Kinetics study on the temperature-dependent reduction of aqueous U(VI) by natural pyrite

Abstract

Previous studies have indicated that acid-washed pyrite is inert toward aqueous U(VI) under most pH conditions at ambient temperature, even though insoluble UO2 is the thermodynamically predicted product for the reduction of U(VI) by pyrite. Considering the exothermic nature of nuclear waste, the interaction between uranyl nitrate/acetate and natural pyrite was studied at temperatures ranging from 25 °C to 85 °C and at pH values between ∼4.0 and ∼9.5, to simulate the scenarios encountered in a high-level radioactive waste repository. The results revealed that the reactivity of pyrite toward aqueous U(VI) significantly increased with rising temperature, and the reaction could be described by a pseudo-first-order kinetic equation. Activation energies were calculated to be 79.4 ± 10.6 and 45.7 ± 3.8 kJ⋅mol−1 for the reduction of uranyl nitrate, and 78.2 ± 5.2 and 42.2 ± 5.8 kJ⋅mol−1 for the reduction of uranyl acetate, at pH values of ∼4.5 and ∼5.0, respectively. These values indicate that the reaction is controlled by the surface chemical processes. In addition, the complete reduction of aqueous U(VI) to UO2 product was first observed for the reactions at pH ∼4.0 to ∼5.5 when the temperature was ≥75 °C. Conversely, non-stoichiometric UO2+x(s) (0 < x ≤ 0.67) was found at lower temperatures within the same pH range, and also at 85 °C with a reaction pH of ∼9.5. Moreover, the ratio of reduced U(IV/V) on pyrite surfaces increased gradually over time, indicating that reaction time played a significant role in the reduction products. The findings are essential not only for the safety assessment of the high-level radioactive waste repository, but also for understanding the metallogenic mechanism of U(IV)-bearing ore deposits under the relevant anaerobic and hydrothermal conditions.