New insights into adsorption mechanism of pristine and weathered polyamide microplastics towards hydrophilic organic compounds

Abstract

The widespread coexistence of hydrophilic organic compounds and microplastics (MPs) in the environment has greatly increased their associated environmental problems. To evaluate the potential carrier effect of oxygen-containing MPs on coexisting pollutants, adsorption behaviors of four hydrophilic organic compounds (benzoic acid, sulfamethoxazole, sulfamerazine and ciprofloxacin) on MPs (pristine and weathered polyamide (PA)) were studied in the aquatic environment. The results showed that the surface morphology, size, oxygen content, molecular structure, surface charge and crystallinity of PA were changed after weathering, and the weathering degree of PA treated with heat-activated potassium persulfate was the highest. The main adsorption mechanisms included hydrogen bonding, hydrophobic interaction, charge-assisted hydrogen bonding, and electrostatic interaction. Hydrogen bonding and hydrophobic interaction contributed to the adsorption, while electrostatic interaction weakened the adsorption under the specific pH conditions. The formation of charge-assisted hydrogen bonding (CAHB) was also verified through pH influence experiments, and this force can overcome the electrostatic repulsion. The high adsorption of KPA (PA weathered by K₂S₂O₈) under alkaline conditions was well explained by the formation of homonuclear CAHB due to the increase of oxygen-containing functional groups compared to the other three PA. Additionally, weathering did not always enhance the adsorption of hydrophilic organic compounds on PA, which was related to the changes in surface charge, crystallinity and hydrophilicity of PA. Overall, the physical and chemical properties (e.g., specific surface area, oxygen content, molecular structure) of PA after weathering and its trend of adsorption were different from other oxygen-free MPs in this study. This work can provide basic data for environmental risk of MPs and contribute to clarify and understand the processes of oxygenated MPs in the aquatic environment.

Keywords: Adsorption; Charge-assisted hydrogen bonding; Hydrophilic organic compounds; Microplastics; Weathering.