Photochemical origin of reactive radicals and halogenated organic substances in natural waters: A review

Highlights: • Photochemical origin of organohalogens in sunlit surface waters is reviewed. • Halide ions can be activated by natural photoactive species. • Sources of ROS and halogen radicals (X/X2-) are summarized. • Formation of halogenated aromatic compounds and methyl halide is highlighted. Halogenated organic compounds, also termed organohalogens, were initially regarded to be of almost exclusively anthropogenic origin. However, recent research has demonstrated that photochemical reactions are important abiotic sources of organohalogen compounds in sunlit surface waters. Halide ions (X⁻, X represents Cl, Br and I) are common anions in natural waters and might be oxidized by reactive species originated from photochemistry of dissolved organic matter (DOM) or inorganic photoactive species. The resulting reactive halogen species may react with organic substances with diverse bimolecular reaction rate constants, depending on the complexity and structure of organic substances. Therefore, the chemical mechanism of halogenation remains challenging to be fully elucidated. To better understand the trends in the existing data and to identify the knowledge gaps that may merit further investigation, this review gives an integrative summary on the sources of reactive oxygen species (ROS) and halogen radicals (X/X₂⁻). Photochemical halogenation of phenolic compounds and formation of methyl halide and brominated organic pollutants are highlighted. By evaluating existing literature and identifying some uncertainties, this review emphasizes the environmental significance of sunlight-driven halogenation and proposes further research directions on mechanistic investigation and rational experimental design close to natural systems.