Evaluation of Speciation Technology - OECD Nuclear Energy Agency

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precipitate (humic acid fraction) were separated. This procedure is shown in Figure 1. Radionuclides separated and determined were 90 Sr (radioactive half life; T 1/2 : 28.8 y), 137 Cs (T 1/2 : 30.1 y), 238 Pu (T 1/2 : 87.7 y), 239,240 Pu ( 239 Pu:T 1/2 : 24 110 y; 240 Pu:T 1/2 : 6 550 y), 241 Pu (T 1/2 : 14.4 y) and 241 Am (T 1/2 : 433 y). Strontium-90 was determined by cation exchange and liquid scintillation counting [14]. Gamma emitters such as 137 Cs were determined using Ge-detectors. 241 Pu, which is a parent nuclide of 241 Am, was determined by liquid scintillation techniques, following a radiochemical method [15]. Transuranic elements except for 241 Pu were determined by radiochemical methods and alpha-ray spectrometry [1]. Ultra filtration was used for water leachates from soil to estimate molecular weights of dissolved materials in water phase. Surface soil (AoH horizon) which showed the highest concentration of radionuclides along the Sahan River was extracted with distilled water. The extracted water was examined for the estimation of dissolved fraction in run off components. After a filtration using a 0.2 µm Millipore filter, extracted water was treated with ultra filtration techniques separating the molecular weight fractions of greater and less than 10 000 Dalton. Each fraction was measured for the radioactivities and stable elements such as calcium. Stable elements in each fraction were measured by an inductivity coupled plasma atomic emission spectrometer (ICP-AES). The dissolved organic materials in each fraction were measured for the dissolved organic carbon (DOC). Results and discussion Depth profile and speciation of deposited radionuclides in surface soil Figure 2 shows a depth profile of deposited radionuclides in surface soil sampled from a pine forest near the Sahan River in 1995. As seen in Figure 2, the highest amount of radionuclides exists in the surface organic layer (AoH horizon). Almost all of the radioactivities exist in the surface organic layer plus 0-3 cm depth horizon in the soil layer, as shown in Figure 2. Figure 3 shows a result from speciation of radionuclides in the 0-1 cm horizon (including organic materials) of surface soil. As shown in Figure 3, the majority of 137 Cs, Pu isotopes and 241 Am in the surface soil were in the humic plus insoluble fraction. About 90% of 90 Sr was determined in the water soluble and the exchangeable fraction. Plutonium isotopes and 241 Am were comparable in the free fulvic acid and the free humic acid fractions. 90 Sr and 137 Cs were less than 4% in the free fulvic and humic acid fractions. Among these radionuclides, 90 Sr was highest in the water soluble and exchangeable fractions, which were accessible to river water as a dissolved fraction to the total fractions in surface soil for all layers. Water soluble and exchangeable fractions of 137 Cs, Pu isotopes and 241 Am were also found, as shown in Figure 3. Pu isotopes and 241 Am are major radionuclides in free humic and free fulvic acid fractions, which have possibility to be dissolved in water. Among them, 241 Am is present to some extent in free fulvic acid fraction, Pu isotopes is present in free humic acid fraction more than in the free fulvic acid fraction. Water leachates of surface soil along a river watershed As shown in Figure 2, the majority of radioactivities exist in the organic AoH horizon. So, water leachate from the AoH horizon was to estimate a dissolved fraction as one of main run off components of radioactivities from the river watershed. Figure 4 shows the species distribution result of water leachates of surface soil along the river watershed. As shown in Figure 4, most Pu (79%) and Am (68%) exist in the molecular weight fractions of beyond 10 000 Dalton, in spite of the fact that most of the dissolved organic carbon fractions (69%) exist in the molecular weight below 10 000 Dalton. This means that transuranic 213
