Abstract

Nanoplastics (NPLs) persist in aquatic habitats, leading to incremental research on their interaction mechanisms with metalloids in the environment. In this regard, it is known that plastic debris can reduce the number of water-soluble arsenicals in contaminated environments. Here, the arsenic interaction mechanism with pure NPLs, such as polyethylene terephthalate (PET), aliphatic polyamide (PA), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), and polystyrene (PS) is evaluated using computational chemistry tools. Our results show that arsenic forms stable monolayers on NPLs through surface adsorption, with adsorption energies of 9–24 kcal/mol comparable to those on minerals and composite materials. NPLs exhibit varying affinity towards arsenic based on their composition, with As(V) adsorption showing higher stability than As(III). The adsorption mechanism results from a balance between electrostatics and dispersion forces (physisorption), with an average combined contribution of 87%. PA, PET, PVC, and PS maximize the electrostatic effects over dispersion forces, while PE and PP maximize the dispersion forces over electrostatic effects. The electrostatic contribution is attributed to hydrogen bonding and the activation of terminal O–C, C–H, and C–Cl groups of NPLs, resulting in several pairwise interactions with arsenic. Moreover, NPLs polarity enables high mobility in aqueous environments and fast mass transfer. Upon adsorption, As(III) keeps the NPLs polarity, while As(V) limits subsequent uptake but ensures high mobility in water. The solvation process is destabilizing, and the higher the NPL polarity, the higher the solvation energy penalty. Finally, the mechanistic understanding explains how temperature, pressure, pH, salinity, and aging affect arsenic adsorption. This study provides reliable quantitative data for sorption and kinetic experiments on plastic pollution and enhances our understanding of interactions between water contaminants.