Surface change of microplastics in aquatic environment and the removal by froth flotation assisted with cationic and anionic surfactants

Microplastics (MPs) are increasingly released into the environment due to the widespread usage and improper management of plastics. Considerable research efforts have been devoted to the remediation of MPs. Froth flotation has been demonstrated as an effective method to remove MPs in water and sediment. However, there is a lack of knowledge on the regulation of the hydrophobicity/hydrophilicity of MPs surfaces. We found that exposure to the natural environment resulted in the increased hydrophilicity of MPs. The flotation efficiencies of polyvinyl chloride (PVC), polypropylene (PP), polystyrene (PS), and polyethylene glycol terephthalate (PET) MPs decreased to zero after six months of natural incubation in rivers. According to various characterizations, the hydrophilization mechanism is mainly correlated with surface oxidation and the deposition of clay minerals. Inspired by surface wettability conversion, we applied surfactants (collectors) to enhance MPs hydrophobicity and flotation efficiency. Anionic sodium oleate (NaOL) and cationic dodecyl trimethyl ammonium chloride (DTAC) were used to regulate surface hydrophobicity. The effects of collector concentration, pH, conditioning time, and metal ions on MPs flotation were thoroughly elucidated. Characterizations and adsorption experiments were performed to describe the heterogeneous adsorption of surfactants on MPs surfaces. The interaction between surfactants and MPs was explained through density functional theory (DFT) simulations. The dispersion energy between hydrophobic hydrocarbon chains attracts collectors on the MPs surface, and the collector molecules wrap and laminate to MPs surfaces. Flotation using NaOL exhibited a higher removal efficiency, and NaOL was environmentally friendly. Subsequently, we investigated the activation of Ca2+, Fe3+, and Al3+ to further improve the collecting efficiency of NaOL. Under the optimized conditions, MPs in natural rivers could be removed by froth flotation. This study shows the great promise of froth flotation for the application of MPs removal.