Quantification of the redox properties of microplastics and their effect on arsenite oxidation

Microplastics have attracted global concern. The environmental-weathering processes control their fate, transport, transformation, and toxicity to wildlife and human health, but their impacts on biogeochemical redox processes remain largely unknown. Herein, multiple spectroscopic and electrochemical approaches in concert with wet-chemistry analyses were employed to characterize the redox properties of weathered microplastics. The spectroscopic results indicated that weathering of phenol-formaldehyde resins (PFs) by hydrogen peroxide (H₂O₂) led to a slight decrease in the content of phenol functional groups, accompanied by an increase in semiquinone radicals, quinone, and carboxylic groups. Electrochemical and wet-chemistry quantifications, coupled with microbial-chemical characterizations, demonstrated that the PFs exhibited appreciable electron-donating capacity (0.264-1.15 mmol e^- g^-1) and electron-accepting capacity (0.120-0.300 mmol e^- g^-1). Specifically, the phenol groups and semiquinone radicals were responsible for the electron-donating capacity, whereas the quinone groups dominated the electron-accepting capacity. The reversible redox peaks in the cyclic voltammograms and the enhanced electron-donating capacity after accepting electrons from microbial reduction demonstrated the reversibility of the electron-donating and -accepting reactions. More importantly, the electron-donating phenol groups and weathering-induced semiquinone radicals were found to mediate the production of H₂O₂ from oxygen for arsenite oxidation. In addition to the H₂O₂-weathered PFs, the ozone-aged PF and polystyrene were also found to have electron-donating and arsenite-oxidation capacity. This study reports important redox properties of microplastics and their effect in mediating contaminant transformation. These findings will help to better understand the fate, transformation, and biogeochemical roles of microplastics on element cycling and contaminant fate.