Iron(II/III) Alters the Relative Roles of the Microbial Byproduct and Humic Acid during Chromium(VI) Reduction and Fixation by Soil-Dissolved Organic Matter

Though reduction of hexavalent chromium (Cr(VI)) to Cr(III) by dissolved organic matter (DOM) is critical for the remediation of polluted soils, the effects of DOM chemodiversity and underlying mechanisms are not fully elucidated yet. Here, Cr(VI) reduction and immobilization mediated by microbial byproduct (MBP)- and humic acid (HA)-like components in (hot) water-soluble organic matter (WSOM), (H)WSOM, from four soil samples in tropical and subtropical regions of China were investigated. It demonstrates that Cr(VI) reduction capacity decreases in the order WSOM > HWSOM and MBP-enriched DOM > HA-enriched DOM due to the higher contents of low molecular weight saturated compounds and CHO molecules in the former. The presence of Fe(II/III) selectively coprecipitates with high molecular weight components (e.g., tannins, lignin, and CHON-rich compounds) to form ferrihydrite and greatly inhibits Cr(VI) transformation and fixation in MBP-enriched DOM but enhances that in HA-enriched DOM. This is probably owing to the combined effects of (1) the increase of DOM electron-donating capacity and Fe(II) generation during the reactions of HA with Fe(II) and Fe(III), respectively; (2) the enrichment of phenolic and carboxyl groups, aromatic compounds, and carbon defects on ferrihydrite surfaces; and (3) the acceleration of HA decomposition and MBP mineralization by hydroxyl radicals. These findings enhance our understanding of the chemodiversity of soil DOM, the complex interactions between Cr(VI), DOM, and Fe(II/III), and can help design remediation strategies for contaminated environments.