Sulfide induces physical damages and chemical transformation of microplastics via radical oxidation and sulfide addition.

• Sulfide treatment results in damages and chemical transformation of microplastics. • •OH radicals formed from spontaneous oxidation of sulfide are primary oxidants. • Radical oxidation reactions enable sulfide addition to surface of microplastics. • Sulfide addition can in turn facilitate radical oxidation of microplastics. • Breakdown of plastics in sulfide-rich zones may be a source of micro-/nanoplastics. Transformation of microplastics in aquatic environments and engineered systems (e.g., wastewater treatment plants) significantly affects their transport, fate and effects. Here, we present the counterintuitive finding that sulfide, a prevalent nucleophile and reductant, can result in oxidation of microplastics, in addition to sulfide addition. Treating four model microplastics (thermoplastic polyurethane, polystyrene, polyethylene terephthalate and polyethylene) with 0.1 mM sulfide in a Tris-buffer solution (pH 7.2, 25 °C) resulted in physical damages (embrittlement and cracking) and chemical transformation (increased O/C ratio and formation of C–S bonds) of the materials. Pre-aging of the microplastics with O 3 or UV treatment had varied effects on their reactivities toward sulfide, depending on the specific structural and surface chemistry properties of the polymers. Electron paramagnetic resonance and radical trapping/quenching experiments showed that sulfide underwent spontaneous oxidation to form •OH radicals, which acted as the primary oxidant to attack the carbon atoms in the polymer chains, leading to surface oxidation and chain scission. Notably, sulfide addition, verified with X-ray photoelectron spectroscopy and 13C-nuclear magnetic resonance spectroscopy analyses, likely contributed to the physicochemical transformation of microplastics together with radical oxidation in a synergistic manner. The findings unravel an important transformation route (and a potential source) of microplastics in the environment. [Display omitted] [ABSTRACT FROM AUTHOR]