Molecular investigation of the multi-phase photochemistry of Fe(<scp>iii</scp>)–citrate in aqueous solution

Abstract

Iron (Fe) is ubiquitous in nature and found as Fe^II or Fe^III in minerals or as dissolved ions Fe²⁺ or Fe³⁺ in aqueous systems. The interactions of soluble Fe have important implications for fresh water and marine biogeochemical cycles, which have impacts on global terrestrial and atmospheric environments. Upon dissolution of Fe^III into natural aquatic systems, organic carboxylic acids efficiently chelate Fe^III to form [Fe^III-carboxylate]²⁺ complexes that undergo a wide range of photochemistry-induced radical reactions. The chemical composition and photochemical transformations of these mixtures are largely unknown, making it challenging to estimate their environmental impact. To investigate the photochemical process of Fe^III-carboxylates at the molecular level, we conduct a comprehensive experimental study employing UV-visible spectroscopy, liquid chromatography coupled to photodiode array and high-resolution mass spectrometry detection, and oil immersion flow microscopy. In this study, aqueous solutions of Fe^III-citrate were photolyzed under 365 nm light in an experimental setup with an apparent quantum yield of (<i>φ</i>) ∼0.02, followed by chemical analyses of reacted mixtures withdrawn at increment time intervals of the experiment. The apparent photochemical reaction kinetics of Fe³⁺-citrates (aq) were expressed as two generalized consecutive reactions of with the experimental rate constants of <i>j</i>₁ ∼ 0.12 min^-1 and <i>j</i>₂ ∼ 0.05 min^-1, respectively. Molecular characterization results indicate that R and I consist of both water-soluble organic and Fe-organic species, while P compounds are a mixture of water-soluble and colloidal materials. The latter were identified as Fe-carbonaceous colloids formed at long photolysis times. The carbonaceous content of these colloids was identified as unsaturated organic species with low oxygen content and carbon with a reduced oxidation state, indicative of their plausible radical recombination mechanism under oxygen-deprived conditions typical for the extensively photolyzed mixtures. Based on the molecular characterization results, we discuss the comprehensive reaction mechanism of Fe^III-citrate photochemistry and report on the formation of previously unexplored colloidal reaction products, which may contribute to atmospheric and terrestrial light-absorbing materials in aquatic environments.