Accumulation of chiral pharmaceuticals (ofloxacin or levofloxacin) onto polyethylene microplastics from aqueous solutions

Abstract

Drug chirality is attracting increasing attention because the enantiomers of the same chiral pharmaceutical usually exhibit different biological activities, metabolic pathways, and toxicities. The ubiquitous presence of microplastics (MPs) can enrich organic pollutants commonly found in the environment. However, knowledge about the enrichment of pharmaceutical enantiomers to MPs is relatively limited. We investigated the occurrence of enantioselectivity of ofloxacin (OFL) and levofloxacin (LEV) in the adsorption processes on polyethylene (PE) and the interactions influenced by environmental factors. The results showed that the adsorption efficiency of OFL was generally 3-5% (p < 0.05) higher than that of LEV, indicating the different affinities of the enantiomers to PE, but the adsorption process of OFL and LEV on PE was both well described by pseudo-first-order kinetics and liner isotherm models. The chirality of OFL and LEV was not affected by sizes of PE particles and solution salinity due to the identical physicochemical properties. An examination of pH effect indicated that OFL showed better acid-base adaptability than LEV. Moreover, the differences in enantiomeric enrichment between OFL and LEV on PE were promoted with increasing UV light exposure time and natural organic matter (NOM) concentrations. Using Fourier transform infrared spectroscopy (FTIR), we demonstrated that the constituents of the functional groups in chiral NOM were greatly related to the enantiomer stereoselectivity of OFL, subsequently affecting their adsorption in a chiral environment. The excitation-emission matrix (EEM) spectra confirmed the enantioselective behaviors of chiral pharmaceuticals under UV light due to the different optical activity and humic acid-like and fulvic acid-like molecular structure of the enantiomers. These findings imply that the enantioselectivity of drug enantiomers should be considered in presence of microplastics, leading to a more accurate environmental fate and risks assessments of chiral pharmaceuticals.

Keywords: Chiral pharmaceuticals; Enantiomeric enrichment; Enantioselectivity; Ofloxacin and levofloxacin; Polyethylene microplastics.