Comprehensive Assessment of Reactive Bromine Species in Advanced Oxidation Processes: Differential Roles in Micropollutant Abatement in Bromide-Containing Water

Reactive bromine species (RBS) are gaining increasing attention in natural and engineered aqueous systems containing bromide ions (Br-). However, their roles in the degradation of structurally diverse micropollutants by advanced oxidation processes (AOPs) were not differentiated. In this study, the second-order rate constants (k) of Br•, Br2•-, BrO•, and ClBr•- were collected and evaluated. Br• is the most reactive RBS toward 21 examined micropollutants with k values of 108-1010 M-1 s-1. Br2•-, ClBr•-, and BrO• are selective for electron-rich micropollutants with k values of 106-108 M-1 s-1. The specific roles of RBS in aqueous micropollutant degradation in AOPs were revealed by using simplified models via sensitivity analysis. Generally, RBS play minimal roles in the UV/H2O2 process but are significant in the UV/peroxydisulfate (PDS) and UV/chlorine processes in the presence of trace Br-. In UV/PDS with ≥1 μM Br-, Br• emerges as the major RBS for removing electron-rich micropollutants. In UV/chlorine, BrO• contributes to the degradation of specific electron-rich micropollutants with removal percentages of ≥20% at 1 μM Br-, while the contributions of BrO• and Br• are comparable to those of reactive chlorine species as Br- concentration increases to several μM. In all AOPs, Br2•- and ClBr•- play minor roles at 1-10 μM Br-. Water matrix components such as HCO3-, Cl-, and natural organic matter (NOM) significantly inhibit Br•, while BrO• is less affected, only slightly scavenged by NOM with a k value of 2.1 (mgC/L)-1 s-1. This study sheds light on the differential roles of multiple RBS in micropollutant abatement by AOPs in Br--containing water.