Selective Transformation of Micropollutants in Saline Wastewater by Peracetic Acid: The Overlooked Brominating Agents

Peracetic acid (PAA) is an emerging alternative disinfectant for saline waters; HOBr or HOCl is known as the sole species contributing to halogenation reactions during PAA oxidation and disinfection. However, new results herein strongly indicated that the brominating agents (e.g., BrCl, Br₂, BrOCl, and Br₂O) are generated at concentrations typically lower than HOCl and HOBr but played significant roles in micropollutants transformation. The presence of Cl^- and Br^- at environmentally relevant levels could greatly accelerate the micropollutants (e.g., 17α-ethinylestraiol (EE2)) transformation by PAA. The kinetic model and quantum chemical calculations collectively indicated that the reactivities of bromine species toward EE2 follow the order of BrCl > Br₂ > BrOCl > Br₂O > HOBr. In saline waters with elevated Cl^- and Br^- levels, these overlooked brominating agents influence bromination rates of more nucleophilic constituents of natural organic matter and increase the total organic bromine. Overall, this work refines our knowledge regarding the species-specific reactivity of brominating agents and highlights the critical roles of these agents in micropollutant abatement and disinfection byproduct formation during PAA oxidation and disinfection.