Electron shuttle-induced oxidative transformation of arsenite on the surface of goethite and underlying mechanisms

The redox process of electron shuttles like cysteine on iron minerals under aerobic conditions may largely determine the fate of arsenic (As) in soils, while the interfacial processes and underlying mechanisms are barely explored. This work systematically investigates the interfacial oxidation processes of As(III) on goethite induced by cysteine. Results show that the addition of cysteine significantly enhances the oxidation efficiency (~ 40%) of As(III) (C₀: 10 mg/L) by goethite at pH 7 under aerobic conditions, which is 19.5 times of that without cysteine. cysteine induces Fe(III) reduction on the surface of goethite, and the generation absorbed Fe(II) species play an important role in As(III) oxidation. In particular, the further complexation of Fe(II) with cysteine is thermodynamically favorable for electron transfer, leading to an enhanced As(III) oxidation efficiency. The oxidation efficiency of As(III) in the goethite/cysteine system increases by increasing cysteine concentration and decreases by elevating pH conditions. In addition, evidence indicates that •O₂^- radicals account for approximately 80% of total oxidized As(III). Meanwhile, only 16% of As(III) oxidation can be attributed to the formed •OH radicals. This work provides new insight into the role of organic electron shuttling compounds in determining As cycling in soils.