Impact of iron/aluminum (hydr)oxide and clay minerals on heteroaggregation and transport of nanoplastics in aquatic environment

Nanoplastics (NPs) are emerging contaminants in the environment, where the transport and fate of NPs would be greatly affected by interactions between NPs and minerals. In the present study, the interactions of two types of polystyrene nanoplastics (PSNPs), i.e., bare-PSNPs and carboxylated PSNPs-COOH, with iron (hydr)oxides (hematite, goethite, magnetite, and ferrihydrite), aluminum (hydr)oxides (boehmite and gibbsite), and clay minerals (kaolinite, montmorillonite, and illite) were investigated. The positively charged iron/aluminum (hydr)oxide minerals could form heteroaggregates with negatively charged PSNPs. Electrostatic and hydrophobic interaction dominate for the heteroaggregation of bare-PSNPs with iron/aluminum (hydr)oxide minerals, while ligand exchange and electrostatic interaction are involved in the heteroaggregation of PSNPs-COOH with iron/aluminum (hydr)oxides minerals. However, heteroaggregation between PSNPs and negatively charged clay minerals was negligible. Humic acid markedly suppressed such heteroaggregation between PSNPs and minerals due to enhanced electrostatic repulsion, steric hindrance, and competition of surface attachment sites. The heteroaggregation rates of both bare-PSNPs and PSNPs-COOH with hematite decreased with increasing solution pH. Increased ionic strength enhanced the heteroaggregation of PSNPs-COOH but inhibited that of bare-PSNPs. The results of the present study suggested that the heteroaggregation of PSNPs in environments could be strongly affected by minerals, solution pH, humic acid, and ionic strength.