Oral Presentations
Friday, 27 September 2013
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9:00&RIDAY  3EPTEMBER
Meeting Room
AAI-01)NVITED

9:30

AAI-02

A. Chatt)NVITED
T. Miura

10:00#OFFEE "REAK

10:20 AAO-01

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

10:40 AAO-02
11:00 AAO-03
11:20 AAO-04
11:40 AAO-05
12:00,UNCH 4IME

13:20

API-03

13:50

APO-04

14:10

APO-05

14:30

APO-06

14:50
15:10

)NVITEDY. Hamajima
GeneralC. Gautier
GeneralT.Yoshimura
GeneralJ.D. Despotopulos#OFFEE "REAK#LOSING #EREMONY－ 103 －

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

Simultaneous Analysis for As, Sb, and Se Species in Waterby Chemical Separation and Neutron Activation
W. Menendez Sanchez, Y. Shi, and A. Chatt
Trace Analysis Research Centre, Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3, Canada
Abstract – APSORC’13 Abstract
Keywords – solid-phase extraction, solvent extraction, HPLC, INAA,
speciation analysis, arsenic, antimony, seleniumI.

INTRODUCTION

Arsenic speciation analysis has become an increasing
health concern since the toxicity of the element depends upon
the chemical species. Inorganic arsenic species are more toxic
than their organic counterparts. Among the inorganic forms,
As(III), the major arsenic species present in fresh water
systems, is considered to be more toxic than As(V). It is wellknown that As(III) and As(V) undergo interconversion inaqueous solutions depending on pH, temperature, oxygen
content, microorganisms, etc. Co-contaminants such as
species of antimony and selenium in water can also affectarsenic speciation. There exists a need for simultaneous
analysis of all these species.
Simultaneous speciation neutron activation analysis(SSNAA) technique has been developed in our laboratory
over the last 20 years or so. This technique can now be used
for the simultaneous determination of not only various
species of a single element but also species of other elements
present in the same sample. Almost all speciation techniques
consist of two steps. The first step involves the separation of
species from a sample followed by the second step of
element-specific detection. Neutron activation analysis(NAA) methods in combination with high-performance liquid
chromatography (HPLC) were developed first for thedetermination of low levels of five arsenic species, namely
As(III),
As(V),
monomethylarsonicacid(MMA),
dimethylarsinic acid (DMA), and arsenobetaine (AsB) in
water samples. Organically bound arsenic (OBAs) and totalarsenic levels were measured. These methods were thenextended to include the determination of arsenic, antimony
and selenium species, namely As(III), As(V), AsB, OBAs,
MMA, DMA, Sb(III), Sb(V), and Se(IV), in natural water
samples by solvent extraction and solid-phase extraction(SPE).
II. EXPERIMENTAL
In the HPLC method [1], OBAs was first separated bysolid phase extraction using a C18 silica column. Next DMA
and AsB were separated in a cation exchange column
followed by injection into HPLC with 10 mM NH4H2PO4/(NH4)2HPO4 buffer as the mobile phase. The effluent

containing MMA, As(III), and As(V) species was theninjected into HPLC with 75 mM NH4H2P04/(NH4)2HP04
buffer at pH 5.5.
An independent solvent extraction method was developed
to separate soluble As(III) and As(V) compounds in waterusing APDC/MIBK [2].
In the SPE method [3], As(V), MMA, and DMA wereseparated and preconcentrated by an Alltech strongly anion
exchange (SAX), namely Extract-Clean SPE SAX, column
and strongly cation exchange (SCX), namely Extract-Clean
SPE SCX, column in tandem while As(III) remained in theeffluent. Once the columns were physically separated, acetate
buffer at pH 3.4 was used to elute MMA from the SAX
column. Then 5 mL of 1 M nitric acid was used to elute
As(V). The SCX column was also eluted with 5 mL of 1 M
nitric acid for DMA determination. This SPE method wasfurther extended to separate As(III), As(V), AsB, OBAs,
MMA, DMA, Sb(III), Sb(V), and Se(IV) in natural water
samples [4].
All samples were irradiated in the Dalhousie University
SLOWPOKE-2 Reactor facility at a neutron flux of either 5
or 2.5×1011 cm-2 s-1. Samples were counted using either aconventional or a Compton suppression gamma-ray
spectrometer. The 559.1-keV �-ray of 76As (t1/2 = 26.3 h) wasused for arsenic determination.
III.

RESULTS AND DISCUSSION

The detection limits (ng mL-1) of the HPLC-NAA method
were found to be 0.005 for OBAs, 0.02 for AsB, DMA,
MMA, As(III), and As(V) and 0.12 for total arsenic. The
detection limits of As(III) and As(V) in the solvent extraction
methods were 0.007 for fish/shellfish, 0.005 for As(III) and
0.006 mg kg-1 for As(V) in plants. The detection limits (ngmL-1) were 0.9, 1.7, 1.6, 3.8 and 16 for As(III), As(V), MMA,DMA and total arsenic, respectively.
References
[1]
[2]
[3]
[4]

－ 104 －

Y. Shi, R. Acharya, A. Chatt, J Radioanal Nucl Chem, 262(2004) 277286.
R. Zwicker, B.M. Zwicker, S. Laoharojanaphand, A. Chatt, JRadioanal Nucl Chem, 287(2011)211-216.
W. Menendez Sanchez, B. Zwicker, A. Chatt, J Radioanal Nucl Chem,
282(2009)133-138
W. Menendez Sanchez, Ph.D. Thesis, Dalhousie University, Halifax,
NS, Canada, 2009.

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

AAI-02

Precise Determination of Bromine in PP Resin Pellet by Instrumental Neutron
Activation Analysis using Internal Standardization
Tsutomu Miura1, Ryo Okumura2, Yuto Iinuma2, Shun Sekimoto2, Koichi Takamiya2, Masaki Ohata1,
Akiharu Hioki1
1

National Metrology Institute of Japan, AIST
Kyoto University Research Reactor Institute2

Abstract – Instrumental neutron activation analysis with theinternal standardization was applied the precise determination ofbromine in PP resin. Gold was used as an internal standard. The
analytical results of Br were in excellent agreement with thevalues obtained by ID-ICPMS. The relative expanded uncertainty(k=2) was 1.9 %, and it was comparable to that of ID-ICP-MS.
Keywords – Neutron activation analysis, Bromine, certified
reference material, Uncertainty

I.

