Comparison of the kinetic rate law parameters for the dissolution of natural and synthetic autunite in the presence of aqueous bicarbonate ions

Abstract

This research evaluated the effect of aqueous hydrogen carbonate solutions on the uranium rate of release from natural Ca-autunite and quantified the process kinetic rate law for a better prediction of the stability of autunite-group minerals. Testing was accomplished via a single-pass flow-through (SPFT) apparatus using buffered aqueous bicarbonate solutions (0.0005 to 0.003M) at temperatures of 23–90°C and pH values of 7–11. The release rate of uranium from Ca-autunite was directly correlated to increasing concentrations of hydrogen carbonate solutions and showed strong pH dependency. Ca-autunite kinetic rate law parameters were compared to the values obtained for synthetic Na-autunite. The power law coefficient and intrinsic rate constant were higher at pH9–11 for Ca-autunite than for Na-autunite. The lower stability of Ca-autunite was attributed to the high Ca-autunite surface cracking, fractures and basal plane cleavages as compared to Na-autunite and the combined effect of the formation of aqueous uranyl–carbonate and calcium uranyl carbonate species as a driving force for uranium(VI) detachment and the formation of secondary Ca–P hydroxyapatite and uranyl phosphate mineral phases as a driving force for phosphate and calcium detachment controlling the net release of elements.