Insight into the effect of natural aging of polystyrene microplastics on the sorption of legacy and emerging per- and polyfluorinated alkyl substances in seawater

<h2>Abstract</h2> Microplastics (MPs) are abundant in aquatic environments and due to their small size, surface properties, and strong hydrophobicity, they can easily sorb chemicals, thus potentially acting as pollutant carriers. To date, most studies investigating the sorption of chemicals on MPs have principally focused on virgin MPs. However, MPs in the environment undergo aging effects, which changes their physical-chemical properties and aptitude to interact with chemicals, such as per- and polyfluorinated alkyl substances (PFAS) referred to as "forever chemicals". In this study, we compared the sorption behavior of nine PFAS, exhibiting different physical-chemical properties, on virgin and naturally aged polystyrene microplastic (PS-MPs) to explore to what extent the environmental aging affects the sorption behavior of the PS-MPs for different legacy and emerging PFAS in seawater. Differences in the morphology and surface properties of aged PS-MPs were examined by infrared spectroscopy, surface area analysis, scanning electron microscopy, and X-ray diffraction. Results revealed that compared to virgin PS-MPs, aged PS-MPs exhibited morphological changes (e.g. cavities, pits, and rough surfaces) with biofilm development and signs of oxidation on the MPs surface. PFAS sorption on PS-MPs was enhanced for the aged PS-MPs compared to virgin PS-MPs with K_d values ranging from 327 L kg⁻¹ for PFOA to 3247 L kg⁻¹ for PFOS in aged PS-MPs. The difference in sorption capacity was mainly attributed to the physical-chemical changes and the adhered biofilm observed in aged PS-MPs. Results also showed that virgin PS-MPs adsorb PFAS mainly through steric hindrance, while the aged PS-MPs may involve more complex sorption mechanisms. This research provides additional insights into the ability of aged MPs as potential carriers of legacy and emerging contaminants in the marine environment.