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Abstract  

Extraction of Pu(IV), Pu(VI) and Am(III) using PEG-2000/ (NH4)2SO4 (40% w/w of each) ABS with 18-crown-6 (18-C-6) as the extractant was studied at four fixed temperatures in the range 288 to 318 K. The distribution ratios follow the order: Pu(VI) > Pu(IV) > Am(III). The species extracted were identified to be [Pu·2(18-C-6)](SO4)2, [PuO2·(18-C-6)]SO4 and [Am·2(18-C-6)](SO4)1.5 for Pu(IV), Pu(VI) and Am(III), respectively. The equilibrium constants (K) evaluated for the extraction reactions follow the order, K Pu(IV) > K Pu(VI) > K Am(III) as expected in accordance with the axial charge experienced by the incoming ligand (18-C-6). The thermodynamic parameters evaluated at 298 K showed the reaction to be stabilized by the decrease in enthalpy and counteracted by the decrease in entropy in all the three cases. The large decrease in the enthalpy observed in all the cases showed that there is direct bonding of crown ether to the central metal atom (i.e., the formation of inner sphere complex).

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Abstract  

Cross-linked hydrogel matrices immobilized with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HA), were prepared to investigate their application in the recovery of radionuclide from acidic waste solutions. Gamma-radiation was used to produce HA immobilized polyvinyl alcohol (PVA) hydrogels (HA-gel). The hydrogels with different characteristics such as: degree of cross-linking (by varying radiation dose) and quantity of extractant immobilized (by starting with aqueous PVA solution containing different amounts of HA), were synthesised. These HA-gels were investigated for solid-liquid phase extraction of U(VI), Pu(IV), Am(III) and some fission products, under various experimental conditions. The concentration of HNO3 in the aqueous phase was found to play an important role in the extraction of these radionuclei. Extraction of U(VI) was more favourable at lower concentration of HNO3 (∼0.001 to 0.5M), while at higher concentrations (∼0.5 to 3M HNO3), more than 90% of Pu(IV) present in the aqueous phase, could be extracted by the HA-gel. The extraction of Am(III) was also found predominant only at lower acidities (at pH∼2 and above). Under optimized conditions, maximum metal loading capacities obtained were 19±0.8 mg, 8±0.4 mg and 11±0.5 mg per gram of swollen HA-gel, for U(VI), Pu(IV) and Am(III), respectively. Under the experimental conditions, extractions of Cs(I) and Sr(II) were observed to be negligible. No leaching out of HA from the HA-gel particles was noted even after its repetitive use for the studied ten cycles of extraction and stripping experiments, as evident from its unchanged extraction efficiency.

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Abstract  

The stability constants of the aqueous mono-fluoride complexes of Pu(III) and Am(III) have been measured using the distribution method. A correlation of the available stability constants of fluoride complexes of trivalent actinides, up to Cf, with fundamental properties like charge and radii of the metal ion has been discussed. Good correlation within the group and as a part of other metal ions was obtained only for transplutonium elements. The reported stability constant values measured by potentiometry and the value obtained by distribution for Pu3+ appear to be much higher than expected from this correlation. However, a better correlation was obtained with transplutonium elements when effective charge instead of formal charge was considered for Pu3+ in the BSE function.

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Abstract  

The extraction behavior of U(VI), Th(IV), Zr(IV), Eu(III) and Am(III) from 3.5M nitric acid with a series of gamma-pre-irradiated symmetrical and unsymmetrical monoamides in benzene has been investigated up to a dose of 100 Mrad. The results indicated that the radiolytic stability is influenced by the structure of amides. Symmetrical monoamides seem to be less affected by radiation compared with unsymmetrical monoamides. Infrared studies identify the final products of radiolysis as the respective carboxylic acids and amines. The radiolytic degradation of the investigated monoamides has been estimated by quantitative IR spectroscopy. Extraction data obtained under similar experimental conditions for U(VI), Th(IV) and Zr(IV) with the TBP/benzene system have also been compared.

