The Adsorption of Per- and Polyfluoroalkyl Substances (PFASs) onto Ferrihydrite Is Governed by Surface Charge

[Image: see text] An improved quantitative and qualitative understanding of the interaction of per- and polyfluoroalkyl substances (PFASs) and short-range ordered Fe (hydr)oxides is crucial for environmental risk assessment in environments low in natural organic matter. Here, we present data on the pH-dependent sorption behavior of 12 PFASs onto ferrihydrite. The nature of the binding mechanisms was investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and by phosphate competition experiments. Sulfur K-edge XANES spectroscopy showed that the sulfur atom of the head group of the sulfonated PFASs retained an oxidation state of +V after adsorption. Furthermore, the XANES spectra did not indicate any involvement of inner-sphere surface complexes in the sorption process. Adsorption was inversely related to pH (p < 0.05) for all PFASs (i.e., C(3)–C(5) and C(7)–C(9) perfluorocarboxylates, C(4), C(6), and C(8) perfluorosulfonates, perfluorooctane sulfonamide, and 6:2 and 8:2 fluorotelomer sulfonates). This was attributed to the pH-dependent charge of the ferrihydrite surface, as reflected in the decrease of surface ζ-potential with increasing pH. The importance of surface charge for PFAS adsorption was further corroborated by the observation that the adsorption of PFASs decreased upon phosphate adsorption in a way that was consistent with the decrease in ferrihydrite ζ-potential. The results show that ferrihydrite can be an important sorbent for PFASs with six or more perfluorinated carbons in acid environments (pH ≤ 5), particularly when phosphate and other competitors are present in relatively low concentrations.