Simulated Solar Light Driven Fe(III)/Fe(II) Redox Cycle for Roxarsone Degradation and Simultaneous Arsenate Immobilization

Abstract Organoarsenicals remediation requires degrading organoarsenicals and simultaneously immobilizing the resulted inorganic arsenic, and is thus a great challenge. In this study, a simulated solar light driven Fe(III)/Fe(II) cycle strategy was developed to degrade roxarsone and immobilize the generated inorganic arsenic via tuning the degree of Fe(III) hydrolysis. At pH values of 2.0 and 3.0, the hydrolysis of Fe(III) in the solution was suppressed to produce photoreactive Fe(III)-hydroxyl complexes, which could be excited by simulated solar light to generate OH for 85.3% of roxarsone degradation into arsenate within 60 min. Density functional theory calculations suggested that Fe(OH)(H2O)52+ with lower energy separation gap was the most photoactive Fe(III)-hydroxyl complex for OH generation. With further increasing pH value to 6.0, the hydrolysis of Fe(III) was promoted to precipitate the arsenate for its immobilization, accompanying with the decrease of final iron ions and arsenate concentrations to 0.012 mmol L-1 and 58 μg L-1, respectively. Meanwhile, the undegraded roxarsone was also adsorbed by the precipitate, increasing the overall roxarsone removal efficiency to 99.0%. This study offers a promising strategy for the efficient organoarsenicals treatment, and also sheds light on the dual effects of iron based materials in organic pollutants degradation and heavy metal ions immobilization.