INTRODUCTION

National Metrology Institute of Japan is responsiblefor developing certified reference materials (CRMs) and forestablishing the traceability of SI (The International System
of Units) on chemical metrology in Japan. To establish SI
traceability, the primary method of measurements should
be applied to the characterization of the CRMs. Recently,
neutron activation analysis (NAA) using comparator
standard is recognized as a potential primary ratio method[1]. Despite the potential of NAA as primary ratio method,the evaluation of the measurement uncertainty is requiredin any analysis.
In general, there are three main
components of uncertainty in NAA, that is, sample
preparation uncertainty, neutron flux homogeneity, andgamma ray measurement uncertainty.
Usually, flux
monitor is used to correct the neutron flux in-homogeneity.
However, although the flux monitor can correct the neutron
flux variation using the count rate of the known amount of
the monitor nuclide, it does not reflect the neutron flux ofthe actual sample. The most practical method to eliminate
neutron flux in-homogeneity and to improve gamma ray
measurement uncertainty is an internal standard method [2].
In this paper, we presented that notable capability ofinternal standardization in NAA for determination of Br in
polypropylene (PP) resin pellet as a candidate CRM.

measurement system consisted of a Canberra GC40707500 Ge detector and a Laboratory Equipment
Corporation MCA600.
B. Results and discussions
It was found that the neutron flux varied according to
the sample position in the irradiation capsule. The relative
standard uncertainty of the in-homogeneity was estimatedto be about 5.1 % by 198Au sensitivity (cps/�g) at 411 keVof the internal standard (n=19). The uncertainty related to
the neutron flux homogeneity significantly contributes tothe overall uncertainty, if an internal standard is not applied.
The calibration curve linearity was also improved byinternal standardization. The calibration curves of 82Br
The relative
showed good and sufficient linearity.
uncertainty related to the calibration curve linearity was
improved to 0.97 % from 2.0 % for 82Br by using aninternal standardization. The analytical results of Br byproposed method were in excellent agreement with thevalues obtained by Isotope dilution-Inductively Coupled
Plasma Mass Spectrometry (ID-ICPMS). The relative
expanded uncertainty (k=2) was 1.9 %, and it wascomparable to that of ID-ICP-MS.

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

A. Instruments and methods
The PP resin pellet candidate CRM was produced
by a mixing machine. The calibration solution was
prepared from NMIJ primary Bromide standard solution.
The Au solution for the internal standard was preparedfrom a high purity metal. The calibration solutions
contained Br and Au. One hundred mg of the PP resin
pellet samples was used for Br analysis. The Au solution
was added to the samples before neutron irradiation. The
neutron irradiations were performed by KUR (Kyoto
University Research Reactor) PN-3(thermal neutron flux:
4.6 x 1012 cm-2s-1) for 10 min and TCPn (thermal neutron
flux: 8.0 x 1010 cm-2s-1) for 30 min. The � ray－ 105 －

Greenberg, R., Bode, P., De Nardi Fernandes, E., Spectrochim. Acta
B, 66 (2011) 193-241.
Miura, T, Chiba, K, Kuroiwa, T, Narukawa, T, Hioki, A, Matsue H.,
Talanta, 82 (2010) 1143-1148.

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

AAO-01Analysis of most popular and/or consumed fish species by neutron activation
analysis in six Asian countries
J. H. Moon1, B. F. Ni2, R. M. Theresia3, N. A. Abd. Salim4, B. Arporn5, C. D. Vu6
1

Korea Atomic Energy Research Institute, Daejeon, Korea
2
China Institute of Atomic Energy, Beijing, P.R. China
3
National Nuclear Energy Agency, Serpong, Indonesia
4
Malaysian Nuclear Agency, Bangi,Kajang, 43000 Selangor, Malaysia
5
Thailand Institute of Nuclear Technology, Bangkok, Thailand
6
Vietnam Atomic Energy Agency, Dalat, Vietnam
Abstract – Since 2000, collaborative studies for applying NAA
have been performed through the Forum for Nuclear Cooperationin Asia (FNCA) sponsored by the Japanese Government. Fishwere selected as a common target sample for a collaborative
study in 2011. Six Asian countries, China, Indonesia, Korea,
Malaysia, Thailand, and Vietnam, are greatly concerned about
the composition of arsenic, heavy metals, and essential traceelements and took part in this work. Fish samples were purchasedfrom commercial markets and prepared by following a protocolthat had been proposed for this study. Samples were analyzed bytheir own NAA systems. Each country has determined toxic and/or
essential elements. These data will be very helpful in themonitoring of the levels of food contamination and to evaluate thenutritional status for people living in Asia.
Keywords–Neutron Activation Analysis, FNCA, Fish Species,
Toxic Metals

I.

INTRODUCTION

Since 2000, collaborative studies applying a neutron
activation analysis (NAA) have been carried out as one of
FNCA (Forum for Nuclear Cooperation in Asia) projects
for the application of nuclear technology for socioeconomic development. Six Asian countries, China,
Indonesia, Korea, Malaysia, Thailand, and Vietnam agreed
to participate in the analysis of the most popular and/or
consumed fish species as a sub-theme of the NAA projectin 2011. The aims of this study were to determine theinorganic elemental contents in fish species of six Asian
countries by NAA and to evaluate the dietary intake levelsof nutritional and toxic elements for population of theparticipating countries.

