JAERI-Conf99-010

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Inquiries about availability of the reports should be addressed to Research

Information Division, Department of Intellectual Resources, Japan Atomic Energy

Research Institute, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195, Japan.

JAERI-Conf 99-010

Proceedings of the Symposium on the Joint Research Program

between JAERI and Universities

- Current Status and Future Perspectives of the Chemistry Research

in the Nuclear Fuel Cycle Backend Field -

January 27, 1999, National Education Center, Tokyo, Japan

Committee for the Joint Research Program between JAERI and Universities

on Backend Chemistry

and

Committee for the Universities' JAERI Collaborative Research

on Backend Chemistry*

Tokai Research EstablishmentJapan Atomic Energy Research Institute

Tokai-mura, Naka-gun, Ibaraki-ken

(Received August 4, 1999)

The first Symposium on the Joint Research Project between JAERI and

Universities was held in Tokyo, January 27, 1999, to present the main achievements of the

project in these 5 years and to discuss future perspectives of the chemistry research relating

to the nuclear fuel cycle. The areas covered by the Joint Research Project are (1) Nuclear

Chemistry for TRU Recycling, (2) Solid State Chemistry on Nuclear Fuels and Wastes, (3)

Solution Chemistry on Fuel Reprocessing and Waste Management, and (4) Fundamental

Chemistry on Radioactive Waste Disposal. The present report compiles the papers

contributed to the symposium and summaries of the panel discussion.

Keywords: Joint Research Project, Nuclear Fuel Cycle Backend, Nuclear Chemistry,

Solid State Chemistry, Solution Chemistry, TRU, Nuclear Fuels, Reprocessing,

Waste Management, Radioactive Waste Disposal

* Research Center for Nuclear Science and Technology, The University of Tokyo

JAERI-Conf 99-010

Contents

1. Opening Address 1

Satoru Tanaka (Univ. Tokyo)

2. Main Activities on the Joint Research program during 1996-1998 3

Session 1: Nuclear Chemistry for TRU Recycling

2.1 Identification of New Neutron-rich Lanthanide Isotopes 4Shin-ichi Ichikawa (JAERI)

2.2 Identification of New Neutron-rich Actinide Isotopes 12Yasuji Ohura (Tokyo Metropolitan Univ.)

Session 2: Solid State Chemistry on Nuclear Fuels and Wastes2.3 Study on Phase Equilibria of Np-Pu-U-O System 20

Noriko Shirasu (JAERI)2.4 Study on Chemical Properties of Uranium Oxide Fuels with Some Additives • • 30

Takeo Fujino (Tohoku Univ.)

Session 3: Solution Chemistry on Fuel Reprocessing and Waste Management2.5 New Method for Separation of Actinides Based on Electrolytic Ion-transfer Reaction

across Aqueous/Organic Interface 46Zenko Yoshida (JAERI)

2.6 On the Extraction Behavior of Np in the PUREX Process 55Shiro Matsumoto (Saitama Univ.)

Session 4: Fundamental Chemistry on Radioactive Waste Disposal2.7 Alteration of Minerals and its Effects on the Migration of Uranium 65

Toshihiko Ohnuki (JAERI)2.8 Study on Corrosion Behavior of Overpack and Migration Behavior of Radionuclides

in Buffer 73Tamotsu Kozaki (Hokkaido Univ.)

3. Panel Discussion "Perspectives and Research Activities in the Next Phase" 813.1 Introductory Remarks Satoru Tanaka (Univ. Tokyo) 813.2 Group 1 Hiromichi Nakahara (Tokyo Metropolitan Univ.) • • 823.3 Group 2 Toshiyuki Yamashita (JAERI) 843.4 Group 3 Shoichi Tachimori (JAERI) 863.5 Group 4 Yoshitaka Minai (Musashi Univ.) 883.6 Discussions Chairman: Satoru Tanaka (Univ. Tokyo) 93

4. Closing Remarks 95Hiroji Katsuta (Director of Dept. Materials Science, JAERI)

iv

JP0050052JAERI-Conf 99-010

2.1 ff7 y 9 J 4Identification of new neutron-rich lanthanoide isotopes

, mmAdvanced Science Research Center, Japan Atomic Energy Research Instutute

Shin-ichi Ichikawa, Masato Asai, Kazuaki Tsukada, Ichiro NishinakaYuichiro Nagame

