Transformation of iron-minerals from natural aquifer media by sulfate-reducing bacteria: Behavior, mechanism, and Cr(VI) removal.

Sulfate-reducing bacteria (SRB) and iron minerals are widespread in subsurface environments, where their mediated Fe and S transformations are crucial for contaminant immobilization. However, the mechanism mediated by SRB to transform natural iron minerals into reduced iron-sulfur compounds and the contaminant removal capacity of the transformation products remain unclear. Herein, the mechanism of native SRB-mediated transformation of iron-minerals from natural aquifer media into biogenic ferrous sulfide (FeS) was revealed and the Cr(VI) removal performance of the transformation product was evaluated. The results showed that Fe2+ production, sulfate reduction, and sulfide production occurred sequentially (rather than simultaneously) in the liquid phase. This suggests new processes and mechanisms for iron-mineral transformation: first, iron minerals dissolve to produce Fe2+ under enzymatic action rather than sulfide reduction; then, the generated Fe2+ accelerates sulfate reduction by SRB, producing sulfide in large amounts; finally, sulfide combines rapidly with Fe2+ to produce FeS. Elevated temperatures markedly shortened the required transformation time to start: maximum Fe production occurred at 18-24 days, 6-12 days, and 0-6 days at 10 °C, 20 °C, and 35 °C, respectively. Ambient temperature strongly affected SRB community composition, with Desulfosporosinus dominant at 10 °C and 20 °C and Desulfotomaculales prevalent at 35 °C. Sequential extraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction analyses confirmed FeS as the main transformation product, which exhibited a highly efficient Cr(VI) removal capacity. Extending transformation time or increasing transformation temperature enhanced the Cr(VI) removal capacity of the transformation product. In column experiments, in-situ stimulation of SRB growth in aquifer media is able to form FeS, the Cr(VI) removal capacity of FeS reached up to 90.1 mg(Cr(VI))/kg(media). These findings suggest that biostimulation of SRB to mediate the in-situ transformation of iron-minerals to FeS has great potential for remediation of contaminated groundwater.