Sulfadiazine chlorination disinfection by-products in constructed wetlands: Identification of biodegradation products and inference of transformation pathways

Disinfection by-products (DBPs) formed from chlorination of antibiotics have greater toxicity than their parent compounds. Herein, this study investigated the biotransformation process of sulfadiazine Cl-DBPs in constructed wetlands (CWs). Results showed that, S atom on sulfonyl group, and N atoms on primary and secondary amine groups were the most reactive sites of sulfadiazine molecule. S1–N4 and S1–C8 of sulfadiazine are the most vulnerable bonds to cleave, followed by C14–N4 and C11–N5 bonds. In the chlorination process, sulfadiazine went through C–N bond cleavage, N-reductive alkylation, halogenation, and desulfonation to produce two aromatic Cl-DBPs. In the biodegradation process in CWs, sulfadiazine Cl-DBPs went through processes mainly including dechlorination, S–N bond cleavage, aniline-NH2 oxidation, desulfonation, phenol-OH oxidation, benzene ring cleavage, C–N bond cleavage, and β-oxidation of fatty acids under the action of a variety of oxidoreductases and hydrolases, during which a total of ten biodegradation products was identified. Moreover, sulfadiazine affected the biodegradation rather than the adsorption process in CWs. The two aromatic sulfadiazine Cl-DBPs had much higher bioaccumulation potentials than their parent sulfadiazine, but for the ten biodegradation products of sulfadiazine Cl-DBPs in CWs, 70% and almost 100% of them had lower bioaccumulation potentials than sulfadiazine and their parent sulfadiazine Cl-DBPs, respectively. The CWs were effective in reducing the environmental risk of sulfadiazine Cl-DBPs. [Display omitted] •For the first time biotransformation pathway of SD Cl-DBPs in CWs was proposed.•S on sulfonyl and N atoms on primary and secondary amine are most reactive sites of SD.•Two aromatic SD Cl-DBPs and their ten biodegradation products in CWs were detected.•Aromatic SD Cl-DBPs had much higher bioaccumulation potential than their parent SD.•CWs were effective in reducing the environmental risk of SD Cl-DBPs.