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Abstract  

Adsorption experiments were performed to measure distribution coefficients of237Np(V),238Pu(IV) and241Am(III) for sedimentary sequential chemical extraction of the adsorbed radionuclides was carried out with water, CaCl2, KCl, NH2OH−HCl, K-oxalate and H2O2 solutions, to elucidate their dominant sorption mechanisms. The distribution coefficient of237Np was two orders of magnitude smaller than that of238Pu and241Am. Most of237Np adsorbed was extracted with CaCl2 solution and its sorption was controlled by a reversible ion exchange reaction. The adsorbed238Pu was mainly extracted with NH2OH−HCl+K-oxalate solution and its sorption was possibly controlled by irreversible reactions.

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Abstract  

Actinide(III), (IV), (V) and (VI) ions were extracted by N,N-dimethyl-N,N-dihexyl-3-oxapentanediamide (DMDHOPDA) and thenoyltrifluoroacetone (HTTA). The extraction behaviors suggested the possibility of the mutual separation, and the convenient separation method of actinide ions (III), (IV), (V) and (VI) without reducing and oxidizing agents was studied. Th(IV) was extracted from the aqueous phase by HTTA (5 mM in toluene) in the first step. The Am(III) and U(VI) ions can be extracted by 1 and 20 mM DMDHOPDA in toluene, and the Np(V) ion can be extracted into nitrobenzene with 100 mM DMDHOPDA in the last step. The residual activities in the aqueous phase were much lower than the initial activities. These activities in the fractions were confirmed by the gamma- and the alpha-spectrometry. The one-through and rough separation is advanced, and in case of the fine isolation of actinide elements, each fraction should be purified in more detail.

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Abstract  

Back-extraction of tri- and tetravalent actinides from diisodecylphosphoric acid (DIDPA) is studied using hydrazine carbonate as back-extractant. In experiments using 0.5M DIDPA–0.1M TBP n-dodecane solution, Am(III), Eu(III), Pu(IV) and Np(IV) are back-extracted, and the distribution ratios are decreased with an increase of hydrazine carbonate concentration. The back-extraction equilibria are confirmed by slope analysis in consideration of neutralization between DIDPA and hydrazine carbonate, which occurs quantitatively during back-extraction. In particular, oxidation of Np(IV) to Np(V) during back-extraction is observed by measuring absorption spectra. The hydrazinium ion acts as an oxidation reagent in the back-extraction of Np(IV). Separation factors of those metals are compared with the results of HDEHP. Hydrazine carbonate back-extracts Np(IV) more selectively from DIDPA than from HDEHP.

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Journal of Radioanalytical and Nuclear Chemistry
Authors: T. Tanaka, M. Mukai, T. Maeda, J. Matsumoto, H. Ogawa, Zhentang Li, Xudong Wang, Zhiwen Fan, Liangtian Guo, and Cunli Liu

Abstract  

Migration experiments with 237Np(V) and 241Am(III) have been performed using a column system, packed with loess, taken from Shanxi, China. The adsorption mechanism of 237Np and 241Am on the loess was examined by a chemical extraction method. Most of 237Np was adsorbed on the influent edge of the column, and the adsorbtion was mainly controlled by surface complexation. However, the migration of 237Np in loess media could be roughly evaluated by the distribution coefficient. In the case of 241Am, particulate, the 241Am species was formed in the influent solution and moved in the column. The 241Am adsorbed on loess was controlled by irreversible reactions. The migration behavior of particulate 241Am in loess media could be expressed by the filtration theory.

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Electromigration of carrier-free radionuclides

XIV. Complex formation of241Am-Am(III) with oxalate and sulfate in aqueous solution

Journal of Radioanalytical and Nuclear Chemistry
Authors: F. Rösch, T. Reimann, V. Buklanov, M. Milanov, V. Khalkin, and R. Dreyer

Abstract  

Using a special type of on-line electromigration measurements of -emitting radio-nuclides in homogeneous aqueous electrolytes free of supporting material, complex formation of carrier-free241Am-Am(III) has been studied in perchlorate electrolytes, T=298.1 (1) K. Stoichiometric stability constants for oxalate ligand of log K1=5.01 (13), 5.11 (13) and 5.38 (18) as well as log K2=3.15 (15), 3.19 (14) and 3.58 (26) were obtained at the overall ionic strength of =0.10, 0.05 and 0.01, respectively. The corresponding thermodynamic stability constants are log K 1 0 =5.90 (15) and log K 2 0 =3.73 (18). The sulfate ligand values of log K1=2.5 (2) were obtained both in acidic and neutral solutions, =0.10.

