Re-evaluation of equilibrium relationships involving U6+/U4+ and Fe3+/Fe2+ in hydrothermal fluids and their implications for U mineralization

Uranium (U) and iron (Fe) are generally considered to have contrasting aqueous geochemical behavior, with U dissolution being favored in oxidizing fluids as oxidized U (U6+) and Fe in reducing fluids as reduced Fe (Fe2+) species. However, high concentrations of both U and Fe have been reported for the ore fluids of uranium deposits, suggesting that the two elements can be co-transported in the same fluid. In this study, geochemical modeling, based on recent thermodynamic and experimental data for U and Fe species and fluid inclusion compositions from two types of hydrothermal U deposits (volcanic-related and unconformity-related), was conducted to investigate the nature and conditions of UFe co-transportation. The results of the modeling indicate that high concentrations of U (>10, up to >100 ppm) and Fe (>1000 ppm) can be dissolved in acidic aqueous fluids (pH < ∼3.3) of moderate to high chlorinity (∼ 55 to 250 g/L Cl), for a wide range of logfO2 above and below the magnetite-hematite (MH) buffer (from ∼ MH-5 to MH + 30), at temperatures from 150 to 250 °C. There are four different combinations of dominant dissolved U and Fe species depending on the pH and redox conditions: U6+ and Fe3+ species (UO2Cl20 and FeCl30) at relatively high fO2, U4+ and Fe2+ species (UCl40 and FeCl42−) at relatively low fO2, and U6+ and Fe2+ species (UO2Cl20 and FeCl42−) or U4+ and Fe3+ species (UCl40 and FeCl30) at intermediate fO2 conditions. Because the most important U mineral in hydrothermal uranium deposits is uraninite (UO2), in which U is present as U4+, a necessary condition for U mineralization is that U is either transported as U4+ species or, if transported as U6+ species, precipitation of uraninite is induced by a reducing agent. The recognition that U6+ and Fe2+ species can be co-transported in the same fluid indicates that uraninite can be precipitated without the need to invoke a reducing agent external to the ore fluid. The driver of uranium mineralization in this case is an increase in pH due to fluid-rock interaction that leads to the alteration of the rocks by clay minerals and associated coupled sorption-reduction. These findings provide for a more extensive range of conditions for U transport and deposition than previously imagined and require that interpretation of the conditions of uranium mineralization consider both oxygen fugacity and pH. This study underscores the potential for uranium deposits to occur in geological settings where reducing agents are either absent or insufficiently abundant to account for the observed mineralization, and the possibility for the transport of U in environments that might otherwise be considered unfavorable.