earthworm samples, whereas
40
K was the radionuclide present at the highest

[2]
[3]
[4]

－ 168 －

International Commission on Radiological Protection (2007) The
2007 recommendation of the Internal Commission on RadiologicalProtection, Publication 103.
J. W. Mietelski et al. J. Radioanal. Nucl. Chem., 262, (2005) 645.
T. Fukuda et al., PLOS ONE, 8, (2013) e54312.
Framework for Assessment of Environmental Impact (2003) The EC
5th Framework programme, Contact FIGE-CT-2000-00102.

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

An EXAFS Study on the Effect of Natural Organic Matter and Mineralogy
Composition on Cesium Mobility in Environment
Qiaohui FAN, Masato TANAKA and Yoshio TAKAHASHI
Department of Earth and Planetary Systems Science, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama,
Higashi-Hiroshima, Hiroshima 739-8526, Japan(Corresponding mail: fanqiaohui@gmail.com)
Abstract: The sorption of Cs was clearly inhibited in the ternary
clay+HA+Cs system (the addition sequence of reagent) with respect
to the blocking to the access of frayed edge sites (FESs) andinterlayer sites by HA for both illite and vermiculite. Both innersphere complexes (ISCs) and outer-sphere complexes (OSCs) of Cs+
have attribution to its adsorption on illite (non-expansion). However,on vermiculite (intermediate expansion), the partially dehydrated
Cs+ was liable to be present as ISCs associated with the siloxanegroup of the ditrigonal cavity in the SiO4 sheet. However, nearlycomplete OSCs were observed at the planar sites of montmorillonite(high expansion).
Keywords: Cesium, EXAFS, Clay mineral, Mobility, Naturalorganic matter

Introduction
There is a consensus that radiocesium (RCs) strongly andselectively interacts with the phyllosilicate fraction of soil,
sediment, and suspended particles such as illite, vermiculite,
and montmorillonite. Natural organic matters (NOMs)
normally play various important roles in the environment
because of its correlations with soil properties and Cs
bioavailability. Herein, the speciation of Cs on clay minerals
in presence of humic acid (HA) were investigated by batch
experiment, modified sequential extraction [1] and Cs LIIIedge EXAFS approaches.
Experimental
IMt-1 illite (Cambrian shale, Silver Hill, Montana) andSWy-2 montmorillonite (Mont) from the University ofMissouri were purchased from The Clay Minerals Society.
Vermiculite (Verm) from Kent, Connecticut was supplied by
Ward's Natural Science Establishment, Rochester, NY, USA.
Cs LIII-edge extended X-ray absorption fine structure(EXAFS) spectra were collected at BL-12C and BL-9A
stations at KEK Photon Factory (Tsukuba, Japan). EXAFS
analysis was performed using REX 2000 (Rigaku Co. Ltd)and FEFF 7.0 [2].
Results and Discussion
Cesium sorption on vermiculite increased significantly
over the pH range of 3.0 to 7.0, whereas weak pH
dependence was observed for Cs sorption on illite. The pH
dependence can be ascribed to the competitive sorption with
proton, wherein the available exchange site for Cs increases

with pH increasing. In Verm+HA+Cs system, Cs sorption isclearly depressed, but this inhibition becomes weaker withincreasing pH. A similar phenomenon could also be found in
the illite+HA+Cs system.
EXAFS analysis demonstrated that Cs speciation strongly
depends on mineralogy and NOMs. The increase in pH from
3.0 to 7.0 increases ISCs from 42% to 80% for illite.
However, in vermiculite system, ISCs mostly dominate Cs
fixation and weakly depend on pH. Vermiculite with a 1.4 nm
layer distance is enough to the entrance of Cs+ and to form
the ISCs associated with the siloxane groups of ditrigonalcavities even at low pH. XRD patterns showed that thecharacteristic peak of vermiculite (6.1o) shifted to a large
angle after Cs adsorption at low Cs concentration even in thepresence of HA and disappears at high Cs concentration. The
dehydrated Cs+ replacement of Mg2+ or K+ causes the partial
collapse of vermiculite layers at low Cs coverage andcomplete collapse at high Cs coverage, which is a more stablestate to Cs [2]. However, no such change was observed in theillite systems. The negative charge of montmorillonite with a
2.0 nm layer distance (high expansibility) is mainly derived
from the isomorphic substitution of Mg2+ for Al3+ in theoctahedral AlO6 sheet, which drives hydrated Cs+ to form
OSCs in the interlayer sites.
EXAFS analysis indicates that HA molecules could
efficiently block the accesses to FESs and interlayer even at
relative large layer distance such as vermiculite (1.4 nm) to
reduce Cs sorption to a large extent. Obviously, the OSCs
proportion increase in the illite+HA+Cs system, because thecoated HA molecules make Cs form OSCs throughelectrostatic attractive force, which was also consistent withthe sequential extraction results.
Conclusion
The strong retard Cs in soil or sediment could attribute to
the ISCs related to the FESs and interlayer of illitic clay
minerals. However, the presence of NOMs could provoke Cs
mobility largely by the indirect effect, i.e., the blocking effect.
Reference
[1]
[2]
[3]

－ 169 －

Rigol A., Roig M., Vidal M. and Rauret G. Environ. Sci. Technol. 33(1999) 887-895.
Zabinsky S. I., Rehr J. J. and Ankudinov A. Phys. Rev. B 52 (1995)
2995-3009.
Kogure T., Morimoto K., Tamura K., Sato H. and Yamagishi A. Chem.
Lett. 41 (2012) 380-382.

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

Using Factorial Design to the Robustness Analysis of the Classic Sample Preparation
Method for 90Sr Determination in Tea Leaf
Chi-Chang Liu1*, Wen-Hsien Tsai1, Ming-Chi Horng1, Ching-Chung Huang1, Yuh-Wern Wu2
1

2

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

Abstract
The classic sample pretreatment method for 90Sr determination based on a series of precipitations including the separation of Sr from Ca byfuming nitric acid is the standard and popular method around world. To select a best set of operational conditions for such an analyticalmethod with numerous of experimental steps is a difficult task. Even when the optimum values of these factors are found, practically it isdifficult in accurately controlling them and sometimes leads to wide variations of results. Procedures for optimization of factors bymultivariate techniques have been encouraged, as they are faster, more economical and effective, and allow more than one variable to be
optimized simultaneously for sample preparation. However, the application of these techniques for the robustness analysis in the method forradiochemical analysis has been limited. In this study, a robustness test was performed to provide a better insight into which critical process
affect 90Sr determination in the sample preparation method. To assess method robustness, the empirical optimum procedures set for thismethod have been test by slightly modified and were evaluated using the factorial design approach at two levels. The evaluated sensitivity ofparameters includes pHs in precipitation procedures, concentration of fuming nitric acid, and times for reactions. The result allows us toanalyze the influence of significant factors upon the 90Sr radioactivity and the recovery of carrier and to establish intervals that ensure therobustness of our method.
Keywords 90Sr, robustness, factorial design, fuming nitric acid method

[1]
[2]

Y. Vander Heyden, A. Nijhuis, J. Smeyers-Verbeke, B. G. M. Vandeginste, and D. L. Massart, “Guidance for robustness/ruggedness tests in method
validation,” Journal of Pharmaceutical and Biomedical Analysis, vol. 24, no. 5-6, pp. 723–753, 2001.
D.G. Montgomery, Design and Analysis of Experiments, 7th Edition, John Wiley and Sons, New York, 2009.

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

23-ENP-11

A simple method for dehydrogenase assay of soil microorganisms to evaluate thebiospheric behavior of C-14 originated in transuranic waste
Kayoko Iwata, Nobuyoshi Ishii, Keiko Tagami, Shigeo Uchida
Office of Biospheric Assessment for Waste Disposal, National Institute of Radiological Sciences
Abstract – When carbon-14 (14C) that originated in transuranic(TRU) waste reaches the ground surface in low molecular weightorganic forms, it is reported that soil microbial activity has
influence on 14CO2 gas production. This study aims to develop a
simple method to determine soil microbial respiratory activity,
which results can be applied to evaluate their correlations with
14
C gasification ratios. Respiratory activity was measured using
2-(p-iodophenyl)-3-(p-nitrophenyl)-5-phenyltetraxolium chloride(INT). Agricultural soil samples were incubated at a solid: liquidratio of 1 to 10, often used in the gasification ratio experiments.
Primarily, INT incubation time, INT-formazan extraction method,and storage time for the extracted INT-formazan were examined.
Keywords – C-14, Soil microbial activity, CO2 production

I.

INTRODUCTION

Carbon-14 (14C) is one of the important radionuclides intransuranic (TRU) waste, which are concerns to humandose assessment due to its relatively long half-life (5730 y)and potential for migration to the biosphere. It was reported
that 14C released from TRU waste is partially released as
low molecular weight organic forms, such as acetic acid,formic acid, and methanol. These forms have low
adsorption properties and are expected to pass throughbarrier materials. However, there is little information
available on the fate of organic 14C after reaching the
ground surface. Although it has been showed that soil
microbial activity influences CO2 gas production [1], few
studies have been conducted to estimate the gasification
ratio using soil microbial activity as an indicator.
Understanding the relationship between soil microbialactivity and CO2 gas production may enable to estimate
gasification ratio of 14C in different soil in the future.
Since CO2 gas production is influenced by microbial
decomposition of organic 14C, microbial respiratory activity
is involved. However, the microbial respiratory activity
determination method corresponding to the 14CO2 gas
production study has not been developed yet. Therefore,
this study was conducted to develop a suitable and easily
replicable method to determine soil microbial respiratory
activities, which results can be applied to evaluate thecorrelation with 14C gasification ratio. For the microbialactivity determination, electron transport system (ETS) was
measured by dehydrogenase assay using the redox dye 2(p-iodophenyl)-3-(p-nitrophenyl)-5-phenyltetraxolium
chloride (INT) as the substrate, which is reduced to INTformazan by the dehydrogenase enzyme. In the method
development, primarily three points were examined—INT
incubation time, extraction method, and storage time for the
extracted INT-formazan.

