Enhanced alteration of poly(vinyl chloride) microplastics by hydrated electrons derived from indole-3-acetic acid assisted by a common cationic surfactant

In this study, a new photo-irradiated reductive dechlorination pathway and the underlying transformation mechanism are described for poly(vinyl chloride) microplastics (PVC-MPs). PVC-MPs underwent photo-reductive dechlorination process with the release of chloride ions. This reaction could be facilitated in the presence of indole-3-acetic acid (IAA) and hexadecyltrimethylammonium bromide (CTAB) under neutral pH and simulated sunlight irradiation conditions. Electrostatic interaction between IAA and CTAB produced neutral IAA/CTAB complex, which might account for the enhanced adsorption of IAA on PVC powders. Upon photo-irradiation, the adsorbed IAA was excited to generate hydrated electrons (e), which could pass through a shorter distance to PVC-MP surface than that derived from homogeneous IAA molecules in aqueous solution. Transient spectra of laser flash photolysis provided direct evidence for the generation of e, which supported the proposed dechlorination mechanism. Based on the results of attenuated total reflectance/Fourier transform infrared (ATR/FTIR) and Raman spectra, C-Cl bond cleavage and polyene formation were involved in the structural transformation of PVC-MPs. Due to the hydrophobic effects and π-π interactions between aromatic rings and polyene structures in PVC-MP surface, the PVC-MP powders irradiated in the presence of IAA/CTAB showed an enhanced sorption for both hydrophobic and hydrophilic aromatic chemicals.