elements, such as Pu and Am, are associated with high molecular weight materials containing carbon such as humic substances in water leachates. On the contrary, most of 137 Cs (85%) and 90 Sr (63%) exist in the molecular weight fraction of below 10 000 Dalton, reflecting the fact that most of them exist in lower molecular forms or ionic forms or associated with low molecular materials. However, some of 137 Cs and 90 Sr exist in the molecular weight of beyond 10 000 Dalton. This means that some parts of 137 Cs and 90 Sr are associated with higher molecular materials. Stable calcium shows almost the same result as 90 Sr. There is an indication that considerable amounts of radiocesium may be carried with water-soluble organic substances [16]. The results reported here were compared with the one of ultra filtration conducted in the same manner as river water of the Sahan River sampled on March 1996 [17]. It shows that most of 239+240 Pu (80%) and 241 Am (62%) are associated with colloidal and higher molecular weight fractions above 10 000 Dalton. On the contrary, about 80% of 90 Sr is present in lower molecular weight form. Most of the dissolved organic fractions (64%) in the river water exist in the molecular weight below 10 000 Dalton. Almost all Fe (99%) exists in the fraction greater than 10 000 Dalton, but almost all Ca (97%) exists in the fraction below 10 000 Dalton. These features are in good agreement with the results from our research except for 90 Sr and calcium. Concerning the transuranic elements, they are likely associated with dissolved humic substances both in river water and in water leachate from soil, and that they are associated much more with humic substances in higher molecular fractions greater than 10 000 Dalton. The differences for 90 Sr and calcium may be attributed to the differences of the change of liquid phase from soil water leachates to river water, such as pH. The pH in the soil solution and the Sahan River was 4.3 and 7.5, respectively. This range of pH is quite sensitive to chemical reactions of precipitation and dissolution. This may be one of the reasons of the slight difference of 90 Sr and Ca between the soil water and the river water. Another possible reason is that the sources of these nuclides between soil leachate and river water might be different. In a river system, major sources of these nuclides come from groundwater mainly in ionic forms, but in water leachates most of them might come from organisms in the form of higher molecular sizes. Conclusion Analysis of depth profiles of long-lived Chernobyl radionuclides in soil showed that most of the deposited radionuclides exists in the surface centimetres. Analysis of speciation of radionuclides in surface soil by means of selective sequential extraction method showed that the majority of 90 Sr was found in the exchangeable fraction which is accessible to river water. Water soluble and exchangeable fractions of 137 Cs, Pu isotopes and 241 Am were also found. Pu isotopes and 241 Am are major radionuclides in free humic and free fulvic acid fractions. While the differences of the fractions between Pu isotopes and 241 Am are not large, 241 Am tends to be associated with in the free fulvic acid fraction. Dissolved long lived radionuclides transferred from surface soils to river water in the exclusion zone (30 km zone) near the Chernobyl Nuclear Power Plant was analysed by means of ultra filtration technique. Concerning the transuranic elements, it showed that they are associated with dissolved humic substances both in river water and in water leachate from soil. They are associated much more with humic substances in higher molecular fractions above 10 000 Dalton in spite of the fact that DOC concentration, both in river water and in water leachate from soil, is much less in the fraction above 10 000 Dalton. 214
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Nuclear Science Evaluation of Speci
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ORGANISATION FOR ECONOMIC CO-OPERAT
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OPENING ADDRESS - Satoshi Sakurai,
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SESSION D Methods for Redox Speciat
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Part D: Methods for Redox Speciatio
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EXECUTIVE SUMMARY The Workshop on E
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Speciation methods evaluated in the
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SPECIATION IMPERATIVES FOR WASTE MA
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matrices poses difficult challenges
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Table 1 lists some of the more comm
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In the complex biosphere there are
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SESSION A Methods for Trace Concent
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Introduction Experimental tests of
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complexes. As a result, fulvic acid