II. MATERIALS AND METHODSAgricultural soil samples that were air-dried and sieved
through a 2-mm mesh were incubated beforehand at asolid: liquid ratio of 1 to 10 (0.5 g to 5 mL), which iscommonly used in the experiments to determine 14CO2
gasification ratio, so as to share the method [2]. After the
incubation, 4mL of supernatant was discarded, and INTaqueous solution (0.05%) was added to the sample. INT
incubation time was evaluated up to four hours bycomparing the amount of extracted INT-formazan detectedwith a spectrophotometer at 480 nm. INT-formazan
extraction methods using methanol as the extractant werealso evaluated, regarding the volume of methanol andextracting time. Storage time of extracted INT-formazan
before absorbance reading was assessed by keeping
samples in the dark at 4� or room temperature (approx.
20�).
III. RESULTS AND DISCUSSION
Based on the experiments, three hours was chosen for
INT incubation time because resultant INT-formazan
increased over time for the first three hours and then started
to be stabilized. As regards INT-formazan extracting
method, our experiment showed that mixing samples with
8mL of methanol vigorously for one minute was sufficient.
Extracted INT-formazan was stable in both conditions atleast for 24 hours. Because our method considered themethod of gasification ratio experiments, it enables theevaluation of correlation between soil microbial activity
and gasification ratio.
This work was partially supported by the Agency for
Natural Resources and Energy, the Ministry of Economy,
Trade and Industry (METI), Japan.
REFERENCES[1][2]－ 171 －

Koga, K. The roles of soil microbes in the global environment. Netsu
Sokutei 34 (2): 77-86, 2007
Ishii, N., Koiso, H., Takeda, H., Uchida, S. Partitioning of 14C into
solid, liquid, and gas phases in various paddy soils in Japan. J. Nuc.
Sci. Technol. 47: 238-243, 2010

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

23-ENP-12

Effect of humic acid on the sorption of selenium (VI) on ferric oxide hydrate
N. Guo, Z. L. Niu, Y. L. Ye, R. Zhang, Z. J. Guo
School of nuclear science and technology, Lanzhou University, Lanzhou, China, 730000
Abstract – Selenium-79 (T1/2= 6.5×105 a) is one of thelong-lived fission products, which is chemically andradiologically toxic, and one of the main radionuclides of
special concerned in the disposal of high level nuclear
waste. In this paper we studied the effect of humic acid
(HA) on the sorption of selenium (VI) on ferric oxide
hydrate (HFO) via batch-type experiments. We researched
the effects of contact time, pH, ion strength, concentrationof Se (VI) and HA on the sorption of Se (VI) and found thatthe equilibrium time of the Se (VI) sorption on HFO wasaround 3 h, the sorption decreased with the increasing pH
and increased with the decreasing ion strength. The sorbed
amount decreased with equilibrium concentration inaqueous phase, and the sorption isotherms were fitted toLangmuir equation to figure out the max sorbed amountwhich was 3.82×10-4 mol/g. HA significantly suppressed
the sorption of Se (VI).
Keywords – selenium, sorption, ferric oxide hydrate, humic
acid



Kd(mL/g)None HA
25mg/LHA





















pH
Fig 1. Effect of HA on the sorption of Se (VI) on HFO: CSe = 1.5×10-4 mol/L, I = 0.1 mol/L (NaCl), T = 25±1 �－ 172 －

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

Uranyl ions Adsorption to Na-GMZ and Interactions with FA Adsorption:
experiments and modeling
Ye Yuanlv, Guo Zhijun*, Wu Wangsuo

Radiochemistry Laboratory, School of Nuclear Science and Technology, LanzhouUniversity, Lanzhou, 730000, China

Abstract –In this work, data for the interactions betwee fulvic acid(FA) with uranyl ions at the surface of Na-GMZ are presented. U
adsorption to Na-GMZ in the presence of FA can be well predictedwith the SCD model (surface and complex distribution). According
to the model calculations, the nature of the interactions between FA
and U at Na-GMZ surface is mainly surface complex.
Keywords –Uranyl ions, Na-GMZ, FA, Surface Complex Model56) SORPTION INTRODUCTION

In the enviromnent, an important factor of radionuclide
mobility is their interaction with mineral–water interfaces. To
predict radionuclide mobility, it is necessary to understandfundamental processes such as surface precipitation andsurface complexation. Studies of uranium sorption onto
mineral surfaces have great practical importance for risk
assessment.what’s more, in recent years it has been revealed
that many groundwaters in granitoidic environments contain
excessive amounts of dissolved U[1].In addition to the effects
for sorption, NOM may influence U(VI) distribution via
some other mechanisms. In addition, some studies also
postulated that U(VI) can form organic complexes with NOM
possibly via metal ion bridging The formation of organic
U(VI) complexes at the mineral surface or in the solution
may decrease or increase U(VI) solubility in groundwater[1-2].






















P(

Figure 1 Adsorption curves of U(VI) vs. pH on Na-GMZ , C[U(VI)]=1.003E-4 mol/ L,m/ V = 20 g/ L , T = 22±1 �, I =0.1 mol/ L (NaCl).


EXIST &!
EXIST &! MODELNO &!
NO &! MODEL

A. Uranyl ions Adsorption to Na-GMZ and Interactions with
FA Adsorption
Figures 1 and 2 show the two relatively gentle sorption edges
from pH 2 to 8. It is also seen that FA causes a relative
enhancement in the U(VI) sorption at pH<6. U adsorption to
Na-GMZ in the presence of adsorbed FA can be well
predicted with the SCD model (surface and complex
distribution) U adsorption to Na-GMZ in the presence ofadsorbed FA can be well predicted with the SCD model(surface and complex distribution).

!L/5/85/ 
!L/5/ /( MODELING
EXPERIMENT DATA56) SORPTION 

I.
























P(

Figure. 2 Adsorption curves of U(VI) vs. pH on Na-GMZ inthe absence and presence of FA, C[U(VI)] =1.012E-4 mol/ L,
C[FA] =10 mg/L, m/ V = 20 g/ L , T = 22±1 �, I =0.1 mol/
L (NaCl).
[1][2]* coresponding author:Guo Zhijun email:Guohij@lzu.edu.cn－ 173 －

Gustafsson, J.P., Dassman, E. and Backstrom, M. (2009) Towards a
consistent geochemical model for prediction of uranium(VI) removalfrom groundwater by ferrihydrite. Applied Geochemistry 24(3), 454462
Weng, L.P., Van Riemsdijk, W.H. and Hiemstra, T. (2008) Humic
Nanoparticles at the Oxide-Water Interface: Interactions with
Phosphate Ion Adsorption. Environmental Science & Technology
42(23), 8747-8752.

23-ENP-14
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Foliar uptake and translocation of stable cesium and iodine by radish
Hidenao Hasegawa1, Hirofumi Tsukada1, Hitoshi Kawabata1, Yuichi Takaku1, Shun’ichi Hisamatsu1
1

Institute for Environmental Sciences

Abstract – We studied foliar uptake of Cs and I by radish (Raphanus
sativus L. cv. Redchim) by applying droplets of a solution of Cs (asCsCl or CsNO3) or I (as NaI or NaIO3) on an upper leaf surface.
The uptake of Cs decreased with increasing CsNO3 concentration in
the applied solution. Approximately 80% of applied Cs wasabsorbed no matter what the initial concentration of the applied
solution. The uptake of I in either form was independent of theconcentration of the applied solution. Approximately 80% of appliedI- was absorbed, whereas 90% of IO3- remained on the surface.

(Fig. 1). When Cs was applied as a CsNO3 solution, the Cs
absorption ratio decreased with increasing Cs concentrationin the applied solution. In contrast, when Cs was applied as a
CsCl solution, the absorption ratio was nearly constant. There
was a clear difference in I absorption ratio between NaI and
NaIO3. This result suggests that the chemical form of I
strongly affected the absorption ratio of I.
CsCl

Keywords – foliar uptake, translocation, cesium, iodide, iodate

INTRODUCTION

Absorption ratio of Cs (%)

I.

CsNO3
CsNO3

100

Direct deposition of radioactive materials onto crops is an
important pathway for radiation dose assessment ofradionuclides released from nuclear facilities. Cesium andiodine radioisotopes are transferred into agricultural products
both by direct deposition from the atmosphere onto the plants
and by absorption from the soil via the roots. We havealready reported that foliar uptake of stable Cs is higher fromdroplets of a CsCl solution than from droplets of a CsNO3
solution. In this study, we investigated the concentration
dependence of the foliar uptake of Cs from a CsCl or CsNO3
solution applied as droplets onto the leaf surface of radish
plants (Raphanus sativus L. cv. Redchim). A similar
experiment was carried out with NaI and NaIO3 solutions.

80
60
40
20
0
0.0001 0.001 0.01

0.1

1

10

Cs concentration in applied solution (g L-1)

NaI

NaIO3
NaIO3

100
Absorption ratio of I (%)

II. MATERIALS AND METHODS
Details of radish plant cultivation and the method for
applying the solutions to leaf surfaces are described
elsewhere [1]. A solution of CsCl or CsNO3 at aconcentration of 0.001, 0.01, 0.1, or 1 g Cs L-1 was applied tothe upper surface of radish leaves (Raphanus sativus L. cv.
Redchim) 28 d after germination. A solution of NaI or NaIO3
at a concentration of 0.2, 0.5, or 1 g I L-1 was also applied in asimilar manner. The plants were harvested 4 d after theapplication of test solutions and were divided into leaves, root
tubers, and lateral roots. The leaves were washed with asolution containing detergent. The washing solution, leaves,and root tubers were analyzed for Cs and I by means of
inductively coupled plasma mass spectrometry.

80
60
40
20
0
0

0.2

0.4

0.6

0.8

1

1.2

I concentration in applied solution (g L-1)
Fig. 1 Absorption ratios of Cs and I into radish plants from upper leaf
surfaces

REFERENCES

III. RESULTS AND DISCUSSION
We determined the absorption ratios of Cs and I,
calculated as (amount of Cs or I detected in the inner leaf orroot tuber)/(applied amount of Cs or I), and we plotted theratios against the Cs or I concentration of the applied solution[1]

H. Hasegawa, H. Tsukada, H. Kawabata, Y. Chikuchi, Y. Takaku, S.
Hisamatsu, J. Environ. Radioact., 100 (2009) 54.

This study was performed under a contract with the government of Aomori
Prefecture, Japan.

