Halogen Radical Oxidants in Natural and Engineered Aquatic Systems

Photochemical reactions contribute to the transformation of contaminants and biogeochemically important substrates in environmental aquatic systems. Recent research has demonstrated that halogen radicals (e.g., Cl^·, Br^·, Cl₂ ^·-, BrCl^·-, Br₂ ^·-) impact photochemical processes in sunlit estuarine and coastal waters rich in halides (e.g., chloride, Cl^-, and bromide, Br^-). In addition, halogen radicals participate in contaminant degradation in some engineered processes, including chlorine photolysis for drinking water treatment and several radical-based processes for brine and wastewater treatment. Halogen radicals react selectively with substrates (with bimolecular rate constants spanning several orders of magnitude) and via several potential chemical mechanisms. Consequently, their role in photochemical processes remains challenging to assess. This review presents an integrative analysis of the chemistry of halogen radicals and their contribution to aquatic photochemistry in sunlit surface waters and engineered treatment systems. We evaluate existing data on the generation, speciation, and reactivity of halogen radicals, as well as experimental and computational approaches used to obtain this data. By evaluating existing data and identifying major uncertainties, this review provides a basis to assess the impact of halogen radicals on photochemical processes in both saline surface waters and engineered treatment systems.