Adsorbability of a wide range of per- and polyfluoroalkyl substances on granular activated carbon, ion exchange resin, and surface modified clay

Abstract

The increased detection of understudied per- and polyfluoroalkyl substances (PFAS) in environmental matrices has highlighted the need to evaluate the treatability of a wide-range of PFAS by sorption-based processes. This study investigated the efficacy of three commercial adsorbents (i.e., granular activated carbon (GAC), surface modified clay (SMC), and anionic exchange resin (AER)) for the removal of a wide range of cationic, zwitterionic, and anionic PFAS from an aqueous film forming foam (AFFF)-impacted groundwater employing rapid small-scale column tests (RSSCTs) coupled with high resolution mass spectrometry (HRMS) and suspect screening analysis (SQ). AER exhibited later breakthrough times for the majority of anionic and zwitterionic PFAS compared to SMC and GAC. However, both AER and SMC exhibited negligible removal of cationic PFAS presumably due to the reliance of these adsorbents on electrostatic interactions and the counteraction of hydrophobic forces caused by the repulsion between cationic PFAS and positively charged surfaces of AER and SMC. GAC, being a non-selective adsorbent, was largely unaffected by the ionic charge of the evaluated PFAS with molecular structure having a bigger impact on adsorbability. The detection of a variety of PFAS classes in the investigated AFFF-impacted groundwater enabled assessment of the relative impact of chemical structure on adsorptive removal of PFAS. Chain-length dependent adsorption was observed across all investigated anionic and zwitterionic PFAS classes. The PFAS structures possessing hydroxyl and/or methyl functional groups exhibited later breakthrough times compared to their homologues lacking these functional groups and cyclic/unsaturated structures were removed less efficiently compared to their linear/saturated homologues. In the case of perfluoroalkyl acid (PFAA)-derivative structures, hydrogen-substituted classes (i.e., H-PFAAs) were removed more efficiency than PFAAs while keto-substituted structures (i.e., K-PFSA) and pentahydrido-fluoroalkane sulfates (PeH-FAOS) exhibited lower adsorbability compared to PFAAs for all adsorbents. Oxa-PFAAs (O-PFSA; isomer class of PFA-OS) on the other hand demonstrated higher adsorbability compared to PFAAs in the case of AER-like adsorbents, while this trend was reversed for GAC.