Dissolved Carbonate and pH Control the Dissolution of Uranyl Phosphate Minerals in Flow-Through Porous Media

摘要

Uranyl phosphate minerals represent an important secondary source of uranium release at contaminated sites. In flow-through column experiments with background porewater (BPW) of typical freshwater aquifer composition (pH 7.0, ～0.2 mM total carbonate (TC))( dissolution of K-ankoleite (KUO_2PO_4·3H_2O), Na-autunite (NaUO_2PO_4·3H_2O), and Ca-autunite (Ca-(UO_2)_2(PO_4)_2·6H_2O) was controlled by mineral solubility at steady-state U release. Effluent concentrations indicated exchange with BPW cations, and postreaction characterization showed alteration of the initial mineral composition, changes in structure (decreased crystallinity, increased disorder, and distortion of U-P mineral sheets) and possible neoformation of phases of similar structure. Increasing the BPW pH and TC to 8.1-8.2 and 2.2-3.7 mM, respectively, resulted in mineral undersaturation and produced ca. 2 orders-of-magnitude higher U and P release without reaching steady state. Minerals incorporated less BPW cations into their structures compared to low carbonate BPW experiments but showed structural disorder and distortion. Faster dissolution rates were attributed to the formation of binary and ternary uranyl carbonate complexes that accelerate the rate-determining step of uranyl detachment from the uranyl-phosphate layered structure. Calculated dissolution rates (log R_s between -8.95 and -10.32 mol m~(-2) s~(-1)), accounting for reaction and transport in porous media, were similar to dissolution rates of other classes of uranyl minerals. In undersaturated solutions, dissolution rates for uranyl phosphate, oxyhydroxide, and silicate minerals can be predicted within 1-2 orders-of-magnitude from pH ～5-10 on the basis of pH/carbonate concentration.