Formation of Aromatic Halogenated Disinfection Byproducts in Swimming Pool Water during Chlorination: Organic Precursors and Mechanisms

Disinfection byproducts (DBPs) in swimming pool water are a significant public health concern. The formation of aromatic halogenated DBPs in swimming pool water has not been clarified previously. In this study, the occurrence of aromatic halogenated DBPs in swimming pool water was examined, and it was found that halohydroxybenzoic acids (HBAs) and halobenzoquinones (HBQs) were the most dominant aromatic halogenated DBPs in swimming pool water that were continuously formed. Thus, the formation of HBAs and HBQs in swimming pool water from different organic precursors, including natural organic matter (NOM), pharmaceuticals and personal care products (PPCPs), during chlorination was examined. The results demonstrate that the formation of HBAs and HBQs from the PPCPs was relatively high compared with that from NOM, suggesting that the PPCPs from human inputs might be important organic precursors of aromatic halogenated DBPs in swimming pool water. The formation mechanisms of HBAs and HBQs from three typical PPCPs (benzophenone-3 (BP-3), methyl p-hydroxybenzoate (MeP) and carbamazepine) were further explored. The results show that the PPCPs containing phenolic groups with higher degradation rates (BP-3 and MeP) possessed higher formation of HBAs and HBQs. The three organic precursors underwent a series of substitution, hydrolysis, oxidation, rearrangement, and intramolecular cyclization reactions to form HBAs and HBQs, while the phenolic groups and ring structures may significantly affect the reactions. The chlorine dose, bromide/iodide concentration, and temperature significantly affected the formation of HBAs and HBQs from MeP during chlorination.