Humic acid inhibits hydroxyl radical generation during oxygenation of Fe(II) on goethite surface

The dark formation of hydroxyl radicals (•OH) by the oxidation of Fe(II) has been increasingly recognized at anoxic–oxic interface. Minerals play significant roles on oxidation of Fe(II) owing to the adsorption changed the reactivity of Fe(II). However, the impact of dissolved organic matter (DOM) on the oxidation of mineral adsorbed Fe(II) and •OH generation remains unknown. Herein, we examined the impact of humic acid (HA) on •OH accumulation during oxygenation of goethite surface-adsorbed Fe(II). We found the addition of 100–500 mg C•L−1 HA inhibited 3.7 % - 24.8 % •OH accumulation, compared to •OH generation facilitated by goethite-adsorbed Fe(II), and the electron utilization efficiency for •OH generation reduced from 15.4 % to 11.8 %. The adsorption experiment under anoxic condition showed that HA compete absorption with Fe(II) on goethite surface. XPS spectroscopy revealed that HA reduces the surface Fe-OH functional group by 4.8 %, thereby reducing the active sites on goethite. Voltammetric cycling curves demonstrated that HA decreased the reducing capacity and inhibited the electrical conductivity of the goethite-adsorbed Fe(II). This study elucidates the effects and mechanisms of HA adsorption on •OH generation during the oxygenation of Fe(II) on goethite surface. © 2025