Investigation of the Impacts of Gamma Radiolysis on an Advanced TALSPEAK Separation

Abstract

The advanced TALSPEAK process is a selective solvent extraction that utilizes 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) to separate lanthanide elements from trivalent actinides, which are held back in the aqueous phase by N-hydroxylethyl-N,N’,N’-ethylenediamine triacetic acid (HEDTA) buffered by citric acid. Gamma irradiation of an experiment containing Eu(III) and Am(III) as representative lanthanide and actinide elements resulted in higher distribution ratios of both and separation factors which decreased in an exponential fashion with increasing dose. Analysis of the reagents showed that the HEDTA concentration also decreased in an exponential fashion, strongly suggesting that degradation was correlated with loss of separation selectivity. In contrast, the concentration of citrate was unaffected, and while the concentration of HEH[EHP] did decrease, its dose-dependent kinetic profile indicated that it was not limiting partitioning. A second set of experiments were conducted using a citrate concentration that was 7.5 X higher, with the expectation that citrate would protect the HEDTA by scavenging radiolytically formed OH radicals. HEDTA degradation was significantly mitigated at higher gamma doses, but the Eu-Am separation was worse than in the low citrate experiments, presumably because at the high citrate concentrations, the Eu-citrate complexes formed in abundances competitive with the Am complexes, and are more effectively held back in the aqueous phase.