Aqueous film-forming foams (AFFFs) are proprietary mixtures containing hydrocarbon surfactants and per-and polyfluoroalkyl substances (PFASs) that are used to extinguish hydrocarbonbased fuel fires. There is limited information on hydrocarbon surfactants in AFFFs and AFFF-contaminated groundwater even though hydrocarbon surfactants are more abundant (5−10% w/w) than PFASs (0.9− 1.5% w/w) in AFFFs. Eight commercial AFFFs manufactured between 1988 and 2012 and 10 AFFF-contaminated groundwaters collected from near source zones of fire-fighter training areas were analyzed for suspect hydrocarbon surfactants by liquid chromatography quadrupole time-of-flight mass spectrometry. A suspect list and a homologous series detection computational tool, enviMass, were combined to screen for hydrocarbon surfactants. Nine classes of hydrocarbon surfactants were detected in AFFFs including octylphenol polyethoxylates, linear alcohol ethoxylates, ethoxylated cocoamines, alkyl ether sulfates, alkyl amido dipropionates, linear alkyl benzenesulfonates, alkyl sulfates, and polyethylene glycols. Of those, six were also found in groundwater along with diethanolamines and alkyl amido betaines, which were not found in the eight archived AFFFs. This indicates that although aerobically biodegradable, hydrocarbon surfactants likely persist in groundwater due to anaerobic aquifer conditions. To the best of our knowledge, this is the first screening for hydrocarbon surfactants in AFFFs and in AFFFcontaminated groundwater.

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