Removal of perfluoroalkyl acids and precursors with silylated clay: Efficient adsorption and enhanced reuse

Organically modified clays (organoclays) have been considered effective adsorbents for the treatment of per- and polyfluoroalkyl substances (PFAS). However, the stability of organoclays prepared through the conventional cation exchange approach has been a major concern for their practical application. In this study, we reported the development of a new organically functionalized clay by grafting pillared clay substrate with an organosilane through covalent bonding. The performance of the silylated clay (QAG-ZrMT) was systematically compared with an organoclay prepared from ion exchange (HDTMA-ZrMT) for the adsorption of two legacy perfluoroalkyl acids: perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), and two precursor compounds 5:3 fluorotelomer carboxylic acid (5:3FTCA) and 6:2 fluorotelomer sulfonic acid (6:2FTS). Compared to HDTMA-ZrMT, QAG-ZrMT showed substantially improved performance for adsorption of less hydrophobic PFAS (e.g., 5:3FTCA), which could be related to the stronger electrostatic interactions between PFAS and QAG-ZrMT than HDTMA-ZrMT. More importantly, QAG-ZrMT could be conveniently regenerated and reused for multiple cycles with robust performance. In contrast, HDTMA-ZrMT almost completely lost its capacity for PFAS removal after regeneration, due to the loss of organic functional groups during solvent regeneration. Results can shed light on the design of efficient and regenerable organoclay adsorbents for remediation of PFAS-contaminated water matrices.