Removal of perfluoroalkyl acids from aqueous media by surfactant-modified clinoptilolites

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are environmentally persistent, bioaccumulating, and toxic compounds that have attracted global attention. It is challenging to reduce the residual concentrations of these compounds to safe discharge limits. In this study, batch experiments were performed to evaluate natural clinoptilolite and clinoptilolites modified (MC) with cetylpyridinium chloride (CPC-MC), didodecyldimethylammonium bromide (DDAB-MC), hexadecyltrimethylammonium bromide (HDTMA-MC), and tetramethylammonium chloride (TMA-MC) as cost-effective aqueous PFAS adsorbents. The removal capacities of the adsorbents for the majority of the PFASs decreased in the following order: DDAB-MC > CPC-MC ≫ modified natural clinoptilolite with hexadecyltrimethyl ammonium bromide (HDTMA-MC) ≫ modified natural clinoptilolite with tetramethylammonium chloride (TMA-MC) ≈ natural clinoptilolite modified with NaCl (NC). In particular, CPC-MC and DDAB-MC reduced PFASs concentration in 50 μg/L by up to 98% for perfluorooctane sulphonate. Within 30 min, CPC-MC (30.5 μg/L) and DDAB-MC (32.1 μg/L) met the PFOS water quality criterion of 36 μg/L in inland surface waters. Both adsorbents met this criterion at the highest solution volume (40 mL) and 0.125 g/L (solid-to-liquid ratio of 1:8). PFASs with short hydrocarbon chains competed more for adsorption. PFASs with sulphonate functional groups were also adsorbed more than carboxyl groups in single- and multi-PFAS solutions. The modified surfaces of clinoptilolites controlled PFAS adsorption through hydrophobic and electrostatic interactions. PFAS removal with surfactant-modified clinoptilolites is cost-effective and protects aquatic environments by using surplus natural materials.