Evaluation of Speciation Technology - OECD Nuclear Energy Agency

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EXECUTIVE SUMMARY The Workshop on Evaluation of Speciation Technology was successfully held at Japan Atomic Energy Research Institute (JAERI) from 26-28 October 1999. This workshop was devoted to: • Exchanging recent progress in the development of speciation technology and its application in the various fields of nuclear fuel cycle. • Discussing the advantages, disadvantages and limitations of each speciation method and preparing a report. • Proposing or recommending possible co-operative works to be performed within the framework or under the auspices of the OECD/NEA/NSC. There were 80 participants gathered together from ten countries. Eleven invited papers were presented on recent progress and applications concerning the following five main topics: • Methods for trace concentration speciation (10 -6 M). • Methods for empirical formula and molecular structure determination. • Methods for redox speciation. • Predictive approach to speciation. The keynote presentation addressed speciation requirements in the context of problems produced by nuclear energy and nuclear weapons production. This talk was followed by two invited presentations for each of the topics mentioned above. These presentations covered: • Radiochemical procedures for actinides in the environment. • LASER spectroscopy nanoscopic speciation. • LASER-based analytical techniques (TRLIF, LA-OES and ES-MS) for direct studies on solids, liquids, etc. • Luminescence lifetime measurement for determination of hydration number. • X-ray absorption fine structure spectroscopy for Hf(IV) sorbed onto silica. • Applications of magnetic resonance methods in the speciation of f elements. 11
• Actinide redox speciation methods, other than chemical separation techniques. • Chemical separation methods for redox speciation of actinides. • Estimation of thermodynamic data in assessing geological disposal. • Chemical analogy in the case of hydrolysis species of f-elements. In the poster session, 27 posters were presented on recent progress and application in each of the five main topics mentioned above. For the speciation methods with regard to trace concentration, eight posters covered the following methods: capillary electrophoresis, mass spectrometry, filtration, X-ray and low-energy γ-ray spectroscopy, and extraction. Concerning speciation methods for macro concentration, reports were given on the following topics: LASER techniques, X-ray application, photospectrometry, vibrational spectroscopy, Mössbauer spectroscopy and NMR. The development of actinide sequestering agents was also addressed. For empirical formula and molecular structure determination, all the posters were related to X-ray techniques: EXANES, EXAFS, XPS and XRD. Electrochemical methods, such as coulometry, polarography, voltammetory and potentiometry with ion-selective electrode were mostly applied for the purpose of redox speciation. Other methods reported were high-performance extraction chromatography and UV-vis-NIR spectroscopy. As posters related to predictive approach to speciation, works on calorimetry for hydroxycarbon species of lanthanides and actinides, data processing for the determination of stability constants, chemometric and computer-intensive techniques for U(VI) and spectrophotometry to obtain data for PUREX process models were presented. After the oral presentation of invited papers and the poster session, five subgroups according to the categories mentioned above were set up. The members of each group discussed needs concerning speciation data, the advantages and limitations of the different speciation methods, and suggestions for future R&D. Resulting from these discussions, subgroup reports were prepared, which are included in these proceedings. The methods evaluated by the subgroups are summarised in the table below. The reports are also available on the NEA web site at: http://www.nea.fr/html/science/spec. Through the comparison of various speciation methods, the participants recognised that while a great deal has been accomplished with regard to speciation techniques and methodologies, much still remains to be done. This is in part due to the difficulty and complexity of the task, caused by the ever-increasing speciation challenges. On the other hand, researchers require more information concerning recent progress in speciation technology. Therefore, it was recommended that a working group would be set up in order to review the reports and integrate them into a site devoted to speciation within the NEA web site. It was agreed among the participants that Dr. Wymer would examine the scope and content of the web site and draft a proposal. 12
Page 1 and 2: Nuclear Science Evaluation of Speci
Page 3 and 4: ORGANISATION FOR ECONOMIC CO-OPERAT
Page 5 and 6: OPENING ADDRESS - Satoshi Sakurai,
Page 7 and 8: SESSION D Methods for Redox Speciat
Page 9 and 10: Part D: Methods for Redox Speciatio
Page 14: Speciation methods evaluated in the
Page 18 and 19: SPECIATION IMPERATIVES FOR WASTE MA
Page 20 and 21: matrices poses difficult challenges
Page 22 and 23: Table 1 lists some of the more comm
Page 24 and 25: In the complex biosphere there are
Page 26: SESSION A Methods for Trace Concent
Page 29 and 30: Introduction Experimental tests of
Page 31 and 32: complexes. As a result, fulvic acid
Page 33 and 34: possibility of selective extraction
Page 35 and 36: Table 1. Data on radiochemical anal
Page 37 and 38: Figure 1. Flowsheet of isolation of
Page 40 and 41: NANOSCOPIC SPECIATION OF AQUATIC AC
Page 42 and 43: A number of spectroscopic methods h
Page 44 and 45: Figure 4. LPAS and UV-Vis spectra o
Page 46 and 47: composite and hence it is called br
Page 48: [11] J.V. Beitz,, J.P. Hessler, “
Page 52 and 53: SPECIATION FROM PHOTON TO ION DETEC
Page 54 and 55: technique for speciation (i.e. the
Page 56 and 57: Figure 2. TRLIF spectra and lifetim
Page 58 and 59: Figure 5. ES-MS of uranium hydroxo
Page 60: [11] “Dual use of Micellar Enhanc
Page 63 and 64:
Introduction The solution chemistry
Page 65 and 66:
of the metal sorbed was less than 9
Page 67 and 68:
For the hydrated ions without any c
Page 69 and 70:
those of sorbed Cm(III) and Eu(III)
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Conclusion The luminescence propert
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[34] Graffeo, A.J., Bear, J.L., J.
