PPCP Degradation by Chlorine-UV Processes in Ammoniacal Water: New Reaction Insights, Kinetic Modeling, and DBP Formation.

The combination of chlorine and UV (i.e., chlorine-UV process) has been attracting more attention in recent years due to its ready incorporation into existing water treatment facilities to remove PPCPs. However, limited information is available on the impact of total ammonia nitrogen (TAN). This study investigated two model PPCPs, N,N-diethyl-3-toluamide (DEET) and caffeine (CAF), in the two stages of the chlorine-UV process (i.e., chlorination and UV/chlor(am)ine) to elucidate the impact of TAN. During chlorination, the degradation of DEET and CAF was positively correlated with the overall consumption of total chlorine by TAN. Reactive nitrogen intermediates, including HNO/NO- and ONOOH/ONOO-, along with •OH were identified as major contributors to the removal of DEET and CAF. During UV irradiation, DEET and CAF were degraded under UV/chlorine or UV/NH2Cl conditions. •OH and •Cl were the major reactive species to degrade DEET and CAF under UV/NH2Cl conditions, whereas •OCl played a major role for degrading CAF under UV/chlorine conditions. Numerical models were developed to predict the removal of DEET and CAF under chlorination-UV process. Chlorinated disinfection byproducts were detected. Overall, this study presented kinetic features and mechanistic insights on the degradation of PPCPs under the chlorine-UV process in ammoniacal water.