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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 Np 4+  and NpO 2  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 Pu 4+  and UO 2  2+  was carried out under identical conditions. The extraction efficiency of the ligands for the tetravalent ions followed the trend:  L   II   &gt;  L   I   &gt;  L   III  , which changed to  L   III   &gt;  L   II   &gt;  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, Pu 4+  was better extracted than Np 4+ , while NpO 2  2+  was marginally better extracted then UO 2  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(NO 3 ) 4 ·mL and MO 2 (NO 3 ) 2 ·nL (M = Np or Pu, 1 &lt; m &lt; 2, n ≃ 1).

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