Aggregation behavior of polystyrene nanoplastics: Role of surface functional groups and protein and electrolyte variation

Aggregation kinetics of plastics are affected by the surface functional groups and exposure orders (electrolyte and protein) with kinds of mechanisms in aquatic environment. This study investigates the aggregation of polystyrene nanoplastics (PSNPs) with varying surface functional groups in the presence of common electrolytes (NaCl, CaCl2, Na2SO4) and bovine serum albumin (BSA). It also examines the impact of different exposure orders, namely BSA + NaCl (adding them together), BSA → NaCl (adding BSA firstly and then NaCl), and NaCl → BSA (adding NaCl firstly and then BSA), on PSNPs aggregation. The presence of BSA decreased the critical coagulation concentration in NaCl (CCCNa+) of the non-modified PS-Bare from 222.17 to 142.81 mM (35.72%), but increased that of the carboxyl-modified PS-COOH from 157.34 to 160.03 mM (1.71%). This might be ascribed to the thicker absorbed layer of BSA onto the PS-Bare surface, known from Ohshima's soft particle theory. Their aggregation in CaCl2 was both increased because of Ca2+ bridging. Different from the monotonous effects of BSA on PS-Bare and PS-COOH, BSA initially facilitated PS-NH2 aggregation via patch-charge attraction, then inhibited it at higher salt levels through steric repulsion. Furthermore, exposure orders had no significant effect on PS-Bare and PS-COOH, but had a NaCl concentration-dependent impact on PS-NH2. At the low NaCl concentrations (10 and 100 mM), no obvious influence could be observed. While, at 300 mM NaCl, the high concentrations of BSA could not totally stabilize the salt-induced aggregates in NaCl → BSA, but could achieve it in the other two orders. These might be attributed to the electrical double layer compression by NaCl, "patch-charge" force and steric hindrance by BSA. These experimental findings shed light on the potential fate and transport of nanoparticles in aquatic environments.