Cationic surfactant-assisted foam fractionation enhances the removal of short-chain perfluoroalkyl substances from impacted water

Several studies have demonstrated that air-bubbling and foam fractionation techniques can efficiently remove long-chain PFAS from contaminated water. However, removing short-chain PFAS is challenging due to its lower surface activity and inability to form self-assembly structures at the air-water interface. In this study, we tested various additives, including salts, surfactants, and polymers, to improve short-chain PFAS (e.g., perfluorobutanesulfonic acid (PFBS) and perfluorobutanoic acid (PFBA)) removal in non-foaming solutions using a bench-scale system. We found that in the presence of cetyltrimethylammonium chloride (CTAC) and salt, air-bubbling can significantly remove 0.5 μg L−1 of PFBS and PFBA in deionized water by >99% (15 min) and 81% (60 min), respectively. The decline of surface tension and the formation of thin foam-like layers during bubbling, controlled by the concentration of CTAC, significantly improved the removal of short-chain PFAS. Adding anionic and neutral surfactants showed no removal of short-chain PFAS during bubbling, suggesting the importance of the electrostatic interactions between short-chain PFAS and the cationic CTAC. We observed a 1:1 M ratio between CTAC and PFBS removed from the solution, suggesting the formation of ion pairs in the solution and enhancing the surface activity of the overall neutral (PFAS-CTAC) complex. A mass balance of the system revealed that the primary mechanism by which PFAS was removed from non-foaming waters was through aerosol generation (70−100%). Using the optimized condition, PFAS mixtures (short- and long-chain PFAS, including five recently regulated PFAS by USPEA, 2 nM each) in deionized water and natural groundwater were successfully removed to below detection (>99% removal;