Role of Reactive Halogen Species in Disinfection Byproduct Formation during Chlorine Photolysis

The multiple reactive oxidants produced during chlorine photolysis effectively degrade organic contaminants during water treatment, but their role in disinfection byproduct (DBP) formation is unclear. The impact of chlorine photolysis on dissolved organic matter (DOM) composition and DBP formation is investigated using lake water collected after coagulation, flocculation, and filtration at pH 6.5 and pH 8.5 with irradiation at three wavelengths (254, 311, and 365 nm). The steady-state concentrations of hydroxyl radical and chlorine radical decrease by 38–100% in drinking water compared to ultrapure water, which is primarily attributed to radical scavenging by natural water constituents. Chlorine photolysis transforms DOM through multiple mechanisms to produce DOM that is more aliphatic in nature and contains novel high molecular weight chlorinated DBPs that are detected via high-resolution mass spectrometry. Quenching experiments demonstrate that reactive chlorine species are partially responsible for the formation of halogenated DOM, haloacetic acids, and haloacetonitriles, whereas trihalomethane formation decreases during chlorine photolysis. Furthermore, DOM transformation primarily due to direct photolysis alters DOM such that it is more reactive with chlorine, which also contributes to enhanced formation of novel DBPs during chlorine photolysis.