Sorption of Perfluoroalkyl Acids to Fresh and Aged Nanoscale Zerovalent Iron Particles.

The sorption of perfluoroalkyl acids (PFAAs), particularly perfluorooctanesulfonic acid (PFOS), to freshly synthesized nanoscale zerovalent iron (nZVI) and aged (oxidized) and sulfidated nZVI, was investigated under anaerobic conditions. The sorption of PFAAs to nZVI was 2-4 orders of magnitude higher than what has been reported for sediments, soils, and iron oxides. The hydrophobicity of the perfluorocarbon chain dominated the sorption, although FTIR spectra indicated specific interactions between sulfonate and carboxylate head groups and nZVI. The contributions from electrostatic interactions depended on the surface charge and pH. Humic acids influenced sorption only at concentrations above 50 mg/L. nZVI aged in deoxygenated water up to 95 days showed similar sorption isotherms for PFOS to fresh nZVI, because Fe(OH)2 was the predominant phase on the nZVI surface independent of aging time. Sulfidation of nZVI reduced sorption of PFOS by 1 log unit owing to the FeS deposited, but the sorption affinity was restored after aging because of formation of Fe(OH)2. Oxidation of nZVI by water and dissolved oxygen also resulted in similar sorption of PFOS as fresh nZVI at environmentally relevant concentrations. The results suggest that injection of nZVI could reduce PFAA concentrations in groundwater despite changes to its surface chemistry with aging.