Evaluation of Speciation Technology - OECD Nuclear Energy Agency

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Table 1 lists some of the more common radioisotopes of interest and the concentrations in water that will produce an effective dose equivalent of 100 mrem per year. Table 2 lists concentrations of some radioisotopes found around several nuclear sites in the United States. Toxic elements Toxic elements, for example beryllium, cadmium, lead, mercury and nickel, are common at most sites involved in nuclear fuel cycle operations as well as in other related operations. These elements have relatively high vapour pressures at elevated temperatures and are found in waste streams. Therefore they comprise part of an especially dangerous class of toxic materials. Because of the unusually high volatility, high toxicity and ubiquitous nature of mercury at nuclear sites it is of special interest. The very toxic methyl mercury may be formed when mercury is present in soils and sediments. Speciation to determine if mercury is elemental or is present as other species is important. Lead is also of special concern. It may be vaporised (presumably as PbO) during construction of radiation shielding. Table 3 gives examples of some toxic elements found around several nuclear sites in the United States and their maximum concentration limits in the US. Many of the toxic elements listed in Table 3 have complex chemistries, forming a wide variety of compounds and complexes. This makes speciation especially important as well as difficult. An example is nickel, which finds use in plating applications. Nickel not only forms a large number of complexes but may form polymers and the highly toxic nickel carbonyl. Most toxic elements exist in several valence states and form a large number of compounds and complexes. In some cases, e.g. chromium, the element is much more toxic in one valence state [Cr (VI)] than in its other valence states. In order to devise chemical processes to deal with the toxic elements it is essential to know the chemical species present. Toxic organic compounds Many organic compounds are toxic. In this report only a few of the organic compounds found in the nuclear industry are mentioned. Many organic compounds have found use in separations and cleaning operations in nuclear plants, for example, chlorinated hydrocarbons. They are commonly found in soils and ground waters in and around the plants as well as in waste storage facilities such as tanks. Because of the extremely low dose limits for many of these compounds and because they are often present in low concentrations in soil and groundwater, their speciation poses an especially difficult challenge for the speciation analyst. Polychlorobiphenyls (PCBs), which were widely used in the past in electrical transformer coolants and some other applications, are a good example of toxic organic compounds. They may be found in and around uranium enrichment gaseous diffusion plants at unacceptable concentrations and are a toxic organic waste. Biological processes that change the chemical composition of the compounds are often present and active at the time of speciation. Incineration of contaminated organic wastes at plants handling radioisotopes produces off gases that may contain a variety of radioelements of concern. These and other toxic organic materials are subject to thermal degradation leading to a range of products, some of which are themselves, toxic. Table 4 gives illustrative examples of some organic compounds found around some nuclear sites in the United States. 21
Mixed wastes Mixtures of radioisotopes and toxic elements and/or organic compounds are common at nuclear sites. These wastes are called mixed wastes, and form a special class of problems for the speciation analyst because both radioactive and toxic materials must be analysed for, often in complex matrices. Mixed wastes may be in waste storage facilities such as tanks, and in soils, groundwater, and sediments, and in structures and equipment. They may be present in a very wide range of concentrations. The baseline treatment for organically contaminated mixed wastes is incineration. However, incineration can produce volatile dioxins and furans and release volatile toxic metals and radionuclides in the off-gases. Consequently, off-gas monitoring is required. Current monitoring processes are time consuming and costly. Continuous-emission monitors for speciation and measurements could potentially overcome these shortcomings. More than 100 000 cubic meters of mixed low level and transuranic waste are stored at more than 20 sites in the US Department of Energy (DOE) complex. Mercury has been identified in more than 50 000 cubic meters of waste at 19 DOE sites. In some cases it may be possible to separate radioactive contaminants from non-radioactive toxic materials, thereby changing both the amounts of various types of waste and the waste disposal options available for them. It will be necessary to know the chemical species present in order to devise separations processes. Sample treatment considerations It is not uncommon for special circumstances to exist that require sample pre-treatment, or special sample handling. The most common situation is that requiring pre-concentration of the sample if it is so dilute that it is impractical to analyse it directly. The usual method of concentrating aqueous samples is by evaporation. A potential problem with this approach is that either an elevated temperature or a change in concentration of chemicals in the sample may change the nature of the species. Equilibria may be shifted, or slowly reversible reactions may occur. This is especially true of species that form colloids, such as tetravalent plutonium, which forms a very stable polymeric or colloidal solution. Other methods of sample concentration include ion exchange, solvent extraction, precipitation, membrane processes, and electrically driven processes. Handling interferences A sample of a waste containing only the material to be speciated is rare. The usual situation is one where several, and often many, additional substances are present. If these are in large enough concentrations, or are similar enough to the material being speciated that they interfere with speciation, they must be removed. A potential problem is that the removal operations may alter the species being analysed for. The methods available for removal of interferences are ion exchange, solvent extraction, precipitation, membrane processes and electrical processes, as mentioned for sample concentration. Speciation requirements for modelling Modelling is used extensively to demonstrate that regulatory requirements have been met in treating hazardous wastes entering or already present in the environment and in determining that the decontamination operations have been effective. It is in modelling that waste speciation finds one of its most important applications. Computer models are often at the heart of demonstrating regulatory compliance. 22
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 12 and 13: EXECUTIVE SUMMARY The Workshop on E
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 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)
Page 71 and 72: Conclusion The luminescence propert
Page 73 and 74:
[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
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Figure 5. Distribution coefficients
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Figure 7. Dissolved fraction of Eu(
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SESSION C Methods for Empirical For
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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
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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,
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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
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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
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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
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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
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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
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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
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Figure 2. Np distribution coefficie
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Figure 6. Np distribution coefficie
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POSTER SESSION Part E: Predictive A
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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
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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
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Table 2. Spreadsheet arrangement of
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Introduction Scientific studies aim
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Figure 2. Comparison of non-linear
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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
Page 430 and 431:
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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