－ 174 －

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

The rapid determination of radiostrontium from a large amount of seawater(within 72hrs) for an emergency situation
Hyuncheol Kim*, Kun-Ho Chung, Hyo-Kook Park, Jong-Myoung Lim, Mun-Ja Kang
Environmental Radioactivity Assessment Team, Korea Atomic Energy Research Institute989-111 Deadeok-daero, Yuseong-gu, Daejeon, 305-353, Korea

Abstract – This paper describes the results of the development of an
automated radionuclide separator from a large seawater sample. It
consists of two parts, which are a concentration part with a cationexchange resin (Dowex50Wx8, Sigma-Aldrich) and a purification
part with Sr resin (Eichrom Technology). The volume of raw
seawater sample was reduced by about 25% at the concentration
part, and radiostrontium was purified at the Sr-resin part. The
chemical yield ranged from 92% to 96%. This automated system cansimultaneously execute four samples. Using liquid scintillation
counting (LSC) and Cherenkov counting, the analysis of Sr-89/90
from seawater could be completed within 3 days.
Keywords – radiostrontium, seawater, automated system, rapid
determination

sample, which did not affect the Sr recovery by Sr resin. The
Sr recovery was quantitative for Ca levels of up to 320mg,
which was higher than that of Ca in the elution sample. About
99% of Sr in seawater from 1L to 10L was collected by theconcentration part. A pre-concentration of Sr from 10L
seawater was completed within 5hrs.
We prepared a Sr resin column using a benchmark glasscolumn (Omnifit Ltd.) in the purification part. The amount of
Sr resin depends on the sample size because the level of Sr inseawater is around 8ppm. All procedures were automaticallycompleted by MARS Sr-sw. It took 4hrs to complete thepurification of Sr from 10L of seawater The Sr recovery was
about 93%.

Radiostrontium is one of the main fission products and canbe released into the environment through nuclear test or NPP
accidents. During emergency situations such as FDNPP, aradionuclide analysis should be completed in a short time tosupport rapid decision making and maintain public safety.
The determination of radiostrontium following traditional
methods involves a significant number of separation steps
such as precipitation which are time-consuming and labor
intensive. This paper describes Modular AutomatedRadionuclides Separator Sr-seawater (MARS Sr-sw) whichallows the purification of radiostrontium from four seawater
samples at the same time within 3 days. MARS Sr-sw canreduce the analytical time and labor intensity.
MARS Sr-sw was based on column chromatography. It
consists of a concentration part and purification part, whichcontain a control module, a pump module, a valve module,
and four column modules. We developed the control software
using LabVIEW (National Instrument). The operational
procedure is shown in figure 1.
In the concentration part, Dowex50Wx8(100~150um) wasused to concentrate a large seawater sample, the volume ofwhich was reduced from 20% to 30%. Seawater consists ofmany cations, such as Ca2+, Mg2+ and Sr2+. However, theselectivity of Sr for Dowex50Wx8 is relatively higher thanthat of Ca or Mg, which are dominant ions in seawater. It
enables Sr concentration from seawater without significant
loss of Sr. In a Sr breakthrough test, 500g of Dowex50Wx8
can isolate 99% of Sr from 10L seawater (0.16mg Sr/g ofDowex50Wx8). The low level of Ca was found in the elution

Concentration part2M HCl (3CV)
DIW (5CV)
2M NaOH (3CV)
DIW (5CV)

Purification part

8M HNO3(5CV)

conditioning

conditioning

loadingloading

DIW (3CV)

rinsingrinsing

8M HNO3(3CV)
3M HNO3+0.05M oxalic acid (2CV)
8M HNO3 (3CV)

5M NaCl (4CV)

elutionelution

DIW(4CV)

SrCO3 bycentrifuge

SrCO3 bycentrifuge

LSC analysis

Figure 1 Procedure of MARS Sr-sw (CV: column volume)

This study suggests that MARS Sr-sw can complete thedetermination of radiostrontium from a large amount ofseawater within 3 days using LSC and Cherenkov counting
which provide spectral information. It allows theidentification of Sr-89/90. The remarkable aspects of MARS
Sr-sw are the automation and capability to handle multiple
samples at the same time.
[1]

[2]

Chung, G.H., Choi, S.D., Choi, G.S., Kang, M.J. Design andperformance of an automated radionuclide separator: its application on
the determination of 99Tc in groundwater. Applied Radiation andisotopes (in press)
Vajda, N. and Kim, C.H. Determination of radiostrontium isotopes: A
review of analytical mehtodoly. Applied Radiation and isotopes, 2010.
2306-2326.

*Corresponding author. E-mail: hckim3@kaeri.re.kr－ 175 －

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

Peak Tailing Correction in Measurement of 222Rn/220Rn Activity Concentration with
��Spectrum Method
1

Lei Zhang1�Qiuju Guo2, Ruoyun Ma2, Lu Guo2

Solid Dosimetric Detector and Method Laboratory, Beijing, 102205, China
State Key Laboratory of Nuclear Physics and Technology, School of Physics, Peking University, Beijing 100871, China

2

Abstract – �������������������������������������������������������
for 222Rn/220Rn concentration measurement. The peak tailing from����� ������� �� ��������� ��� ���� ������� ������� �nfluences the������������ �������������� ��� �������� �� ��������� �������� ����theory of peak tailing was analyzed and a series of calibrating
experiments was carried out. For a commercial radon monitor ERS2, the experiment values of peak tailing correction factors C5 and K4
is 15.25%±0.24% and 36.23%±0.68%, the calibration factors of222
Rn and 220Rn(KFRn and KFTn) is 2.08±0.02 Bq•m-3/cph and5.23±0.28 Bq•m-3/cph. After peak tailing correction, themeasurement results agree with reference value very well.
Keywords – 222Rn/220Rn; �����������������; peak tailing correction
factor; calibration factors－ 176 －

23-ENP-17
�����������������������������������������������������������������������
������������������������������������������������������������������
������������������������������������������������������������������������������������������������ �����������������������������������������������

������������������������������������������������������������������������������������������
Abstract Ð The increasing number and size of marine reserves comes with additional challenges and responsibilities
concerning environmental monitoring, including sediment chemistry. The characterisation of sediments can shed light on past
events like anthropogenic contamination and natural events as well as provide information to guide mineral exploration.
However, the costs associated with the monitoring of sediment chemistry are high and traditional methods can disturb the
sediment and influence the results. Here we present original results of X-ray fluorescence measurements performed underwater,
in-situ, using an autonomous underwater vehicle in the Derwent Estuary, which is located in South East Tasmania Australia
and has a long history of contamination from heavy metals. To demonstrate the capability of performing in situ, underwater
analysis of sediments we analysed three distinctive sites on the Derwent estuary floor. XRF spectra with good signal-to-noise
ratios have been recorded. The results show spatial variation of zinc, lead and iron concentration. The contamination of heavy
metals we found reflects proximity to potential sources and patterns of the hydrodynamics of the estuary. We suggest that XRF
in submersible autonomous platforms could be used to perform an initial, cost effective, assessment of heavy metals
contamination of sediments to guide comprehensive surveys.
Keywords Ð XRF, Sediments, AUV

XRF spectra recorded underwater. Typical least-squares fitted XRF spectrum record at site D (Ralphs Bay) at
10m-depth. The broader line between 10 keV and 30 keV overlaps Lead, Bromine and Strontium signals and arecaused by bremsstrahlung from the XRF housing (high density polypropylene).

－ 177 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201323-RPP-01

Development of the in-line, multiple elution cartridge-based radioisotope
concentrator device for increasing 99mTc and 188Re concentration of commercial
radionuclide generator eluates
Le, Van So1,2*; Morcos, Nabil1; McBrayer, James1; Bogulski, Zac1; Buttigieg, Charles1; Phillips,
Graham1
1

CYCLOPHARM Ltd, NSW, Australia
2
MEDISOTEC, NSW, Australia

I. INTRODUCTION
Tc is used in approximately 85% of diagnostic imaging
procedures in nuclear medicine world-wide. 188Re is
important radio-therapeutic radionuclide. The expansion of99m
Tc and 188Re application depends on the generator
availability. However, the cost-effective utilisation of 99mTc
and 188Re generators and the quality of SPECT imaging
diagnosis and radiotherapy are controlled by the 99mTc and188
Re generator operation/elution management, which isdetermined by the 99mTc and 188Re concentration in thegenerator eluate. Generally 99mTc and 188Re eluates areproduced from the generators in fixed volume and the99m
Tc and 188Re concentration of the eluates decreases withthe life time of the generators due to radioactive decay ofparent nuclides 99Mo and 188W, respectively. Consequently,
the useful life time of the generator is also a function ofavailable 99mTc and 188Re concentration of the eluate. The
injection dose activity of 99mTc- and 188Re-based
radiopharmaceuticals delivered in 1 mL solution (99mTc- or
188
Re- concentration, mCi/mL) is an important factor in
determining the useful life time of the 99mTc and 188Re
generators and the quality of 99mTc based SPECT imaging
diagnosis or 188Re –based radiotherapy, respectively. So,
the radioisotope concentrator device should be developed
to increase the concentration and quality of injectable 99mTc
and 188Re eluates and the life time of the generators.
99m

II. METHODS
A multi-elution, radioisotope concentrator device [1], inline eluted via evacuated-vial and through disposable sterile
filters was developed to increase the concentration of 99mTc
or 188Re in the elution of aged commercial 99mTc or 188Re
generators. The increase in 99mTc concentration in theeluate enhances the utilisation of technetium in Technegas
generator-based lung perfusion (100-250 mCi/mL) andother SPECT (20-30 mCi/mL) imaging studies. A selfshielded radioisotope concentrator device (Fig. 1a) was
created based on a newly developed sorbent/concentrator
column which selectively retains 99mTcO4- ions fromdownstream of 10 mL 99mTc solution eluted from thegenerator. The eluate is freed from Cl- and MoO4- ions bypassing through a competitive ion-selective column. 99mTc
is then eluted from the concentrator column with 1.0 mL
saline into an evacuated vial through a millipore filter andready for injection. The design of the device in form of adisposable cartridge was optimised to make elution processeffective, simple, sterile and radiation safe. Gentech 99mTc
generator of 110 GBq activity eluted with 10 mL saline waschosen to test our radioisotope concentrator device.

III. RESULTS
As a result obtained from our project, the 99mTc eluate wasconcentrated more than 10-fold with a 99mTc recovery yieldof > 85% using this radioisotope concentrator device. 5 or
10 repeated elutions were successfully performed with eachcartridge coupled to the 10 mL or 5 mL saline solution
eluted generators, respectively. So, each cartridge can beeffectively used for one week in the hospital environment
for radiopharmaceutical formulation. The useful lifetime of
the 99mTc generator was significantly extended from 10-20
days for the generators of 300-3000 mCi activity,
respectively. The 99Mo impurity in the 99mTc solution eluted
from the Gentech generator was totally eliminated by thisradioisotope concentrator device (Fig. 1c).
IV. CONCLUSION
We conclude that the radioisotope concentrator device
functioned well and is robust in operation. This device will,
to some extent, mitigate the global 99mTc crisis. This
concentrator device is under patent-pending.

