Chemical and biological effects of zero-valent iron (ZVI) concentration on in-situ production of H2 from ZVI and bioconversion of CO2 into CH4 under anaerobic conditions

Abstract

The conversion of carbon dioxide (CO2) to methane (CH4) is a strategy for sequestering CO2. Zero-valent iron (ZVI) has been proposed as an alternative electron donor for the CO2 reduction to CH4. In this study, the effects of ZVI concentrations on the abiotic production of H2 (without the action of microorganisms) in the first part and on the biological conversion of CO2 to CH4 using ZVI as a direct electron donor in the second part were examined. In the abiotic H2 production, the increase in the ZVI concentration from 16 to 32, 64, and 96 g/L was found to have positive effects on both the amounts of H2 generated and the rates of H2 production because the extent of ZVI oxidation positively correlates with increasing surface area. Nevertheless, the increase in ZVI concentration from 96 to 224 g/L did not benefit the H2 production because the ZVI dissolution was suppressed by the increasing aqueous pH above 10. In the bioconversion of CO2 to CH4 using ZVI as an electron donor, the main methanogenesis pathway occurred via hydrogenotrophic methanogenesis at pH 8.7–9.5 driven by the genus Methanobacterium of the class Methanobacteria. At ZVI concentrations of 64 g/L and above, the production of volatile fatty acid (VFA) became clear. Acetate was the main VFA, indicating the induction of homoacetogenesis at ZVI concentrations of 64 g/L and above. In addition, the presence of propionate as the second major VFA suggests the production of propionate from CO2 and acetate under conditions with high H2 partial pressure. The results indicated that the pathway for ZVI/CO2 conversion to CH4 was competitive between hydrogenotrophic methanogenesis and homoacetogenesis.