III. RESULTS
China determined 14 elements from 10 fish species andmost element concentration from the sea fish is higher thanfreshwater fish. Indonesia determined 17 elements from 6
types of fish samples, and As concentrations in sea fish ishigher than in freshwater fish and Hg is contained in all
types of fish. In Korea, 17 elements including As, Cr, andHg were analyzed from 7 fish species. Malaysia determined
Cr, Hg, Se, and Zn on eight species of marine fish, and thelevel of mercury in several fish showed a high value in
dietary intakes levels compared to the EPA guideline value.
Thailand analyzed As, Cd, Co, Cr, Fe, Hg, Rb, Sb, Sc, Se
and Zn in 10 fish species As in all fresh water fish species
does not exceed the standard recommended (2ug/g) but
exceeds it in all marine fish species, while Hg in two fresh
water fish species and three marine fish species exceed thestandard recommended (0.5ug/g). Vietnam analyzed 18
elements in 10 samples of 6 sea fish species and As from
Scad fish in the Vinh Hai district is higher than the WHO
tolerable value.
ACKNOWLEDGEMENT
This research has been carried out by the support of the
Ministry of Education, Culture, Science and Technology ofJapan.
REFERENCES[1]

II. EXPERIMENTAL[2]

Each participating country selected six to ten fish
species and purchased them from the commercial market
for this study. Analytical samples were prepared by cutting
the edible parts of the fish, cleaning, grounding, freezedrying, and homogenizing fish samples. The samples
prepared by each country were analyzed using their own
NAA facilities. Samples were activated by short and longirradiation to detect short-, median- and long-lived nuclides.
To detect the gamma-rays emitted from the irradiatedsamples, HPGe detectors coupled to multichannel analyzers
were used. The elemental content was determined byrelative method and/or k0-method.

－ 106 －

Ebihara M, Chung YS, Chueinta W, Ni BF, Otoshi T, Oura Y,
Santos FL, Sasajima F, Sutisna, Wood AKBH (2006) J. Radioanal.
Nucl. Chem. 269(2): 259-266
World Health Organization (2006) Trace elements in humannutrition and health. Geneva, WHO, Belgium

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

Current status and future perspective on time-of-flight prompt gamma-ray analysis
combined with gamma-ray coincidence technique
Y. Toh1, M. Ebihara2, K. Hara1, A. Kimura1, H. Harada1, S. Nakamura1, M. Koizumi1, K. Furutaka, F.
Kitatani1
12Research Group for Applied Nuclear Physics, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo 192-0397,
Japan

Keywords – Prompt gamma-ray analysis (PGA); Time-of-flight(TOF); Coincidence method; Pulsed neutron; High-purity Ge
detectors

Prompt gamma-ray analysis (PGA) is a rapid, nondestructive and a nuclear analytical technique which canperform both qualitative and quantitative multi-element
analysis of elemental and isotopic compositions. The multiple
gamma-ray detection method, also known as the coincidence
method, is widely used in nuclear spectroscopy. By applying
the multiple gamma-ray detection method to PGA, called
MPGA (multiple prompt gamma-ray analysis), the signal-tonoise ratio (S/N) can be improved. The kinetic energy of aneutron can be measured with the time-of-flight (TOF)
technique at a pulsed neutron source by measuring the time ittakes a neutron to reach a sample. The neutron capture crosssections of most nuclides exhibit strong variations with theenergy of neutron. Therefore, the energy of the neutron
obtained by TOF method can be used for identification of
nuclides (elements). For further improvements of the S/N andsensitivity, we have developed a time-of-flight prompt
gamma-ray analysis combined with multiple gamma-ray
detection method (TOF-MPGA).
The Accurate Neutron-Nucleus Reaction Measurement
Instrument (ANNRI) has been designed and developed for
PGA, nuclear cross-section data and nuclear astrophysics(See Fig.1). ANNRI is located at the beamline No. 04 at theMaterial and Life Science Experimental Facility (MLF) of theJapan Proton Accelerator Research Complex (J-PARC). MLF
is high intensive pulsed neutron facility, which operates atapproximately 300 kW proton beam power, and will be
increased up to 1 MW in the near future. The germanium
detector-array, which consists of two cluster-Ge detectors,
eight coaxial-Ge detectors and BGO Compton suppression
detectors surrounding cluster-Ge and coaxial-Ge detectors,
was installed at the flight length of 21.5m in ANNRI. It is
designed to provide high gamma-ray energy resolution andhigh detection efficiency. The typical time resolution of Ge
detector is rather poor but this is not a disadvantage becauseof the proton beam pulse width of approximately 100ns(100ns double pulse, bunches separated by 600 ns). Frame
overlap occurs when fast neutrons from a given pulse cancatch-up with slower neutrons from a succeeding pulse.
Whenever there is frame overlap there is a problem because
the neutron energy cannot be unambiguously determined.
Disk choppers consisting of a neutron absorbing disk areplaced upstream of the Ge detectors. The disc choppers areused to prevent frame-overlap problems by limiting theneutrons which arrive at a sample. The rotation frequency ofthe choppers is the same as the source repetition rate (25Hz)
under normal operation.
We present some remarks regarding the current status ofexperiments in TOF-MPGA development and its future
perspective. The results of some standard sample
measurements are discussed. These are compared with theresults of the experiments of MPGA at Japan Research
Reactor-3, and the similarity and difference are also
discussed.

Figure 1 The Accurate Neutron-Nucleus Reaction Measurement Instrument (ANNRI)－ 107 －APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

AAO-03

Simultaneous and Multielemental Analysis by Muonic X-rays for Inside JapaneseBronze and Gold Coins
K. Ninomiya1, M. K. Kubo2, T. Nagatomo3, G. Yoshida1, M. Inagaki1, A. Shinohara1, T. Suzuki2,
N. Kawamura3, P. Strasser3, K. Shimomura3, Y. Miyake3, Y. Kobayashi4, W. Higemoto5, S.
Sakamoto5,
T. Saito6
1

Graduate School of Science, Osaka University
Colleage of Liberal Arts, International Christianity University
3
Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK)4
Nishina Center for Accelerator-Based Science, RIKEN
5
J-PARC Center, Japan Atomic Energy Agency (JAEA)
6
National Museum of Japanese History
2

Abstract – A nondestructive, quantitative and multielemental
analysis method for bulk samples was developed, which was
based on the measurement of high-energy muonic X-rays emitted
from muonic atoms inside material after muon irradiation. We
demonstrated quantitative determination of the elemental
composition inside archaeological artifacts without sample
destruction.

quantitative analysis, we also carried out muon irradiation
for some standard alloys to obtain the relation between
their elemental compositions and the muonic X-ray
intensities.

Keywords – Elemental Analysis, Muonic Atom, Muonic X-ray

Muonic X-ray spectrum of the tempo-koban is shown in
Figure 1. Muonic X-rays originated muon capture in Au
and Ag atoms were identified. We easily determined that
tempo-koban was alloy made from Au and Ag, and thecompositions of the other elements were low. We also
found incident muon momentum dependence of muonic Au
X-ray intensity for the tempo-koban. This result showedthat elemental composition of tempo-koban changed as its
depth. The elemental composition inside the tempo-koban( > 5 �m in depth) was quantitatively determined (Au: 56%,
Ag: 44%). Our result well reproduced the previous analysis
result with destructive method [2]. The details will bereported in our presentation.