Fig. 1. Radioisotope concentrator device withstandard accessories (a) and the radioisotope
concentrator device coupled with 99mTc generator for
in-line elution/concentration of 99mTc eluate (b).

REFERENCE[1] Le V.S, McBrayer J., Morcos N. (2012) Australian Patent
AU2012904683APSORC’13 Body Text

－ 178 －

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

Production and Preclinical Evaluation of Diagnostic and Therapeutic Radionuclides
in Tumor-Bearing Mice: Recent Developments at Paul Scherrer Institute
A. Türler1,2, M. Behe3, M. Bunka1,2, H. Dorrer1,2, A. Hohn3, K. Johnston4, U. Köster5, C. Müller3,
J. Reber3, R. Schibli3, N.T. van der Walt6, K. Zhernosekov1,2
1

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

Abstract – At PSI we have initiated a close collaboration of theLaboratory of Radiochemistry and Environmental Chemistry andthe Center for Radiopharmaceutical Sciences to bring novel
diagnostic and therapeutic radiopharmaceuticals to the point ofclinical trials. Pre-clinical studies using tumor-bearing mice wereconducted at PSI and ETH Zürich. At the university hospital in Bernthe required infrastructure for clinical trials was established.
Keywords – theranostics, diagnostic radionuclides, 44Sc, 152Tb, 155Tc,
therapeutic radionuclides, 149Tb, 161Tb, DOTA-folate conjugate,
targeted radionuclide therapy,

I.

INTRODUCTIONRadiopharmaceuticals which comprise metallic radionuclides are valuable diagnostic and therapeutic tools in
nuclear oncology. Several clinics worldwide have started
targeted radionuclide therapies based on 177Lu- or 90YDOTA-TOC, a somatostatin receptor targeting peptide totreat metastatic gastro-entero-pancreatic neuroendocrine
tumors. For diagnostic purposes 177Lu can be replaced withthe short-lived positron emitter 68Ga available from a68
Ge/68Ga generator system.
Further development and implementation of suchinnovative radiometallated drugs depend, however, directlyon the availability of radiometals. Compared to otherlanthanides, the element Tb comprises a quadruplet ofclinically attractive radionuclides, such as 152Tb and 155Tb,
with suitable decay properties for PET and SPECT imaging,and, 149Tb and 161Tb, suitable for targeted alpha- and betaradionuclide therapy. To assess the diagnostic and therapeutic
features of these four radioisotopes we employed the folic
acid/folate receptor (FR)-targeting strategy.
In addition, we investigated the use of 44Sc (t1/2 = 3.97 h,
E+av = 632 keV) as a valuable alternative to short-lived 68Ga
(t1/2 = 68 min, E�+av = 830 keV) for imaging of cancer prior
to 177Lu-based radionuclide therapy. The aim of the study was
the preclinical evaluation of a folate conjugate labeled withcyclotron-produced 44Sc and to compare these data with thoseof the 177Lu-labeled match.

A. Production of Radionuclides
The neutron deficient 149Tb, 152Tb, and 155Tb wereobtained in several beam times at CERN-ISOLDE byspallation of a Ta target with 1 GeV protons followed bymass separation. The low energy isobaric ion beams were
implanted in Zn covered Au foils.
A production facility for up to 20 GBq of n.c.a. 161Tb was
established at PSI. Samples of enriched 160Gd were irradiatedat PSI-SINQ, FRM-II Munich, or ILL Grenoble. It waspossible to routinely produce 161Tb of excellent radionuclidic
purity and highest specific activity (i.e. >3700 GBq/mg), sothat labeling of i.e. DOTATATE was possible with a molar
161
Tb:DOTATATE – ratio of 1:3.5 with 99.41 % yield.
44
Sc was produced via the 44Ca(p,n)44Sc-nuclear reaction
at the PSI Injector 2 cyclotron using highly enriched 44Catargets. Separation from the target material was carried out by
a semi-automated process using extraction- and cationexchange chromatography.
B. Preclinical Evaluation
A summary of results obtained in in-vivo experiments withall four Tb-isotopes is shown in Figure 1.
Control�Treated4B THERAPYWITH ALPHAPARTICLEStutu

4B 0%4

IN VIVOAPPLICATION

tu

tu

Tumor

KidneyControl�Treated
Tumor

Kidney

tu

tu

tu

tu
4B THERAPYWITH LOW ENERGYBETA PARTICLES

4B 30%#4

IN VIVOAPPLICATION

Figure 1: Left-hand side: treatment of tumor bearing mice withTb (�-particle therapy) and 161Tb (�-particle therapy) DOTA-FOLATE.
Right-hand side: PET and SPECT images of tumor bearing mice with 152Tb
and 155Tb DOTA-FOLATE, respectively.
149

[1]

－ 179 －

C. Müller et al., J. Nucl. Med. 53, 1951-1959 (2012).

23-RPP-03
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201399

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

Nozomi SATO1, Masako KAWABATA1, Yasuki NAGAI1, Kazuyuki HASHIMOTO1,
Yuichi HATSUKAWA1, Hideya SAEKI1, Shoji MOTOISHI1, Tadahiro KIN2, Chikara KONNO3,
Kentaro OCHIAI3, Kosuke TAKAKURA3, Futoshi MINATO4, Osamu IWAMOTO4,
Nobuyuki IWAMOTO4, and Shintaro HASHIMOTO4
1

Nuclear Engineering Research Collaboration Center, Japan Atomic Energy Agency
2
Faculty of Engineering Sciences, Kyushu University
3
Fusion Research and Development Directorate, Japan Atomic Energy Agency
4 Nuclear Science and Engineering Directorate, Japan Atomic Energy Agency

Abstract – We proposed a new route to produce a medical
radioisotope 99Mo by the 100Mo(n,2n)99Mo reaction using
accelerator neutrons. A high-quality 99Mo with a minimum level ofradioactive waste can be obtained by the proposed reaction. The
decay product of 99Mo, 99mTc, is separated from 99Mo by the
sublimation method. The proposed route could bring a major
breakthrough in the solution of ensuring a constant and reliablesupply of 99Mo.
Keywords – 99Mo radioisotopes, diagnosis, accelerator neutrons,
neutron induced reaction, SPECTI.

of 2 cm was irradiated by neutrons. The sample was placed 2
cm downward from the natC or 9Be target.
The 99Mo harvest frequency, determined by the ratio, R =99
N( Tc)/N(99mTc), is also important. Here, N(99Tc) andN(99mTc) are the numbers of 99Tc (T1/2 = 2.1 � 105 y, uselessin diagnostic use), and 99mTc. The calculated R values were
1.2, 3.0, and 11 for one, two and six-days of irradiation. The
harvest frequency will be every two or three days byconsidering the available amounts of 100Mo and the 99Mo
decay during the 100Mo sample irradiation.
III. EXPERIMENT AND RESULTINTRODUCTION

99m

Tc (half-life, T1/2 = 6.0 h), the daughter nuclide of 99Mo
(T1/2 = 66 h), is the most common radioisotope used indiagnosis, and its use accounts for 80% of all nuclear
medicine procedures worldwide.1) 99mTc has a versatile
chemistry that allows it to be incorporated into all sorts ofmolecules, and because of the short half-life of 99mTc, 99mTc
is routinely produced in 99Mo/99mTc generators. 99Mo has
been mostly produced by the fission reaction of highly
enriched 235U in research reactors. However, an unscheduled
shutdown of some of these reactors has recently caused acrisis shortage of 99Mo worldwide, which triggered
widespread discussions on the 99Mo supply.2) The 99Mo
production using a charged-particle induced nuclear reaction,such as the 100Mo(p,pn)99Mo, 100Mo(d,p2n)99Mo, and100Mo(p,2n)99mTc reactions, has been investigated.3) We
proposed a new route to produce 99Mo using fast neutrons
from an accelerator,4) and we have been carrying out
important steps necessary to obtain high-quality 99mTc.
II. 99MO PRODUCTION BY ACCERELATOR NEUTRONSIntense neutrons with an average energy of 14 MeV arenecessary to produce a large amount of 99Mo by the100
Mo(n,2n)99Mo reaction. Neutrons can be produced fromthe natC(d,n) or 9Be(d,n) reactions at deuteron energy of 40
MeV. The production yield of 99Mo was estimated using theevaluated cross section of 100Mo(n,2n)99Mo,5) and the neutron
intensity. Typically, we assumed a metallic 100Mo sample(251 g, 100% enriched) with a radius of 2 cm and a thickness

99

Mo was produced by irradiating an enriched 100MoO3
sample with �14 MeV neutrons from the 3H(d,n)4He reaction
at the Fusion Neutronics Source (FNS) facility of Japan
Atomic Energy Agency (JAEA). Gamma-rays from the decayof 99mTc and 99Mo were clearly observed. Yields of impurity
isotopes, such as 97Zr and 97Nb, were much smaller than thatof 99Mo.
To separate high-quality 99mTc from the produced 99Mo,
we used the sublimation method, which is based on adifferent volatility of Tc2O7 and MoO3.6) The irradiated100
MoO3 sample was placed in a furnace, and heated so as toform gaseous materials containing vaporized 99mTc2O7 in a
stream of oxygen carrier gas. 99mTc was condensed at the exitof the furnace, and was eluted with a saline solution. As aresult of the �-ray measurement of the separated 99mTc, theupper limits of �-rays from any impurity isotopes were foundto be very small. A sublimation method allows us to recycle
any irradiated enriched 100Mo. Labeling efficiency, an
important factor in the compounding and dispensing ofradiopharmaceuticals, was shown to be higher than 90% by
formulating a radiopharmaceutical.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]

－ 180 －

F. F. Knapp, Jr. and S. Mirzadeh: Eur. J. Nucl. Med. 21 (1994) 1151.
J. R. Ballinger: J. Labelled Compd. Radiopharm. 53 (2010) 167.
K. Bertsche: Proceedings of IPAC’10, Kyoto, Japan. (2010) 121.
Y. Nagai and Y. Hatsukawa: J. Phys. Soc. Jpn. 78 (2009) 033201.
K. Shibata, et al.: J. Nucl. Sci. Technol. 48 (2011) 1.
C. Perrier and E. Segre: J. Chem. Phys. 5 (1937) 712.

