Solubility and dissimilatory reduction kinetics of iron(III) oxyhydroxides: A linear free energy relationship

Rates of reduction of Fe(III) oxyhydroxides by the bacterium Shewanella putrefaciens were measured as a function of the bacterial density and the Fe(III) substrate concentration. The results show that an earlier reported positive correlation between the solubility products (^*K_so) and the maximum cell-specific reduction rates (v_max) of predominantly poorly crystalline Fe(III) oxyhydroxides also applies to insoluble and crystalline Fe(III) oxyhydroxides. The mineral solubilities were measured by a dialysis bag technique under acidic conditions (pH 1 up to 2.5) at 25 °C. Initial iron reduction rates by S. putrefaciens were determined in the presence of excess lactate as electron donor. In all cases, the microbial reduction rate exhibited saturation behavior with respect to the Fe(III) oxyhydroxide concentration. On a double logarithmic scale, the maximum rates v_max and the solubility products defined a single linear free energy relationship (LFER) for all the Fe(III) oxyhydroxides considered. The solubility provided a better predictor of v_max than the specific surface area of the mineral phase. A rate limitation by the electron transfer between an iron reductase and a Fe(III) center, or by the subsequent desorption of Fe²⁺ from the iron oxide mineral surface, are both consistent with the observed LFER.