Gaseous products generated from polyethylene and polyethylene terephthalate during ultraviolet irradiation: Mechanism, pathway and toxicological analyses

The generation of various degradation products from microplastics (MPs) has been confirmed under ultraviolet (UV) irradiation. The gaseous products, primarily volatile organic compounds (VOCs), are usually overlooked, leading to potential unknown risks to humans and the environment. In this study, the generation of VOCs from polyethylene (PE) and polyethylene terephthalate (PET) under UV-A (365 nm) and UV-C (254 nm) irradiation in water matrixes were compared. More than 50 different VOCs were identified. For PE, UV-A-derived VOCs mainly included alkenes and alkanes. On this basis, UV-C-derived VOCs included various oxygen-containing organics, such as alcohols, aldehydes, ketones, carboxylic acid and even lactones. For PET, both UV-A and UV-C irradiation induced the generation of alkenes, alkanes, esters, phenols, etc., and the differences between these two reactions were insignificant. Toxicological prioritization prediction revealed that these VOCs have diverse toxicological profiles. The VOCs with the highest potential toxicity were dimethyl phthalate (CAS: 131-11-3) from PE and 4-acetylbenzoate (3609-53-8) from PET. Furthermore, some alkane and alcohol products also presented high potential toxicity. The quantitative results indicated that the yield of these toxic VOCs from PE could reach 10 μg g under UV-C treatment. The degradation mechanisms of MPs included direct scission by UV irradiation and indirect oxidation induced by diverse activated radicals. The former mechanism was dominant in UV-A degradation, while UV-C included both mechanisms. Both mechanisms contributed to the generation of VOCs. Generally, MPs-derived VOCs can be released from water to the air after UV irradiation, posing a potential risk to ecosystems and human beings, especially for UV-C disinfection indoors in water treatments.