Every year, large quantities of plastics are produced and used for diverse applications, growing concerns about the waste management of plastics and their release into the environment. Plastic debris can break down into millions of pieces that adversely affect natural organisms. In particular, the photolysis of micro/nanoplastics can generate reactive oxygen species (ROS). However, their oxidative roles in initiating redox chemical reactions with heavy and transition metals have received little attention. In this study, we investigated whether the photolysis of polystyrene (PS) nanoplastics can induce the oxidation of Mn2+(aq) to Mn oxide solids. We found that PS nanoplastics not only produced peroxyl radicals (ROO•) and superoxide radicals (O2•-) by photolysis, which both play a role in unexpected Mn oxidation, but also served as a substrate for facilitating the heterogeneous nucleation and growth of Mn oxide solids and controlling the formation rate and crystalline phases of Mn oxide solids. These findings help us to elucidate the oxidative roles of nanoplastics in the oxidation of redox-active metal ions. The production of ROS from nanoplastics in the presence of light can endanger marine life and human health, and affect the mobility of the nanoplastics in the environment via redox reactions, which in turn may negatively impact their environmental remediation.
Keywords: abiotic Mn2+ oxidation; heterogeneous nucleation; nanoplastics; peroxyl radicals; photochemistry; superoxide radicals.