Evaluation of speciation technology : workshop proceedings, Tokai-mura, Ibaraki, Japan, 26-28 October, 1999.

438 Pages·2001·4.763 MB·English

by  OECD

Nuclear Science
E
valuation of
Speciation Technology
Workshop Proceedings
Tokai-mura, Ibaraki, Japan
26-28 October 1999
N U C L E A R • E N E R G Y • A G E N C Y
Nuclear Science
Evaluation of
Speciation Technology
Workshop Proceedings
Tokai-mura, Ibaraki, Japan
26-28 October 1999
NUCLEAR ENERGY AGENCY
ORGANISATION FOR ECONOMIC CO-OPERATION AND DEVELOPMENT
ORGANISATION FOR ECONOMIC CO-OPERATION AND DEVELOPMENT
Pursuant to Article 1 of the Convention signed in Paris on 14th December 1960, and which came into force on
30th September 1961, the Organisation for Economic Co-operation and Development (OECD) shall promote policies
designed:
− to achieve the highest sustainable economic growth and employment and a rising standard of living in
Member countries, while maintaining financial stability, and thus to contribute to the development of
the world economy;
− to contribute to sound economic expansion in Member as well as non-member countries in the process
of economic development; and
− to contribute to the expansion of world trade on a multilateral, non-discriminatory basis in accordance
with international obligations.
The original Member countries of the OECD are Austria, Belgium, Canada, Denmark, France, Germany,
Greece, Iceland, Ireland, Italy, Luxembourg, the Netherlands, Norway, Portugal, Spain, Sweden, Switzerland, Turkey,
the United Kingdom and the United States. The following countries became Members subsequently through accession at
the dates indicated hereafter: Japan (28th April 1964), Finland (28th January 1969), Australia (7th June 1971), New
Zealand (29th May 1973), Mexico (18th May 1994), the Czech Republic (21st December 1995), Hungary (7th May
1996), Poland (22nd November 1996), Korea (12th December 1996) and the Slovak Republic (14 December 2000). The
Commission of the European Communities takes part in the work of the OECD (Article 13 of the OECD Convention).
NUCLEAR ENERGY AGENCY
The OECD Nuclear Energy Agency (NEA) was established on 1st February 1958 under the name of the OEEC
European Nuclear Energy Agency. It received its present designation on 20th April 1972, when Japan became its first
non-European full Member. NEA membership today consists of 27 OECD Member countries: Australia, Austria,
Belgium, Canada, Czech Republic, Denmark, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy,
Japan, Luxembourg, Mexico, the Netherlands, Norway, Portugal, Republic of Korea, Spain, Sweden, Switzerland,
Turkey, the United Kingdom and the United States. The Commission of the European Communities also takes part in
the work of the Agency.
The mission of the NEA is:
− to assist its Member countries in maintaining and further developing, through international
co-operation, the scientific, technological and legal bases required for a safe, environmentally friendly
and economical use of nuclear energy for peaceful purposes, as well as
− to provide authoritative assessments and to forge common understandings on key issues, as input to
government decisions on nuclear energy policy and to broader OECD policy analyses in areas such as
energy and sustainable development.
Specific areas of competence of the NEA include safety and regulation of nuclear activities, radioactive waste
management, radiological protection, nuclear science, economic and technical analyses of the nuclear fuel cycle, nuclear
law and liability, and public information. The NEA Data Bank provides nuclear data and computer program services for
participating countries.
In these and related tasks, the NEA works in close collaboration with the International Atomic Energy Agency
in Vienna, with which it has a Co-operation Agreement, as well as with other international organisations in the nuclear
field.
© OECD 2001
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FOREWORD
It has been widely recognised among researchers that speciation data are essential for proper and
reliable modelling of radionuclide behaviour in nuclear reprocessing systems, in developing improved,
more specific separation agents and in the migration of radionuclides in the near and far field areas of
nuclear waste repository systems.
For this reason, the NEA Nuclear Science Committee decided to hold a workshop with the aim of
preparing a report on various speciation methods. The Workshop on Evaluation of Speciation
Technology was successfully held at Japan Atomic Energy Research Institute (JAERI), from
26-28 October 1999, with 80 participants from 10 countries. Eleven invited papers and 27 posters
were presented on recent progress and application in each of the following five main topics:
• Methods for trace concentration speciation (<10-6 M).
• Methods for macro concentration speciation (>10-6 M).
• Methods for empirical formula and molecular structure determination.
• Methods for redox speciation.
• Predictive approach to speciation.
