Insights into sunlight-driven transformation of tetracycline by iron (hydr)oxides: The dominating role of self-generated hydrogen peroxide

Iron (hydr)oxides are abundant in surface environment, and actively participate in the transformation of organic pollutants due to their large specific surface areas and redox activity. This work investigated the transformation of tetracycline (TC) in the presence of three common iron (hydr)oxides, hematite (Hem), goethite (Goe), and ferrihydrite (Fh), under simulated sunlight irradiation. These iron (hydr)oxides exhibited photoactivity and facilitated the transformation of TC with the initial phototransformation rates decreased in the order of: Hem > Fh > Goe. The linear correlation between TC removal efficiency and the yield of HO• suggests that HO• dominated TC transformation. The HO• was produced by UV-induced decomposition of self-generated H2O2 and surface Fe2+-triggered photo-Fenton reaction. The experimental results indicate that the generation of HO• was controlled by H2O2, while surface Fe2+ was in excess. Sunlight-driven H2O2 production in the presence of the highly crystalline Hem and Goe occurred through a one-step two-electron reduction pathway, while the process was contributed by both O2-induced Fe2+ oxidation and direct reduction of O2 by electrons on the conduction band in the presence of the poorly crystalline Fh. These findings demonstrate that sunlight may significantly accelerate the degradation of organic pollutants in the presence of iron (hydr)oxides.