Jarosite is a common metastable iron mineral in acid sulfate-rich environments, which is known to retain antimony (Sb) and arsenic (As). Sunlight has emerged as a critical driver for the dissolution of iron minerals, especially in the presence of dissolved organic matter (DOM). However, the mechanisms governing jarosite dissolution and associated Sb/As migration under the coexistence of sunlight and DOM remain poorly understood. Here, we employed a series of techniques, including in situ attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), scanning transmission electron microscopy (STEM), and chemical extraction, to investigated the photochemical behavior of Sb(Ⅴ)/As(Ⅴ)-bearing jarosite with the representative DOM-oxalate (OA) under simulated sunlight. The results indicated that OA was predominantly adsorbed onto the jarosite surface via mononuclear bidentate (MB) binding geometry. Under light irradiation, OA underwent photolysis on the jarosite surface, thereby inducing reductive dissolution of the mineral. The dissolution rate of jarosite was faster under anoxic conditions than under oxic conditions, and both rates increased with increasing OA dosage. Notably, high OA dosage (2.5 mM) induced jarosite transformation to humboldtine under anoxic conditions and to lepidocrocite under oxic conditions. This difference in transformation gave rise to distinct mobility of Sb and As, as the results demonstrated that the formed lepidocrocite exhibited a superior capability to fix Sb and As compared to humboldtine. Additionally, the photoaged Sb preferentially partitioned into the poorly crystalline phase, whereas As tended to adsorb onto the mineral surface. These findings provide new insights into the photochemical interactions between iron minerals and DOM, and reveal the differences in the photochemical transformation of jarosite under anoxic and oxic environments. These are crucial for predicting the behavior of Sb and As in sunlit environments.
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