pH-dependent microbial reduction of uranium(VI) in carbonate-free solutions: UV-vis, XPS, TEM, and thermodynamic...

U(VI)_aq bioreduction has an important effect on the fate and transport of uranium isotopes in groundwater at nuclear test sites. In this study, we focus on the pH-dependent bioreduction of U(VI)_aq in carbonate-free solutions and give mechanistic insight into the removal kinetics of U(VI)_aq. An enhancement in the removal of U(VI)_aq with increasing pH was observed within 5 h, e.g., from 19.4% at pH 4.52 to 99.7% at pH 8.30. The removal of U(VI)_aq at pH 4.52 was due to the biosorption of U(VI)_aq onto the living cells of Shewanella putrefaciens, as evidenced by the almost constant UV-vis absorption intensity of U(VI)_aq immediately after contact with S. putrefaciens. Instead, the removal observed at pH 5.97 to 8.30 resulted from the bioreduction of U(VI)_aq. The end product of U(VI)_aq bioreduction was analyzed using XPS and HRTEM and identified as nanosized UO₂. An increasing trend in the biosorption of U(VI)_aq onto heat-killed cells was also observed, e.g., ~ 80% at pH 8.38. Evidently, the U(VI)_aq that sorbed onto the living cells at pH > 4.52 was further reduced to UO₂, although biosorption made a large contribution to the initial removal of U(VI)_aq. These results may reveal the removal mechanism, in which the U(VI)_aq that was sorbed onto cells rather than the U(VI)_aq complexed in solution was reduced. The decreases in the redox potentials of the main complex species of U(VI)_aq (e.g., [Formula: see text] and [Formula: see text]) with increasing pH support the proposed removal mechanism.