New insights into long-lasting Cr(VI) removal from groundwater using in situ biosulfidated zero-valent iron with sulfate-reducing bacteria

Sulfidation enhances the reactivity of zero-valent iron (ZVI) for Cr(VI) removal from groundwater. Current sulfidation methods mainly focus on chemical and mechanical sulfidation, and there has been little research on biosulfidation using sulfate-reducing bacteria (SRB) and its performance in Cr(VI) removal. Herein, the ability of the SRB-biosulfidated ZVI (SRB-ZVI) system was evaluated and compared with that of the Na2S-sulfidated ZVI system. The SRB-ZVI system forms a thicker and more porous FeSx layer than the Na2S-sulfidated ZVI system, resulting in more sufficient sulfidation of ZVI and a 2.5-times higher Cr(VI) removal rate than that of the Na2S-sulfidated ZVI system. The biosulfidated-ZVI granules and FeSx suspension are the major components of the SRB-ZVI system. The SRB-ZVI system exhibits a long-lasting (11 cycles) Cr(VI) removal performance owing to the regeneration of FeSx. However, the Na2S-sulfidated ZVI system can perform only two Cr(VI) removal cycles. SRB attached to biosulfidated-ZVI can survive in the presence of Cr(VI) because of the protection of the biogenic porous structure, whereas SRB in the suspension is inhibited. After Cr(VI) removal, SRB repopulates in the suspension from biosulfidated-ZVI and produce FeSx, thus providing conditions for subsequent Cr(VI) removal cycles. Overall, the synergistic effect of SRB and ZVI provides a more powerful and environmentally friendly sulfidation method, which has more advantageous for Cr(VI) removal than those of chemical sulfidation. This study provides a visionary in situ remediation strategy for groundwater contamination using ZVI-based technologies.