The fate of photoreduction of Hg(II) in aqueous solution by aged microplastic particles and their leached DOM

The transformation of Hg(II) and Hg(0) in aqueous systems governs the speciation and biogeochemical cycling of Hg. However, with the increasing amount of microplastics in the aqueous environment, little is known about the different effects of microplastic particles and their leached DOM on the photoreduction of Hg(II) to Hg(0) after long-term photoaging. In this study, we found that aged microplastic particles significantly inhibited the photoreduction efficiency (6.40-15.64 %) of Hg(II) compared to the control without any microplastic (31.02 %) and pristine microplastic particles (9.95-34.10 %). This inhibition was due to the adsorption of Hg by the microplastic particles, which decreased the amount of available Hg(II) (Hg(II)) that could participate in the photoreduction reaction. The characteristics of aged microplastic particles also indicated rougher surfaces and more oxygen-containing functional groups after photoaging, which may enhance their adsorption capacity compared to pristine microplastic. Interestingly, the photoreduction efficiency of Hg(II) was 11.58-53.28 % higher in the presence of microplastic leach DOM compared to the control. With increasing age, the microplastic leach DOM obviously promotes the photoreduction of Hg(II). Free radical inhibition and electron paramagnetic resonance spectra demonstrated that O in microplastic leach DOM contributed to the photoreduction of Hg(II) under light irradiation. Moreover, X-ray absorption near edge structure analyses demonstrated that microplastic leach DOM produced Hg(I) as the primary photoproduct, accounting for 43.17 % of the total Hg in the photoreaction solution and likely reducing it to Hg(0). This study provides novel insights into forecasting the synthesized risks of microplastic aging in the biogeochemical cycle of Hg within aqueous environments.