On the second and third days of the workshop, subgroups according to the categories mentioned
above were set up to evaluate speciation technology. The aims of these subgroups were to examine
speciation data that are needed, the advantages and limitations of the different methods that can be
applied to obtain this data and suggestions for future R&D to improve present methods or to develop
new methods of speciation. The report prepared through each subgroup discussion would serve to
guide researchers in choosing the most useful technique.
It was recommended that a web site should be established by OECD/NEA to make information
on speciation technology easily available (see Annex).
These proceedings contain the abstracts and full papers presented at the workshop and the subgroup
reports prepared by the participants. The editors, Professor Gregory R. Choppin, Professor Jean Fuger
and Dr. Zenko Yoshida, and other anonymous referees reviewed the full papers. The editors wish to
acknowledge and thank these reviewers.
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OPENING ADDRESS – Satoshi Sakurai, OECD/NEA
It is a great pleasure for me to welcome you to this workshop on behalf of the OECD Nuclear
Energy Agency. The OECD Nuclear Energy Agency is an international organisation based in Paris,
France, with the basic mission to contribute to the viability of the nuclear power option. The Agency
pursues this mission, for example by bringing together expertise in Member countries in co-operative
projects, by disseminating important information, by developing consensus opinions and by arranging
meetings and workshops such as this one.
The NEA work programme addresses all the key issues in the nuclear energy area, such as
nuclear safety, radioactive waste management, radiation protection, legal aspects, economics and
nuclear science. In addition, the NEA Data Bank provides a direct cost-free service on nuclear data
and computer programs to scientists in Member countries. For those of you who would like to know
more about the NEA, I have brought with me a number of leaflets both concerning the NEA and its
Data Bank. The information is also available on the NEA’s web page, www.nea.fr.
A large part of the NEA’s scientific programme is devoted to reactor and fuel cycle physics.
However, in recent years, this programme has also been extended to cover nuclear fuel cycle
chemistry issues. One preoccupation in the nuclear fuel cycle is the separation of radioactive elements
from various materials. For this reason, the NEA established a small group of experts to review the
different techniques and chemical processes used in the separation of actinides. The group, with the
leadership of Dr. Wymer, produced a state-of-the-art report entitled Actinide Separation Chemistry in
Nuclear Waste Streams and Materials. The report was published in 1997, and a limited number of
copies are still available.
As a follow up to this state-of-the-art report, the NEA arranged the Workshop on Long-lived
Radionuclide Chemistry in Nuclear Waste Treatment. This was organised by the CEA, France, in
June 1997 at Villeneuve-lès-Avignon, France. The objective of this workshop was to provide up-to-date
information on the chemistry of radionuclides and to provide guidance on future activities that could
be undertaken in the framework of the NEA. The outcome was a recommendation that the NEA
organise two workshops, one on the Evaluation of Speciation Technology (the current workshop), and
the other on Speciation, Techniques and Facilities for Characterisation of Radioactive Materials at
Synchrotron Light Source, which was held in October 1998 at Grenoble, France. The proceedings of
the workshop was recently published and I have here one copy that will be made available for
consultation. The second meeting is planned to be held, again at Grenoble, in September 2000.
Concerning the organisation of the present workshop, I would first of all like to thank Professors
Choppin and Fuger for the important role they have played in the arrangement of this meeting, both as
initiator and also as an active member of the organising committee. I know that organising a meeting
such as this is very hard work, and I particularly want to thank Dr. Yoshida and his colleagues, who
have laid the basis for a very successful and stimulating meeting. I am also grateful to Japan Atomic
Energy Research Institute for hosting this workshop. Many thanks go also to Dr. Maeda, General
Chairperson, and to International Scientific and Local Organising Committee members. I am sure that
you will spend an interesting, instructive and profitable three days here in Tokai-mura. I wish you all a
very successful meeting.
