In this study, the formation of iodinated trihalomethanes (I-THMs) was systematically evaluated and compared for three treatment processes - (i) chlorination, (ii) monochloramine, and (iii) dichloramination - under different pH conditions. The results demonstrated that I-THM formation decreased in the order of monochloramination > dichloramination > chlorination in acidic and neutral pH. However, the generation of I-THMs increased in the dichloramination < chlorination < monochloramination order in alkaline condition. Specifically, the formation of I-THMs increased as pH increased from 5 to 9 during chlorination and monochloramination processes, while the maximum I-THM formation occurred at pH 7 during dichloramination. The discrepancy could be mainly related to the stability of the three chlor (am) ine disinfectants at different pH conditions. Moreover, in order to gain a thorough insight into the mechanisms of I-THM formation during dichloramination, further investigation was conducted on the influencing factors of DOC concentration and Br − /I − molar ratio. I-THM formation exhibited an increasing and then decreasing trend as the concentration of DOC increased from 1 to 7 mg-C/L, while the yield of I-THMs increased with increasing Br − /I − molar ratio from 5:0 to 5:10. During the three processes mentioned above, similar I-THM formation results were also obtained in real water, which indicates that the excessive generation of I-THMs should be paid special attention during the disinfection of iodide-containing water.
Chlorination of ammonia or chloramine-containing waters induces breakpoint chlorination reactions, producing a hydroxyl radical (•OH), but enhances the formation of undesirable N-nitrosamines. The prevailing view attributes •OH formation to a nitrosyl intermediate derived from the hydrolysis of dichloramine, but this pathway is unlikely at neutral or acidic pH. This study reveals a novel mechanism where •OH is generated via interactions between trichloramine (NCl3) and dichloramine (NHCl2), which also form nitrosation agents. Our experiments demonstrated that the NCl3–NHCl2 interaction degrades micropollutants with kinetics 2–3 times faster than breakpoint chlorination. Using electron paramagnetic resonance, we detected •OH in the NCl3–NHCl2 reaction. Micropollutant removal was unimpaired under low dissolved oxygen (O2(aq)) conditions, aligning with negligible O2(aq) changes during the NCl3–NHCl2 reaction and suggesting O2(aq) does not participate in •OH formation. Using benzene as a probe in 18O-labeled H2O, we confirmed water contributes to the oxygen source of •OH in NCl3–NHCl2 interactions, through which parallel reactions occur, leading to the formation of one mole of •OH alongside 1.92 mol of N2. A kinetic model developed in this study accurately predicted •OH and N2 and demonstrated the NCl3–NHCl2 interaction as the primary pathway for •OH formation in breakpoint chlorination, providing new insights into breakpoint chemistry.
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