Photoaging effects on polyethylene microplastics: Structural changes and chlorpyrifos adsorption

Microplastics (MP) are a global concern due to their small size, insolubility in water, and non-degradable nature, and long-term environmental persistence. Weathering processes, such as ultraviolet (UV) radiation, can alter their properties, enhancing their ability to absorb pollutants or release harmful substances, such as pesticides, which is also an environmental concern, thereby complicating their environmental impact and mitigation efforts. This study investigates the impact of UVB-induced photoaging on polyethylene (PE) microplastics and their sorption behavior towards the pesticide chlorpyrifos (CP). PE microplastics were exposed to varying UVB aging durations, leading to significant changes in their physicochemical and morphological properties. The sorption experiments revealed that aged microplastics exhibited increased affinity for CP, with adsorption capacity rising by 17.9% compared to pristine PE. This enhanced adsorption was attributed to the (1) introduction of oxygen-containing functional groups, facilitating the formation of hydrogen bonds between the microplastic surface and surrounding water molecules, thereby contributing to the adsorption of CP; (2) formation of irregular micropores and surface roughness, potentially providing ample sites for pesticide adsorption and (3) reduction in crystallinity from 35% to 30%, which favors the sorption of hydrophobic organic pollutants. Density Functional Theory (DFT) calculations supported these findings by showing changes in the electronic structure of PE that facilitate interactions with CP. These results provide critical insights into the environmental behavior of aged microplastics and their potential to adsorb hazardous chemicals, underscoring the need for further research on the environmental impact of microplastic aging.