Iron redox transformations in continuously photolyzed acidic solutions containing natural organic matter: kinetic and mechanistic insights

In this work, the various pathways contributing to the formation and decay of Fe(II) in photolyzed acidic solutions containing Suwannee River fulvic acid (SRFA) are investigated. Results of experimental and computational studies suggest that ligand to metal charge transfer (LMCT), superoxide-mediated iron reduction and interaction with reduced organic species that are present intrinsically in SRFA each contribute to Fe(III) reduction with LMCT the most likely dominant pathway under these conditions. Fe(II) oxidation occurs as a result of its interaction with a variety of light-generated species including (i) short-lived organic species, (ii) relatively stable semiquinone-like organic species, and (iii) hydroperoxy radicals. While not definitive, a hypothesis that the short-lived organic species are similar to peroxyl radicals appears most consistent with our experimental and modeling results. The semiquinone-like organic species formed during photolysis by superoxide-mediated oxidation of reduced organic moieties are long-lived in the dark but prone to rapid oxidation by singlet oxygen (¹O₂) under irradiated conditions and thus play a minor role in Fe(II) oxidation in the light. A kinetic model is developed that adequately describes all aspects of the experimental data obtained and which is capable of predicting Fe(II) oxidation rates and Fe(III) reduction rates in the presence of natural organic matter and light.