Sulfurization alters phenol-formaldehyde resin microplastics redox property and their efficiency in mediating arsenite oxidation

Microplastics weathering by various types of oxidants in the oxic environment and their interaction with environmental contaminants have drawn numerous scientific attention. However, the environmental fate of microplastics under a reducing environment has been largely unresolved. Herein, the change of physicochemical and redox properties of microplastics during the weathering under a sulfate-reducing environment and the interaction with arsenite were addressed. The sulfurization of phenol-formaldehyde resin microplastics under a sulfate-reducing environment generated smooth and porous particles with the induction of organic S species. Multiple spectroscopic results demonstrated thioether and thiophene groups formed by the substitute removal of O-containing functional groups. Moreover, the sulfurization process induced the reduction of carbonyl groups and oxidation of phenolic hydroxyl groups and resulted in the formation of semiquinone radicals. The O-containing functional groups contributed to microplastics redox property and As(III) oxidation while S-containing functional groups showed no obvious effect. The sulfurized microplastics had lower efficiency in mediating arsenite oxidation than the unsulfurized counterparts due to the decreased electron donating capacity. Producing hydrogen peroxides by electron-donating phenol groups and semiquinone radicals and the direct semiquinone radicals oxidation could mediate arsenite oxidation. The findings of this study help us understand the fate of microplastics in redox fluctuation interfaces.