Mechanistic insights into the detoxification of Cr(VI) and immobilization of Cr and C during the biotransformation of ferrihydrite-polygalacturonic acid-Cr coprecipitates

Coupled reactions among chromium (Cr), organic matter (OM), and iron (Fe) minerals play significant roles in Cr and carbon (C) cycling in Cr-contaminated soils. Although the inhibitory effects of Cr or polysaccharides acid (PGA) on ferrihydrite transformation have been widely studied, mechanistic insights into detoxification of Cr(VI) and immobilization of Cr and C during the microbially mediated reductive transformation of ferrihydrite remain unclear. In this study, underlying sequestration mechanisms of Cr and C during dissimilatory Fe reduction at various Cr/Fe ratios were investigated. Solid-phase analysis showed that reductive transformation rates of ferrihydrite were impeded by high Cr/Fe ratio and more magnetite was found at low Cr loadings. Microscopic analysis showed that formed Cr(III) was immobilized by magnetite and goethite through isomorphous substitution, whereas PGA was adsorbed on the crystalline Fe mineral surface. Spectroscopic results uncovered that binding of Fe minerals and PGA was achieved by surface complexation of structural Fe with carboxyl functional groups, and that the adhesion order of PGA functional groups and Fe minerals was influenced by the Cr/Fe ratios. These findings have significant implications for remediating Cr contaminants, realizing C fixation, and developing a quantitative model for Cr and C cycling by coupling reductive transformation in Cr-contaminated environments.