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

Production and Separation of 64Cu and 67Cu using 14 MeV Neutrons
Masako Kawabata1, Kazuyuki Hashimoto1, Hideya Saeki1, Nozomi Sato1, Shoji Motoishi1, Kosuke
Takakura2, Chikara Konno2 and Yasuki Nagai11

1,2

Nuclear Engineering Research Collaboration Centre, 2Fusion Research and Development Directorate
Japan Atomic Energy Agency (JAEA), 2-4 Shirane, Shirakata, Tokai, Naka-gun, Ibaraki, 319 1195, Japan

Abstract –64Cu and 67Cu were produced from 14 MeV neutron
irradiated natural ZnO and enriched 64ZnO targets via 64Zn(n,p)64Cu and 67Zn(n,p)67Cu reactions. The ZnO disc targets were
irradiated for 6 hours by 14 MeV neutrons, which are generated bybombarding a tritiated titanium target with deuteron beam at the
Fusion Neutronics Source (FNS) at Japan Atomic Energy Agency(JAEA). After irradiation, ion chromatographic separations werecarried out to obtain purified no-carrier-added Cu radionuclides.
Elution pattern clearly showed separation of 64Cu and 67Cu giving ayield of > 90%, and a very low radionuclide impurity ratio of 65Zn
within the purified 64Cu.

with 20 ml of 2 M HCl and passed through an AG1-X8
column (0.8� � 12.0 cm) to remove traces of Zn followed by
a washing with 10 ml 2 M HCl [10]. The drop rate wasregulated to be 1 ml/min throughout the separation. The
purified 64,67Cu solution was evaporated and dissolved in 1 ml
0.4 M ammonium acetate (pH5.5), filtered, and then reactedwith TETA (1,4,8,11-tetraazacyclotetradecane-1,4,8,11tetraacetic acid) solution for 2 hours [11]. The labeling yield
was determined by silica gel TLC / 1:1 methanol-10 �
ammonium acetate.

Keywords – 64Cu, 67Cu, radioisotope production, 14 MeV neutrons,
nuclear medicine,III. RESULTS & DISCUSSIONI.

INTRODUCTION

64

Cu (T1/2 12 h, E.C.= 43%, �+ = 18%, �- = 40%) and 67Cu
(T1/2 62 h, �- = 100%) [1] have attracted attention inradiopharmaceutical applications for their unique decay
properties and chemical characteristics [2]. Being a positron
and a beta emitter, 64Cu is a strong candidate for the agents ofboth positron emission tomography imaging and targetedradiotherapy. 67Cu, a longer-lived beta emitter can be used forradiotherapy to treat small tumors with a diameter of 2-3 mm[3]. Cu radionuclides can be produced either with cyclotrons
by bombarding Ni or Zn targets with proton beams, e.g.
64
Ni(p,n)64Cu, 68Zn(p,�n)64Cu, 68Zn(p,2p)67Cu, or in a nuclear
reactor by bombarding a target with thermal neutrons [4,5].
The studied methods using cyclotron generated proton beams,
however, include relatively expensive targets, unwanted
radionuclides or complex chemical separation [5-8]. The
current study investigates a production route of 64Cu and 67Cu
from 64Zn(n,p)64Cu and 67Zn(n,p)67Cu reactions, by
irradiating natZnO or 64ZnO with 14 MeV neutrons [9], and asubsequent chemical separation.
II. EXPERIMENTAL
nat

ZnO and 64ZnO (99.935% enriched 64Zn) disc targets(20� � 5 mm, 5 g) were individually irradiated by 14 MeV
neutrons at FNS in JAEA for 6 hours. The average neutron
flux was ca. 1.0 � 1011 n/s generated via 3H(d,n)4He reaction.
The irradiated target was dissolved in 20 ml of 36 wt% HCl
after which the pH was adjusted to 3.5-4.0 with 10 M NaOH.
The sample was passed through a Chelex-100 exchange
column (1.1� � 11.5 cm) followed by washing with 100 ml of
0.001 M HCl to remove Zn [10]. The 64,67Cu was then eluted

The production of 64, 67Cu by irradiating nat, 64ZnO with 14
MeV neutrons reduced the consequent chemical separation
process because of fewer side products (e.g. only 65Zn ifenriched 64ZnO is used), which saves considerable time incomparison with 64, 67Cu production by proton-irradiation [8,10]. The time required for the column separation process was
3 hours and could be shortened further if the system was fully
automated. Over 95% of the 65, 69Zn side products wereseparated by the ion exchange Chelex-100 column, which canbe recovered as Zn(OH)2 by alkaline precipitation anddecomposed to ZnO upon heating [8]. Radioactivity of 0.79
MBq/g 64Cu, 6.3 kBq/g 67Cu from natZnO and 2.5 MBq/g 64Cu
were obtained from 64ZnO at the end of bombardment. A
high separation efficiency was observed from the Chelex-100(98%) and the AG1-X8 (95%) based on the 64Cu yield of two
experiments, with the final product having a 65Zn
radionuclide impurity below the detection limit of gamma-ray
spectrometry. The labeling efficiency of Cu-TETA forclinical radiotherapy applications was found to be good at
94.4%.
REFERENCES
[1]
[2]
[3]

Monographie BIPM-5, Table of radionuclides, Vol. 2, 2004
Blower P.J, Lewis J.S. et al., Nucl med biol, 23, 957, 1996
Ting G.,Chang,C.-H. et al., J Biomed Biotechnol, 2010, ID953537,
2010[4] Qaim S.M., Radiochim Acta, 100, 635, 2012[5] Novak-Hofer I. and Schubiger P.A., Eur J Nucl Med, 29(6), 821, 2002
[6] McCarthy D.W., Shefer R.E. et al., Nucl med biol, 24, 35, 1997
[7] Le,V.S., Pellegrini P. et al, J Radioanal Nucl Ch, 277(2), 451, 2008[8] Katabuchi T., Watanabe S. et al., J Radioanal Nucl Ch, 277(2), 467,
2008[9] Kin T., Nagai, Y. et al., J Phys Soc Jpn, 82,034201-1, 2013[10] Schwarzbach R., Zimmermann K. et al., Appl Radiat isot, 46(5), 329,
1995
[11] Sun X., Wuest M. et al., J Biol Inorg Chem, 8, 217, 2003

－ 181 －

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

Novel radiochemical separation of arsenic from selenium for 72Se/72As generator.
Ewelina Chajduk1, Halina Polkowska-Motrenko1, Aleksander Bilewicz1
1

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

Keywords–
selenium-arsenic
separation,
chromatography, PET, 72Se/72As generator

extraction

The potential usage of arsenic isotopes for nuclear
medicine has been reported recently. One of theway for obtaining appropriate radioarsenic species
is using radionuclide generator, where As isformed by the radioactive decay, eg.72Se� 72As. A
new radiochemical separation scheme based on
extraction chromatography for isolation As fromSe is presented. The distribution coefficients of As
and Se on prepared sorbents were determined inorder to find the best condition for separation ofboth elements. Batch experiments were verified bycolumn studies.
Elaborated radiochemical
separation scheme insures high selectivity andradionuclide purity of separated arsenic fraction,
whereas examined sorbents have been found tohave a very high selectivity with reference toselenium (IV). Arsenic is easily eluted by diluted
HCl and NaCl solutions. Proposed approach
insures high selectivity and radionuclide purity ofseparated arsenic fraction; it is also characterizedby high elution efficiency (>95 %) using small
volume (2 mL) of 0.9 % NaCl with very low
breakthrough (<0.01 %) of selenium.
Acknowledgments: This work was partly supportedby the grant of Polish Ministry of Science andHigher
Education,
Poland,(Nr2713/B/H03/2011/40)－ 182 －

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

Training Program of Synthesizing a Radiopharmaceutical in KAERI
1

S. Yang1, Y. H. Chung2

Advanced Radiation Technology Institute, Korea Atomic Research Institute, Jeongeup, 580-185, Korea
Department of Chemistry, Hallym University, 1 Hallymdaehak-gil, Chuncheon 200-702, Korea; yhchung@hallym.ac.kr

2

Radiopharmaceuticals have widely been used in diagnosesof various medical conditions. Medical facilities using
radiopharmaceuticals such as 2-deoxy-2-[18F]fluoroglucose(18F-FDG) have increased in number in Korea. 18F-FDG isabsorbed into cells such as brain and kidney along withcancer cells. Without the hydroxyl group replaced to 18F it
fails to undergo glycolysis in the cell and cannot leave it
before its radioactive decay, which provides a quantitative
distribution of glucose uptake and phosphorylation in cells.
As 18F-FDG is used in many medical facilities, a reliable
quality control system is needed in its synthesis in addition
to technical staff who can handle the process. KAERI
recently started to operate its own 30-MeV cyclotron at
Jeongeup, where 18F-FDG is to be produced. A month-longtraining program is planned for college undergraduates andgraduates to learn synthesis of 18F-FDG and its handling,which would fill national future demand of skilled technicalpersonnel.

－ 183 －

23-RPP-07

APSORCÕ13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013��������������������������������������������������������������������������
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Yumi Sugo, Ichiro Sasaki, Shigeki Watanabe, Yasuhiro Ohshima, Noriko S. Ishioka
Quantum Beam Science Directorate, Japan Atomic Energy Agency

Abstract Ð 64Cu was produced by the cyclotron using
64
Ni(p,n)64Cu nuclear reaction. MARSGL peptide has high affinity
to HER2/neu overexpressing in various cancer cells. In this study,
64
Cu-DOTA-MARSGL was designed and synthesized as a novel
PET imaging probe for HER2/neu overexpressing tumors.

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Keywords Ð 64Cu, Positron, DOTA, Peptide, HER2/neu

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Copper-64 is an attractive radionuclide for positronemission tomography (PET) imaging as well asradiotherapy due to its half-life (T1/2=12.7 h) and decay
characteristics (�+ 17.4%, �- 39%). MARSGL (H-Met-AlaArg-Ser-Gly-Leu-OH) is a linear peptide having highaffinity to HER2/neu overexpressing in various cancer cells[1].
1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetic
acid (DOTA) is a macrocyclic ligand for various metal ions.

EDCIáHCl, HOBt

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In this study, we designed Cu-labeled MARSGL
peptide conjugated with DOTA as an imaging probe for
HER2/neu overexpressing tumors.

