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

Previous studies have indicated that acid-washed pyrite is inert toward aqueous U(VI) under most pH conditions at ambient temperature, even though insoluble UO 2 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 UO 2 product was first observed for the reactions at pH ∼4.0 to ∼5.5 when the temperature was ≥75 °C. Conversely, non-stoichiometric UO 2+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. [ABSTRACT FROM AUTHOR]