Photodegradation of Uranium-Citrate Complex with Uranium Recovery

Abstract

Upon exposure to visible light, uranyl citrate complex showed photodegradation of citric acid to acetic acid and carbon dioxide, with the precipitation of uranium as uranium trioxide (UO[sub 3][center dot]2H[sub 2]O). The initial pH and presence of oxygen affected the rate and extent of photochemical degradation of the complex, the formation of intermediate organic degradation products, and uranium speciation. Under aerobic conditions at pH 3.5, acetic, acetoacetic, 3-oxoglutaric, and malonic acids and acetone were detected; at pH 6.0, 3-oxoglutaric and acetic acids were present. The uranyl U(VI) ion was reduced to uranous U(IV) ion and was subsequently reoxidized to the hexavalent form and precipitated out of solution as uranium trioxide. Uranium trioxide precipitate was insoluble at near-neutral pH and was soluble in acidic pH (<4.1). Under anaerobic conditions, the uranyl citrate complex showed only partial (57%) degradation, and uranium was present in the reduced form as U(IV). Excess citric acid retarded the precipitation of uranium. 26 refs., 9 figs., 1 tab.