No abstract

Remediation of groundwater impacted by per- and polyfluoroalkyl substances (PFAS) is particularly challenging due to the resistance of the molecule to oxidation because of the strength of the carbon–fluorine bond and the need to achieve low nanogram per liter drinking water targets. Previous studies have shown that activated carbon is an effective sorbent for removal of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) in conventional water treatment systems. The objective of this study was to evaluate the in situ delivery and sorptive capacity of an aqueous suspension containing powdered activated carbon (PAC) stabilized with polydiallyldimethylammonium chloride (polyDADMAC). Batch reactor studies demonstrated substantial adsorption of PFOA and PFOS by polyDADMAC-stabilized PAC, which yielded Freundlich adsorption coefficients of 156 and 629 L/g–n , respectively. In columns packed with 40–50 mesh Ottawa sand, injection of a PAC (1000 mg/L) + polyDADMAC (5000 mg/L) suspension created a sorptive region that increased subsequent PFOA and PFOS retention by 3 orders of magnitude relative to untreated control columns, consistent with the mass of retained PAC. Experiments conducted in a heterogeneous aquifer cell further demonstrated the potential for stabilized-PAC to be an effective in situ treatment option for PFAS-impacted groundwater.

The environmental fate of per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs) remains largely unknown, especially under the conditions representative of natural subsurface systems. In this study, the biotransformation of 8:2 fluorotelomer alcohol (8:2 FTOH), a component of new-generation AFFF formulations and a byproduct in fluorotelomer-based AFFFs, was investigated under nitrate-, iron-, and sulfate-reducing conditions in microcosms prepared with AFFF-impacted soils. Liquid chromatography–tandem mass spectrometry (LC–MS/MS) and high-resolution mass spectrometry (HRMS) were employed to identify biotransformation products. The biotransformation was much slower under sulfate- and iron-reducing conditions with >60 mol % of initial 8:2 FTOH remaining after ∼400 days compared to a half-life ranging from 12.5 to 36.5 days under nitrate-reducing conditions. Transformation products 8:2 fluorotelomer saturated and unsaturated carboxylic acids (8:2 FTCA and 8:2 FTUA) were detected under all redox conditions, while 7:2 secondary fluorotelomer alcohol (7:2 sFTOH) and perfluorooctanoic acid (PFOA) were only observed as transformation products under nitrate-reducing conditions. In addition, 1H-perfluoroheptane (F­(CF2)6CF2H) and 3-F-7:3 acid (F­(CF2)7CFHCH2COOH) were identified for the first time during 8:2 FTOH biotransformation. Comprehensive biotransformation pathways for 8:2 FTOH are presented, which highlight the importance of accounting for redox condition and the related microbial community in the assessment of PFAS transformations in natural environments.