Effect of chlorination on the characteristics of effluent organic matter and the phototransformation of sulfamethoxazole in secondary wastewater

Chlorination is the most common disinfection technology used to treat wastewater effluent discharged into receiving aquatic environments. Effluent organic matter (EfOM) abundant in wastewater is a well-known photosensitizer and it greatly affects phototransformations of antibiotics in water. However, effects of chlorination on the characteristics and photochemical properties of EfOM have not been studied in sufficient detail. This paper investigated effects of chlorination on the characteristics of EfOM, and its impact on the phototransformation of sulfamethoxazaole (SMX). Correlations between the EfOM characteristics and steady-state concentrations of reactive intermediates (RI) formed in the system were established. Chlorination was shown to preferentially remove the aromatic protein-like substances in EfOM, and the incorporation of chlorine into followed by the cleavage of the aromatic rings in EfOM molecules led to the formation of low molecular aliphatic organic matter. Both unaltered and chlorinated EfOM promoted the photodegradation of SMX whose rate constant in the wastewater was 1.32-1.65 times higher than that in pH 8 phosphate buffer. However, the rate of SMX photodegradation decreased at higher chlorination concentration. The photodegradation of SMX was found to proceed through direct photolysis and oxidation by the RIs generated from EfOM and the self-sensitization of SMX. The steady-state concentrations of ·OH, 1O2 and 3EfOM* were 2.15-5.50 × 10-16, 0.42-1.51 × 10-13, and 2.54-5.82 × 10-14 M in unaltered and chlorinated wastewater. The steady-state concentrations of ·OH were well correlated with the removal of the fluorescence regional integration (ΔFRI) for humic-like and soluble microbial products (SMPs), while the photodegradation rate constant of SMX and the steady-state concentration of 1O2 and 3EfOM* showed good correlations with ΔFRI for tryptophan and fulvic-like substances. Six transformation products (TPs) of SMX were identified. These findings provide new insights into the photochemical properties of chlorinated EfOM in the aquatic environments and its roles in the degradation of antibiotics and other trace-level pharmaceuticals.