Reactive chlorine species in the enhanced degradation of UV stabilizers during the sunlight/free chlorine process

Abstract

Benzotriazole (BT) and 5-methyl-1H-benzotriazole (5-MeBT) are the most commonly used UV stabilizers and recalcitrant contaminants that are widely distributed in aquatic environments. The novelty of this study was to investigate the role of RCSs in the enhanced degradation of BT and 5-MeBT during the sunlight/free chlorine process. The results showed that sunlight/free chlorine could enhance the degradation of BT and 5-MeBT compared with that obtained with sunlight irradiation and chlorination alone, and this process was well described by pseudo-first-order kinetics. The degradation rate constants of BT and 5-MeBT during sunlight/free chlorine treatment at pH 7 were 0.094 ± 0.001 min^-1 and 0.134 ± 0.002 min^-1, respectively. The degradation rates further increased with increases in the chlorine dosage and under alkaline conditions (3.818 ± 0.243 min^-1 for BT and 7.754 ± 0.716 min^-1 for 5-MeBT at pH 9). The enhanced removal obtained during the sunlight/free chlorine process could be attributed to the generation of HO• and reactive chlorine species (RCSs), such as Cl• and ClO•. Under alkaline conditions, RCSs were the dominant reactive species, and their contribution increased from 21.2% to 98.7% with increases in the pH from 7 to 9; this phenomenon was due to changes in free chlorine and BT speciation. Radical scavenging tests further verified that BT was mainly decomposed by ClO•, and ClO• showed high reactivity toward deprotonated BT through second-order rate constant estimation. A byproduct analysis demonstrated that BT underwent hydroxylation and chlorine substitution, and a high yield of 1-chlorobenzotriazole (1-ClBT) formation was observed. Even though the sunlight/free chlorine process resulted in a low level of mineralization, no Microtox® toxicity was detected in the treated solutions. Briefly, the significant contribution of ClO• to BT removal under alkaline conditions implies that sunlight/free chlorine could be utilized in a broader range of treatment conditions.

Keywords: Byproducts; Reactive chlorine species; Sunlight/free chlorine; Toxicity; UV stabilizers.