Triplet states of dissolved organic matter (3DOM*) can sensitize the generation of halogen radicals in marine water. The generation pathways of halogen radicals from 3DOM* is still not fully understood. In this study, the generation of halogen radicals from DOM was investigated with Suwanee River fulvic acid (SRFA) as a representative and detailed generation pathways were further revealed with anthraquinone-2-sodium sulfonate (AQ2S) as a triplet sensitizer. The results showed that in SRFA solutions with halogen ions, various halogen radicals can be generated. Among which, Br is formed by the reaction of Br- with 3AQ2S*, and Cl is produced by the reaction of Cl- with AQ2S+ that generated in the presence of dissolved oxygen (DO). Cl2- and Br2- were generated via the subsequent combination of Cl/Br with another Cl-/Br-. In solutions without DO, BrCl- is mainly generated through the combination of Br with Cl-, and BrCl- could also be generated through the combination of Cl with Br- in solutions with DO. This study provides deep insights into the generation mechanisms of different halogen radicals from 3DOM* and is helpful for understanding the photochemical processes of halogen radicals in marine waters.
Keywords: Anthraquinone-2-sodium sulfonate; Environmental photochemistry; Halogen radical; Suwanee River fulvic acid.
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