�64

Cu was produced by the AVF cyclotron of Takasaki
Ion Accelerators for Advanced Radiation Application
facility at Japan Atomic Energy Agency using the nuclear
reaction of 64Ni(p,n)64Cu. Radiochemical separation of 64Cu
was carried out by chelating ion-exchange method [2].
Protected MAR(Pbf)S(tBu)GL-Trt(2-Cl) resin was
prepared by solid-phase peptide synthesis using automatic
peptide synthesizer (Aapptec, Titan 357). As shown in
1,4,7,10-tetraazacyclododecaneFig.1,
tri-tert-butyl
1,4,7,10-tetraacetate was allowed to react with the peptide
resin by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimidehydrochloride(EDCIáHCl)and1-hydroxy-1Hbenzotriazole (HOBt) in dimethylformamide. And then thecleavage and the deprotection were performed at the sametime using trifluoroacetic acid (TFA), 1,2-ethanedithiol(EDT), and triisopropylsilane (TIS).
64

Cu-labeling of DOTA-MARSGL was carried out inacetate buffer. The formation of 64Cu-DOTA-MARSGL
was determined by reversed-phase TLC and HPLC.

TFA:EDT:H2O:TIS=94:2.5:2.5:1
�� �

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�

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Fig. 1 Synthesis of DOTA-MARSGL by solid-phase conjugation.

REFERENCES[1][2]

In order to evaluate the usefulness of 64Cu-DOTAMARSGL peptide as a PET imaging probe, in vitro
stability and affinity to HER2 are under investigation.

－ 184 －

M. Houimel et al., Int. J. Cancer, ��, 748 (2001).
Sh. Watanabe et al., Nucl. Med. Biol, ��, 587 (2009).

���

APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201323-RPP-08

Molybdenum Isotope Fractionation in Ion Exchange Reaction
by using Anion Exchange Chromatography
Masafumi Inaki1, Yu Tachibana1, Masao Nomura2 and Tatsuya Suzuki1
Department of Nuclear System Safety Engineering, Nagaoka University of Technology
2
Reserch Laboratory for Nuclear Reactors, Tokyo Institute of Technology

Abstract – The molybdenum isotope fraction in ion exchange
reaction in hydrochloric acid solution was investigated by using
the anion exchange chromatography. We confirmed that theheavier isotopes are enriched in solution phase.
Keywords – technetium-99m, molybdenum-99, molybdenum
isotope, isotope enrichment

I.

INTRODUCTION
99m

Technetium-99m ( Tc) is one of the most importantradioisotopes in nuclear medicine. 99mTc is generated frommolybdenum-99 (99Mo). Now, 99Mo is mainly produced byfission of highly enriched uranium-235 (HEU). However,the supply of 99Mo becomes unsteady, since the reactors
for the generation of 99Mo become older. In addition, theuse of HEU causes the problem of nuclear proliferation.
Thus, new production technologies for 99Mo and 99mTc by
non-use of HEU are required and investigated [1,2]. The
typical technologies use the molybdenum targets, such as
100
Mo(n, 2n)99Mo [3], 100Mo(p,x)99Mo or 99mTc [4],98Mo(n,�)99Mo [5]. These methods are required theenriched molybdenum isotopes. We are investigating themolybdenum isotope separation by chemical exchange. In
the present work, the molybdenum isotope fractionation by
ion exchange is studied. The geochemists have also muchinterest in the molybdenum isotope fraction in chemical
reaction, recently [6,7]. Our study may help theunderstanding of molybdenum fraction in nature.
II. EXPERIMENTAL
1. Materials
Na2MoO4·2H2O supplied by Junsei Chemical Co., Ltd.
was used. The purity of Mo(VI) was more than 99.0 %. The
acidic concentrations of the solutions dissolved Mo speciesof 0.1 M(M = mol/L) were adjusted to 0.1, 0.5, 1.0, 2.0, 4.0,
6.0, 9.0, and 11.2 M using HCl. The high-porous
benzimidazole-type anion-exchange resin embedded inhigh-porous silica beads which has two functional groups
consisted of 4-(1-methylbenzoimidazole-2-yl)phenyl and 4(1,3-dimethyl-benzoimidazole-2-yl)phenyl was used for
Mo isotope fractionation.
2. Chromatography Experiments
Five columns connected in series were used for theisotope fractionation chromatography. Each column has thediameter of 0.8 cm and the length of 100 cm. Total volumeof the resin packed into these columns was 84.8 mL. The
temperature of columns was kept at 308 K. The
breakthrough experiments using 0.1 M of Mo species
dissolved in 0.10 - 11.2 M HCl were performed. The flowrate was controlled at 0.35 mL/min by using the highpressure pump made of Nihon Seimitsu Kagaku Co., Ltd.
The Mo isotope ratios were measured using ICP-MS(7700x,
Agilent). Mo concentrations in samples for isotope ratio
measurements were adjusted at ca. 1.0 ppb (ppb = ng/g),
and all sample solutions was used as 2.0 % HNO3.
III. RESULTS AND DISCUSSION
The breakthrough experiments for Mo isotope
fractionation were carried out under conditions, [Mo]T =0.1 M(subscript T means total concentration), [HCl]T = 0.1- 11.2 M, and Temp. = 308 K. The typical result of Mo
isotope fractionation was shown in Figure 1. As shown in
the figure, it was found that heavier isotopes are
disproportionately distributed into a solution phase. The
hexavalent molybdenum in solution is known to have many
type of chemical species, such as oxoacid ions, complexes,
and their combines. Mo isotope fractionations are attributed
to the chemical exchange among their species.

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Figure 1. Molybdenum breakthrough curve and molybdenum isotope
fractionation by anion exchange chromatography using 2 M HCl solution.

ACKNOWLEDGEMENT
This work was partially supported by the Grant-in-Aid
for Challenging Exploratory Research (KAKENHI No.
24656567).
[1]
[2]
[3]
[4]
[5]
[6]
[7]

－ 185 －

IAEA Nuclear Energy Series No. NF-T-5.4 (2013)
IAEA TecDoc 1065 (1999)
Y.Nagai, Y. Hatsukawa, J. Phys Soc. Jpn. 78(2009)33201
K. Gagnon, et al. Nucl. Medicine & Biology 38(2011)907.
A. Kimura, et al, IOP conf. Series : Mat. Sci & Eng. 18(2011)42001
T. Kashiwabara, et al. Geochem. J. 43(2009e31.
J. Barling, A.D.Anbar Earth & Planetary Sci. Lett. 217(2004)315.

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

The Mechanism of Oxidized Multi-walled Carbon Nanotubes across Placental
Barrier and Its Effects on Pregnany
QI Wei1, BI Juanjuan1, WANG Jing1, LI Zhan2, LIU Peng1, WU Wangsuo1*
Radiochemical Laboratory, Lanzhou University, Lanzhou, Gansu, China, 730000
2
Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou, Gansu, China, 730000
1

Abstract
The mechanism of nanoparticles across placental barrier wasstudied post injected intravenously with solution of oxidized multiwalled carbon nanotubes (oMWCNTs) labeled by technetium-99m
into pregnant mice, the rate and mechanisms of abortion were also
investigated via measuring content of progesterone and estradiol inmaternal serum. The results indicated that oMWCNTs could acrossplacental barrier and enter into fetus body, and caused highdistribution of fetal lung, and then eliminated gradually; oMWCNTs
could decrease level of progesterone and increase level of estradiol
in serum, that depended on exposure dosage and time, but weakened
with the extension of gestational ages; the abortion rate ofprimiparous, second-parous and fourth-parous pregnant micecaused by oMWCNTs was 70%, 40% and 50%, respectively, andalso the maternal body weight growth were inhibited until
gestational age of 13, 10 and 11 days, respectively. Therefore,
oMWCNTs can damaged normal pregnancy, and that was more
serious for primiparous.
Keywords: oMWCNTs; placenta; biodistribution; abortion rate;
progestational hormone.

Table 1.The statistics of abortion rates after exposure oMWCNTs (n=10).

GroupFirstoMWCNTsFirst-control
SecondoMWCNTs
Second-control
FourthoMWCNTs
Fourth-control

Ectroma(colpobleeding)

Average weightchange before andNormalparturition after production/g

Figure. The exposure time of oMWCNTs effects on the progesterone in themice at gestational age of 18 days (n=4-5, *p<0.05, group.vs normal,&
p<0.05,group vs. Et-500ug).

Total
abortion
rate

7

3

8.57±8.95*

70%

1

9

20.73±9.00

10%

4

6

13.99±9.44

40%

0

10

15.83±4.24

0

5

5

11.18±5.82

50%

3

7

12.72±5.7830%*p<0.05, group vs. normal.

*Corresponding author: WU Wangsuo, Tel & Fax:(+86)09318913594, Email address: wuws@lzu.edu.cn,－ 186 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

23-APP-02

Prompt Gamma Test of a Large Volume Lanthanum Bromide Detector
Naqvi, A. A*1 , M. A. Gondal1; M. Raashid1; Khateeb-ur-Rehman1, M. Dastegeer1
1Department of Physics,
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
Abstract – Response of a large LaBr3:Ce detector has been tested
over broad range of gamma rays using prompt gamma ray
neutron activation analysis technique,. Due to its larger size,

the detector has poorer energy resolution a 76 mm x 76 mm(diameter x height ) cylindrical LaBr3:Ce detector

Keywords – Large LaBr3:Ce detector, performance tests using
prompt gamma rays, portable neutron generator, chlorine,
mercury and cadmium contaminated bulk water samples

I.

INTRODUCTION

The application of Prompt Gamma-ray Neutron Activation
Analysis (PGNAA) technique is growing further due to thefabricationofradiation

hardenedlanthanum-halide(LaBr3:Ce and LaCl3:Ce ) gamma ray detectors. Although
LaCl3:Ce detectors and LaBr3:Ce detectors have a fast risetime, excellent light output and energy resolution but they
have intrinsic activity, which increases with detector
volume.

This may limit their utilization in PGNAA

application. King Fahd University of Petroleum andMinerals , Dhahran, Saudi Arabia

has acquired acylindrical 100 mm x 100 ( diameter x height ) LaBr3:Ce
detectorfor

its

promptgamma

rayprogram.

A prompt gamma ray neutron activation analysis setup has
been developed using a MP320 D-D reaction-based
portableneutrongenerator

toanalyzeelemental

concentration of bulk samples. Response of the cylindrical
100 mm x 100 mm (diameter x height) LaBr3:Ce detector
has been measured for detection of chlorine, mercury andcadmium contaminatedbulk water samples, Comparedwith performance of a smaller 76 mm x 76 mm LaBr3:Ce
detector reported earlier [ 1], the larger volume LaBr3:Ce
detector has higher intrinsic activity and poorer energy
resolution. Results of the study will be presented.
[1]

Performance test of the large volume detector
were carried out over broad range of gamma rayenergies emitted in thermal neutron capture inbulk samples.

