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.

Automated summary

Microplastics (MPs), resulting from the breakdown of plastic wastes, are widely distributed in the environment. Under ultraviolet (UV) radiation, the further fragmentation of MPs may lead to the formation of environmentally persistent free radicals (EPFRs). This study investigated the correlation between EPFRs concentrations and UV energy, using different types of plastics and UV light sources. The results showed that the structure of MPs and the level of UV energy influenced the generation of EPFRs. It was also observed that UVC radiation led to faster formation of free radicals compared to UVB and UVA. The study provides insights into the mechanisms of EPFRs formation on microplastic particles and highlights the broad impacts of EPFRs on the fate and transport of MPs in aquatic environments.