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Abstract  

The interactions of dissolved or colloidal actinides with tuffaceous rock are being studied at Los Alamos National Laboratory in support of the Nevada Nuclear Waste Storage Investigations project. We have used small columns of crushed tuff to obtain information on the sorption of neptunium, plutonium and americium during short (<1 day) time spans. Data from these experiments supplement information obtained from longer term batch-type experiments and provide insight concerning sorption kinetics, speciation, and colloid migration. We find that Np(V), Pu(VI) and Pu(V) show limited sorption on crushed tuff. Pu(IV) polymer and Am(III) are largely retained by the tuff, with a small fraction of the imput material moving through the column as colloids.

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Abstract  

A method for the precipitation of plutonium(IV) oxalate from homogeneous solutions using diethyl oxalate is reported. The precipitate obtained is crystalline and easily filterable with yields in the range of 92–98% for precipitations involving a few mg to g quantities of plutonium. Decontamination factors for common impurities such as U(VI), Am(III) and Fe(III) were determined. TGA and chemical analysis of the compound indicate its composition as Pu(C2O4)2·6H2O. Data are obtained on the solubility of the oxalate in nitric acid and in mixtures of nitric acid and oxalic acid of varying concentrations. Green PuO2 obtained by calcination of the oxalate has specifications within the recommended values for trace foreign substances such as chlorine, fluorine, carbon and nitrogen.

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Abstract  

The position of Pu/III/ within lanthanides in respect to G0, H0 and S0 of complex formation with nitrate and thiocyanate ligands was determined by the extraction method. It was found that in respect to G0, Pu/III/ is a light pseudolanthanide for nitrate ligands and a heavy pseudolanthanide for thiocyanate ligands. A comparison of the positions of Pu/III/ and Am/III/ in respect to G0, H0 and S0 shows that the radius of plutonium is greater than that of americium in the An/NO3/ 5 2– complex and smaller in the An/NCS/3/TBP/n complex. The increase in the radii between plutonium and americium in the thiocyanate complex points out to a contribution from 5f orbitals to bonding.

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Abstract  

The radiation stability was investigated of organic phases containing tertiary benzyldialkylamines and quaternary benzyltrialkylammonium salts which are sultable for the separation of lanthanides and americium from irradiated nuclear fuel. Attention was paid to changes of the extraction properties in Eu(III) and Am(III) extraction. The influence of the individual components forming the organic phase (extractant, solvent, solubilizer and nitric acid) on the decrease of the extraction capacity of the organic phase after irradiation is discussed. The greatest changes in the distribution coefficients DEu and DAm after irradiation were shown for extraction in the presence of nitric acid. As regards the absorbed dose, these systems can be considered as stable in comparison with organophosphorus extractans.

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Abstract  

Previously it was found that in the extraction separation on lanthanides and americium from acidic nitrate solutions of nuclear fission products, benzyldimethyldodecylammonium nitrate gives high values of separation coefficients. The change in the extraction capacity of this agent and its solutions in benzene in the extraction of Eu(III) and Am(III) was investigated as a function of the adsorbed dose of ionizing radiation. The slight reduction in the extraction of both metals is caused mainly by the radiolysis products of nitric acid in the organic phase that enter into secondary reactions with both the solvent and the extractant. Comparison of the radiation stability of benzyldimethyldodecylammonium nitrate systems with tertiary amines show that the changes in distribution coefficients in the range of investigated absorbed doses are significantly lower in the former case. The investigated system may be characterized as radiation stable up to about 100 kGy even in the presence of nitric acid.

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