Evaluation of Speciation Technology - OECD Nuclear Energy Agency

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The HOPOs are of particular interest, since they selectively display a high affinity for ferric and other metal ions of charge/radius ratio comparable to Pu(IV) within the physiological pH range. The formation constants, of Fe(III)-HOPO complexes are 4-9 orders of magnitude greater than those formed with biologically essential divalent cations [2b]. Enterobactin Fe(III)-Enterobactin complex Model actinide complex OH OH O HN O HO OH O N H O O O O NH O O HO OH We have developed de-rivatised 1,2-HOPO [2c] and 3,2-HOPO [2b] binding units with a carboxy group (adjacent to the hydroxy group on the HOPO ring) which can be easily attached to an amine backbone through an amide linkage. The resultant ligand has a favourable co-ordination geometry, as shown below, stronger acidity, and therefore has increased solubility and complexation ability. Catecholamide complex 1,2-HOPO-6-ylamide complex (Me-3,2-HOPO)-4-ylamide complex O R N H O O M R O N H N O O M O N H A very important feature of (Me-3,2-HOPO)-4-ylamide and 1,2-HOPO-6-ylamide ligands (abbreviated as (Me-3,2-HOPO) and (1,2-HOPO) ligands below) is that, as observed in the catcholamide complexes, strong hydrogen bonds between the amide proton and adjacent oxygen donor enhance the stability of their metal complexes [2b]. X-ray crystal structures of all the metal complexes of these ligands exhibit this hydrogen bonding. N R CH3 O O M Plutonium sequestering agents The complexes of Pu(III) and Pu(V) with organic ligands are stable only in a very narrow pH range. Under biological conditions, organic sequestering agents cause disproportion to only the Pu(IV) complexes. Better understanding of the Pu(IV) co-ordination chemistry is essential for the design of potent in vivo Pu(IV) sequestering agents. Due to the intense α-radiation of most of the plutonium isotopes and the decomposition of Pu(IV) complexes by self-radiation, we have chosen Ce(IV) complexes as model for studying Pu(IV) co-ordination chemistry [3a]. The ionic size of Ce(IV) is the same as Pu(IV) (0.94 Å). The aqueous co-ordination chemistry of Ce(IV) parallels that of Pu(IV), giving identical shifts in the M(IV)/M(III) redox potentials. A series of octadentate and tetradentate HOPO ligands have been designed and synthesised to match the co-ordination requirement of Pu(IV) (forming 1:1 and 1:2 complexes) [2b,2c]. These ligands are: 3,4,3-LI-(1,2-HOPO), H(2,2)-(Me-3,2- HOPO), 5-LIO-(Me-3,2-HOPO) and 5-LI-(Me-3,2-HOPO). 249
5LI-(Me-3,2-HOPO (X=CH2 5LIO-(Me-3,2-HOPO) (X=O) 3,4,3-LI-(1,2-HOPO) H(2,2)-(Me-3,2-HOPO) O NH OH N O CH 3 X HN O HO O N CH 3 HN N N NH O O O O HO N HO N HO N HO N O O O O N N O NH O NH HN O HN O HO OH HO OH O N N O O N N O CH 3 CH 3 CH 3 CH 3 The X-ray structures of Ce(5LI-(Me-3,2-HOPO))2 (from organic solvent) and Ce(5LIO-(Me-3,2- HOPO))2 (from water) have been determined. In each case, the central Ce(IV) is eight co-ordinated from two tetradentate ligands [2a]. The co-ordination polyhedra of the two complexes are essentially square antiprisms. Solution thermodynamic studies gave overall formation constants (log β2) for Ce(5LI-(Me-3,2-HOPO))2 and Ce(5LIO-(Me-3,2-HOPO))2 of 41.9 and 41.6 respectively. From these constants, extraordinarily high pM values for Ce(IV) are obtained with the two ligands (37.5 and 37.0 respectively). The constants for Pu(IV) are expected to be essentially the same. The great affinity of the tetradentate Me-3,2-HOPO ligands for Pu(IV) under physiological conditions has been demonstrated in animals [2b,3b]. In mice, 5LI- or 5LIO-(Me-3,2-HOPO) ligand (30 µmol/kg) injected intraperitoneally 1 hr after intravenous injection of 238 Pu(IV)) removed about 82-84% of injected Pu(IV) from mice, a much better result than was obtained with an equimolar amount of CaNa3DTPA (67%). It is notable that, unlike the catecholamide ligands, the tetradentate (Me-3,2-HOPO) ligands injected at the standard dosage promote as much Pu(IV) excretion as the octadentate ligands 3,4,3-LI-(1,2-HOPO)(86%) or H(2,2)-(Me-3,2-HOPO) (81%). Apparently, the ligand concentration established in the tissues at the standard injected dosage are large enough to allow the tetradentate ligands to complex Pu(IV) in competition with biological ligands. However, octadentate ligands have a 1:1 stoichiometry when binding Pu(IV), and when these are given at a low dosage or orally, their potency for reducing Pu(IV) in animal tissues exceeds that of tetradentate or hexadentate HOPO ligands. For example, for the octadentate ligand 3,4,3-1,2-HOPO, the same degree of efficacy is observed at injected dosages as low as 0.3 µmol/kg, and it is orally active. All of the tetradentate ligands need larger dosages (at least 10 times) and are not as orally active. Figure 1 shows the efficacy of multidentate ligands (30 µmol/kg) for removing 238 Pu(IV) from mice intraperitoneally or orally. Figure 1(a). Removal of Pu(IV) by injected ligands Figure 1(b). Removal of Pu(IV) by ingested ligands 3,4,3-LI-(1,2HOPO) H(2,2)-(Me-3,2-HOPO) 5LIO-(Me-3,2-HOPO) Skeleton Live r Soft tissue Kidneys 3,4,3-LI-(1,2-HOPO) H(2,2)-(Me-3,2HOPO) 5LIO-(Me-3,2-HOPO) Skel eton Liver Soft ti ssue K idneys 5LI-(Me-3, 2HOPO) 5LI-(Me-3,2-HOPO) CaNa3DTPA CaNa3DTPA Control Control 0 20 40 60 80 100 0 20 40 60 80 100 Percent of Pu Retained at 24 h Percent of Pu Retained at 24 h A new octadentate, mixed HOPO, ligand was designed and synthesised recently: 3,4,3-LI-(1,2- Me-3,2-HOPO) [3]. It shows highest ability for removing Pu(IV) at physiological pH, compared with octadentate 3,4,3-LI-(1,2-HOPO) or H(2,2)-(Me-3,2-HOPO), at injected dosages of 0.01 to 0.3 µmol/kg and when the ligands are given orally. The effectiveness of this mixed ligand is remarkable when it is 250
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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
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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
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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
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 214 and 215: precipitate (humic acid fraction) w
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: Introduction The actinide elements
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
Page 264: Figure 1. Plots of log Ka-2 D(I) vs
Page 267 and 268: As demonstrated above, laser induce
Page 270: DIRECT SPECTROSCOPIC SPECIATION OF
Page 273 and 274: 4 Energy relative to Pu(IV) 3 2 1 0
Page 275 and 276: Introduction In R&D on the “back
Page 277 and 278: distribution ratios of Am are not s
Page 279 and 280: Figure 1. The crystal structure of
Page 281 and 282: Table 1. Selected geometrical param
Page 283 and 284: Introduction The two important oxid
Page 285 and 286: to these two minerals. Ferrihydrite
Page 287 and 288: REFERENCES [1] J.K. Osmond and M. I
Page 290 and 291: ELECTROANALYTICAL DATA ON URANIUM,
Page 292 and 293: - system of Eq. (2), which is measu
Page 294 and 295: The following consideration indicat
Page 296: 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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