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Figure 1. Luminescence decay consta
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Figure 3. Plot of the inner-sphere
Page 79 and 80:
Figure 5. Distribution coefficients
Page 81 and 82:
Figure 7. Dissolved fraction of Eu(
Page 84:
SESSION C Methods for Empirical For
Page 87 and 88:
Introduction The application of X-r
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The mica was left in the solution f
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That the GIXAS spectra of the Hf(IV
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[7] Frauenfelder, H., Steffen, R.M.
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Figure 3. Grazing incidence XAFS be
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Figure 7. Hf L3 edge GIXAFS spectra
Page 99 and 100:
Introduction Nuclear magnetic reson
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ecause there is no longer an anisot
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20-30 MHz is observed for slowly tu
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[12] P. Caravan, J.J. Ellison, T.J.
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Figure 4. NMRD curves of free Gd 3+
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SESSION D Methods for Redox Speciat
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What is meant by speciation In the
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• It is non-invasive and non-pert
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Table 1. Selected absorption bands
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Figure 3. Shift in absorption edge
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Introduction Energy production reli
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then Pu in higher oxidation states
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• Reliability and reproducibility
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Conclusion Currently existing techn
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Table 1. Systems studies; the metho
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SESSION E Predictive Approach to Sp
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Introduction Thermodynamic data pro
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secondary mineral formation in immo
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Additionally, if a phase is impure,
Page 141 and 142:
REFERENCES [1] T. Murakami, T. Ohnu
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Figure 1. (a) Backscattered electro
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CHEMICAL ANALOGY IN THE CASE OF HYD
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4f-electrons of the lanthanides, an
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Since water molecules are substitut
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REFERENCES [1] D. Rai, J.L. Swanson
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Table 3. Effective charges of actin
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Figure 3. Atomic number dependence
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POSTER SESSION Part A: Methods for
Page 161 and 162:
Introduction Several complementary
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migration. Consequently, only one p
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Some solutions are under test, such
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DEVELOPMENT PROGRAMME OF ANALYTICAL
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Evaluation of the footprints in the
Page 172 and 173:
REFERENCES [1] B. Pellaud, “IAEA
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MATRIX-ASSISTED LASER DESORPTION/IO
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Preparation of the samples There ar
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Acknowledgement SHIMADZU Handelsges
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Figure 3. Clusters of uranium(VI) o
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ASSOCIATION OF ACTINIDES WITH DISSO
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carried out by the ultra-filters wi
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REFERENCES [1] N.A. Marley, J.S. Ga
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Figure 3. Molecular size distributi
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SPECIATION OF “HOT PARTICLE” BY
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The clear results were obtained reg
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in some tens volt per centimetre an
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APPLICATION OF X-RAY AND LOW ENERGY
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of 12.5 keV to 23.0 keV. The coeffi
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[7] R.C. Gatti, H. Nitsche, et al.,
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Figure 1. Calibration results for 2
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Introduction HQ was used as the ext
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Iron(III) speciation can be achieve
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Figure 1. Solubility of HMOnQ in 4
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SPECIATION OF ENVIRONMENTAL RADIONU
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precipitate (humic acid fraction) w
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Acknowledgements This research has
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Figure 1. Speciation procedure A: e
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POSTER SESSION Part B: Methods for
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Introduction The possibility of dis
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fluorescence decay rate of the diff
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Table 1. Spectroscopic characterist
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Figure 3. Peak deconvolution of a m
Page 232 and 233:
SPECIATION ANALYSIS ON EU(III) IN A
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ACTINYL(VI) SPECIATION IN CONCENTRA
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Preparation and characterisation of
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Characterisation of solid AnO2CO3 T
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Solubility data of uranyl in carbon
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CHARACTERISATION OF OXIDE FILMS FOR
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Figure 1. Relative concentration of
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Figure 4. Schematic structure of ox
Page 249 and 250:
Introduction The actinide elements
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5LI-(Me-3,2-HOPO (X=CH2 5LIO-(Me-3,
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Uranium sequestering agents Uranium
