Aggregation kinetics of different surface-modified polystyrene nanoparticles in monovalent and divalent electrolytes

The intentional production and degradation of plastic debris may result in the formation of nanoplastics. Currently, the scarce information on the environmental behaviors of nanoplastics hinders accurate assessment of their potential risks. Herein, the aggregation kinetics of different surface-modified polystyrene nanoparticles in monovalent and divalent electrolytes was investigated to shed some light on the fate of nanoplastics in the aquatic environment. Three monodisperse nanoparticles including unmodified nanoparticles (PS-Bare), carboxylated nanoparticles (PS–COOH) and amino modified nanoparticles (PS–NH₂), as well as one polydisperse nanoparticles that formed by laser ablation of polystyrene films (PS-Laser) were used as models to understand the effects of surface groups and morphology. Results showed that aggregation kinetics of negatively charged PS-Bare and PS-COOH obeyed the DLVO theory in NaCl and CaCl₂ solutions. The presence of Suwannee river natural organic matters (SRNOM) suppressed the aggregation of PS-Bare and PS-COOH in monovalent electrolytes by steric hindrance. However, in divalent electrolytes, their stability was enhanced at low concentrations of SRNOM (below 5 mg C L⁻¹), while became worse at high concentrations of SRNOM (above 5 mg C L⁻¹) due to the interparticle bridging effect caused by Ca²⁺ and carboxyl groups of SRNOM. The cation bridging effect was also observed for PS-laser in the presence of high concentrations of divalent electrolytes and SRNOM. The adsorption of SRNOM could neutralize or even reverse surface charges of positively charged PS-NH₂ at high concentrations, thus enhanced or inhibited the aggregation of PS-NH₂. No synergistic effect of Ca²⁺ and SRNOM was observed on the aggregation of PS-NH₂, probably due to the steric repulsion imparted by the surface modification. Our results highlight that surface charge and surface modification significantly influence aggregation behaviors of nanoplastics in aquatic systems.