I.

INTRODUCTION

Quantitative elemental analysis is one of the mostimportant themes in the field of natural science. In
particular, non-destructive elemental analysis for insidematerial is very useful in the field of archeology. The
archeological sample surface is usually oxidized and coated.
The destructive analysis methods are never applied to thevery valuable sample. The elemental analysis methods
inside bulk material are strongly desired.
In this paper, we report the development of a nondestructive,
position-sensitive,
quantitative
andsimultaneous multielemental analysis method for bulk
samples by muonic X-ray measurements [1]. Muonic atomis the exotic atoms that has one negatively charged muon in
its atomic orbital. When a muon is stopped in material, amuonic atom is formed, and characteristic X-rays (muonic
X-rays) were emitted from the muonic atom. Because themass of a muon is 207 times larger than that of an electron,
the energies of muonic X-rays are very high. Therefore
muonic X-ray can penetrate a bulk sample layer and themuonic X-rays from inside sample are detectable. In
addition, this elemental analysis method has position
sensitivity; the depth of muonic atom formation in thesample is controllable by adjusting the incident muonenergy.
II. EXPERIMENTAL
We performed muon irradiation experiments at Muon
Science Establishment (MUSE) in J-PARC (Japan). We
measured muonic X-rays emitted from an old Japanesebronze coin (tempo-tsuho) and an old Japanese gold coin(tempo-koban) using high purity germanium detectors. For

III. RESULTS AND DISCUSSION

Figure 1: Muonic X-ray spectrum for old Japanese gold coin (tempokoban). Muonic Au and Ag X-rays were clearly detected and no X-ray
peaks originated from the other elements were identified.
[1][2]－ 108 －

K. Ninomiya et. al., Bull. Chem. Soc. Jpn., 85, 228 (2012)
M. Ueda et. al., IMES Discussion paper series, 96-E-26 (1996)

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

AAO-04

Rapid Analysis for Selenium in Urine Samples using the 17.4-s Neutron Activation
Product 77mSe
Michiko Fukushima1, Amares Chatt2, Yoshitaka Nakamura3, Megumi Haga4,
Seiko Hoshi5, Takashi Sakata1
1Ishinomaki Senshu University, Ishinomaki, Miyagi, Japan;
2
Dalhousie University, Halifax, NS, Canada;
3
Meiji Co., Ltd., Odawara, Kanagawa, Japan;
4
formerly at Shokei Gakuin University, Natori, Miyagi, Japan;
5
Shokei Gakuin University, Natori, Miyagi, Japan

Abstract – APSORC’13 Abstract
Keywords – Selenium, urine samples, NAA, short half- life nuclide

I.

INTRODUCTION

Selenium is an essential trace element for humans.
Selenium deficiency causes dysfunction of various organs,including skeletal and cardiac muscles. The recommended
dietary allowance (RDA) levels for Se in Japan [1] are 10
and 15 µg d-1 for 1-2 and 3-5 years old children,
respectively. Although Se intake levels can be estimatedby directly analyzing foods and diets [2], some researchers
prefer to use bodily fluids or excretions as a betterreflection of body burden of Se. For example, Dael et al.
[3] used stable isotopes, namely 76Se as selenate and 74Se as
selenite as supplements given to infants, analyzed theirurine samples, and reported total Se intake of 60.8 ± 4.6 ��
per 72 h, apparent Se absorption of 45.6 ± 5.2 �� per 72 h,
and total urinary Se excretion 21.0 ± 4.2 �g per 72 h.
The techniques commonly used for the determination of
Se in biological fluids are atomic absorption spectrometry(AAS), inductively-coupled plasma (ICP) atomic emission
spectrometry (AES), and ICP mass spectrometry (ICP-MS).
All of these techniques are suitable but time-consuming.
The objective of the present project was to investigate a
rapid method for the quantitative determination of Se in
urine samples of children.
We have developed an
instrumental neutron activation analysis (INAA) method
for this purpose using the short-lived nuclide 77mSe (halflife = 17.4 s).

them with tap water followed by distilled water, and drying
them in an oven. About 0.7 g of pure sucrose was added toeach vial containing 1 mL urine and dried under IR lamp
overnight in a fumehood. The vials were then heat-sealed.
Comparator standards, for calculating Se concentrationsin urine samples using the relative NAA method, wereprepared by adding 1 mL of the Se standard solution����������� ����� ����� ��� ���� ��� ��� ��� ��� ����� ��� ��������
using the same procedure as the urine samples. Samples,comparator standards and various reference materials were
irradiated for 10 s in a neutron flux of 5×1011 cm-2s-1 at the
Ghana Research Reactor-1 (GHARR-1). After a 10-s
decay time the samples were counted for 30 s using a
conventional gamma-ray spectrometer. The Se levels wereassayed using the 161.9-keV gamma-ray of 77mSe. It isevident that the INAA part of the analysis can beaccomplished within 60 s which is quite rapid.
III.

RESULTS AND DISCUSSION

To evaluate the accuracy of the INAA method
developed here the following standard reference material(SRM) and certified reference material (CRM) were used:
NIST SRM 2670a Toxic Elements in urine (Freeze Dried),
NIST SRM 1549 Non-Fat Milk Powder, NIST SRM 1577b
Bovine Liver, and NRC DOLT-3 Dogfish Liver. Our
values agreed within ± 10% of the certified values. Out of
the 75 urine samples analyzed by the INAA method
described above, only 4 samples were below the detection
limit of 10 ng mL-1. The average level of 71 samples was
79.2 ± 46.8 ng mL-1 with the highest value of 242 ng mL-1.

