Synergistic/antagonistic effects and mechanisms of Cr(VI) adsorption and reduction by Fe(III)-HA coprecipitates.

ABSTRACT

Widespread Fe(III)-humic acid (HA) coprecipitates (FHCs) have substantial impacts on the adsorption and reduction of Cr(VI) in soils and sediments, but whether this process is equal to the sum of their individual components remains unknown. In this study, ferrihydrite (Fh)- and HA-like FHCs (C/Fe<3 and C/Fe>3, respectively) were synthesized by controlling the initial C/Fe ratios (0.5-18) to explore the potential synergistic/antagonistic effects during the adsorption and reduction of Cr(VI). According to the results, antagonistic effects on Cr(VI) adsorption (5%-80%) were observed on Fh- and HA-like FHCs, where the antagonistic intensity increased with increasing HA proportions, respectively caused by the more serious occupation of adsorption sites and the stronger electrostatic repulsion to Cr(VI). Notably, significant synergistic reduction effects (5%-650%) occurred on Fh-like FHCs were found to be achieved by the activation of low-molecular HA (0.1-0.3 kDa) with primary/secondary hydroxylic groups, which might be induced by the inductive effect of Fh on complexed HA molecules according to density-functional theory (DFT) calculation. While slight antagonistic reduction effects (2%-45%) by HA-like FHCs were attributed to the decreasing accessibility of Cr(VI) to reductive phenolic groups, which might be blocked within FHC particles or complexed with Fe(III) ions through cation bridges.