Impacts of Perfluoroalkyl Substances on Aqueous and Nonaqueous Phase Liquid Dechlorination by Sulfidized Nanoscale Zerovalent Iron

Per- and poly fluoroalkyl substances (PFASs) are often encountered with nonaqueous phase liquid (NAPL) in the groundwater at fire-fighting and military training sites. However, it is unclear how PFASs affect the dechlorination performance of sulfidized nanoscale zerovalent iron (S-nFe⁰), which is an emerging promising NAPL remediation agent. Here, S-nFe⁰ synthesized with controllable S speciation (FeS or FeS₂) were characterized to assess their interactions with PFASs and their dechlorination performance for trichloroethylene NAPL (TCE-NAPL). Surface-adsorbed PFASs blocked materials' reactive sites and inhibited aqueous TCE dechlorination. In contrast, PFASs-adsorbed particles with improved hydrophobicity tended to enrich at the NAPL-water interface, and the reactive sites were re-exposed after the PFASs accumulation into the NAPL phase to accelerate dechlorination. This PFASs-induced phenomenon allowed the materials to present a higher reactivity (up to 1.8-fold) with a high electron efficiency (up to 99%) for TCE-NAPL dechlorination. Moreover, nFe⁰-FeS₂ with a higher hydrophobicity was more readily enriched at the NAPL-water interface and more reactive and selective than nFe⁰-FeS, regardless of coexisting PFASs. These results unveil that a small amount of yet previously overlooked coexisting PFASs can favor selective reductions of TCE-NAPL by S-nFe⁰, highlighting the importance of materials hydrophobicity and transportation induced by S and PFASs for NAPL remediation.