The difference of aggregation mechanism between microplastics and nanoplastics: Role of Brownian motion and structural layer force

In recent years, microplastics (MPs) and nanoplastics (NPs) have attracted worldwide attention because of the potential risks they pose to aquatic environments, but there are few studies on the difference of aggregation mechanism between MPs and NPs. In this study, 100 nm and 1 μm polystyrene plastics were selected as models to explore the aggregation mechanism of MPs/NPs under different aquatic environments. The influence of ion species and concentrations on the aggregation behaviors and kinetics were systematically investigated to predict the effects of water quality on the occurrence form of MPs and NPs based on DLVO theory and revised modified Smoluchowski theory. Results showed concentration, valence and hydrated ability of cations jointly affected the aggregation behavior of NPs. The critical coagulation concentration ratio of cations were consistent with Schulze-Hardy rules. But the different aggregation rate coefficients of same valent cations were ascribed to the structural layer force. Anion species played a role in the reaction-controlled regime by producing hydrogen ions to neutralize negative charges on NPs surfaces. Due to the strong Brownian motion and structural layer force, NPs would be stable in freshwater but preferentially aggregated when transport through brackish water, estuaries, eutrophication and high hardness areas and sea water, forming the accumulation hot spots of NPs in the sediment. While for MPs, physical process controlled the aggregation mechanism of them, leading to high stability in natural water and eventually transporting into marine environments. This study provided a theoretical foundation for assessing the transport, distribution, fate and ecological risks of MPs and NPs in realistic aquatic environments.