Extraction of tetra- and hexavalent actinide ions from nitric acid solutions using some diglycolamide functionalized calix[4]arenes

Neptunium is one of the most important minor actinide elements with some of its isotopes having very long half-lives, therefore necessitating its separation from acidic radioactive wastes. Solvent extraction of Np4+ and NpO2 2+ was studied using three multiple diglycolamide (DGA) extractants with n-propyl, n-octyl and 3-pentyl substituents termed as L I , L II and L III , respectively, in a mixed diluent of 5% isodecanol and 95% n-dodecane. For comparison purpose, the extraction of Pu4+ and UO2 2+ was carried out under identical conditions. The extraction efficiency of the ligands for the tetravalent ions followed the trend: L II > L I > L III , which changed to L III > L II > L I for the hexavalent ions. While the extraction of the tetravalent ions was reasonably good (ca. 90–98%) with an extremely low (5.0 × 10−5 M) ligand concentration, poor extraction (ca. 5–16%) of the hexavalent ions was seen even with a 20 times higher concentration of the ligand. In general, Pu4+ was better extracted than Np4+, while NpO2 2+ was marginally better extracted then UO2 2+. A ‘solvation’ type extraction mechanism was proposed based on the extraction profiles obtained as a function of the concentrations of the feed nitric acid, extractant as well as nitrate ion. The extracted species were found out to be M(NO3)4·mL and MO2(NO3)2·nL (M = Np or Pu, 1 < m < 2, n ≃ 1).