Chromium(VI) and Nitrate Removal from Groundwater Using Biochar-Assisted Zero Valent Iron Autotrophic Bioreduction: Enhancing Electron Transfer Efficiency and Reducing EPS Accumulation

Abstract

Current strategies primarily utilize heterotrophic or mixotrophic bioreduction for the simultaneous removal of Cr(VI) and NO₃^- from groundwater. However, given the oligotrophic nature of groundwater, autotrophic bioreduction could be more appropriate, though it remains notably underdeveloped. Here, an autotrophic bioreduction technology utilizing biochar (BC)-assisted zero valent iron (ZVI) is proposed. The pyrolysis temperature of BC was optimized to enhance electron transfer efficiency and reduce extracellular polymeric substances (EPS) accumulation. BC500, with the superior electron transfer capabilities, was the most effective. After an 11-week period, the ZVI+BC500 biotic column still achieved 100% removal efficiency for Cr(VI) and 93.37±0.33% for NO₃^-, with initial concentrations of 26 mg/L and 50 mg/L, respectively. Its performance significantly surpasses that of ZVI alone, effectively reducing the interference of Cr(VI) on denitrification. The presence of quinone and phenolic compounds in BC500, serving as electron-accepting and electron-donating groups, improves the efficiency of electron transfer between ZVI and microbes. Metagenomic analysis showed an increase in the growth of autotrophic bacteria such as Hydrogenophaga spp. and Rhodanobacter denitrificans, and heterotrophic bacteria including Arenimonas daejeonensis and Chryseobacterium shandongense. The promotion facilitates the expression of genes associated with Cr(VI) reduction (chrR, nemA) and denitrification (narG, nirS). BC500 also enhanced EPS production, which facilitates the adsorption and reduction of Cr(VI), mitigating its inhibitory effects on denitrification. Notably, in the ZVI+BC500 biotic column, the accumulated EPS primarily consists of loosely bound EPS rather than tightly bound EPS, potentially reducing the risk of pore clogging during in-situ groundwater treatment.