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possibility of selective extraction
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Table 1. Data on radiochemical anal
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Figure 1. Flowsheet of isolation of
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NANOSCOPIC SPECIATION OF AQUATIC AC
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A number of spectroscopic methods h
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Figure 4. LPAS and UV-Vis spectra o
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composite and hence it is called br
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[11] J.V. Beitz,, J.P. Hessler, “
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SPECIATION FROM PHOTON TO ION DETEC
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technique for speciation (i.e. the
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Figure 2. TRLIF spectra and lifetim
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Figure 5. ES-MS of uranium hydroxo
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[11] “Dual use of Micellar Enhanc
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Introduction The solution chemistry
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of the metal sorbed was less than 9
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For the hydrated ions without any c
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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
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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
Page 163 and 164: migration. Consequently, only one p
Page 165 and 166: Some solutions are under test, such
Page 168 and 169: DEVELOPMENT PROGRAMME OF ANALYTICAL
Page 170 and 171: Evaluation of the footprints in the
Page 172 and 173: REFERENCES [1] B. Pellaud, “IAEA
Page 174 and 175: MATRIX-ASSISTED LASER DESORPTION/IO
Page 176 and 177: Preparation of the samples There ar
Page 178 and 179: Acknowledgement SHIMADZU Handelsges
Page 180 and 181: Figure 3. Clusters of uranium(VI) o
Page 182 and 183: ASSOCIATION OF ACTINIDES WITH DISSO
Page 184 and 185: carried out by the ultra-filters wi
Page 186 and 187: REFERENCES [1] N.A. Marley, J.S. Ga
Page 188 and 189: Figure 3. Molecular size distributi
Page 190 and 191: SPECIATION OF “HOT PARTICLE” BY
Page 192 and 193: The clear results were obtained reg
Page 194 and 195: in some tens volt per centimetre an
Page 196 and 197: APPLICATION OF X-RAY AND LOW ENERGY
Page 198 and 199: of 12.5 keV to 23.0 keV. The coeffi
Page 200 and 201: [7] R.C. Gatti, H. Nitsche, et al.,
Page 202: Figure 1. Calibration results for 2
Page 205 and 206: Introduction HQ was used as the ext
Page 207 and 208: Iron(III) speciation can be achieve
Page 209 and 210: Figure 1. Solubility of HMOnQ in 4
Page 212 and 213: SPECIATION OF ENVIRONMENTAL RADIONU
Page 216 and 217: Acknowledgements This research has
Page 218 and 219: Figure 1. Speciation procedure A: e
Page 220: POSTER SESSION Part B: Methods for
Page 223 and 224: Introduction The possibility of dis
Page 225 and 226: fluorescence decay rate of the diff
Page 227 and 228: Table 1. Spectroscopic characterist
Page 229 and 230: Figure 3. Peak deconvolution of a m
Page 232 and 233: SPECIATION ANALYSIS ON EU(III) IN A
Page 234 and 235: ACTINYL(VI) SPECIATION IN CONCENTRA
Page 236 and 237: Preparation and characterisation of
Page 238 and 239: Characterisation of solid AnO2CO3 T
Page 240 and 241: Solubility data of uranyl in carbon
Page 242 and 243: CHARACTERISATION OF OXIDE FILMS FOR
Page 244 and 245: Figure 1. Relative concentration of
Page 246: Figure 4. Schematic structure of ox
Page 249 and 250: Introduction The actinide elements
Page 251 and 252: 5LI-(Me-3,2-HOPO (X=CH2 5LIO-(Me-3,
Page 253 and 254: Uranium sequestering agents Uranium
Page 255 and 256: REFERENCES [1] (a) K.N. Raymond, in
Page 258 and 259: SPECIATION OF PU(IV) COMPLEXES WITH
Page 260 and 261: 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
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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
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YASUOKA, Hiroshi Tel: +81 29 282 50
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RAI, Dhanpat Tel: +1 509 373 5988 P
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Participants of the Workshop on Eva
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ORDER FORM OECD Nuclear Energy Agen
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