First experimental determination of the solubility constant of coffinite

Dissolution experiments have been performed in order to determine the solubility constant of coffinite, USiO4. Several assemblages of phases were used in under-saturated experiments performed in 0.1 mol L−1 HCl under Ar atmosphere, as well as in air. These samples were fully-characterized and were composed of either USiO4, solely, or USiO4 and additional oxide byproducts that resulted from the synthesis procedure. The solubility constant of coffinite was determined at 25 °C and 1 bar (log *KS°(USiO4, cr) = −5.25 ± 0.05), as well as the standard free energy of formation of coffinite (ΔfG°(298 K) = −1867.6 ± 3.2 kJ mol−1), which enables one to infer the relative stability of coffinite and uraninite as a function of groundwater composition. Geochemical simulations using PHREEQC 2 software and the Thermochimie data base indicate that coffinite precipitates at 25 °C under reducing conditions, at pH = 6, for H4SiO4(aq) concentration of 7 × 10−5 mol L−1 and U(OH)4(aq) concentration of 10−11 mol L−1. The ΔfG° value determined was used to calculate the standard free energy associated with the formation of coffinite from a mixture of uraninite and quartz. The value obtained (Δr,oxG° = 20.6 ± 5.2 kJ mol−1) indicates unambiguously that coffinite is less stable than the quartz + uraninite mixture at 25 °C. Geochemical simulations using PHREEQC 2 software indicate that coffinite precipitates in solutions supersaturated with respect to UO2(cr), but undersaturated with respect to UO2(am) in aqueous solutions with silica concentrations typical of groundwater. These favorable conditions during the formation of sedimentary uranium ore deposits, as well as slow dissolution kinetics, explain the common occurrence of coffinite.