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REFERENCES [1] (a) K.N. Raymond, in
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SPECIATION OF PU(IV) COMPLEXES WITH
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will have an absorption spectrum th
Page 262 and 263:
As shown in our earlier work, Eq (1
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Figure 1. Plots of log Ka-2 D(I) vs
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As demonstrated above, laser induce
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DIRECT SPECTROSCOPIC SPECIATION OF
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4 Energy relative to Pu(IV) 3 2 1 0
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Introduction In R&D on the “back
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distribution ratios of Am are not s
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Figure 1. The crystal structure of
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Table 1. Selected geometrical param
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Introduction The two important oxid
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to these two minerals. Ferrihydrite
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REFERENCES [1] J.K. Osmond and M. I
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ELECTROANALYTICAL DATA ON URANIUM,
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- system of Eq. (2), which is measu
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The following consideration indicat
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Figure 1. Coulopotentiograms for U,
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SEPARATION AND DETERMINATION OF URA
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HPEC procedure An aqueous solution
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REFERENCES [1] T. Braun, G. Ghersin
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Figure 3. Effect of pH on the reten
Page 309 and 310:
Introduction Voltammetry or polarog
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voltammograms in Figures 2(a)-2(c)
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Figure 2. Voltammograms for U(VI) s
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Introduction One of the most unique
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The ∆V1/2 of anodic and cathodic
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Table 1. Half wave potential for ac
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REDOX SPECIATION OF NP IN TBP EXTRA
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Analyser). Nitric acid concentratio
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papers dealing with Np oxidation in
Page 328 and 329:
Figure 2. Np distribution coefficie
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Figure 6. Np distribution coefficie
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POSTER SESSION Part E: Predictive A
Page 335 and 336:
Introduction In the back-end of the
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CO2 in the solution and were calcul
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Table 1. Thermochemical cycles for
Page 341 and 342:
Introduction The essence of data pr
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(sensitivity analysis). In order to
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[G15] = LOG(SUM(D15:F15)) (25) Here
Page 347 and 348:
Table 2. Spreadsheet arrangement of
Page 349 and 350:
Introduction Scientific studies aim
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Figure 2. Comparison of non-linear
Page 353 and 354:
The analysis shows a probability of
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Internationally accepted QA/QC stan
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SUBGROUP REPORTS 357
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Advantages On-line CE-MALDI/TOF MS
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• Colloidal state: - Membrane fil
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[10] P.A. Bertrand, G.R. Choppin,
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METHODS FOR MACRO CONCENTRATION SPE
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Advantages are a complete structure
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X-ray photoelectron spectroscopy: X
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The advantages are: • A multi-ele
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[12] S. Tsutsui, M. Nakada, M. Saek
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[44] H. Capdevila, P. Vitorge, E. G
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Molecular structure Molecular struc
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The detection limit of these method
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By analysing the chemical shifts an
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Current Chemistry. No. 157, K. Yosh
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AN OVERVIEW OF ACTINIDE REDOX SPECI
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Related to this technique is comple
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Main advantages of the electrochemi
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Extraction method with use of PMBP,
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[37] W. Runde, M.P. Neu, S.D. Conra
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Reagent BaSO4 Silica gel CaCO3 Tabl
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Figure 1. X-ray absorption edge ene
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The following sections address the
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priority and are supplemented by do
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has been addressed, albeit somewhat
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Table 1: Comparison of •G° f for
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The full range of environmental par
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[21] P.L. Brown, R.N. Sylva, “Uni
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RECOMMENDATION It was recommended t
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There should be allowance for datab
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Annex 1 LIST OF PARTICIPANTS BELGIU
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ARISAKA, Makoto Tel: +81 29 282 549
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NAGAISHI, Ryuji Tel: +81 29 282 549
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YASUOKA, Hiroshi Tel: +81 29 282 50
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RAI, Dhanpat Tel: +1 509 373 5988 P
Page 435 and 436:
Participants of the Workshop on Eva
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ORDER FORM OECD Nuclear Energy Agen
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