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TABLE OF CONTENTS
Foreword.................................................................................................................................................. 3
Opening Address..................................................................................................................................... 4
Executive Summary............................................................................................................................... 11
Opening Session...................................................................................................................................... 15
R.G. Wymer
Speciation Imperatives for Waste Management and Environmental Pollution.............. 17
SESSION A Methods for Trace Concentration Speciation (<10-6 M)............................................ 25
B.F. Myasoedov, A.P. Novikov
Radiochemical Procedures for Speciation of Actinides in the Environment:
Methodology and Data Obtained in Contaminated Regions of Russia by
Radionuclides................................................................................................................... 27
J.I. Kim
Nanoscopic Speciation of Aquatic Actinide Ions by Laser Spectroscopy...................... 39
SESSION B Methods for Macro Concentration Speciation (>10-6 M).......................................... 49
C. Moulin
Speciation from Photon to Ion Detection........................................................................ 51
T. Kimura ,Y. Kato, H. Takeishi, Y. Takahaski, Y. Minai, G.R. Choppin
Determination of the Hydration Number of Actinides(III) and Lanthanides(III) by
Luminescence Lifetime Measurement and its Application to the Speciation Study...... 61
SESSION C Methods for Empirical Formula and Molecular Structure Determination............ 83
M.A. Denecke, J. Rothe, C. Pohlmann, H. Geckeis, D. Degering, J. Janssen
X-ray Absorption Fine Structure Spectroscopy for Radionuclide
Speciation Studies............................................................................................................ 85
J.F. Desreux, B. Lambert, V. Jacques
Magnetic Resonance Techniques in Speciation of Actinides and
Fission Products................................................................................................................ 97
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SESSION D Methods for Redox Speciation...................................................................................... 109
D. Rai, N.J. Hess
An Overview of Actinide Redox Speciation Methods, Other than Chemical
Separation Techniques: Their Applicability, Advantages and Limitations.................... 111
A. Saito
Chemical Separation Methods for Redox Speciation of Actinides................................. 119
SESSION E Predictive Approach to Speciation............................................................................... 131
D. Read
Estimation of Thermodynamic Data in Assessing the Geological
Disposal of Radioactive Waste........................................................................................ 133
H. Moriyama, H. Yamana, K. Fujiwara, A. Kitamura
Chemical Analogy in the Case of Hydrolysis Species of f-elements............................. 145
POSTER SESSION................................................................................................................................ 157
Part A: Methods for Trace Concentration Speciation (<10-6 M)................................. 157
M. Illemassène, S. Hubert, P. Tarapcik
Use of Capillary Electrophoresis for Speciation Purposes Involving f-elements;
Application to the Systems Nd3+/H PO (3-n)- and UO 2+/IO -........................................... 159
n 4 2 3
Y. Hanzawa, M. Magara, F. Esaka, K. Watanabe, S. Usuda, Y. Miyamoto,
K. Gunji, K. Yasuda, H. Nishimura, T. Adachi
Development Programme of Analytical Techniques for Ultra Trace Amounts
of Nuclear Materials in Environmental Samples for Safeguards – From a
Viewpoint of Speciation Technology ............................................................................. 167
J. Havel, D. Gajdošová, J. Soto-Guerrero
Matrix-assisted Laser Desorption/Ionisation Time-of-flight Mass
Spectrometry as a Tool for Speciation Analysis?............................................................ 173
S. Nagao, Y. Sakamoto, T. Tanaka, H. Ogawa
Association of Actinides with Dissolved Organic Materials in
Organic-rich Groundwaters.............................................................................................. 181
I. Dryapachenko, B. Rudenko
Speciation of “Hot Particle” by Fission Product Element Identification........................ 189
T. Asakura, G. Uchiyama, M. Sawada, H. Hagiya, S. Fujine, P.J.A. Howarth
Application of X-ray and Low Energy Gamma-ray Spectroscopy to
Determination of Actinide Concentration in Reprocessing Solution.............................. 195
K. Ohashi, K Ougiyanagi, S.Y. Choi, H. Ito, H. Imura
Cloud Point Extraction and Speciation of Iron(III) of 10–7-10–6 M Level
Using 8-quinolinol Derivatives and Triton X-100.......................................................... 203
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H. Amano, Y. Hanzawa, M. Watanabe, T. Matsunaga, T. Ueno, S. Nagao
N. Yanase, Y. Onuma
Speciation of Environmental Radionuclides in the Chernobyl 30 km Zone.................. 211
Part B: Methods for Macro Concentration Speciation (>10–6 M)............................... 219
P. Paviet-Hartmann, Th. Fanghänel, R. Klenze, Th. Könnecke,
J.I. Kim, W. Hauser, H. Weger, K.K. Park, K.H. Chung,
Cm(III) Speciation in Brines by Time Resolved Laser Fluorescence
Spectroscopy..................................................................................................................... 221
