Structural Fe(II)-induced generation of reactive oxygen species on magnetite surface for aqueous As(III) oxidation during oxygen activation

Magnetite is a reductive Fe(II)-bearing mineral, and its reduction property is considered important for degradation of contaminants in groundwater and anaerobic subsurface environments. However, the redox condition of subsurface environments frequently changes from anaerobic to aerobic owing to natural and anthropogenic disturbances, generating reactive oxygen species (ROS) from the interaction between Fe(II)-bearing minerals and O-2. Despite this, the mechanism of ROS generation induced by magnetite under aerobic conditions is poorly understood, which may play a crucial role in As(III) oxidation. Herein, we found that magnetite could activate O-2 and induce the oxidative transformation of As(III) under aerobic conditions. As(III) oxidation was attributed to the ROS generated via structural Fe(II) within the magnetite octahedra oxygenation. The electron paramagnetic resonance and quenching tests confirmed that O-2(center dot-), H2O2, and center dot OH were produced by magnetite. Moreover, density function theory calculations combined with experiments demonstrated that O-2(center dot-) was initially formed via single electron transfer from the structural Fe(II) to the adsorbed O-2; O-2(center dot-) was then converted to center dot OH and H2O2 via a series of free radical reactions. Among them, O-2(center dot-) and H2O2 were the primary ROS responsible for As(III) oxidation, accounting for approximately 52 % and 19 % of As(III) oxidation. Notably, As(III) oxidation mainly occurred on the magnetite surface, and As was immobilized further within the magnetite structure. This study provides solid evidence regarding the role of magnetite in determining the fate and transformation of As in redox-fluctuating subsurface environments.