II. EXPERIMENTAL

References24-h urine samples were collected from 75 healthy 3-5year-old children by their families in their own houses
living in two different cities of Miyagi Prefecture, Japan.
The average total volume of urine was 503 mL d-1. The
urine samples were kept in cold and dark place for twodays. After bringing the samples to the laboratory, they
were frozen until the analysis.
Prior to analysis the urine samples were defrosted and 1
mL of each sample was transferred to a precleaned
polyethylene irradiation vial using a calibrated Eppendorf
pipette. These vials were precleaned using the following
steps: soaking overnight in 2 mL of 4 M HNO3, washing

[1]
[2]
[3]

－ 109 －

Ministry of Health, Labour and Welfare of Japan. Dietary Reference
Intakes for Japanese, 2010.
Reiko Yamamoto, Rie Okita, Akane Hiruta, Tosiko Konno,
Research Reports of Shohkei Gakuin College 52 (2006) 205-218.
Peter Van Dael, Lena Davidsson, Rafael Munoz-Box, Laurent B.
Fay, Denis Barclay, British J. Nutrition 85 (2001) 157-163.

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

AAO-05

Neutron activation analysis of iron meteorite
Naoki Shirai1, Yoshihiro Hidaka1, Shun Sekimoto2, Mitsuru Ebihara1, Hideyasu Kojima3,4
1

Tokyo Metropolitan University
Kyoto University Research Reactor Institute3
National Institute of Polar Research
4
Graduate University for Advanced Sciences

2

I.

INTRODUCTION

Iron meteorites are made of Fe-Ni metal phases with suchminor minerals as schreibersite, troilite, cohenite and other
Fe-Ni carbides [e.g., 1]. As most iron meteorites are
believed to be samples of the metallic core of asteroidal
parent bodies, petrological, mineralogical and chemical
studies of iron meteorites are fundamental for unravelingthe process of planetary differentiation.
Based on structure, iron meteorites were classified intohexahedrites, octahedrites and ataxites. Hexahedrites andataxites are nearly made of kamacite and taenite,
respectively. Octahedrites consist of kamacite and taenite
and they are further divided into six subgroups on the basisof the width of the kamacite from finest (<0.2 mm) tocoarsest (>3.3 mm). Almost all iron meteorites areclassified into octahedrites. Therefore, it is difficult todetermine representative elemental abundances of ironmeteorites due to their heterogeneity. Bulk elemental
abundances for iron meteorites have been obtained by using
neutron activation analysis (NAA) [e.g., 2]. Other
analytical methods such as inductively coupled plasma
mass spectrometry (ICP-MS) have not been very often
applied to iron meteorites [3, 4]. As subgroup IVB ironmeteorites are made of ataxites and these chemicalcompositions are highly homogeneous, Campbell andHumayun [3] applied laser ablation with ICP-MS (LA-ICPMS) to this subgroup. However, other subgroups have notbeen analyzed by using LA-ICP-MS for determination of
their bulk chemical compositions. D’Orazio and Folco [4]analyzed iron meteorites by using solution nebulization
ICP-MS. However, elements having smaller mass number
than 80 significantly suffered spectral interferences causedby molecular ions such as FeO+. There is a possibility ofvaporization of Ge as GeCl4 during the digestion of ironmeteorites. Kong et al. [5] developed the INAA procedurefor iron meteorites by using a TRIGA Mark II reactor at theInstitute for Atomic Energy, St. Paul’s University. In thisstudy, Kyoto University Research Reactor was used for
determination of elemental abundances of iron meteorites
and the analytical capability was evaluated in comparison
with the procedure of Kong et al. [5].

a neutron flux of 4.6 x 1012 cm-2s-1 at KURRI for
determination of Cu, Ge and Rh. The samples werereirradiated for 4 hrs at a neutron flux of 5.6 x 1012 cm-2s-1
at KURRI and were measured for gamma rays several
times with different cooling intervals. JB-1 and the Allendemeteorite were also analyzed for reference samples. In
addition, chemical standard samples were prepared for thedetermination of Cu, Ga, Ge, Mo, Ru, Rh, Pd, Sb, W, Re,
Os, Ir, Pt and Au. The analytical procedure used in thisstudy is basically similar to that described by Kong et al.
[5].
III. RESULTS AND DISCUSSIONSIn short irradiation of Canyon Diablo, 60mCo, 65Ni, 66Cu,
Ge and 104Rh could be detected. Among these elements,
Cu, Ge and Rh contents were calculated and shown in
Table 1, where literature values were also indicated forcomparison. Our values are in good agreement withliterature values [2,6].
The plots of Ni vs. Ga, Ge and Ir can separate ironmeteorites into about 12 subgroups. Usually, Ge has been
determined by using radiochemical NAA [2] and Ni data
have been obtained by INAA with long irradiation.
Considering that short-irradiation INAA is able todetermine both Ni and Ge. Therefore, our INAA procedure
is simple and effective in classification of iron meteorites.
75

Reference: [1] Goldstein J. I. et al. (2009) Chemie der Erde,69, 293-325. [2] Wasson J.T. and Kallemeyn G. W. (2002)
GCA, 66, 2445-2473. [3] Campbell A. J. and Humayun M.
(2005) GCA, 69, 4733-4744. [4] D’Orazio M. and Folco L.
(2003) Geostand. Newsl., 27 (3), 215-225. [5] Kong P. et al.
(1996) Anal. Chem., 68, 4130-4134. [6] Nichiporuk W. and
Brown H. (1965) J. Geophys. Res., 70 (2), 459-470.
Table 1. Cu, Ge and Rh abundances (in ppm) of Canyon
Diablo in comparison with literature.
This work
Literature
148, 150[2]Cu 136 ± 11
154 ± 10323, 330[2]Ge 329 ± 22314 ± 21
1.5[6]
Rh 1.33 ± 0.11 1.08 ± 0.10

II. EXPERIMENTAL
As the Canyon Diablo iron meteorite was used for control
sample in considering that it has been vigorously analyzed
and its elemental abundances were well established. A
piece of Canyon Diablo was cut into square plates
weighing 33 and 41 mg by using a ISOMET Low Speed
Saw. In INAA, samples were firstly irradiated for 10 sec at－ 110 －

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

What has been revealed in the Low-Level Radioactivity Measurement?
- Low Level Gamma-Ray Counting in Ogoya Underground Laboratory Yasunori Hamajima
Kanazawa Univ. LLRL.
Abstract – In Ogoya Underground Laboratory, low-level
radioactivity measurement is performed. We have 18 low
background Ge detectors and all detectors provide excellent
counting efficiency. We report recent results.
Keywords – low-level counting, underground laboratory, well-

type Ge detecto
I.

