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Polycyclic aromatic hydrocarbon derivatives onto polar microplastics of polyurethane: equilibrium, thermodynamics, and kinetics of monolayer-multilayer adsorption
Summary
Laboratory experiments measured how four different polycyclic aromatic hydrocarbon (PAH) derivatives — found in oil and combustion pollution — adsorb onto polyurethane foam microplastics in water and artificial seawater. The PAH compounds bonded to polyurethane through multiple mechanisms including hydrogen bonding and pi-pi stacking, and formed multiple layers of adsorption rather than just a single surface layer, leading to higher uptake than simpler plastics. Because polyurethane microplastics are widely present in aquatic environments, they may carry large loads of toxic PAH derivatives to organisms that ingest them.
The study of the adsorption of polycyclic aromatic hydrocarbons on microplastics (MPs) has attracted much attention as to how microplastics can act as carriers of these pollutants. Polyurethane (PU) is one of the MPs found in aquatic environments, containing different functional groups it can interact with polar and nonpolar molecules. PAH derivatives (dPAHs) present different properties and thus can be adsorbed by different interactions; thus, this study investigated the adsorption of fluorene (FLN), dibenzothiophene (DBT), dibenzofuran (DBF), and carbazole (CBZ) onto PU MP. The Langmuir, Freundlich, and BET isotherm models were examined, and the BET model best fitted. The adsorption was a nonspontaneous process, exothermic for mono- and multilayer formation for FLN, DBT, and CBZ, and endothermic for DBF monolayer formation. The adsorption monolayer was formed by van der Waals forces, H─bonding, and π─π interactions, while the formation of the multilayer can be explained by π─π and hydrophobic interactions. The pseudo-second-order model proved to be more consistent for the adsorption of dPAHs. The adsorption in artificial seawater shows no significant differences for the monolayer but favored the adsorption multilayer due to the salting-out effect. Due to the existence of several adsorption mechanisms, PU MP interacts with dPAHs in greater quantities when compared to a MP with a simpler structure.
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