Research on per- and polyfluoroalkyl substances (PFASs) released from aqueous film-forming foams (AFFFs) has primarily focused on soil and groundwater contamination, or atmospheric transport. However, gas-phase PFAS release from AFFF has not been well examined. We investigated the presence of volatile PFASs in the headspace above agitated AFFF concentrate produced within the past two years using two analytical techniques. One method utilized polyurethane foam and XAD resin with liquid chromatography mass spectrometry to quantify 30 PFASs and is similar to methods used by others to measure PFASs in air. A second, more exploratory approach used a thermal desorption sampler and gas chromatography and mass spectrometry (GC-MS) to measure 22 PFASs. Sixteen PFASs were detected in the headspace, including five fluorotelomer alcohols (0.5–38.1 μg/m3), 10 perfluorinated carboxylic acids (0.4–13670 μg/m3), and one fluorotelomer sulfonate (72.1 μg/m3). The most abundant PFAS detected in the headspace was perfluorooctanoic acid (13670 μg/m3), although it was detected only by GC-MS. Five additional fully fluorinated, iodinated, and ethenyl fluorocarbons were identified but not quantified. It is likely that firefighters are exposed to these compounds, but the risk is not yet known.

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