Photo-transformation of ofloxacin in natural aquatic conditions: Impact of indirect photolysis on the product profile and transformation mechanism.

ABSTRACT

The natural phototransformation of organic pollutants in the environment depends on several water constituents, including inorganic ions, humic substances, and pH. However, the literature information concerning the influence of various water components on the amount of phototransformation and their impact on the development of various transformation products (TPs) is minimal. This study investigated the phototransformation of ofloxacin (OFL), a fluoroquinolone antibiotic, in the presence of various water components such as cations (K+, Na+, Ca2+, NH4+, Mg2+), anions (NO3-, SO42-, HCO3-, CO32-, PO43-), pH, and humic substances when exposed to natural sunlight. The study reveals that neutral pH levels (0.39374 min⁻1) enhance the phototransformation of OFL in aquatic environments. Carbonate, among anions, shows the highest rate constant (2.89966 min⁻1), significantly influencing OFL phototransformation, while all anions exhibit a notable impact. In aquatic environments, indirect phototransformation of OFL, driven by increased reactive oxygen species, expedites light-induced reactions, potentially enhancing OFL phototransformation. A clear difference was visible in the type of transformation products (TPs) formed during direct and indirect photolysis. The impact of indirect photolysis in the product profile was evaluated by examining the unique properties of TPs in direct and indirect photolysis. The primary transformation products were generated by oxidation and cleavage processes directed towards the ofloxacin piperazinyl, oxazine, and carboxyl groups. The toxicity assessment of TPs derived from OFL revealed that among the 26 identified TPs, TP3 (demethylated product), TP7 and TP8 (decarboxylated products), and TP15 (piperazine ring cleaved product) could potentially have some toxicological effects. These findings suggest that the phototransformation of OFL in the presence of various water components is necessary when assessing this antibiotic's environmental fate.