H. Hotokezaka, S. Tanaka, S. Nagasaki
Speciation Analysis on Eu(III) in Aqueous Solution Using Laser-induced
Breakdown Spectroscopy................................................................................................. 231
W. Runde, M.P. Neu, C. Van Pelt, S. Reilly, Y. Xu
Actinyl(VI) Speciation in Concentrated Sodium Chloride Solutions............................. 233
Y. Kameo
Characterisation of Oxide Films Formed on Steel Surface in BWR Environment........ 241
J. Xu, P.W. Durbin, K.N. Raymond
Actinide Sequestering Agents: Design, Structural and Biological Evaluations............. 247
F. Wastin, E. Colineau, T. Gouder, J. Rebizant, G.H. Lander
Transuranium Compounds Characterisation Facility at ITU-Karlsruhe......................... 255
J.M. Berg, D.K. Veirs
Speciation of Pu(IV) Complexes with Weak Ligands from Visible Spectra................. 257
Y. Takahashi, T. Kimura, Y. Kato, Y. Minai
Laser-induced Luminescence Lifetime Measurement as an Analytical Probe for
Speciation of Polycarboxylates in Aqueous Solutions.................................................... 265
Part C: Methods for Empirical Formula and Molecular Structure
Determination.................................................................................................................. 267
R. Klenze
Direct Spectroscopic Speciation of Actinide Ions at the Water/Mineral Interface........ 269
D.T. Reed, A.J. Kropf, S.B. Aase, S. Zygmunt, L. Curtiss
Oxidation State and Structure of Actinides in Environmental Samples Using
Synchrotron-based Techniques........................................................................................ 271
T. Yaita, M. Hirata, H. Narita, S. Tachimori, H. Yamamoto,
N.M. Edelstein, J.J. Bucher, D.K. Shuh, L. Rao
Co-ordination Properties of Diglycolamide (DGA) to Trivalent Curium
and Lanthanides Studied by XAS, XRD and XPS Methods........................................... 273
T. Ohnuki, H. Isobe, T. Kamiya, T. Sakai, T. Murakami
Speciation of Uranium in Minerals by SEM, TEM, µ-PIXE, XPS and XAFS.............. 281
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Part D: Methods for Redox Speciation.......................................................................... 287
S. Kihara, K. Maeda, Y. Yoshida, Z. Yoshida, H. Aoyagi, Y. Kitatsuji, O. Shirai
Electroanalytical Data on Uranium, Neptunium and Plutonium Ions in
Acidic Aqueous Solutions................................................................................................ 289
J.R. Duffield, J.A. Jarratt
Polarographic Validation of Chemical Speciation Models............................................. 297
H. Imura, M. Michiguchi, K. Nakano, K. Ohashi, H. Aoyagi, Z. Yoshida
Separation and Determination of Uranium(IV,VI) by High-performance
Extraction Chromatography with 2-thenoyltrifluoroacetone and Citric Acid................ 299
Z. Yoshida, T. Kimura, Y. Kato, Y. Kitatsuji, H. Aoyagi, Y. Meguro, S. Kihara
Voltammetric Speciation of U(VI) in the Aqueous Solution of pH 2-6 under CO
2
Gas/Aqueous Solution/UO CO Solid Phases Equilibrium............................................ 307
2 3
Y. Kitatsuji, H. Aoyagi, Z. Yoshida, S. Kihara
Ion-selective Electrode Method for the Speciation of Actinide Ions.............................. 313
K-W. Kim, K-C. Song, E-H. Lee, I-K. Choi, J-H. Yoo
Redox Speciation of Np in TBP Extraction Process Based on Electrochemical
Oxidation State Control of Np......................................................................................... 321
Part E: Predictive Approach to Speciation.................................................................... 331
F. Rorif, J. Fuger, J.F. Desreux
Contribution to Lanthanide and Actinide Speciation: Thermodynamic Studies
of Hydroxycarbonate Species.......................................................................................... 333
O. Tochiyama
Data Processing for the Determination of Stability Constants........................................ 339
G. Meinrath, T. Kimura, Y. Kato, Z. Yoshida, S. Lis
Chemometric and Computer-intensive Techniques for Speciation................................ 347
R.J. Taylor, I. May
PUREX Process Modelling – Do We Really Need Speciation Data?............................ 355
SUBGROUP REPORTS........................................................................................................................ 357
Trace Concentration Speciation (<10-6)........................................................................... 359
Methods for Macro Concentration Speciation (>10-6 M)................................................ 367
Methods for Empirical Formula, Molecular Structure Determination
and Colloid Characterisation............................................................................................ 379
An Overview of Actinide Redox Speciation Methods: Their Applicability,
Advantages and Limitations............................................................................................. 389
Predictive Approach to Speciation................................................................................... 403
8
Recommendation.................................................................................................................................... 417
Closing Remarks..................................................................................................................................... 421
Annex 1 – List of Participants................................................................................................................ 423
Annex 2 – Workshop Organisation........................................................................................................ 433
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