Enhanced photolysis of tetracycline by Zn(II): Role of complexation

Zn(II) is a necessary additive during antibiotic production and aquaculture, leading to the coexistence of Zn(II) and antibiotics in aquatic environment, especially in receiving waters of pharmaceutical and aquaculture wastewater. However, the roles of Zn(II) in the photochemical behavior of antibiotics are still not clear, which limits the understanding of the fate of antibiotic in nature. In this study, tetracycline (TC) was selected as typical antibiotic to evaluate the effect of Zn(II) on antibiotic photolysis. The removal of TC was accelerated by 22.75 % with TC:Zn(II) molar ratio at 1:5. The mechanism of Zn(II)-induced TC photolysis was explored via reactive oxygen species (ROS) analysis and density functional theory (DFT) calculation for the first time. Zn(II) could enhance the formation of TC excited states and further produce more singlet oxygen (12.54 % higher than control group) to promote indirect photolysis. Besides, Zn(II) could react with TC via complexation, and the complex was more vulnerable to attack by reactive oxygen species due to more active sites. Furthermore, the structure and toxicity of intermediates were identified with mass spectrometer, T.E.S.T. and ECOSAR software. Zn(II) hardly changed the degradation path of TC, and TC was mainly degraded via ring opening, demethylation, deamidation, and hydrogen abstraction with more toxic intermediates than the parent molecule. This work is significant to better understand the environmental fate of antibiotics, and also provides new insight into wastewater treatment in the pharmaceutical and aquaculture industry.