Department of Materials Science, Japan Atomic Energy Research Institute

£ TOAkihiko Osa

mm s# , ™ mDepartment of Energy Engineering and Science, Nagoya University

Michihiro Shibata, Kiyoshi Kawade

Yasuaki KojimaApplied Nuclear Physics, Faculty of Engineering, Hiroshima University

wm %, ±m mmMinoru Sakama, Yasuji Oura

Department of Chemistry, Tokyo Metropolitan University

Abstract

Six new neutron-rich lanthanoide isotopes produced in the proton-induced fission of 238Uwere identified with the JAERI on-line isotope separator (JAERI-ISOL) coupled to a gas-jettransport system. The observed K x-ray following the /?~-decay of products in the mass-separated fraction provided direct identification of isotope. New isotopes observed, withvalues of their half-lives given in parentheses, are 159Pm (2 ± 1 s), 161Sm (4.8 ± 0.8s), 165Gd(10.3 ± 1.6 s), 166Tb (21 ± 6 s), 167tb (19.4 ± 2.7 s) and 168Tb (8.2 ± 1.3 s). Furthermore,the level energies of first 2 + and 4 + states of the daughter nuclides 166Dy and 168Dy werederived through the £~-decay studies of 166Tb and 168Tb.

v 7 ̂ • -f ̂ y t B e •*> p b mfo t <DW&^£j^z^to*frtMttym\tz> r t (- «t *>

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JAERI-Conf 99-010

(1) Y. Yoshida, M. Matsui, O. Shirai, K. Maeda, S. Kihara, Anal. Chim. Acta, 374

(1998)pp.213- 225.

(2) ^f f l#fr , *EJt£ t t , &/vi£g, (1987)pp. 472-479.

(3) S. Kihara, K. Maeda, Prog. Surf. Sci., 47(1/2), (1994)pp.l-54.

(4) 7K^Ht#. nMlk¥&£t$TMmWlk'¥ (DenkiKagaku) , 63(1995)pp.363-368.

(5)Y. Yoshida, Z. Yoshida, H. Aoyagi, Y. Kitatsuji, S. Kihara, Anal. Chim. Acta,

in preparation.

(6) Y. Kitatsuji, H. Aoyagi, Z. Yoshida, S. Kihara, Anal. Sci., 14 (1998)pp.67- 70.

(7) Z. Yoshida, S. Kihara, J. Electroanal. Chem, 227(1987)pp.l71-181.

(8)Y. Kitatsuji, H. Aoyagi, Z. Yoshida, S. Kihara, Anal. Chim. Acta, in press.

(9)S. Kihara, Z. Yoshida, Talanta, 31(1984)pp.789-797.

(10)Y. Yoshida, M. Matsui, K. Maeda, S. Kihara, Anal. Chim. Acta, 374

(1998)pp.269- 281.

JAERI-Conf 99-010

[O] iz1

[W]

o ' ' o

[o] iz+o+ I V ± iz+

+ jw

i -

QooO

-2

-3

. 2

— D -

• 1

«- A

^ /

— B—^C —

-6 -5 -4 -3 -2 -!

Fig. 1 Possible mechanisms for an ion-pairextraction.

Fig. 2 Theoretical relations betweendistribution ratios of M+ with X-from an aqueous to an organic solutioncalculated based on Eqn. (15).1: In the absence of complexing agentsin the organic solution 2: In the presenceof an complexing agent in the organicsolution

uo.

-0.1

1oV

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0

xr

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if+0.1

^ : ;

1

+0.2E

: p N u p o ! ° -

""NpOj*Ph Ph

s f ' S P " 'n II

BDPPN^+0.3

/ V vs.TPhE

Fig. 3 Polarograms for the transfer ofactinide ions from aqueous toDCE solution facilitated by BDPPM.Concentration of actinide ion inaqueous: 1O4 M Concentration ofBDPPM in DCE: 10-3 M

Fig. 4 Apparatus for controlled potentialdifference electrolysis at the aqueous/organic interface.WE: Working electrode, CE: Counterelectrode, RE: Reference electrodeW: Aqueous solution containing UC>22+,Pu*+, NpO2

+ and 0.2 M H2SO4.DCE:DCE solution containing 10-2 M BDPPMand 0.05 M crystal violet tetraphenylborate (CV+TPhB-)

