The role of natural Fe(II)-bearing minerals in chemoautotrophic chromium (VI) bio-reduction in groundwater.

To date, comparatively little is known about the role of natural Fe(II)-bearing minerals in bioremediation of chromium (VI) contaminated aquifers subject to chemoautotrophic conditions. This work employed four kinds of Fe(II)-bearing minerals (pyrite, mackinawite, wustite, and magnetite) as inorganic electron donors to support Cr(VI) bio-reduction. In batch experiments, mackinawite (FeS) performed best, with Cr(VI) removal efficiency of 98.1 ± 1.21 % in 96 h. Continuous column experiments lasting 180 d implied that groundwater chemistry and hydrodynamics influenced the Cr(VI) removal process. A breakthrough study suggested that biotic and abiotic contributions to Cr(VI) reduction were 76.0 ± 1.12 % and 24.1 ± 1.43 %, respectively. Cr(VI) was reduced to insoluble Cr(III), whereas Fe(II) and S(-II) in mackinawite were finally oxidized to Fe(III) and sulfate. Mackinawite evolved progressively into pyrrhotite. High-throughput 16S rRNA gene sequencing indicated that mackinawite-driven Cr(VI) reduction was mediated through synergistic interactions of microbial consortia; i.e. autotrophs as Acidovorax synthesized volatile fatty acids as metabolic intermediates, which were consumed by Cr(VI) reducers as Geobacter. Genes encoding enzymes for S oxidation (soxB) and Cr(VI) reduction (chrA, yieF) were upregulated. Cytochrome c participating in Fe(II) oxidation increased significantly. This work advances the development of sustainable techniques for Cr(VI) polluted groundwater remediation.