Formation processes of iron-based layered hydroxide in acid mine drainage and its implications for in-situ arsenate immobilization: Insights and mechanisms

The immobilization of arsenate in transformed minerals depends on their states in acid mine drainage (AMD). In this study, an iron-based layer hydroxide mineral was derived from the transformation of ferrihydrite under co-existing Mg2+ ions in AMD. The immobilization behavior of arsenate on the mineralized LDHm and pre-prepared LDHad was distinguished. 99 % immobilization efficiency was achieved from the mineralized LDHm, maintaining stability without subsequent releases, across initial arsenate concentrations ranging from 10 to 60 mg/L. LDHm outperformed the pre-prepared LDHad, which was synthesized from AMD for arsenate adsorption. Electron energy loss spectroscopy line profiles revealed predominant incorporation of arsenate in the LDHm structure, supported by higher bulk As signals within LDHm. Density functional theory calculations indicated primary arsenate incorporation into LDHm, forming stable bonds with lower energy activation barriers. Importantly, LDHm exhibited a superior electron rearrangement configuration, resulting in enhanced electron state activity and affinity for arsenate. In contrast, arsenate adsorption predominantly occurred on the pre-prepared LDHad, with notable As signals detected particularly at the edges. Adsorption energy evaluation indicated arsenate preference for bonding to Fe3+ sites on LDHad. These findings provide important insights into the role of stable LDH-like minerals for long-term arsenate immobilization in the natural AMD attenuation processes.