Heavy metal-mediated adsorption of antibiotic tetracycline and ciprofloxacin on two microplastics: Insights into the role of complexation

Microplastics (MPs) have recently become an emerging environmental concern. Nevertheless, limited informa-tion is known about the adsorption of MPs for organic contaminants under combined heavy metals pollution, with an emphasis on the role of complexation. Thus, this study aims to comprehensively compare and investigate the adsorption performance of antibiotic tetracycline (TC) and ciprofloxacin (CIP) on two polar MPs (polyamide (PA) and polyvinyl chloride (PVC)) affected by Cu(II) and Cd(II) with contrasting complexation abilities. Batch adsorption experiments were used in combination with speciation calculation, zeta potential determination, FTIR spectroscopy characterization and investigation of the affinity of MPs for heavy metals. Results showed that the sorption kinetics and isotherms of TC and CIP on PA and PVC could be well fitted to pseudo-second-order and Langmuir models, respectively, both in the absence and presence of Cu and Cd, suggesting that multiple in-teractions and monolayer adsorption played an important role in the adsorption process. The presence of Cu substantially improved TC and CIP adsorption and obviously changed the pH dependence of their adsorption onto both MPs, which may result from the Cu-induced strong complexation with TC and CIP. The presence of Cd slightly enhanced TC adsorption on both MPs while reduced CIP adsorption especially on PVC, which may be ascribed to the Cd-induced cationic bridging effects in TC adsorption and the competitive adsorption of Cd in CIP adsorption. Therefore, the heavy metal-mediated complexation effects may play a dominant role in antibiotic adsorption by MPs only in the presence of heavy metals with strong complexation ability while the adsorption performance in the presence of heavy metals with negligible complexation capacity may be influenced by effects other than complexation. This study helps further understand the heavy metal-mediated adsorption behavior of organic contaminants on polar MPs and the role of complexation reactions therein.