Transformation of bromophenols by aqueous chlorination and exploration of main reaction mechanisms

Bromophenols (BPs) are ubiquitous phenolic contaminants and typical halogenated disinfection byproducts (DBPs) that are commonly detected in aquatic environments. The transformation of 2,4-dibromophenol (2,4-DBP) during chlorination process was fully explored in this research. It was found that active chlorine can react with 2,4-DBP effectively in a wide pH range of 5.0-11.0, with an apparent second-order rate constant (k_app) varying from 0.8 M^-1 s^-1 to 110.3 M^-1 s^-1. The addition of 5 mM ammonium ions almost completely suppressed the reaction via competitive consumption of free chlorine. With the concentration of HA increasing from 1.0 to 10.0 mg L^-1, the inhibition on the degradation of 2,4-DBP increased from 8.7% to 63.4%. By contrast, bromide ions at a concentration of 5 mM accelerated the process by about 4 times, due to the formation of hypobromous acid. On the basis of the eleven products (with eight nominal masses) identified by LC-TOF-MS, electrophilic substitution reactions and single-electron transfer reactions were mainly involved in the chlorination process. The concentration of primary chlorine-substituted products was about 4 times that of the dimer products, demonstrating that electrophilic substitution reaction was predominant during chlorination of 2,4-DBP. Density functional theory (DFT) based calculations revealed that HOCl is the dominant active oxidizing species for elimination of 2,4-DBP and coupling reaction occurs more easily at para and ortho position of hydroxyl group in the phenolic moiety. These findings could provide some new insights into the environmental fate of bromophenols during chlorine disinfection of water and wastewaters.