Photo-aging of polyvinyl chloride microplastic in the presence of natural organic acids

In this study, a new photo-aging pathway in the aquatic environments and the underlying transformation mechanism were described for polyvinyl chloride microplastic (PVC-MP). Our results indicated that the photo-aging of PVC-MP was strongly dependent on particle size and the aging reaction could be facilitated in the presence of low-molecular-weight organic acid (LMWOA) and LMWOA-Fe(III) complex under simulated and natural sunlight irradiation and ambient conditions. The hydroxyl radical (OH•) generated from the photolysis of LMWOA or its ferric complexes played a dominant role in enhancing PVC-MP degradation. In situ Fourier transform infrared and Raman spectroscopic techniques and theoretical calculations further confirmed that C–Cl bond cleavage and formation of polyene and carbonyl underwent on the PVC-MP surface, especially in the presence of LMWOA and LMWOA-Fe(III). Moreover, PVC-MP surface oxidation also led to the increase of the specific surface area and affinity towards water as indicated by the results of scanning electron microscopy, Brunauer-Emmett-Teller tests and contact angles for water, which would further enhance the adsorption of polar contaminants on PVC-MP and thus increase the health risk of PVC-MP on aquatic organisms. [Display omitted] •A new photo-aging pathway in the aquatic environments is described for PVC-MP.•The photo-aging of PVC-MP was strongly dependent on particle size.•The aging process could be facilitated in the presence of LMWOA and LMWOA-Fe(III).•CO2.•- and ROS could be generated via the photolysis of LMWOA and LMWOA-Fe(III).•OH.• played a dominant role in enhancing PVC-MP degradation.