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JAERI-Conf 99-010

Fig. 5 The structure of Pu3+ - ion selectiveelectrode (ISE).© Silver/silver electrode, @ Innersolution, ® Nitrobenzene membrane® Porous Teflon membrane,(5) Porous glass filter

-10 -8 -6 -4 -2 0log [Pu3+] in test solution

Fig. 6 The response of Pu3+ - ion selectiveelectrode (ISE).Concentration of HCl in the test solution;1: 1M, 2:0.1 M, 3: 0.01 M,4: 0.001 M

Table 1 Transfer free energies (AG,,0) of actinide and other metal ions at the

aqueous/nitrobenzene interface

Ions

UO22+

NpO22+

PuO22+

NpO2+

Mg2+

Ca2+

Sr2+

Ba2+

Li+

AG.0

kJmol1

71±1

67±2

71±1

>50.4

69.6*

67.3*

66.0*

61.7*

38.2b

Na+

K+

Rb+

Cs+

34.2"

23.4b

19.4b

15.4b

*V. Marecek and Z. Samec, Anal. Chim. Ada, 15.1(1983) 265bJ. Rais, Collect. Czech. Chem. Commun., 36 (1971) 3253

J. Rais, P. Selucky and A. Krys, J. Inorg. Nucl. Chem., 38 (1976) 1376

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JAERI-Conf 99-010

(1) SIDDALL, T. H. Ill, DUKES, E. K.: J. Am. Chem. Soc, 81, 790 (1959).

(2) SWANSON, J. L.: BNWL-1017, Battelle Pacific Northwest Laboratories (1969).

(3) TANAKA, T., NEMOTO, S., TSUBOYA, T., HOSHINO, T.: PNCT-841-71-35, Power Reactor

and Nuclear Fuel Development Corporation of Japan (1971).

(4) MOULIN, J. P.,: CEA-R-4665, Commissariat a l'Energie Atomique (1975).

(5) TOCHIYAMA, O., NAKAMURA, Y., KATAYAMA, Y., INOUE, Y.,: J. Nucl. Sci. Technol., 32,

50 (1995).

(6) TOCHIYAMA, O., NAKAMURA, Y., HIROTA, M., INOUE, Y.: J. Nucl. Sci. Technol., 32, 118

(1995).

(7) MORITA, Y., KUBOTA, M.: JAERI-M 84-043 (1984), [in Japanese].

(8) SRINIVASAN, N., RAMANIAH, M. V., OATIL, S. K., RAMAKRISHNA, V. V.: J. Radional.

Chem., 8, 223 (1971).

(9) NAIRN, J. S., COLLINS, D. A., MCKAY, A. C , MADDOCK, A. G.: Proc. Second Int. Conf.

Peaceful Uses of Atomic Energy, Geneva, 17, 216 (1958).

(10) NAIRN, J. S., COLLINS, D. A.: "Progress in Nuclear Energy, Series III", Pergamon Press, Inc.,

New York, vol. 2, p.518 (1958).

(11) OCHSENFELD, W., BAUMGARTNER, F., BAUDAR, U., BLEYL, H. J., ERTEL, D., KOCH, G.:

KfK-2558 (1977).

(12) FLANARY, J. R., PARKER, G. W.: "Progress in Nuclear Energy, Series III", Pergamon Press,

Inc., New York, vol. 2, p.501 (1958).

(13) ISHIKAWA, K. and , SATO, S.: Chem. Eng. Progr. Symp. Ser. 94, 65, p.102 (1969).

(14) YAMANA, H.: Proc. 4th Int. Conf. on Nuclear Fuel Reprocesing and Waste Management,

RECOD'94, London, Vol. I (1994).

(15) KOMATSU, H., HIRANO, H., YAMANA, H., KUSANO, T.: Preprint 1988 Annu. Mtg. of At.

Energy Soc. Jpn., H5, [in Japanese].

(16) NEMOTO, S., KOMA, Y., SHIBATA, A., SAKAKIBARA, T., and TANAKA, Y., PNC TNI340

96-003, Power Reactor and Nuclear Fuel Development Corporation (1996) [in Japanese].

(17) KOLARIK, Z. and SCHULER, R., Proc. Extraction "84: Symp. Liquid-Liquid Extraction

Science, Dounreay, Scotland, November 27-29, 1984, IChE. Symp. series No.88 (1984).

(18) UCHIYAMA, G., FUJINE, S., HOTOKU, S., and MAEDA, M., Nucl. Technol., 102, 341 (1993).

