The biogeochemical behaviour of U(VI) in the simulated near-field of a low-level radioactive waste repository

Abstract

Microbial processes have the potential to affect the mobility of radionuclides, including U in radioactive wastes. A range of geochemical, molecular biological and mineralogical techniques were applied to investigate stable element biogeochemistry and U solubility in the simulated “near-field” (or local environment) of a low-level radioactive waste (LLW) repository. The experiments used a microbial inoculum from the trench disposal area of the UK LLW repository at Drigg, Cumbria, England, in combination with a synthetic trench leachate representing the local environment at the Drigg site. In batch culture experiments in the absence of U, a classic redox progression of terminal electron accepting processes (TEAPs) occurred in the order NO 3 - , Fe(III) and SO 4 2 - reduction. When 126 μM U was added to the system as U(VI) aq, up to 80% was reduced to U(IV) by the indigenous microbial consortium. The U(IV) was retained in solution in these experiments, most likely by complexation with citrate present in the experimental medium. No U(VI) aq was reduced in sterile cultures, confirming that U(VI) aq reduction was microbially mediated. Interestingly, when U(VI) aq was present, the progression of TEAPs was altered. The rate of Fe(III) reduction slowed compared to experiments without U(VI) aq, and SO 4 reduction occurred at the same time as U(VI) reduction. Finally, an experiment where SO 4 2 - -reducing microorgansisms were inhibited by Na molybdate showed no ingrowth of sulfide minerals, but U(VI) reduction continued in this experiment. This suggested that sulfide minerals did not play a significant role in abiotically reducing U(VI) in these systems, and that metal-reducing microorganisms were dominant in mediating U(VI) reduction. Bacteria closely related to microorganisms found in engineered and U-contaminated environments dominated in the experiments. Denaturing gradient gel electrophoresis (DGGE) on 16SrRNA products amplified from broad specificity primers showed that after incubation, differences in diversity and abundance of the microbial culture were observed between U and non-U experiments. These results indicate that the biogeochemistry of the LLW repository near-field stimulates reduction of U(VI) (aq) to U(IV) under anaerobic conditions and that the fate of reduced U(IV) will depend on the complexants present in LLW systems.