Molecular characteristics and plastic additives in dissolved organic matter derived from polystyrene microplastics:...

Microplastic-derived dissolved organic matter (MP-DOM), released during ultraviolet-induced aging of microplastics (MPs), has emerged as a critical yet underexplored topic regarding the environmental impacts of MPs. However, the effects of irradiation intensity on the release and molecular diversity of MP-DOM, including plastic additives, remain poorly understood. In this study, the photoaging processes of polystyrene MPs (PS-MPs) were simulated under varying cumulative irradiation (irradiation intensity × irradiation duration) and PS-MPs concentrations (1 - 5 g/L). The PS-derived DOM (PS-DOM) was characterized using fluorescence spectroscopy, Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS), and liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS). After 21 days of irradiation, the amount of leached PS-DOM ranged from 7.76 to 39.40 mg-C/g. Cumulative irradiation significantly accelerated PS-MPs aging and PS-DOM leaching (p < 0.001). Initially, these processes proceeded slowly until the cumulative irradiation exceeded 75 kWh/m². Beyond this threshold, PS-MPs exhibited substantial size reduction, increased oxidation, and enhanced PS-DOM leaching. FT-ICR MS analysis revealed that PS-DOM contained 30.1 %-31.8 % unique components compared to natural organic matter, with greater degradability at lower PS-MPs concentrations. Furthermore, LC-HRMS identified 13 oxidation products and 25 plastic additives in PS-DOM, with their amounts decreasing as PS-MPs concentrations increased, from 17.05 to 3.24 mg/g and 4.88 to 1.85 mg/g, respectively. Notably, lower PS-MPs concentrations resulted in greater cumulative irradiation per unit mass, intensifying PS-DOM leaching, enhancing degradability, and increasing plastic additives release. This study highlights the environmental implications of per unit cumulative irradiation on MP-DOM leaching and its molecular composition, providing insights into its ecological risks and potential impacts on aquatic systems.