(19) UCHIYAMA, G., HOTOKU, S., KIHARA, T., FUJINE, S., and MAEDA, M., Solvent Extraction

1990, (1990).

(20) POE, W. L., JOYCE, A. W., MARTENS, R. I.: Ind. Eng. Chem. Process Des. Dev., 3, 314-222

(1964).

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JAERI-Conf 99-010

(21) ISAACSON, R. E., JUDSON, B. F.: "Ind. Eng. Chem., Process Design Develop., 3, 296-301

(1964).

(22) DUCKWORTH, J. P., MICHELS, L. R.: Ind. Eng. Chem., Process Design Develop., 3, 302-305

(1964).

(23) DUCKWORTH, J. P., LARIVIERE, J. R.: Ind. Eng. Chem., Process Design Develop., 3, 306

(1964).

(24) CHESN*. A: Ind. At., 7/8, 71 (1966).

(25) GROH, H. J., SCHLEA, C. S.: "Progress in Nuclear Energy, Series III", Pergamon Press, Inc.,

New York, vol. 4, p.507 (1970).

(26) BENEDICT, M., PIGFORD, T. H., LEVI, H. W.: "NUCLEAR CHEMICAL ENGINEERING", 2nd

ed., McGraw-Hill Book Company, New York, p.544 (1981).

(27) HOMMA, S., TAKANASHI, M., KOGA, J., MATSUMOTO, S., OZAWA, M.: Nuclear Technology

116,108-114

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JAERI-Conf 99-010 JP0050058

2.7 tf tO'lI t f O1) 7

l , Wmt2 l , » t # M 1 , 2 , fe

Alteration of Minerals and its Effects on the Migration of Uranium

Toshihiko Ohnuki1 , Nobuyuki Yanase 1, Hiroshi Isobe * '2l

Tsutomu Sato1 '3

Satoshi Utsunomiya4, Takashi Murakami4

1 : mot,2 -.3 -.4 :

Abstract

For the long-term behavior of radioactive wastes, our major concern isin actinides because of their long-lasting hazard. The rock-forming mineralsare altered structurally and chemically with time by geochemical processes suchas water-rock interactions. The relationships between alteration and actinidesare characterized by reactions, especially, sorption and desorption tocoexisting minerals. One important process to be noted is how actinides oncesorbed on a mineral behaves during the alteration. Thus, if we are to understandthe radionuclide migration over a long, geologic time, knowledge of thealteration of minerals and its effects on the migration of actinides areindispensable along with those of the migration characteristics of actinidesin geosphere.

We have worked on the clarification of the alteration of minerals andits effects on the migration of uranium at Koongarra, Australia under thecollaboration programme between JAERI and University of Tokyo. We clarifiedthat uranium is fixed by the mineralization of uranium at the boundary of ironminerals. The fixation will be occurred in phosphate minerals, such as apatite.These results show that geosphere has higher performance on the retardation ofradionuclides migration than that expected by the Kd model which involvesadsorption of radionuclides on minerals.

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[1] Murakami, T. et al.: Alligator Rivers Analogue Project Final Report Vol.9, Australian

Nuclear Science & Technology Organization 1992).

[2] Snelling, A. A.: Alligator Rivers Analogue Project Final Report Vol.2, Australian Nuclear

Science & Technology Organization 1992).

[3] Ohnuki, T. et al., to be published.

[4] Isobe, H., J. Nucl. Mater., 190, 174-187(1992).

[5] Murakami, T., et a l . , Am. Mineral. 82, 888-899 (1997).

[6] Sato T., et a l . , Environ. Sci. Technol. 31, 2854-2858 (1997).

[7] Ohnuki, T., et al., J. Nucl. Sci. Tech., (1997)(in print).

(OOhnuki^ Isobe, Yanase, Nagano, Sakamoto, Sekine : Change in Sorption Characteristicsof Uranium during Crystallization of Amorphous Iron Minerals, J. Nuclear Sci. and Tech.,34, 1153-1158(1997).(2)0hnuki, Kozai, Isobe, Murakami, Yamamoto, Aoki, Naramoto : Sorption Mechanism of Europiumby Apatite Using Rutherford Backscattering Spectroscopy and Resonant Nuclear ReactionAnalysis, J. Nuclear Sci. and Tech., 34, 58-62(1997).

