Sulfur-based autotrophic biosystem for efficient vanadium (V) and chromium (VI) reductions in groundwater

Vanadium and chromium co-exist commonly with elevated levels in groundwater at vanadium smelting sites. While bioremediation has been recognized promising for this co-contamination treatment in aquifer, interactions during vanadium (V) [V(V)] and chromium (VI) [Cr(VI)] bio-reductions under autotrophic condition remain largely unknown. In this study, efficient reductions of V(V) and Cr(VI) from synthetic groundwater were realized simultaneously in a continuous flow autotrophic sulfur-based biosystem, with more than 85% overall removals under hydrochemical and hydrodynamic fluctuations during 276-d operation. Soluble Cr(VI) was reduced to insoluble Cr(III) preferentially, while reduction of soluble V(V) to insoluble V(IV) was easily inhibited. Elemental sulfur [S(0)] was bio-oxidized to sulfate. Analyses of carbon isotope, microbial community and metabolic pathway revealed the synergetic mechanisms. Autotrophs (e.g., Sulfuricurvum) utilized energy released from S(0) oxidation to synthesize volatile fatty acids (VFAs), which were consumed by heterotrophic V(V) and/or Cr(VI) reducers (e.g., Geobacter). Functional genes responsible for S(0) oxidation and reduction of V(V) and Cr(VI) were detected. V(V) and Cr(VI) reductions were catalyzed by both cytochrome c and nicotinamide adenine dinucleotide. VFAs were also transformed to glycogen in cells to store energy. Robust remediation strategy is thereby proposed for aquifer co-contaminated by V(V) and Cr(VI).