Elucidating the co-transport of bisphenol A with polyethylene terephthalate (PET) nanoplastics: A theoretical study of the adsorption mechanism.

Polyethylene terephthalate (PET) is a possible key component of nanoplastics in water environments, which can migrate pollutants through co-transport. In this regard, the co-transport of endocrine disruptors (such as bisphenol A, BPA) by nanoplastics is of emergent concern because of its cytotoxicity/bioaccumulation effects in aquatic organisms. In this work, a computational study is performed to reveal the BPA adsorption mechanism onto PET nanoplastics (nanoPET). It is found that the outer surface of nanoPET has a nucleophilic nature, allowing to increase the mass transfer and intraparticle diffusion into the nanoplastic to form stable complexes by inner and outer surface adsorption. The maximum adsorption energy is similar (even higher) in magnitude with respect to nanostructured adsorbents such as graphene, carbon nanotubes, activated carbon, and inorganic surfaces, indicating the worrying adsorption properties of nanoPET. The adsorption mechanism is driven by the interplay of dispersion (38-49%) and electrostatics effects (43-50%); specifically, dispersion effects dominate the inner surface adsorption, while electrostatics energies dominate the outer surface adsorption. It is also determined that π-π stacking is not a reliable interaction mechanism for aromatics on nanoPET. The formed complexes are also highly soluble, and water molecules behave as non-competitive factors, establishing the high risk of nanoPET to adsorb and migrate pollutants in water ecosystems. Furthermore, the adsorption performance is decreased (but not inhibited) at high ionic strength in salt-containing waters. Finally, these results give relevant information for environmental risk assessment, such as quantitative data and interaction mechanisms for non-biodegradable nanoplastics that establish strong interactions with pollutants in water.