Photoaging mechanisms of microplastics mediated by dissolved organic matter in an iron-rich aquatic environment

As emerging pollutants, microplastics (MPs) have aroused worldwide concern due to their ubiquitous distribution, environmental persistence, and potential ecological risks. However, the ageing mechanisms, environmental behaviours and risks of photoaged MPs mediated by environmental factors remain obscure. Herein, systems containing a light source, humic acid (HA) and Fe were established to investigate the natural photoaging process of MPs including polyvinyl chloride (PVC) and polyethylene terephthalate (PET). The dehydrochlorination reaction of PVC-MP was inhibited by HA and Fe, which resulted from the coeffect of photon competition, excited state quenching, radical deactivation or transformation, and defect structure destruction. In contrast, the enhanced fluorescence effect suggested that the photooxidation reactions of PET-MP were promoted by HA and Fe. Therefore, the presence of HA and Fe in the environment inhibited the photoreduction of MPs while favoring the photooxidative process. Additionally, the adsorption capacity for 17α-ethinylestradiol and the cytotoxicity of MPs were increased after ageing in the hv + HA and hv + HA + Fe systems, which was attributed to the changes in morphology, elements and functional groups. This study provided new insight into the ageing behaviours of MPs in the natural environment with widespread dissolved organic matter and Fe.