Peroxide activation by microbially synthesized sulfidated iron: Comparison against abiotic iron-based materials in terms of treatment efficiency and oxidative degradation pathway

This study demonstrated the application of biogenic sulfidated iron (B-FeS), produced via anaerobic digestion of Desulfovibrio desulfuricans using sulfate as the terminal electron acceptor, for peroxide activation. B-FeS was assessed against chemically prepared zerovalent and sulfidated iron (ferrous sulfide and pyrite) with respect to their ability to activate peroxydisulfate (PDS) and H₂O₂. Regardless of the peroxide type, B-FeS outperformed benchmark iron activators in treating 4-chlorophenol due to its resistance to iron corrosion and the high content of reduced sulfur. The roles of oxidizing radicals were confirmed based on the effects of alcohol-based quenchers, multi-activity assessment, electron paramagnetic resonance spectral features, and product analysis. The pH-dependent efficiency of sulfoxide-to-sulfone conversion suggested that high-valent iron species acted as the secondary oxidant in all iron/peroxide systems, and the contribution was more pronounced when PDS and B-FeS were used. Microbial sulfidation as a catalyst regeneration strategy recovered the peroxide activation capacity of oxidized B-FeS.