?vy>tm.<Dis&-, tkto&mmvoWR, 2, 121(1996)(4)Murakami, Ohnuki, Isobe, Sato : Mobility of uranium during weathering, Am. Mineral. 82,888-899 (1997).(5)Isobe, Hidaka, Ohnuki : SIMS Analysis of Lead Isotopes in the Primary Ore Body of theKoongarra Deposit Australia: Behaviour of Lead in the Alteration of Uranium Minerals,Scientific Basis for Nuclear Waste Managemen XXI, 687(1998).(6)Yanase, Sato, Iida, Sekine : Distribution of uranium-series radionuclides in rock andmigration rate of uranium at the Koongarra uranium deposit, submitted to Radiochim. Acta(WJ40 .(7)Murakami, Isobe, Sato, Ohnuki : Weathering of Chlorite in a Quartz-Chlorite Schist: I.Mineralogical and Chemical Changes, Clays and Clay minerals 44, 144(1996).(8)T. Tanaka and T. Ohnuki, Colloidal Migration Behavior of Radionuclides Sorbed on FineParticles through a Sand Layer, J. Nuclear Science and Technology, 33, 62-68(1996).(9)T. Murakami, H. Isobe, T. Sato, T. Ohnuki : Weathering of Chlorite in a Quartz-ChloriteSchist: I. Mineralogical and Chemical Changes, Clays and Clay minerals 44, 144(1996).(10) T. Sato, T. Murakami, N. Yanase, H. Isobe, Payne, T. E. s Airey, P. L. : Iron nodulesscavenging uranium from groundwater, Environ. Sci. Technol. 31, 2854-2858 (1997).*(11) Y.Suzuki, T. Murakami, T. Kogure, H. Isobe, T. Sato, Crystal chemistry andmicrostructures of uranyl phosphates, submitted to Scientific Basis for Nuclear WasteManagement XXI, 839(1998).

JAERI-Conf 99-010

Appendix

Symposium on the Joint Research Program between JAERI and Universities

- Current Status and Future Perspectives of the Chemistry Researchin the Nuclear Fuel Cycle Backend Field -

January 27, 1999Tokyo, Japan

10:00-10:15 Opening address Satoru Tanaka (Univ. Tokyo)

Part 1: Main Activities on the Joint Research Program during 1996-1998

10:15-12:15 Chairman: Hiromichi Nakahara (Tokyo Metropolitan Univ.)

<Session 1: Nuclear Chemistry for TRU Recycling>10:15 Identification of New Neutron-rich Lanthanide Isotopes

Shin-ichi Ichikawa (JAERI)10:45 Identification of New Neutron-rich Actinide Isotopes

Yasuji Ohura (Tokyo Metropolitan Univ.)

<Session 2: Solid State Chemistry on Nuclear Fuels and Wastes>11:15 Study on Phase Equilibria of Np-Pu-U-O System

Noriko Shirasu (JAERI)11:45 Study on Chemical Properties of Uranium Oxides Fuel with Some Additives

Takeo Fujino (Tohoku Univ.)

12:15-13:15 Lunch

13:15-15:15 Chairman: Shoichi Tatimori (JAERI)

<Session 3: Solution Chemistry on Fuel Reprocessing and Waste Management13:15 New Method for Separation of Actinides Based on Electrolytic Ion-transfer

Reaction across Aqueous/Organic InterfaceZenko Yoshida (JAERI)

13:45 On the Extraction Behavior of Np in the PUREX ProcessShiro Matsumoto (Saitama Univ.)

<Session 4: Fundamental Chemistry on Radioactive Waste Disposal>14:15 Alteration of Minerals and its Effects on the Migration of Uranium

Toshihiko Ohnuki (JAERI)14:45 Study on Corrosion Behavior of Overpack and Migration Behavior of

Radionuclides in BufferTamotsu Kozaki (Hokkaido Univ.)

15:15-15:30 Coffee Break

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JAERI-Conf 99-010

Part 2: Panel Discussion "Perspectives and Research Activities in the Next Phase"

15:30 Introductory Remarks Satoru Tanaka (Univ. Tokyo)Group 1 Hiromichi Nakahara (Tokyo Metropolitan Univ.)Group 2 Toshiyuki Yamashita (JAERI)Group 3 Shoichi Tachimori (JAERI)Group 4 Yoshitaka Minai (Musashi Univ.)Discussions Chairman: Satoru Tanaka (Univ. Tokyo)

17:30 Closing Remarks Hiroji Katsuta (JAERI)

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