Degradation of Polystyrene Nanoplastics in UV/NaClO and UV/PMS Systems: Insights into Degradation Efficiency, Mechanism, and Toxicity Evaluation

Nanoplastics have gradually become a concern due to the wide use of plastics. Nanoplastics in aqueous phase can be exposed to users through water supply networks and cannot be efficiently removed by conventional water treatment processes. This work studied the degradation of polystyrene nanoplastics (PS-NP) by two commonly used advanced oxidation systems: UV/NaClO and UV/peroxymonosulfate (PMS). Results showed that almost no turbidity was detected in the PS-NP solution (5.00 mg/L) after treated by both UV/NaClO and UV/PMS for 360 min, suggesting the excellent turbidity removal ability. Yet, scanning electron microscope (SEM) and total organic carbon (TOC) removal tests demonstrated that PS-NP could not be completely degraded by UV/NaClO. The mineralization rate using UV/NaClO was only 7.00% even when the NaClO concentration increased to 5.00 mM, and many PS-NP particles could still be observed in SEM images. By contrast, the mineralization rate reached 63.90% in the UV/PMS system under the identical experimental conditions, and no spherical particles appeared in the SEM results. Density functional theory (DFT) calculations revealed that the different reaction sites and energy barriers of SO4•− and •Cl on PS-NP resulted in the differences in mineralization rates and degradation intermediates. The degradation pathway of PS-NP by UV/NaClO and UV/PMS was proposed accordingly. Additionally, the intermediates toxicity evaluation by a luminescent bacteria test showed that the inhibition rate in the UV/NaClO system (2.97%) was not markedly different from that in the control group without any treatment (1.98%); while that in UV/PMS system increased sharply to 98.19%. This work demonstrated that UV/PMS was more effective in PS-NP degradation than UV/NaClO, and the chemical risks of degradation intermediates were non-negligible.