Influence of chemical speciation on photochemical transformation of three fluoroquinolones (FQs) in water: Kinetics, mechanism, and toxicity of photolysis products.

ABSTRACT

This study investigated the contribution of direct, indirect, and self-sensitized photolysis to the photochemical fate of three model fluoroquinolones (FQs), i.e., lomefloxacin (LOM), norfloxacin (NOR), and ofloxacin (OFL), and demonstrated the influence of chemical speciation on their photodegradation behavior, a topic that has received relatively little attention. Results suggest that these FQs in water transformed mainly via direct photolysis, while hydroxyl radical played a key role in their indirect and self-sensitized photolysis. Chemical speciation of such zwitterionic compounds significantly affected the kinetics of their phototransformation, with the quantum yields of photodegradation decreased in the order of zwitterionic (FQsH) > anionic (FQs-) > cationic (FQsH2+). The photodegradation pathways of FQs depended on both their structures and chemical speciation. Defluorination for LOM in C-8 and NOR in C-6 was more significant when they were present in zwitterionic form than in the other forms. Cationic FQs underwent direct piperazinyl ring cleavage, and zwitterionic ones underwent piperazinyl ring oxidation, while the degradation pathway of piperazinyl ring for FQs in anionic form was structure dependent. Decarboxylation for zwitterionic FQs occurred more slowly compared to both cationic and anionic ones, and the FQs bearing electron-donating groups in C-8 position degraded more easily in cationic form than the anionic ones, while the opposite was true for the FQs without such a group in C-8 position. Results of Vibrio fischeri bioluminescence inhibition tests showed the toxicity of zwitterionic NOR and OFL significantly decreased after photodegradation, while the degradation products of LOM exhibited greater toxicity. These findings indicate that chemical speciation of zwitterionic compounds could affect the kinetics and pathways of their photochemical transformation, and thus have important implications on their fate and risk in aquatic environment.