Sorption affinity and mechanisms of per-and polyfluoroalkyl substances (PFASs) with commercial sorbents: Implications...

Effective monitoring tools, including passive samplers, are essential for the wide range of per- and polyfluoroalkyl substances (PFASs) in aquatic matrices. However, knowledge of the extent and mechanisms of PFASs sorption with sorbents in a passive sampling context is limited. To address this, sorption behavior of 45 anionic, neutral and zwitterionic PFASs ranging in perfluorocarbon chain length (C₃-C₁₆) and functional groups with 11 different commercial sorbents (cross-linked β-cyclodextrin polymers, activated carbon, anion exchange (AE), cation exchange, hydrophilic-lipophilic balanced (HLB) and non-polar) was investigated. A broad range of equilibrium sorbent-MilliQ water (MQ) distribution coefficients (K_d) were observed (10^-1.95 to 10^8.30 mL g^-1). Similar sorbent types (e.g., various AE and HLB sorbents) exhibited very different sorption behavior, likely due to their different polymeric structures and relative importance of sorbate/sorbent interactions other than coulombic interactions. HLB and AE with hydroxyl functionalities are most effective for sampling of the full suite of PFASs. Reduced sorptive affinity was observed in the presence of matrix co-constituents in wastewater influent for most PFASs. HLB had the smallest reduction in log K_d in wastewater suggesting that these sorbents are appropriate for applications in complex matrices. Sufficient sorbent capacity was observed for linear uptake of many target analytes which facilitates passive sampling.