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The project was devoted to the design of phosphoryl- and sulphur-containing ionophores for selective separation of radionuclides (Cs, Sr, Eu, Am, Ru, Pd) from liquid solutions containing high-level radioactive wastes. 33 new ionophores including 31 functionalised calixarenes have been prepared and tested as extractants. It has been shown that calixarenes functionalised at the wide rim by phosphine oxide substituents (for lanthanides and actinides) or those with CH(2)-S-Alk substituents (for platinum metals) extract metal cations 100-1000 times more efficiently than their monodentate analogues. Mixtures of calix(4)-tetraamide and chlorinated cobalt dicarbollide display synergistic effects in the extraction of actinides and improve the actinide/lanthanide separation. Ruthenium can be efficiently extracted from nitrate-nitrite media by phosphoryl-containing ligands in the presence of some metals (M=Ni, Co, Zn, Cu), co-extracted as hetero-metallic complexes. The structure of such Ru/M complexes in extracts has been investigated by IR, EXAFS and XANES spectroscopies and quantum mechanics calculations.

The calixarene-based Ru/M complexes predicted by theoretical calculations were subsequently experimentally discovered. The mechanism of synergistic extraction of Sr{2+} by mixtures of chlorinated cobalt dicarbollide and polyethers (PEG, crown-ethers) has been investigated experimentally (IR spectroscopy) and theoretically (MD simulations in solution). A number of efficient solid extracants based on trialkylphosphine oxide, carbamoyl phosphine oxides, and sulphur- and phosphoryl-containing calixarenes have been prepared and used for Am, Pu, Eu, Pd and Ru recovery from simulated and real HLW in the MAYAK radiochemical plant (Russia) and ENEA (Italy). A new type of solid extracant based on solid carbamoyl phosphine oxides has been developed. A new technological approach of extraction and separation of actinides, Pd, Ru and Rh from HLW has been proposed..

Additional information

Authors: KALCHENKO V, National Academy of Sciences, Institute of Organic Chemistry, Kiev (UA);TORGOV V, Russian Academy of Science, Institute of Inorganic Chemistry, Novosibirsk (RU);SMIRNOV I, V G Khlopin Radium Institute, St Petersburg (RU);FERRANDO M, ENEA, Saluggia (IT);WIPFF G, Louis Pasteur University, Strasbourg (FR)
Bibliographic Reference: EUR 19951 EN (2001), pp. 96. Euro: 16.00
Availability: Available from EUR-OP sales agent URL:
ISBN: ISBN 92-894-1745-5
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