INTRODUCTION

In gamma ray measurements, it is important to reduce thebackground noise of detectors and activation of shielding
materials derived from secondary cosmic ray components(muons and neutrons). It is difficult to reduce thesecomponents by conventional shield at aboveground. The
intensity of secondary components decreases with the depthof overburden at the underground facility. Ogoya
Underground Laboratory (OUL) is in a 546 m tunnel of theformer Ogoya Copper Mine. It is located 270 m from thetunnel entrance, where the overburden is 270 mwe. The
background count rates of OUL detectors are about 1/100 of
the aboveground ones.

natural radio nuclides, fission products and activated nuclides
induced by environmental neutrons and fission neutrons.
In the recent results of extraterrestrial science, “Neutron
Activation Analysis of a Particle Returned from Asteroid
Itokawa” was in Science, 333, 1119-1121, (2011), and“Radar-Enabled Recovery of the Sutter’s Mill Meteorite, aCarbonaceous Chondrite Regolith Breccia” was reported in
Science 338, 1583-1587, (2012).
In those of Oceanography, “Surface pathway ofradioactive plume of TEPCO Fukushima NPP1 released
134Cs and 137Cs” was reported in Biogeosciences, 10, 30673078, (2013), and “Cross equator transport of 137Cs from
North Pacific Ocean to South Pacific Ocean (BEAGLE2003
cruises)” was in Progress in Oceanography, 89, 7-16, (2011).

Table 1. Specifications of Ge crystals and backgroundcounting rates.

I
J
K

planarplanarplanar18%(28cm2 x 2cm)
34%(38cm2 x 3cm)
34%(38cm2 x 3cm)

BG
(min
-1)
0.48
0.57
0.52

L

planar

18%28cm2 x 2cm)

0.57

II. DETECTORS AND SHIELDING IN OUL

M

planar22%(28cm2 x 2.8cm)

OUL has 11 well, 6 planar, and 1 coaxial Ge detectors, as
shown in Table 1. In order to measure a wide energy range
from 20 keV to about 3 MeV, the planar type detectors havelarge diameters and thicknesses and the well type detectors
have also large diameters. For most of detectors, ultra lowbackground aluminum was used for the end-cap. The cryostat
is the J-type and/or U-type and the preamplifier is locatedoutside of the lead shield. The lead shield is 15 to 25 cm thick,and its upper part is covered by 10 to 15 cm of iron. The
inner 3 to 5 cm of the lead shield is made of lead refined 200
years ago. The space near the detector head is filled with Hgshield encapsulated in a polyethylene bag and nitrogen gas
from the Dewar is blown to the top of the end cap.

N
C
D
A
B
G
H
W
X
Y
E

planarwell(10�x40mm)
well(21�x62mm)
well(21�x62.5mm)
well(21�x62.5mm)
well(21�x66.5mm)
well(21�x66.5m
well(21�x60mm)
well(21�x68mm)
well(21�x68mm)
well(21�x60mm)

22%(28cm2 x 3cm)
37%(61�x56mm,)
56% (72.0�x74.8mm)
56% (72.0�x75.0mm)
56% (72.0�x74.7mm,)
71.5%(74.0�x79mm)
71.7%(74.0�x80mm)
65% (75.1�x81mm)
73.4%(74.3�x80mm)
70.5%(74.3�x80mm)
68%(74.06�x80mm)

0.9
2.51
2
1.93
2.83
2.09
1.72
1.69
1.4
1.7

F

well(21�x55mm)

56%(75�x55mm)

2.1

U

coaxial

94% (78.9�x81mm)

1.12

Ge

III. RECENT RESULTS IN OUL
Some significant measurements have been made at OUL
such as the detection of low level cosmogenic nuclides,

Type(Al end cap)

Relative Eff, (size)"' INTEGRATED COUNT RATE  n  KE6－ 111 －APO-04
APSORC’13 - 5th Asia-Pacific Symposium on Radiochemistry
Kanazawa, Japan, 22-27 September 2013

Zr and U determination at trace level in simulated deep groundwater by Q ICP-MS
using TRU-based and TODGA-based extraction chromatography
1

C. Gautier1, M. Coppo1, C. Caussignac2, I. Laszak2, P. Fichet1, F. Goutelard1
Operator Support Analyses Laboratory, Atomic Energy Commission, CEA Saclay, DEN/DANS/DPC/SEARS/LASE,
Building 459, PC171, 91191 GIF SUR YVETTE CEDEX, FRANCE
2
Nuclear, Isotopic Elementary Analytical Development Laboratory, Atomic Energy Commission, CEA Saclay,
DEN/DANS/DPC/SEARS/LANIE, Building 391, PC33, 91191 GIF SUR YVETTE CEDEX, FRANCE

Abstract – APSORC’13 Abstract

In the past decades, metallic fuels, such as UZr metallic alloys, wereused as nuclear fuels. Direct disposal in deep geological repository
can be an option for the long-term management of spent nuclear
fuels. In the framework of such an issue, it is necessary to develop asource-term model for the release of radionuclides from the spent
nuclear fuels. The validation of the dedicated model requires theimplementation of leaching experiments in the conditions of a deep
geological repository. For the spent UZr fuels studied in France, theleaching and the release of two major radionuclides, 235U and 93Zr,
have to be investigated in the reference groundwater which isplanned to be a deep clayey Callovo-Oxfordian groundwatercontaining high concentrations of salts (alkali and alkaline earth
metals). Given the expected concentrations of 235U and 93Zr isotopes(< 10-6 mol L-1 or < 0.2 mg L-1) in leaching solutions, Q ICP-MS
can be considered as the most promising technique for theirsimultaneous measurements. However, due to the groundwatercomposition, sample dilution has to be applied before ICP-MS
analysis to avoid matrix effects. This option is incompatible with ourrequirements in terms of detection limits. Consequently, a fullanalytical procedure was implemented to determine Zr and U at
trace level in a simulated deep Callovo-Oxfordian groundwater by
Q ICP-MS.

