Factors Affecting the Adsorption of Per- and Polyfluoroalkyl Substances (PFAS) by Colloidal Activated Carbon

The immobilization of per- and polyfluoroalkyl substances (PFAS) by colloidal activated carbon (CAC) barriers has been proposed as a potential in-situ method to mitigate the transport of plumes of PFAS in the subsurface. However, if PFAS are continuously released from a source zone, the adsorptive sites on CAC will eventually become saturated, upon which point the breakthrough of PFAS in the barrier will occur. To predict the long-term effectiveness of CAC barriers, it is important to evaluate the factors that may affect the adsorption of PFAS on CAC. In this study, the adsorption of 7 PFAS on a polymer-stabilized CAC (i.e., PlumeStop®) and on a polymer-free CAC was investigated using batch experiments. The adsorption affinity of PFAS to CAC was in the following order: PFOS > 6:2 FTS > PFHxS > PFOA > PFBS > PFPeA > PFBA. This result indicates that hydrophobic interaction was the predominant adsorption mechanism, and that hydrophilic compounds such as PFBA and PFPeA will break through CAC barriers first. The partition coefficient K_d for the adsorption of PFAS on the polymer-stabilized CAC was 1.3 - 3.5 times smaller than the K_d for the adsorption of PFAS on the polymer-free CAC, suggesting that the polymers decreased the adsorption, presumably due to competitive sorption. Thus, the PFAS adsorption capacity of PlumeStop CAC barriers is expected to increase once the polymers are biodegraded and/or washed away. The affinity of PFOS and PFOA to CAC increased when the ionic strength of the solution increased from 1 to 100 mM, or when the concentration of Ca²⁺ increased from 0 to 2 mM. In contrast, less PFOS and PFOA were adsorbed in the presence of 1 - 20 mgC/L Suwannee River Fulvic Acid, which represented dissolved organic carbon, or in the presence of 10 - 100 mg/L diethylene glycol butyl ether (DGBE), which is an important component in some aqueous film-forming foam (AFFF) formulations. The presence of 0.5 - 4.8 mg/L benzene or 0.5 - 8 mg/L trichloroethylene, the co-contaminants that may comingle with PFAS at AFFF-impacted sites, diminished PFOS adsorption but had no effect or even slightly enhanced PFOA adsorption. When the initial concentration of TCE was 8 mg/L, the K_d (514 ± 240 L/g) for the adsorption of PFOS was approximately 20 times lower than that in the TCE-free system (K_d = 9,579 ± 829 L/g). The results of this study provided insights into some key factors that may affect the adsorption of PFAS in in-situ CAC barriers.