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Separation of trivalent actinide (An) and lanthanide (Ln) elements is one of the burning topics in the back end of the nuclear fuel cycle due to the similarity in their chemical behaviour. A significant amount of research is being carried out worldwide to develop suitable ligands for the separation of the trivalent actinides and lanthanides. Some of the research groups are engaged in continuous improvement of the di-ethylene-triamine-penta acetic acid (DTPA) based Ln/An separation method, whereas extensive research is going on for the development of the lipophilic and hydrophilic ‘N’ donor heteropolycyclic ligands as the actinide selective ligand. A number of ‘S’ donor ligands are also explored for the Ln/An separation. In the present review, we made an attempt to highlight various separation processes based on soft donor ligands developed for Ln/An separations. Beside the conventional solvent extraction processes, separation possibilities membrane based and solid phase extraction techniques are evaluated for the Ln/An separation and are compiled in the present review.

Extraction of Am 3+ from acidic feed solutions was investigated using novel solvent systems containing a tripodal diglycolamide (T-DGA) in three room temperature ionic liquids (RTIL), viz. [C 4 mim][NTf 2 ], [C 6 mim][NTf 2 ] and [C 8 mim][NTf 2 ]. Compared to the results obtained with N,N,N9,N9-tetra-n-octyl diglycolamide (TODGA), T-DGA gave significantly higher distribution coefficients in these RTILs. The D Am values decreased with increasing carbon chain length in the RTILs, which was related to the solubility of the RTIL in the aqueous phase. The distribution studies included the effect of equilibration time, aqueous phase acid concentration variation and T-DGA concentration variation. In general, significantly higher equilibration times were observed for the extraction systems, which was partly due to the viscous RTIL phase and partly due to the slow conformational changes of the T-DGA ligand during complexation. Apart from Am 3+ , extraction of Pu 4+ , UO 2 2+ , Eu 3+ , Sr 2+ and Cs + was also investigated, since they have significant implications in radioactive waste processing. Stripping studies indicated .99% stripping in three stages using 0.5 M EDTA or DTPA in 1 M guanidine carbonate. Slope analysis indicated the extraction of 1 : 1 complexed species of Am(III) with T-DGA. Time resolved laser fluorescence spectroscopy (TRLFS) studies showed a strong complexation with no inner-sphere water molecules in the Eu(III)-T-DGA complexes for [C 4 mim][NTf 2 ] as the diluent. Radiolytic degradation studies of the solvent systems containing T-DGA in the three RTILs were also carried out and while the D Am values decreased marginally when the solvents were exposed to 500 kGy absorbed dose, a relatively sharp decrease (60%) was seen when the solvents were exposed further to 1000 kGy absorbed dose, suggesting the possibility of recycling. Extraction studies were also carried out at varying temperatures and the thermodynamic parameters were calculated.

The separation of trivalent actinides and lanthanides is a challenging task for chemists because of their similar charge and chemical behavior. Soft donor ligands like Cyanex-301 were found to be selective for the trivalent actinides over the lanthanides. Formation of different extractable species for Am(3+) and various lanthanides (viz. La(3+), Eu(3+), and Lu(3+)) was explained on the basis of their relative stabilities as compared to their corresponding trinitrato complexes calculated using the density functional method. Further, the metal-ligand complexation energy was segregated into electrostatic, Pauli repulsion, and orbital interaction components. Higher covalence in the M-S bond in the dithiophosphinate complexes as compared to the M-O bond in the nitrate complexes was reflected in the higher orbital and lower electrostatic interactions for the complexes with increasing number of dithiophosphinate ligands. Higher affinity of the dithiophosphinate ligands for Am(3+) over Eu(3+) was corroborated with higher covalence in the Am-S bond as compared to the Eu-S bond, which was reflected in shorter bond length in the case of the former and higher ligand to metal charge transfer in Am(III)-dithiophosphinate complexes. The results were found to be consistent in gas phase density functional theory (DFT) calculations using different GGA functional. More negative complexation energies in the case of Eu(3+) complexes of Me(2)PS(2)(-) as compared to the corresponding Am(3+) complexes in spite of marginally higher covalence in the Am-S bond as compared to the Eu-S bond might be due to higher ionic interaction in the Eu(3+) complexes in the gas phase calculations. The higher covalence in the Am-S bond obtained from the gas phase studies of their geometries and electronic structures solely cannot explain the selectivity of the dithiophosphinate ligands for Am(3+) over Eu(3+). Presence of solvent may also play an important role to control the selectivity as observed from higher complexation energies for Am(3+) in the presence of solvent. Thus, the theoretical results were able to explain the experimentally observed trends in the metal-ligand complexation affinity.

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Studies on the extraction of actinide ions from radioactive feeds have great relevance in nuclear fuel cycle activities, mainly in the back end processes focused on reprocessing and waste management. Room temperature ionic liquid (RTIL) based diluents are becoming increasingly popular due to factors such as more efficient extraction vis-à-vis molecular diluents, higher metal loading, higher radiation resistance, etc. The fascinating chemistry of the actinide ions in RTIL based solvent systems due to complex extraction mechanisms makes it a challenging area of research. By the suitable tuning of the cationic and anionic parts of the ionic liquids, their physical properties such as density, dielectric constant and viscosity can be changed which are considered key parameters in metal ion extraction. Aqueous solubility of the RTILs, which can lead to significant loss in the solvent inventory, can be avoided by appending the extractant moieties onto the ionic liquid. While the low vapour pressure and non-flammability of the ionic liquids make them appear as 'green' diluents, their aqueous solubility raises concerns of environmental hazards. The present article gives a summary of studies carried out on actinide ion extraction and presents perspectives of its applications in the nuclear fuel cycle. The article discusses various extractants used for actinide ion extraction and at many places, comparison is made vis-à-vis molecular diluents which includes the nature of the extracted species and the mechanism of extraction. Results of studies on rare earth elements are also included in view of their similarities with the trivalent minor actinides.