Adsorption behavior of imidacloprid pesticide on polar microplastics under environmental conditions: critical role of photo-aging

● Small molecular chains formed on photo-aged polylactic acid microplastics (MPs). ● Oxygen-containing functional groups generated on photo-aged polyamide MPs. ● Photo-aging has the opposite influence on the imidacloprid adsorption on two MPs. ● Electrostatic interactions and hydrogen bonds were the main mechanisms. ● High pH value and low ionic strength increase the adsorption capacity. The photo-aging behavior of microplastics (MPs) in natural environment has become a global concern. The ultraviolet radiation has enough energy to change the polymer structure and physical-chemical properties of MPs. Less attention has focused on the interactions of the photo-aged polar and biodegradable MPs with organic pollutants. This work investigated the structural properties of aged polar polyamide (PA) MPs and biodegradable polylactic acid (PLA) MPs exposed to ultraviolet irradiation and their adsorption behavior and mechanism for neonicotinoid insecticide imidacloprid (IMI). The results showed that the MPs had extensive changes in surface morphology and chemical properties after photo-aging. The C–N bond of PA MPs was disrupted to form more carbonyl groups. The oxygen-containing functional groups on the surface of aged PLA MPs were broken and generated relatively smaller molecules. The adsorption capacity of IMI on PA MPs decreased by 19.2 %, while the adsorption capacity of IMI on PLA MPs increased by 41.2 % after photo-aging. This depended on the natural structure of the MPs and their ability to absorb ultraviolet light. The electrostatic interactions, hydrogen bonds, van der Waals interactions, and polar-polar interactions were the main adsorption mechanisms of IMI on MPs. High initial solution pH and low ionic strength favored the adsorption of IMI by altering charge distribution on the MPs surface. The formation of the humic acid-IMI complexes decreased the concentration of IMI in the water phase and further decreased the adsorption on MPs. These results are enlightening for a scientific comprehension of the environmental behavior of the polar MPs.