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Abstract  

The separation of minor actinides from high level liquid waste (HLLW) belongs to the principal challenges in current nuclear treatment. A derivative based on two cobalt bis(dicarbollide) (1) ions covalently bound to the N,N′-di-n-octyl diglycolyl amide platform via diethyleneglycol chain with the formula {[(N,N′-(8-(OCH2 CH2)2-1,2-C2B9H10)(1′,2′-C2B9H11)-3,3′-Co)(N,N′-n-C8H17)NCOCH2]2O}Na2 (TODGA-COSAN), dissolved in low polar mixture of hexyl methyl ketone and n-dodecane, was used as an extractant for efficient Am(III)/Eu(III) separation from PUREX HLLW. Am(III) could be selectively stripped from loaded organic phase by using a stripping agent composed from 0.05 M DTPA and 1 M citric acid as a buffer and 1 M NaNO3 at pH 3.0. Separation factor between europium and americium of 13 was achieved. The europium remaining in the organic phase could be consecutively effectively stripped by using solution of ammonium citrate or ammonium citrate with ammonium DTPA at pH~7.

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Abstract  

The ability of the back-fill and the host rock materials to take up radioisotopes like 241Am, 85,89Sr and 137Cs has been examined as a function of contact time, pH, amount of sorbent, sorbate concentration, and the presence of complementary cations. A batch technique using actual borehole water from the granite formation has been utilized. In general, the uptake of nuclides by bentonite is much higher than that with granite. The sorption order of nuclides on bentonite is Am>Cs>Sr. The presence of complementary cations, Na+, K+, Ca2+ and Mg2+ depresses the sorption of Cs and Sr on bentonite. The sorption data have been interpreted in terms of Freundlich and Langmuir isotherm equations. Utilizing the Langmuir isotherm equation, the monolayer capacity, V m ,and the binding constant, K, have been evaluated. The change in free energy for the sorption of nuclides on bentonite has also been calculated.

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Abstract  

The extraction of UO 2 2+ , Am3+, and Th4+ by 1-phenyl-3-methyl-4-benzylpyrazolone with crown ethers was studies using 0.1M (NaClO4) aqueous phase and toluene. The crown ethers were 12C4, 15C5, 18C6, DB18C6 and DCH18C6. The synergic equilibrium constant did not show correlation between the cationic radii and the ether cavity size nor did the values follow a simple order of ether basicity. The ether basicity, steric effects, and the number of ether oxygens bound to the cation are the combined factors which seemingly determine the pattern of M(PMBP)n—CE interaction.

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Abstract  

On the basis of distribution dependences, an analysis of the effect of the macrocomponent (lanthanide) on the extraction of the microcomponent (americium) by benzyl-dialkylamines and benzyltrialkylammonium salts has been made. Assuming the validity of DLn=f(c Ln o ) and DAm=f(c Ln o ), the power function of the general expression log D=logP-Qlog c Ln o has been calculated, the constants have been determination of the equation applying to individual extraction systems and their physical and chemical characteristics have been discussed.

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Abstract  

In order to be more confident of the performance assessment of high-level radioactive waste disposal, radionuclide transport must be investigated in more detail in the disturbed host rock region adjacent to the engineered barriers where disturbance has been introduced during the construction and waste-emplacement period. Geochemical, hydrological, and rock-mechanical properties should be quite different from those of undisturbed host rock. We have to elucidate the effect of bentonite intrusion into intersecting fractures from the standpoint of radionuclide confinement. In the present work, sorption distribution ratios (Kd's) of Np and Am are measured experimentally for various values or redox potential (Eh) in a simulated rock fracture filled with bentonite. The Kd of Am is approximately 6.5×103 ml/g and found to be insensitive to the redox potential. Under anaerobic conditions, the Kd of Np is approximately 6×104 ml/g. Under aerobic conditions, Kd is as small as 30 to 100 ml/g. This is the first report to measure the sorption behavior of Np and Am in a simulated rock fracture filled with bentonite (namely, in a disturbed zone) under pH, Eh and ionic strength control. We aan make use of these Kd data for numerically evaluating the mass transfer from bentonite filled fractures into the water-flowing fracture network1.

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Abstract  

We have investigated the effect of coextraction of lanthanides and yttrium on the distribution coefficients DAm in the extraction of americium by benzyldimethyldodecylammonium nitrate (BDMLNNO3) from nitrate solutions. In the coextraction of lanthanides, the extraction of Am(NO3)3 is suppressed, which is markedly manifested in the extraction of light lanthanides (La, Ce, Pr); of the series of lanthanides their extraction is the highest. The effect of nitric acid and the possibility of separation of lanthanides and americium by the application of three-stage multiple extraction is discussed.

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