Formation of environmentally persistent free radicals on microplastics under UV irradiations

Microplastics (MPs) are widely distributed in the environment due to breakdown of widespread plastic wastes through physicochemical and biological processes. Environmentally persistent free radicals (EPFRs) might be generated as intermediates when MPs are further fragmented and decomposed under ultraviolet (UV) radiation. Formation of EPFRs is highly depended upon the radiation energy level. This study was designed to establish the correlation between EPFRs concentrations and UV energy. Polystyrene (PS) and polyethylene (PE) were employed to investigate the generation of EPFRs under the irradiation of three ultraviolet light sources (long -wave UVA, medium-wave UVB and short-wave UVC). Electron paramagnetic resonance (EPR) spectroscopy revealed that free radical signals were detected on PS irradiated by UVC and UVB and PE irradiated by UVC, which may be due to the difference in the MPs structure and UV energy. The g-factor and Delta Hp-p of EPR suggested that three different types of EPFRs may be formed on PS while two types of EPFR may be formed on PE. Meanwhile, EPFRs were detected within shorter time under UVC radiation than UVB and UVA, indicating that UVC radiation could lead to faster generation of free radicals. Results of Fourier transform infrared spectroscopy (FTIR) and two-dimensional correlation spectroscopy revealed that tertiary alkyl radicals, peroxy radicals and tertiary alkoxy radicals were dominant in PS whereas alkoxy radicals and keto radicals for PE. The study provides insight to the mechanisms for EPFRs formation on ubiquitously found microplastic particles. Our finding is of great significance as EPFRs may not only play important roles in decomposition of MPs and abiotic reactions of MPs-bound pollutants, but also affect physicochemical properties of MPs and MPs toxicity to aquatic organisms, hence possessing broad impacts on MPs fate and transport in aquatic environmental systems.