－ 187 －

Naqvi A. A., M.S. Al-Anezi, Zameer Kalakada, Faris A. Al Matouq,
M. Maslehuddin , M. A. Gondal , A. A. Isab, Khateeb-ur-Rehman.

and M. Dastageer Response Tests of a LaCl :Ce Scintillation3

Detector With Low Energy Prompt Gamma Rays From Boron andCadmium. Applied Radiation and Isotopes, Vol.70 (2012) pp. 882887.

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

Radiation-Induced Reactions in D, L-�-Alanine Adsorbed in Solid Surfaces
E Aguilar, A. Negrón-Mendoza, and C. Camargo
Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Mexico DF 04510, Mexico

Abstract
The aim of this work is to study the behavior under irradiation of D,
L and D-L �-alanine adsorbed in solid surfaces, as possible phasein the chemical evolution that may have occurred on the primitive
Earth or in extraterrestrial environments and to evaluate thecontribution of solids (a clay mineral) as shields for the adsorbed
amino acids against a external energy source. The results show that
�-alanine is adsorbed in the surfaces as function of pH and its yieldof decomposition in mineral suspension is lower than the system
without the solid surface. These results show the importance of
nuclear techniques in these types of studies.
Keywords – �-Alanine, chemical evolution, gamma radiation, clay
mineralwas analyzed by X-ray, IR and electron spin resonance. The
experiment was carried out 15 times to check the repeatabilityof the results.
III.

RESULTS

The adsorption data shows that the �-alanine (D and L or
D; L) is absorbed readily in the clay. The adsorption occurs toa maximum degree at low pH. At basic pH the adsorption
was very low. The gamma irradiation of samples show low
yield of recovery of the amino acid without clay. The
summary of the recovery percent is in Table I.
Table I Survival Percent of �-Alanine after irradiationI.

INTRODUCTION

The emergence of life on Earth needed a physical andchemical preamble. There is a large variety of experimental
data to support the hypothesis for the abiotic formation oforganic compounds [1, 2]. Although much knowledge has
been obtained, many questions remain. One important factor
in chemical evolution is related to the importance of randomchemical synthesis/decomposition versus more selective
pathways forming compounds of biological relevance. It is
important then to explore chemical mechanisms able to narrow
the variety of prebiotic chemical compounds liable to be usedin the construction of primitive living systems. We study asimple chemical system: an amino acid adsorbed in a clay
mineral and exposed to ionizing radiation.
Our interest is twofold: (1) to evaluate the role that a solid
surface plays to protect the compound adsorbed in the solid. (2)To show experimentally that biased reactions might haveoccurred in geologically relevant conditions on the primitive
Earth, for example to study if there is a preferential destruction
by ionizing radiation of one of the optical isomers of �-alanine.
II.

EXPERIMENTAL PROCEDURES

The solid surface was sodium montmorillonite of Wyoming
bentonite. Aqueous solutions of �-alanine were tested (racemicand pure enantiomeric forms) at concentrations of 0, 01 M anddifferent pH values (2, 4, and 6). The oxygen was removed bypassing argon through the solutions. The irradiations werecarried out in a 60Co- gamma source. The radiation doses werefrom 0 to 91 kGy. The analyses were made by high pressureliquid chromatography with a Chiral column (ChirobioticT®),
coupled to light scattered detector (ELSD). The solid phaseIV.

REMARKSIt was observed that the presence of mineral drasticallydecreases the damage to that amino acid by action of the
gamma radiation. The observed general tendency shows theL-�-alanine as the most resistant to ionizing radiation,
especially when is radiated in enantiomerically pure solutions,the difference is very slight, but this small difference may be
amplified with time and by other mechanism. This resultshows the important role of minerals in chemical evolution
processes.
ACKNOLEDGEMENTS
This work was supported by PAPIIT Grant No. IN1107123 and the CONACyT Grant No. 168579/11. The technicalsupport from C. Camargo, B. Leal, and F. García-Flores is
acknowledged.
REFERENCES[1][2]－ 188 －A. Negrón Mendoza, S. Ramos-Bernal and G. Mosqueira, Int. J.
Astrobiol. 3, 295-300, 2005
. S. L. Miller and L. Orgel, The Origins of Life on Earth, Prentice-Hall,
Inc. New Jersey, 1974.

23-APP-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 201336

Cl determination in steel radioactive waste

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

Operator Support Analyses Laboratory, Atomic Energy Commission, CEA Saclay, DEN/DANS/DPC/SEARS/LASE,
Building 459, PC171, 91191 GIF SUR YVETTE CEDEX, FRANCE

2

Electricité de France, EDF – CIDEN / Département Etudes - Division Déconstruction/Groupe Inventaire et Agréments, 154
Avenue Thiers, CS 60018, 69458 LYON CEDEX 06

Abstract – APSORC’13 Abstract
Within the framework of the nuclear power plants
dismantling, approximately 3600 tons of metallic radioactive
wastes will be generated. Located near the reactor core,some of them are highly activated and 36Cl produced from thenatural stable isotope 35Cl, due to high mobility and long halflife, becomes one of the radionuclides that significantly
control the ultimate disposal. In steel materials,
concentrations between 0.15 and 12.9ppm have beenreported [1, 2]. Depending on neutron flux intensity, 36Cl
activity calculated for a stable chlorine concentration of
1ppm varies from 0.03 to 91 Bq/g, while the upper
acceptance limit for medium activity waste is 5 Bq/g. 200
steel samples have already been collected in nuclear plants
under dismantling. Without further available data on stablechlorine content, 36Cl has to be measured.
French standard methods [3] dedicated to 36Cl measurement
in wastes does not describe this first step in details and theradiochemical method includes no more than 3mmole ofstable chlorine used as carrier and chemical yield tracer.
36
Cl is measured by liquid scintillation. A radiochemical
process dedicated to 36Cl measurement in steel radioactive
waste, has been developed in order to� ensure a detection limit far below 5Bq/g,
� treat a great flow of samples.
Furthermore, it must be adapted to as well as carbon thanstainless steel samples. And, as 36Cl is an activated product, a
total dissolution must be guaranteed.
A dissolution mixture of nitric and chlorhydric acid needed toassure a complete dissolution specially for stainless steel
samples has been optimized in order to minimize the quantityof chlorine added. Nevertheless, 25mmole of chlorine are
required to dissolve 0.2g of stainless steel, while 15mmole
are necessary for 1g of carbon steel. As a result, thefollowing separation steps have to be adapted. The
experimental set-up for the dissolution step is a three-neckflask, containing the sample and KCl as chloride source.
After gently added nitric acid, nitrogen is bubbled in thesolution in order to carry on the gas Cl2, in a trapped bottle.
With this process, only volatile radionuclides such as 14C,
129
I… are trapped.

In order to sort the samples, an aliquot of the bubbler
solution is directly analyzed. For sample with an activity
higher than 3Bq/g, the radiochemistry is carried on to isolate
36
Cl in a pure fraction in only two days. The recovery yield isdetermined at the different stages of the radiochemical
procedure,measuringstablechlorinebyionic
chromatography.
The method has been evaluated in terms of recovery yield andlimit of detection according to the French AFNOR NFT90210 standard [4]. Thus, a limit of quantification of 0,15Bq
has been experimentally verified. Considering the mass
analyzed and the limit of quantification the limit of detectionis 3 times lower than this limit of quantification, leading to alimit of detection at 0,3Bq/g and 0,15 Bq/g for stainless steel
and carbon steel samples respectively.
Results on activated steel will be presented.

[1] C.S. Sastri, G. Blondiaux, P. Mijller, H. Petri
Determination of chlorine in metals and ceramics materials
by low energy deuteron activation analysis, Nuclear
instruments and methods in physics research B, vol.119,1996
p425-428.
[2] NIREX report 772, T/REP/20021/P/08 (date d’émission :31/03/1997).
[3] Norme NF M 60-332, Détermination du chlore-36 dansles effluents et déchets par scintillation liquide, mai 2009.
[4] Norme NF T 90-210, Protocole d’évaluation initiale desperformances d’une méthode dans un laboratoire, mai 2009.

－ 189 －

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

Naturally Occurring Radioactive Materials(NORM) in Malaysian Oil Sludge
Samples
1
1

2

Mohamed B.A. Teiara and 2Sukiman B. Sarmani

Department of Physics, University of Al-Zaituna, Tarhruna, Libya
School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan,
Malaysia, Bangi, 43600, Malaysia

It was in the early 70’s, when concern was started
regarding the presence of NORM associated with the oil &gas production. During 1980’s a lot of work has been
devoted to the hazards arising from the measured elevatedconcentration of NORM in this field. Recently, mostpublications concern about the effect of NORM on
personnel and environment. It was the scope of this paper
to analyze the sludge waste resulted from the Malaysian oil
fields for the presence of Naturally Occurring Radioactive
Materials (NORM) and investigated the hazardous risk
associated. This can be also used in future as a reference
data to monitor any level changes. About 30 dried sludge
samples were characterized using gamma-ray spectroscopy
based on a well shielded HPGe detector for thedetermination of the activity concentrations of 238U, 232Th,
their important progenies and 40K. The range of activity
concentrations were (10.1 – 51.0) Bq/Kg for 226Ra (186keV), (6.2 – 34.8) Bq/Kg for 214Pb (352keV), (4.7 – 17.7)
Bq/Kg for 208Tl (583 keV), (5.8 – 40) Bq/Kg for 214Bi(609keV), (5.45 – 15.7) Bq/Kg for 228Ac (911keV) and(9.2 – 46) Bq/Kg for 40K (1460keV). The radiation doses
resulted from the sample total activities were measured andcompared with standard dose limits which would be
investigated in the full manuscript.

