The effects of functional groups on the sorption of naphthalene on microplastics

Ubiquitous microplastics were recognized as an ideal carrier for polycyclic aromatic hydrocarbons (PAHs) to spread in nature or transfer to biota, thus posing risks to human health. However, little is known about how the functional groups in PAH derivatives influence their sorption onto microplastics as compared to parent PAHs. This study investigated the sorption of naphthalene (NAP) and its derivatives onto polystyrene microspheres with (MP-COOH) or without (MP) surface modification of the carboxyl group. NAP derivatives with charged groups (e.g., –NH2, –OH and –COOH) reached the sorption equilibrium more early than NAP and its derivative with an uncharged group (e.g., –CH3), whereas their sorption capacities (Kd = 6.0–8.4 L/g for MP, Kd = 4.5–6.3 L/g for MP-COOH) were significantly lower than that of the latter (Kd = 11.6–12.0 L/g for MP, Kd = 9.4–10.0 L/g for MP-COOH). The inhibition of charged groups on sorption could be attributed to their facilitation on molecular polarity and, thus, their lower hydrophobicity (LogKOW) since hydrophobicity was the crucial factor controlling the sorption of NAP and NAP derivatives onto both MP and MP-COOH. Computational modeling further showed that charged functional groups would weaken the π-π interaction or strengthen the repulsion between NAP or NAP derivative molecule and MP or MP-COOH molecule, which might also contribute to the suppressed sorption. This study provides new insight into the affinity of PAH derivatives with microplastics, which, therefore, improves our understanding of the environmental fates of microplastics and the organic pollutants. [Display omitted] •Naphthalene derivatives with charged groups have lower sorption on microplastics.•The derivatives with uncharged groups have a similar sorption as naphthalene.•LogKOW controls the sorption of naphthalene and its derivatives on microplastics.•Charged groups enhance the molecular polarity, thus inhibiting the LogKOW.•Charged groups weaken intermolecular π-π interaction or enhance the repulsion.