Enhanced chlorination of diclofenac using ABTS as electron shuttle: Performance, mechanism and applicability.

Chlorination, one of the most common oxidation strategies, performed limited degradation capacity towards many emerging organic contaminants under neutral pH conditions. In this study, 2,2'-azinobis(3-ethylbenzothiazoline)-6-sulfonate (ABTS) was discovered to possess an outstanding activation property towards free available chlorine (FAC) during the chlorination of diclofenac (DCF) among pH 6.0-9.5. ABTS radical (ABTS) primarily accounted for the elimination of DCF in the ABTS/FAC system, although hydroxyl radicals, reactive chlorine species, and singlet oxygen were also generated via the self-decomposition of FAC. ABTS acted as the electron shuttle to degrade DCF in the ABTS/FAC system, where ABTS was firstly oxidized by FAC to ABTS via single electron transfer, and followed by the elimination of DCF with the generated ABTS. Eight DCF degradation intermediates were identified by LC/Q-TOF/MS, and four DCF degradation pathways were proposed. Real water bodies, humic acid, and the coexistent anions of Cl, HCO, NO, and SO performed negligible influence on DCF removal in ABTS/FAC system. ABTS/FAC system was much superior to sole chlorination in terms of toxicity reduction and anti-interference capacity. Overall, this study innovatively introduced ABTS as the electron shuttle to enhance the oxidative capacity of FAC under neutral pH conditions and provided a new insight that the ABTS-like organic/synthetic components might play an important role in degrading emerging organic contaminants by chlorination in water treatment.