Thermodynamic controls on the microbial reduction of iron-bearing nontronite and uranium

Iron-bearing phyllosilicate minerals help establish the hydrogeological and geochemical conditions of redox transition zones because of their small size, limited hydraulic conductivity, and redox buffering capacity. The bioreduction of soluble U(VI) to sparingly soluble U(IV) can promote the reduction of clay-Fe(III) through valence cycling. The reductive precipitation of U(VI) to uraninite was previously reported to occur only after a substantial percentage of clay-Fe(III) had been reduced. Using improved analytical techniques, we show that concomitant bioreduction of both U(VI) and clay-Fe(III) by Shewanella putrefaciens CN32 can occur. Soluble electron shuttles were previously shown to enhance both the rate and extent of clay-Fe(III) bioreduction. Using extended incubation periods, we show that electron shuttles enhance only the rate of reduction (overcoming a kinetic limitation) and not the final extent of reduction (a thermodynamic limitation). The first 20% of clay-Fe(III) in nontronite NAu-2 was relatively "easy" (i.e., rapid) to bioreduce; the next 15% of clay-Fe(III) was "harder" (i.e., kinetically limited) to bioreduce, and the remaining 65% of clay-Fe(III) was effectively biologically unreducible. In abiotic experiments with NAu-2 and biogenic uraninite, 16.4% of clay-Fe(III) was reduced in the presence of excess uraninite. In abiotic experiments with NAu-2 and reduced anthraquinone 2,6-disulfonate (AH ₂DS), 18.5-19.1% of clay-Fe(III) was reduced in the presence of excess and variable concentrations of AH₂DS. A thermodynamic model based on published values of the nonstandard state reduction potentials at pH 7.0 (E′_H) showed that the abiotic reactions between NAu-2 and uraninite had reached an apparent equilibrium. This model also showed that the abiotic reactions between NAu-2 and AH₂DS had reached an apparent equilibrium. The final extent of clay-Fe(III) reduction correlated well with the standard state reduction potential at pH 7.0 (E ′_H) of all of the reductants used in these experiments (AH₂DS, CN32, dithionite, and uraninite).