－ 190 －

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

On the Use of 233U and 237Np as Radiotracers for Redox Potential Measurements
Stellan Holgersson
Chalmers University of Technology, Department of Chemical and Biological Engineering, Nuclear Chemistry, Kemivägen 4,
SE41296 Göteborg , Sweden
Abstract
Reduction/oxidation(redox)potential
measurements
inenvironmental samples are usually made with electrodes. However,these have certain weaknesses in terms of stability and memory
effects. Alternative methods for determination of redox are thereforeof interest and the use of radioactive tracer elements may be one
such method, which is the subject of this investigation. It issuggested that the actinides are particularly appropriate for use as
indicators of redox, provided that their different redox states can beseparated in a fast and reliable way. A literature survey show thatsolvent extraction is an established method for separation of tracer
amounts of actinides into their redox states and three of the mostcommonly used extraction reagents of the beta-diketone type were
investigated:
thenoyltrifluoroacetone (TTA), dibenzoylmethane(DBM) and 4-benzoyl -3-methyl-1-phenyl pyrazol-5-one (PMBP). U
and Np were reduced to tetravalent state, which was confirmed with
spectropscopic measurements. Extraction curves in the pH range
0.6-7 were then measured for An(IV),(V) and (VI) . It was found that
0.5M DBM in chloroform and 0.05M PMBP in xylene gave the best
separation factor (SF=1700 resp. 1100) for actinide (IV)/(VI) and(IV)/(V) oxidation state separation, respectively, when pH ofaqueous phase was in the region 1-2. Actinide tracer was used forredox determinations of prepared samples with an artificial
groundwater, with or without addition of grains of rock and pyrite
and also a Fe(II)/Fe(III) redox-buffer. Comparison with electrode(Pt/Ag/AgCl) measurements gave values that were considerable
lower: for example 30mV for a non-redox-buffered synthetic
groundwater measured with actinide speciation, compared with
about 300mV with electrode. The actinide speciation reflects aslower response to redox changes and a preservation of an earlier
redox state of the groundwater, while the electrode responds seems
to respond fasterto changes but is thereby also more sensitive toundesirable Eh drift. It was also found that U and Np redox
speciation method also have a limited working range of about 100>Eh<100 mV so an absolute correspondence between themethods may therefore be impossible to attain if Eh is outside thisrange.

Keywords – Redox potential measurements, Groundwater, Uranium,
Neptunium, Solvent extraction－ 191 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

23-APP-07!NALYSIS OF )) RATIOS FROM UNDERGROUND FLUIDS COLLECTED IN *APAN
N. Okabe1, Y. Muramatsu1, M. Arai1, H. Matsuzaki2, M. Takahashi3, K. Kazahaya3
1

Gakushuin University, Japan
University of Tokyo, Japan
3
AIST, Japan

2+EYWORDS – )  DATING UNDERGROUND FLUIDS

1.

INTRODUCTION

There are many isotopes of iodine. Specialty, the longlived iodine isotope, 129I is produced by the spallation of
atmospheric and by spontaneous fission 238U. 129I and thestable isotope 127I are in steady state before being released
and mixed with anthropogenic 129I. So this ratio wasmeasured in order to provide an estimation of the age of
iodine.
The purpose of this study is to understand the origin ofhigh salinity groundwaters related to the geological settingsof the area. In this study we analyzed 129I (half-life 15.7m.y.) in the fluids in older to estimate the age of the
dissolved iodine in hot spring waters collected from various
places in Hokkaido. It is known that several hot springs in
Hokkaido, the northern Japanese island, contain highconcentrations of halogens including iodine. However, theorigin of the salts in these springs is not well known. We
analyzed I, Br and Cl concentrations.

(0.3-0.4×10-12, Tomaru et al. 2009) and Satsuma-Iwojima(0.78×10-12, Snyder et al. 2002). Considering the 129I
systematics (Fehn et al. 2004), iodine age in Hokkaido
samples of the lowest 129I/127I ratios is estimated to be 6070 Ma. This indicates that the iodine-rich fluids are likely
be derived from old marine sediment, which was later
uplifted to form older rock formations in the present day
coastal region of Hokkaido.

0.100
0.093
0.064
0.094
0.068

※Values are sample of
129I/127I ratio（×10-12）

0.075 0.100
0.051

0.051
0.094

0.075

0.064

0.068

0.082

2. Samples and Analytical method

3.

Results and discussion

Fig. 1 Mapping of location of low 129I/127I ratio samples in Hokkaido

4Ⅵb
129I/127I ( 10-12 )Hot springs and groundwaters were collected in Hokkaido.
In the sampling interpretation of sample types weconsidered the classification based on Matsunami et al(1999).
Concentrations of Cl in the hot spring samples were
determined by an ion chromatography. Concentrations of I
and Br were determined by ICP-MS.
The 129I/127I ratios were determined by accelerator mass
spectrometry (AMS). Samples were precipitated as AgI(target cell) after separated iodine, and analyzed by AMS at
MALT (Micro Analysis Laboratory, Tandem accelerator,
University of Tokyo).

Ⅶb
Ⅶc

0.4

Ⅷ
Ⅸ
Ⅹ

In the Hokkaido hot spring samples, the relationshipbetween iodine concentration and 129I/127I ratios isclassified in 2 types. In general, if iodine concentrations
increase, 129I/127I ratios are higher. But, a part of sample
didn’t show this trend.
129 127
I/ I ratios ranged between 0.05×10-12 and 0.38×10-12
in Hokkaido hot springs samples. Samples collected from
north-western area showed very low 129I/127I ratios of 0.05
×10-12 to 0.1×10-12. Low values are also observed along
the longitude 141-142. These values are markedly lower
than the 129I/127I ratios observed in iodine-rich fluids inother areas in Japan, such as Chiba (0.18×10-12), Niigata－ 192 －

0.04
0.001

Ⅺa
0.01
1/I ( μM-1 )0.1

Fig. 2 Iodine concentrations vs. 129I/127I ratios

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

Radiocarbon Dating of Ancient Japanese Calligraphy Sheets: Checks with AncientDocuments of Known Age and Its Application to Kohitsugire Calligraphies
Hirotaka Oda1, Kazuomi Ikeda2, Hiroaki Yasu3, Shoji Sakamoto4
1

Center for Chronological Research, Nagoya University
2
Faculty of Letters, Chuo University
3
Taga High School
4
Degital Archives Research Center, Ryukoku University
Abstract – Radiocarbon ages of ancient documents, sutras andbooks of known age were measured by AMS. The calibrated
radiocarbon ages corresponded to the years in which they were
written. The result shows that Japanese paper is suitable forradiocarbon dating. Radiocarbon dating on ancient calligraphies of
unknown age clarified their historical ages and academic value.
Keywords – AMS, Radiocarbon dating, Ancient calligraphy.

I.

radiocarbon ages of the documents correspond to thepaleographical ages. Although ancient Japanese paper can beconsidered as a wooden sample, it was made from short-lived
branches of trees. In addition, old paper is not used for
calligraphy because it repels India ink and is unsuitable for
elegant handwriting. The result indicates that ancientJapanese paper is suitable for radiocarbon dating.

INTRODUCTION

Kohitsugire are ancient paper sheets or fragments
containing elegant calligraphy. They were originally pages ofancient manuscripts. The old manuscripts written before the14th century hardly remain as complete books; therefore,
kohitsugire potentially has high academic value. However,among kohitsugire attributed to famous calligraphists,many copies and counterfeits written several
centuries later are in circulation. Therefore, in this study,
we measured radiocarbon ages of kohitsugire by accelerator
mass spectrometry (AMS). In the first, we measured ancient
documents, sutras and books of known age for check of themethod. Then, we applied to kohitsugire calligraphies of
unknown age to determine their historical ages and academic
value.
II. EXPERIMENTAL
Paper samples were cut from the margins of kohitsugire. A
kohitsugire is commonly mounted on other paper sheets thatform a lining. The samples were soaked in distilled water topeel the surface sheet of the calligraphy from the mounts. The
surface sheets were first washed in distilled water with anultrasonic cleaner and then treated with 1.2N HCl and 1.2N
NaOH solutions (60-70°C). After re-treating with 1.2N HCl
and rinsing with distilled water, they were combusted using
CuO (850°C, 3h) to form CO2. The CO2 was reduced tographite by H2 (650°C, cat-Fe, 6h). The radiocarbon ages
were measured by AMS.

Fig. 1. Result on the known-age documents

IV. RESULTS AND DISCUSSION: KOHITSUGIRECALLIGRAPHIES
We applied to kohitsugire of unknown age to clarify their
historical ages and academic value. For example, Fig. 2 is
kohitsugire attributed to Nakatomi no Kamatari (614-669).
However, radiocarbon dating indicated that it was written in
the 14th century and is not his genuine handwriting.
According to legend, calligraphy of Fig. 3 is Shibunritsu sutrabrought from China by the priest Ganjin (688-763). Althoughradiocarbon dating cannot show that the legend is true or not,it indicated that it is old sutra written in the 7-8th centuries as
the legend.

III. RESULTS AND DISCUSSION: THE KNOWN-AGE
DOCUMENTS
The results of the known-age documents, sutras and books
were plotted on the calibration curve (Fig. 1). The obtained－ 193 －

Fig. 2. Kohitsugire attributed to
Nakatomi no KamatariFig.3 Shibunritsu sutra

23-APP-09
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013µ-XRF study on Wiangkalong pottery
1

K. Won-in1, S. Tancharakorn2, W. Tanthanuch2, P. Dararutana3

Department of Earth Sciences, Faculty of Science, Kasetsart University, Bangkok 10900 Thailand
2
Synchrotron Light Research Institute, Nakhon Ratchasima 30000 Thailand
3
The Royal Thai Army Chemical School of the Royal Thai Army Chemical Department, Bangkok 10900 Thailand

Abstract- It was proved that non-destructive andnon-sampling methods were used to analyze thecomposition of the archaeological objects. It was
well-known that differences of them found in
Thailand such as glasses, potteries and metal
wares. Due to the complex nature of materials andobjects, extremely sensitive, spatially resolved,
multi-elemental
andversatile
analytical
instruments are needed. In this work, micro-beam
X-ray fluorescence spectroscopy (µ-XRF) based onsynchrotron radiation was firstly used tocharacterize the elemental composition of ancientWiangkalong pottery. Wiangkalong was one ofmajor ceramic production cities in northern ofThailand, once colonized by the ancient Lanna
Kingdom (1290 A.D.). Potteries were producedwith shapes and designs as similar as those of theChinese Yuan and Ming Dynasties. The results
showed the variations in elemental composition of
the body matrix, the glaze and the painting. µ-XRF
was successfully to characterize the elemental
composition of this ancient pottery.
Keywords – Wiangkalong pottery, µ-XRF[1][2]

Praichanjit, S. (2011). Archaeology of Ceramics in Lanna NorthernSiam, Samaphun Publishing Co.Ltd., Bangkok.
Won-in, K., Pongkrapan, S, Dararutana, P., Thawwornmongkolkij, M.
and Wathanakul, P. (2010). Raman spectroscopic study of ancientpotteries in Thailand: Wiangkalong pottery, 5th Mid-European Clay
Conference; August 25-29, 2010: Budapest, Hungary.

－ 194 －