Asymmetrical changes of electron-donating and electron-accepting capacities of natural organic matter during its interaction with Fe oxyhydroxides

Abstract

The electron gain and loss of natural organic matter (NOM) plays an important role in the biogeochemical cycling of element and contaminant attenuation. The electron-donating capacity (EDC) and electron-accepting capacity (EAC) of NOM determine its electron exchange ability. However, the influences of bonded matrices on EDC and EAC of NOM remain unclear. Here we investigated the variations in EDC and EAC of NOM during its interaction with Fe oxyhydroxides. Compared to original NOM, the presence of Fe oxyhydroxides slightly decreased the EDC of dissolved NOM by 0.58–2.08 mmol e⁻/g C and of adsorbed NOM by 0.33–2.67 mmol e⁻/g C. However, the EAC of dissolved NOM and adsorbed NOM significantly (p < 0.05) increased by 1.92–14.17 and 3.08–36.67 mmol e⁻/g C, respectively. The excessive increase of EAC was mainly attributed to changes in NOM chemical components, particularly increases in oxidative components such as Fe(III) and quinonoid carbonyls, rather than changes in EDC. For dissolved NOM, the heightened EAC was mainly attributed to the complexation of Fe(III) by carboxyl in NOM. For adsorbed NOM, the boosted EAC was predominantly linked to the enrichment of quinonoid carbonyl through the selective molecular fractionation and the oxidative polymerization of polyphenols in NOM. Our finding highlights the previously overlooked phenomenon of asymmetrical changes of EDC and EAC of NOM during its interaction with Fe oxyhydroxides. The increased EAC could potentially affect various biogeochemical processes, such as methane production, anaerobic ammonium oxidation and microbial Fe(III) reduction.