Effects of photochlorination on the physicochemical transformation of polystyrene nanoplastics: Mechanism and environmental fate

With the increasingly severe plastic pollution, the environmental behavior and effects of nanoplastics (NPs) have attracted much attention. The transformation of NPs in natural and engineered environments (e.g., photooxidation, disinfection) can significantly alter the physicochemical properties and thus affect the fate and toxicity of NPs. However, how solar irradiation with free chlorine, an inevitable process once NPs enter the environment from wastewater treatment plants, affects the physicochemical properties of NPs is still unclear. In this study, the behavior and mechanism of polystyrene (PS) NPs transformation in the solar/chlorine process were evaluated. The results demonstrated that solar irradiation significantly enhanced the physicochemical transformation of PS NPs during chlorination, including chain scission, surface oxidation, and organic release. In addition, two-dimensional correlation spectroscopy analysis using Fourier transform infrared spectroscopy and reactive species quenching experiments showed that chain scission and surface oxidation of PS NPs were primarily caused by direct oxidation of hydroxyl radicals and ozone, while reactive chlorine species played an indirect role. Moreover, photochlorination-induced changes in the properties of PS NPs enhanced the colloidal stability in synthetic wastewater solution and toxicity to Caenorhabditis elegans. These findings reveal an important transformation behavior of nanoplastics in the environment and emphasize the importance of accounting for photochlorination to accurately assess the ecological risk of nanoplastics.