New insights on zero-valent iron permeable reactive barrier for Cr(VI) removal: The function of FeS reaction zone downstream in-situ generated by sulfate-reducing bacteria

The biogeochemical behavior downstream of the zero-valent iron permeable reactive barrier (ZVI-PRB) plays an enormous positive role in the remediation of contaminated-groundwater, but has been completely neglected for a long time. Therefore, this study conducted a 240-day SRB-enhanced ZVI-PRB column experiment, focusing on what exactly happens downstream of ZVI-PRB. Results show that biosulfidation of SRB inside ZVI-PRB prolonged the complete Cr(VI) removal longevity of ZVI-PRB from 38 days to at least 240 days. More importantly, unlike previous studies that focused on improving the performance of ZVI-PRB itself, this study found an in-situ generated FeS reduction reaction zone downstream of the ZVI-PRB. When the ZVI-PRB fails, the downstream reaction zone can continue to play a role in Cr(VI) removal. The maximum Cr(VI) removal capacity of the aquifer media from the reaction zone reached 155.1 mg/kg, which was 39.7% of commercial ZVI capacity. The reduction zone was further confirmed to be predominantly FeS rather than FeS₂. Biogeochemistry occurring within and downstream of ZVI-PRB leads to the formation of FeS. Gene sequencing revealed significantly higher SRB abundance downstream of ZVI-PRB than within the ZVI-PRB. The understanding of the downstream FeS reaction zone provides new insights for more effective remediation using ZVI-PRB.