Kinetics and mechanism of triclocarban degradation by the chlorination process: Theoretical calculation and experimental verification

Triclocarban (TCC) is an antimicrobial agent commonly used in many household and personal care products, and has been found persistent in the aquatic environment. Here we elucidate the kinetics and mechanism of TCC degradation during chlorination process by density functional theory (DFT) calculation and experimental verification. Results showed that hypochlorous acid (HOCl)/hypochlorite (OCl−) reacted with TCC via Cl-substitution, OH-substitution and C–N bond cleavage pathways. The reactivity of OCl− (2.80 × 10−7 M−1 s−1) with TCC was extremely low and HOCl (1.96 M−1 s−1) played the dominant role in TCC chlorination process. The N site of TCC was the most reactive site for chlorination. The second-order rate constants, which are determined using density functional theory (DFT) (kTCC−chlorineC, 1.96 M−1 s−1), can be separated into reaction rate constants related to the reactions of HOCl and OCl− with different isomers of TCC (TCC2 and TCC6). The obtained kTCC−chlorineC was consistent with the experimental determined second-order rate constant (kTCC−chlorineE, 3.70 M−1 s−1) in chlorination process. Eight transformation products (TP348, TP382, TP127, TP161, TP195, TP330, TP204, and TP296) were experimentally detected for chlorination of TCC, which could also be predicted by DFT calculation. Explicit water molecules participated in the chlorination reaction by transmitting the proton and connecting with TCC, HOCl/OCl− and other H2O molecules, and obviously reduced the energy barrier of chlorination. [Display omitted] •Chlorination of antimicrobial triclocarban (TCC) was investigated.•The major reaction pathways were Cl-substitution, OH-substitution and C–N bond cleavage.•HClO played the major role in chlorination process to degrade TCC.•Explicit water molecules reduced the energy barrier of TCC chlorination.•Eight products calculated by DFT were confirmed by experimental identification.