Adsorption of 2-hydroxynaphthalene, naphthalene, phenanthrene, and pyrene by polyvinyl chloride microplastics in water and their bioaccessibility under in vitro human gastrointestinal system

Abstract

The interaction of microplastics (MPs) and organic pollutants has recently become a focus of investigation. To understand how microplastic residues affect the migration of organic pollutants, it is necessary to examine the adsorption and desorption behavior of organic pollutants on MPs. In this study, integrated adsorption/desorption experiments and theoretical calculations were used to clarify the adsorption mechanism of 2-hydroxynaphthalene (2-OHN), naphthalene (NAP), phenanthrene (PHE), and pyrene (PYR) by polyvinyl chloride microplastics (PVC-MPs). Based on the phenomenological mathematical models, the rate-limiting step for analyte adsorption onto PVC-MPs was adsorption onto active sites (R2 = 0.865–0.995). Except for PHE, analyte adsorption isotherms were well described by the Freundlich model (R2 = 0.992–0.998), and adsorption thermodynamics showed that analyte adsorption on PVC-MPs was a spontaneous exothermic process (ΔH0 < 0; ΔG0 < 0). Based on the order of adsorption efficiency of 2-OHN < NAP < PHE < PYR, which is identical to the competitive adsorption experiment, polycyclic aromatic hydrocarbon (PAH) adsorption on PVC-MPs increased as the aromatic ring number increased and the hydroxyl content decreased. The release of 2-OHN (49 %–52 %) from PVC-MPs into the simulated gastrointestinal environment was greater than that of NAP (5.5 %–5.7 %). Theoretical calculations and adsorption tests indicated that hydrophobic interaction was the primary influence on the adsorption of PAHs and their hydroxylated derivatives by PVC-MPs. These findings improve our understanding of MPs' behavior and dangers as pollutant carriers in the aquatic environment and help us develop recommendations for the pollution control of MPs.