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Automated in-line exctraction of uranium(VI) from raffinate streams with on-line detection by cathodic stripping voltammetry
Elteren, Johannes Teun van ...
An automated method for on-site monitoring of uranium(VI) in raffinate streams originating from nuclear fuel reprocessing plants is described. An in-line stripping procedure (based on liquidžliquid ...extraction) was developed to extract U(VI) from this stream, a solvent mixture of 20% tributyl phosphate and nitric acid in kerosene, into an aqueous sodium sulfate solution,Degradation products in the solvent mixture, especially dibutyl phosphate, give rise to very strong complexes and are responsible for moderate but constant U(VI) recoveries (similar to 50%), Optimal conditions forin-line stripping comprise a mixing ratio of extractant (0.5 M sodium sulfate in water)žsolvent mixture of similar to 3 and a pumping rate of similar to 0.4 mL min(-1) of the solvent mixture. The determination of U(VI) was by on-line cathodic stripping voltammmetry (CSV), preceded by adsorptive collection of the U(VL) as an oxine complex onto a hanging mercury drop electrode, Quantities of 1-2 mL of the aqueous extract were pumped into the voltammmetric cell and diluted (1ž5 to 1ž10) with a background electrolyte containing 0.1 M PIPES buffer, 2 x 10(-4) M oxine, 10(-4) M EDTA, and 0.2 M hydrazine hydrate (pH 9.0), The CSV peak for U(VI) was obtained at -0.68 V with a detection limit of 20 nM in the raffinate stream using an adsorption time of 120 s, Both the inline stripping procedure and the on-line measurement were fully automated, with a relative standard deviation in the measurements of < 5%.
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