Dominant Dissolved Oxygen-Independent Pathway to Form Hydroxyl Radicals and the Generation of Reactive Chlorine and Nitrogen Species in Breakpoint Chlorination

Due to the complexities of the interactions between ammonia, chlor(am)ine, and intermediate species such as ONOOH, the radical formation in breakpoint chlorination and the consequential removal of micropollutants remain largely unexplored. In this study, the dominant generation pathway of HO^•, as a primary radical in breakpoint chlorination, was examined, and the generations of HO^•, reactive chlorine species (RCS), and reactive nitrogen species (RNS) were quantitatively evaluated. A dissolved oxygen (DO)-independent pathway was verified by ¹⁸O labeling and contributed over 90% to HO^• generation. The commonly believed pathway, the decomposition of ONOOH involving DO, contributed only 7% to HO^• formation in breakpoint chlorination. The chlorine to nitrogen (Cl/N) ratio and pH greatly affected the generations and speciations of the reactive species. An optimum Cl/N mass ratio for HO^•, Cl₂^•-, and RNS generations occurred at the breakpoint (i.e., Cl/N mass ratio = 9), whereas excessive free chlorine shifted the radical speciation toward ClO^• at Cl/N mass ratios above the breakpoint. Basic conditions inhibited the generations of HO^• and RNS but significantly promoted that of ClO^•. These findings improved the fundamental understanding of the radical chemistry of breakpoint chlorination, which can be extended to estimate the degradations of micropollutants of known rate constants toward the reactive species with influences from the Cl/N ratio and pH in real-world applications.