The photochemical behaviors of microplastics through the lens of reactive oxygen species: Photolysis mechanisms and enhancing photo-transformation of pollutants

The photoaging mechanisms of various polymers have been explored based on the basic autoxidation scheme (BAS) before 10 years ago, however current research verified some defects in the BAS in both thermodynamic and dynamics. These defects are troublesome because they are associated with the hydrogen abstraction which is central to continuously perform the photooxidation process of microplastics. These found indicated that we might wrongly inferred photo-oxidation process of some microplastics. In addition, the important role of reactive oxygen species (ROS) in the type-dependent photoaging process of various microplastics has been revealed recently. In this case, fully and accurately understanding the photoaging mechanisms of different microplastics in environment is a priority to further manage the ecological risk of microplastics. Herein, this review aims to revise and update the degradation process of microplastics based on the revised BAS and in the perspective of ROS. Specifically, the modification of BAS is firstly discussed. The photoaging mechanisms of representative microplastics (i.e., polyethylene, polystyrene and polyethylene terephthalate) are then updated based on the corrected BAS. Additionally, the role of ROS in their photolysis process and the possibility of microplastics as photosensitizers/mediators to regulate the fate of co-existent pollutants are also analyzed. Finally, several perspectives are then proposed to guide future research on the photoaging behaviors of microplastics. This review would pave the way for the understanding of microplastic photoaging and the management of plastic pollution in environments.