Comparison of rhodamine B adsorption and desorption on the aged non-degradable and degradable microplastics: Effects of charge-assisted hydrogen bond and underline mechanism

The accumulation of microplastics (MPs) in the environment and their role as carriers for ionic organic pollutants are increasingly attracting attention. This study evaluated the adsorption-desorption characteristics of the cationic organic pollutant on virgin and UV-aged non-degradable polystyrene (PS) as well as degradable poly(butylene succinate) (PBS) and poly(butylene adipate-co-terephthalate) (PBAT) MPs. The results showed that aging treatment made the surface of MPs rougher and more porous, causing the adsorption to shift from monolayer to multilayer adsorption. Aging increased the oxygen-containing groups on MPs, significantly enhancing the H bond (HB) donor capabilities of degradable aged PBS and PBAT, thereby improving adsorption by more than 10 times. This significant increase in adsorption is mainly due to the combined effects of strong HB (including ordinary HB (OHB) and charge-assisted HB (CAHB)), electrostatic interactions, and π-π interactions. Notably, the stronger HB enabled aged PBS and PBAT to achieve efficient and stable adsorption of rhodamine B over a wide pH range, with significant desorption hysteresis (HI > 1.80). This indicates that degradable aged MPs can act as carriers for long-distance pollutant transport. The significant total desorption of cationic pollutants from aged PBS and PBAT in simulated animal gastrointestinal fluids confirmed the greater environmental hazards of degradable aged MPs. This work is the first to demonstrate that degradable aged MPs, as unique HB donors, can primarily adsorb ionic organic pollutants through strong HB (CAHB and OHB), which helps assess the environmental fate of biodegradable microplastics and pollutants in aquatic systems.