An experimental investigation of the solubility and speciation of uranium in hydrothermal ore fluids

Abstract

Experimental data on the solubility and speciation of uranium in hydrothermal solution is required to improve genetic models for the formation of ore deposits, yet very few data of this type have been published. Of particular interest is the oxidation state of the uranium in solution, as conventional wisdom suggests that U is dissolved in the oxidized U(VI) state and precipitated as reduced U(IV) minerals, yet recent experiments have shown ppm-level solubility for U(IV). This study investigated the mobility of reduced U(IV) and oxidized U(VI) in acidic (pH = 2), fluoride- bearing and alkaline (pH = 10), chloride-bearing solutions at 100-200°C and 1 to 15.8 bars (0.1-1.58 MPa). Preliminary data for the mobility of U(IV) in pH 2 fluids with 0.01 m F- show concentrations of 1.76 to 3.92 ppm U at 200°C, indicating that, contrary to common belief, the reduced U(IV) can be transported in solution. We have also conducted experiments on U(VI) solubility in pH 2 fluoride-bearing, and pH 10 chloride-bearing solutions. Uranium concentrations in the F- -bearing experiments ranged from 624 to 1570 ppm (avg. 825 ppm, n = 6) at 100°C, 670 to 1560 ppm (avg. 931 ppm, n = 4) at 150°C, and 3180 to 7550 ppm (avg. 5240, n = 9) at 200°C. In comparison, U concentrations in the Cl- -bearing runs range from 86.1 to 357 ppm (avg. 185 ppm, n = 15) at 200°C. Clearly, oxidized U(VI) is very readily mobilized in hydrothermal fluids. However, the measured concentrations of U(VI) are independent of those of F- or Cl-, suggesting the formation of U oxide or hydroxide species rather than U chlorides or fluorides. These experimental data will be verified and supplemented in future experiments, which will be used to derive the stoichiometry and thermodynamic constants for the dominant uranium species in hydrothermal solutions. The data from this study will then be integrated into a comprehensive genetic model for uranium ore-forming systems.