Effects of Fe(II) on As(III) oxidation in Fe(II)-As(III) co-oxidation: Limiting and driving roles

The co-oxidation of Fe(II) and As(III) occurs under aerobic conditions, and Fe(II) may largely determine the fate of As(III), but the effect of Fe(II) on the As(III) oxidation is barely explored. In this research, the limiting and driving roles of Fe(II) in As(III) oxidation were systematically studied through batch kinetic studies in combination with X-ray photoelectron spectroscopy (XPS) depth profiling, scanning electron microscopy and energy dispersive X-ray spectrometry (SEM-EDS), and quenching experiments. The results showed that As(III) oxidation efficiency increased with the increase of Fe/As molar ratio (from 63.1% to 98.3%), but decreased with the increase of pH (from 96.0% to 44.2%) and the increase of air flow rate (from 88.1% to 75.1%). The Fe(II) oxidation rate increased with the increase of pH and air flow rate. When Fe(II) was oxidized rapidly, As(III) was more likely to be immobilized in the "inner sphere" of formed Fe (hydr)oxides, limiting As(III) oxidation. On the other hand, Fe(II) was oxidized to produce Fe (hydr)oxides to adsorb or fix As(III); meanwhile, the ROS generated by Fenton-like reaction of Fe(II) promoted As(III) oxidation, especially, •O₂^- and H₂O₂ were important ROS that drove the As(III) oxidation. These findings might provide a new insight for Fe(II) and As(III) geochemistry cycling in naturally occurring environment.