Effect of hydro-oleophobic perfluorocarbon chain on interfacial behavior and mechanism of perfluorooctane sulfonate in oil-water mixture

Perfluorocarbon chain of perfluorooctane sulfonate (PFOS) is not only hydrophobic but also oleophobic, and its effect on PFOS distribution in oil-water mixture and underlying mechanism are unclear. For the first time, we propose that PFOS can emulsify oil-water mixture only in the presence of air, completely different from hydrocarbon surfactants. The perfluorocarbon chain repels hydrophobic compounds and its oleophobicity increases with decreasing polarity of organic solvents. The formed emulsion in oil phase contains high concentrations of PFOS, resulting in PFOS decrease in water. The increase of shaking speed and time as well as oil and air volume all increase the emulsification and decrease PFOS concentrations in water. During the settling process, the emulsion gradually disappears and the concentrated PFOS is released into water. The emulsification mechanism of PFOS based on air bubbles is proposed, and PFOS partitions to the interfaces of air bubbles with the hydro-oleophobic perfluorocarbon chain stretching into air bubbles and the polar head in water. This study clarifies the ambiguous understanding of the oleophobicity of perfluorocarbon chain in PFOS, and it is helpful for the understanding of the transport and fate of PFOS at oil-water interfaces in aquatic environments as well as the enhanced removal of PFOS from wastewater.