Chromate (Cr­(VI)), as one of ubiquitous contaminants in groundwater, has posed a major threat to public health and ecological environment. Although various electron donors (e.g., organic carbon, hydrogen, and methane) have been proposed to drive chromate removal from contaminated water, little is known for microbial chromate reduction coupled to elemental sulfur (S(0)) or zerovalent iron (Fe(0)) oxidation. This study demonstrated chromate could be biologically reduced by using S(0) or Fe(0) as inorganic electron donor. After 60-day cultivation, the sludge achieved a high Cr­(VI) removal efficiency of 92.9 ± 1.1% and 98.1 ± 1.2% in two independent systems with S(0) or Fe(0) as the sole electron donor, respectively. The deposited Cr­(III) was identified as the main reduction product based on X-ray photoelectron spectroscopy. High-throughput 16S rRNA gene sequencing indicated that Cr­(VI) reduction coupled to S(0) or Fe(0) oxidation was mediated synergically by a microbial consortia. In such the consortia, S(0)- or Fe(0)-oxidizing bacteria (e.g., Thiobacillus or Ferrovibrio) could generate volatile fatty acids as metabolites, which were further utilized by chromate-reducing bacteria (e.g., Geobacter or Desulfovibrio) to reduce chromate. Our findings advance our understanding on microbial chromate reduction supported by solid electron donors and also offer a promising process for groundwater remediation.

Vanadium (V) is an emerging contaminant in groundwater that can adversely affect human health. Although bioremediation has been shown effective, little is known on autotrophic V(V) bioreduction in the context of oligotrophic characteristics of groundwater. In this study, we demonstrate that efficient V(V) bioreductions can be coupled with bio-oxidation of elemental sulfur (S(0)) or zerovalent iron (Fe(0)), and the V(V) removal efficiencies reached 97.5 ± 1.2% and 86.6 ± 2.5% within 120 h using S(0) and Fe(0), respectively. V(IV) is the main reduction product and precipitates naturally in near-neutral conditions. Microbial community, functional gene, and metabolites analyses reveal that synthetic metabolisms among autotrophs and heterotrophs played major roles in V(V) reduction using S(0) and Fe(0). These results demonstrate a new approach for V(V) contaminated groundwater remediation.

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