20 fold factor for Zr and U measurements at trace level by Q ICPMS.
The leaching experiments are requested to be performed in hot cellsof the LECI laboratory (Laboratory for Studies on Irradiated Fuel)at CEA (French Alternative Energies and Atomic Energy
Commission) Saclay. Blank samples (containing 0.5M HNO3 +0.005M HF) were introduced during one week in the selected hot
cell where spent fuels are usually handled. The solutions wereanalyzed by Q ICP-MS to check whether the atmosphere of the hotcell induces problems of blank contamination for Zr and U
measurements at trace level. The measured concentrations werelower than the limits of quantification validated at 0.008 µg L-1 after
separation, which proved the feasibility of the scheduledexperiments.
The developed procedure was demonstrated to be very efficient forthis application but it could be also used for many other issues
concerning analysis of trace amount of radionuclides contained inhigh salt matrix.

Separation procedures based on extraction chromatography weredeveloped to eliminate the high salt contents and to concentrate Zr
and U simultaneously. Since U and Zr display different chemical
behaviors in solution, their speciation was first discussed.
Theoretical and experimental speciation studies showed theimportance of adjusting the medium to HNO3/HF (0.5M/0.005M) to
guarantee the stability over time of the analytes before removal ofthe matrix. Two preconcentration methods based on TRU® and
TODGA® resins were optimized for the simultaneous isolation of Zr
and U prior to Q ICP-MS measurements. Using TRU resin, alkali
and alkali earth metals contained in the deep groundwater were
removed with 2M HNO3 whereas Zr and U were recovered with a
HNO3/NH4HC2O4 (0.02M/0.05M) medium. For the separation
protocol based on TODGA resin, alkali and alkali earth metals were
eliminated with 3M and 11M HNO3 while Zr and U were
simultaneously stripped with a HNO3/HF (0.5M/0.2M) medium. The
procedure optimized on TODGA resin was the only one validatedwith the French AFNOR NF T90-210 standard by studying linearity,
limits of quantification (LOQ) and separation yields. The LOQ wasdetermined to be 0.008 µg L-1 for Zr and U after the separation.
Both analytes were recovered quantitatively. Compared to a direct
Q ICP-MS analysis after sample dilution, the developed
preconcentration method allowed improving the sensitivity up to a

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

Photoluminescence of Five- and Six-coordinate Tetracyanidonitridotechnetium(V)and –rhenium(V) Complexes
Takashi Yoshimura1, Hayato Ikeda2, Akitaka Ito3, Eri Sakuda3, Noboru Kitamura3, Tsutomu Takayama4
Tsutomu Sekine5, Atsushi Shinohara2
1

Radioisotope Research Center, Osaka University
Department of Chemistry, Graduate School of Science, Osaka University
3
Department of Chemical Sciences and Engineering, Graduate School of Chemical Sciences and Engineering, Hokkaido
University
4
Department of Chemistry, Daido University
5
Center for Advancement of Higher Education, Tohoku University
2

Abstract – Six-coordinate tetracyanidonitrido Re(V) and Tc(V)complexes with a volatile organic compound (VOC) and fivecoordinate complexes were synthesized and characterized.
Reversible luminescence switching between six- and five-coordinate
Re(V) complexes and between the relevant six-coordinate Re(V)complexes was achieved by exposing them to VOC vapor in the solidstate at room temperature. Luminescence changes were observed
from the five-coordinate Tc(V) complexes in a MeOH vapor
atmosphere in the solid state. In contrast, no vapochromic
luminescence was observed from the five-coordinate and sixcoordinate complexes in an acetone vapor atmosphere.
Keywords – Technetium, Rhenium, PhotoluminescenceI.

INTRODUCTION

Among the Group 7 metal ions, a very small number oftechnetium complexes have been reported to show
photoluminescence. In coordination compounds, molecularsensing can be done based on the color change of a complex
through changes in the coordination environments and/or
direct interaction of the metal ion with a molecule to besensed. In contrast, molecular sensing based on thevapochromic luminescence through a ligand substitution
reaction and the coordination number of a metal ion in thesolid state has been rarely reported. We report novel sixcoordinate nitrido Re(V) and Tc(V) complexes and their fivecoordinate square pyramidal complexes without an axial
ligand. The present study demonstrated for the first time thatthe nitrido Tc(V) complex showed luminescence in the solid
phase at room temperature. We demonstrate for the first timeinterconversion between the six-coordinate Re(V) complexes
through a solid state substitution reaction upon exposure to
VOC vapor, and between the five-/six-coordinate complexes
by a solid state ligand coordination/elimination reaction.[1]Re(V) and Tc(V) complexes were bistable between the fivecoordinate square pyramidal and six-coordinate octahedral
coordination environments. All of the five-coordinate squarepyramidal and six-coordinate octahedral complexes showedphotoluminescence in the solid state at room temperature.
The emission spectra and photophysical data of the fivecoordinate [ReN(CN)4]2- were significantly different fromthose of the relevant six-coordinate complexes.
Vapochromic luminescence between the bistable five- andsix-coordinate Re complexes with the VOCs (MeOH, EtOH,
acetone, or MeCN) and between the six-coordinate
complexes was investigated. We found unique reversible
coordination and elimination of a VOC at the axial site of the
Re complex in the solid state that gave rise to changes in theemissionmaximum
wavelength,
demonstrating
photoluminescence switching and sensing of VOC by thepresent Re(V) complexes at room temperature. Upon
exposure of MeOH vapor to the five-coordinate Tc complex,
the emission spectrum changed to that of the MeOH
coordinate complex. The coordinating MeOH molecule canbe removed by evacuation of the complex in vacuo. In
contrast, the emission band shapes of the five-coordinate Tc
complex remained unchanged even upon exposure of acetone
vapor. The emission spectrum of MeOH coordinate Tc
complex changed to that of the five-coordinate complex by
exposure to acetone vapor. This suggests that thecoordinating MeOH molecule in the Tc complex was
eliminated under acetone vapor atmosphere, but acetone was
not incorporated and did not coordinate at the axial site in the
Tc complex.
.

.#

-

.#

.

#.
#.

, VAPOR
IN VACUO

Six-coordinate Re(V) and Tc(V) complexes with a VOC,
(PPh4)2[MN(CN)4L] (M = Re, L = MeOH, EtOH, acetone, or
MeCN; M = Tc, L = MeOH), and five-coordinate(PPh4)2[MN(CN)4] (M = Re or Tc), were synthesized andtheir spectroscopic and photophysical properties were
investigated. Results demonstrate that the tetracyanidonitrido

2E

.#
,

#.
#.

