Aggregation of carboxyl-modified polystyrene nanoplastics in water with aluminum chloride: Structural characterization and theoretical calculation

Nanoplastics (NPs) pollution of aquatic systems is becoming an emerging environmental issue due to their stable structure, high mobility, and easy interactions with ambient contaminants. Effective removal technologies are urgently needed to mitigate their toxic effects. In this study, we systematically investigated the removal effectiveness and mechanisms of a commonly detected nanoplastics, carboxyl-modified polystyrene (PS-COOH) via coagulation and sedimentation processes using aluminum chloride (AlCl) as a coagulant. PS-COOH appeared as clearly defined and discrete spherical nanoparticles in water with a hydrodynamic diameter of 50 nm. The addition of 10 mg/L AlCl compressed and even destroyed the negatively charged PS-COOH surface layer, decreased the energy barrier, and efficiently removed 96.6% of 50 mg/L PS-COOH. The dominant removal mechanisms included electrostatic adsorption and intermolecular interactions. Increasing the pH from 3.5 to 8.5 sharply enhanced the PS-COOH removal, whereas significant loss was observed at pH 10.0. High temperature (23 °C) favored the removal of PS-COOH compared to lower temperature (4 °C). High PS-COOH removal efficiency was observed over the salinity range of 0 - 35‰. The presence of positively charged AlO did not affect the PS-COOH removal, while negatively charged SiO reduced the PS-COOH removal from 96.6% to 93.2%. Moreover, the coagulation and sedimentation process efficiently removed 90.2% of 50 mg/L PS-COOH in real surface water even though it was rich in inorganic ions and total organic carbon. The fast and efficient capture of PS-COOH by AlCl via a simple coagulation and sedimentation process provides a new insight for the treatment of NPs from aqueous environment.