Concentration-Governed Transition in DOM Function: From Surface Reductant to Performance Barrier on FeMnOx for Optimal Cr(VI) Removal

Loading dissolved organic matter (DOM) onto iron-manganese oxides (FeMnOx) was a promising strategy for enhancing the hexavalent chromium (Cr(VI)) removal from wastewater. To optimize this process and gain deeper mechanistic insight, this study systematically investigated the DOM loading characteristics onto FeMnOx and its subsequent effect on Cr(VI) adsorption. DOM loading onto FeMnOx was significantly affected by the initial concentration of DOM and pH, with optimal loading conditions identified as a DOM concentration of 75 mg/L, pH of 4, ionic strength of 0.005 mol/L, temperature of 50 °C, and contact time of 4 h. During loading, FeMnOx preferentially adsorbed low-molecular-weight/low-aromaticity components such as tryptophan-like (C1) and fulvic acid-like (C2) substances. The adsorption process followed a non-uniform monolayer surface adsorption and involved multiple stages dominated by chemical interactions. DOM coating on FeMnOx significantly enhanced the Cr(VI) removal, and the maximum adsorption capacity under optimal loading conditions increased from 18.46 mg/g to 23.26 mg/g. Characterization by SEM-EDS, BET, ICP-MS, XPS, FTIR, and CV revealed that a moderate DOM loading (55-75 mg/L) enhanced the material's surface reducibility and mesoporous structure. This improvement was attributed to the reduction of surface Mn(IV) to more-reactive Mn(III) by reductive functional groups in DOM, thereby promoting Cr(VI) adsorption and reduction. In contrast, excessive DOM loading (105 mg/L) formed a dense organic layer that masked active sites and hindered electron transfer, ultimately compromising the long-term reductive capability. These findings elucidate the concentration-dependent regulatory role of DOM in modifying FeMnOx properties, providing a theoretical foundation for the rational design of efficient DOM-metal oxide composites for heavy metal remediation in aquatic environments.