-  4C 2E

.
.#

-

.#
,

-  4C 2E

II. RESULTS AND DISCUSSION

.#

.
#.

, VAPOR.##.

, VAPOR

.#

2E

#.
#.

,

Scheme 1.
[1]－ 113 －

H. Ikeda, T. Yoshimura, A. Ito, E. Sakuda, N. Kitamura, T. Takayama,
T. Sekine, A. Shinohara, Inorg. Chem., 51, 12065-12074 (2012).

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

3TUDIES OF &LEROVIUM AND %LEMENT  (OMOLOGS WITH -ACROCYCLIC %XTRACTANTSJohn D. Despotopulos1,2, Narek Gharibyan1, Roger A. Henderson1, William Kerlin2, Kenton J. Moody1,
Dawn A. Shaughnessy1, Evgeny Tereshatov1, Ralf Sudowe2
1
Lawrence Livermore National Laboratory,Chemical Sciences Division, Livermore, California 94551, USA
2
University of Nevada Las Vegas, Las Vegas, Nevada 89154, USA!BSTRACT – 2ECENT STUDIES OF THE CHEMICAL BEHAVIOR OF #OPERNICIUM
#N ELEMENT  AND &LEROVIUM &L ELEMENT  TOGETHER WITH THE
DISCOVERY OF ISOTOPES OF THESE ELEMENTS WITH HALF LIVES SUITABLE FORCHEMICAL STUDIES HAVE SPURRED A RENEWED INTEREST IN THE DEVELOPMENT
OF RAPID SYSTEMS DESIGNED TO STUDY THE CHEMICAL PROPERTIES OF
elements with Z ≥ 114 [1,= $UE TO THE SHORT HALF LIVES OF THE
TRANSACTINIDE ELEMENTS FAST AND EFFICIENT SEPARATIONS ARE NECESSARY
TO EVALUATE THEIR PROPERTIES SUCH AS IONIC RADII AND CHEMICALSPECIATION BY COMPARING TO THEIR LIGHTER HOMOLOGS 3EPARATIONSBASED ON EXTRACTION CHROMATOGRAPHY RESINS USING MACROCYCLICEXTRACTANTS SHOW PROMISE FOR ACHIEVING THE SHORT SEPARATION TIMESLARGE EXTRACTION YIELDS AND HIGH SEPARATION FACTORS REQUIRED FOR
TRANSACTINIDE STUDIES )N THIS STUDY THE POTENTIAL OF DIFFERENT
MACROCYCLIC EXTRACTANTS FOR THEIR FUTURE APPLICATION TO A &L AND
ELEMENT  CHEMICAL SYSTEM HAS BEEN INVESTIGATEDEichrom’s commercially available Pb resin is based on the dit-butylcyclohexano-18-crown-6 extractant sorbed to the resin
backbone in isodecanol. Consequently, this resin exhibitshigh selectivity for Pb2+ [4]. Thiacrown ethers, which replace
the oxygen atoms with sulfur, act as softer Lewis bases
compared to traditional crown ethers [5]. This uniqueproperty of thiacrowns should make them even better
extractants for softer metals such as Pb. Hexathia-18-crown-6(fig. 2) was synthesized and investigated.

+EYWORDS – 4RANSACTINIDE HOMOLOG ELEMENT  SEPARATIONSI.

INTRODUCTION

Fig. 2: Hexathia-18-crown-6.

Studies of the chemical properties of superheavy
elements (SHE) pose interesting challenges due to their shorthalf-lives and low production rates. Chemical systems musthave extremely fast kinetics to be able to probe the chemical
properties of interest, such as chemical speciation, before theSHE decays to another element. To achieve chemistry onsuch time scales (~ seconds), the chemical system must also
have the potential to be easily automated. The transactinides(elements with Z > 103) are predicted to exhibit changes intheir chemical behavior compared to that of their lighter
homologs (elements in the same chemical group) or pseudohomologs (elements with the same oxidation state and similar
ionic radii) due to relativistic effects [3].
II. EXPERIMENTAL! %XTRACTANTS AND 2ESINS
Crown ethers and their derivatives show high selectivity
for metal ions based on their size compared to the cavity ofthe ether. Di-t-butylcyclohexano-18-crown-6 (fig. 1) is
known to show high affinity for the Pb 2+ ion.

" %XTRACTION 3TUDIES
Batch experiments were performed for the direct
homologs of Fl (Pb and Sn) and element 115 (Bi and Sb)
using the Eichrom Pb resin. Promising results were obtained
from HCl/KI matrices as well as from simple mineral acidmatrices. Column studies were performed to asses these
extractions under dynamic conditions. Liquid-liquid
extractions were also performed using hexathia-18-crown-6
to determine its suitability and compare it to that of thestandard crown ether.
!CKNOWLEDGMENT 4HIS WORK WAS PERFORMED UNDER THE AUSPICES OF
THE 53 $EPARTMENT OF %NERGY BY ,AWRENCE ,IVERMORE .ATIONAL,ABORATORY UNDER #ONTRACT $% !# .! 4HIS WORK WAS
FUNDED BY THE ,ABORATORY $IRECTED 2ESEARCH AND $EVELOPMENT
0ROGRAM AT ,,., UNDER PROJECT TRACKING CODE  %2$ REFERENCES
[1]
[2]
[3]
[4]
[5]

Fig. 1: Di-t-butylcyclohexano-18-crown-6.

LLNL-ABS-631618－ 114 －

R. Eichler ET AL, Chemical characterization of element 112, .ATURE,
, 447, 72-75.
R. Eichler ET AL, Indication for a volatile element 114, 2ADIOCHIM !CTA,
, 98, 133-139.
P. Pyykko, Relativistic effects in structural chemistry, #HEMICAL
2EVIEWS, , 88, 563-594.
E. P. Horwitz, ET AL, A lead-selective extraction chromatographic resin
and its application to the isolation of lead from geological samples,!NALYTICAL #HEMICA !CTA , 292, 263-273.
E. Sekido, ET AL Liquid-liquid extraction of some class b metal ionswith thiacrown ether 1,4,8,11-tetrathiacyclotetradecane, !NALYTICAL
3CIENCES, , Vol. 1, 363-368.