Hunting the missing fluorine in aqueous film-forming foams containing per- and polyfluoroalkyl substances

Since aqueous film-forming foams (AFFFs) are major sources of per- and polyfluoroalkyl substances (PFAS), understanding the quantity and type of PFAS present in AFFFs is crucial for assessing environmental risk and remediation. We characterized 25 foams from Canada and Europe, including two non-AFFFs and two fluorine-free AFFFs. We used liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) to identify novel PFAS, as well as total oxidizable precursor assays (TOP) and total organofluorine (TOF) measurements for comparison. LC-HRMS showed that the two non-AFFF foams and two PFAS-free AFFFs contained little or no PFAS, confirmed by TOF measurement using combustion ion chromatography (CIC). The PFAS-containing AFFFs, however, spanned a wide concentration range of TOF (2200-45,000 mg F/L) and contained 22 new classes of polyfluoroalkyl substances not previously reported. As a result of identifying new compounds, LC-HRMS was fully able to capture the oxidizable precursors determined by TOP assay in all tested fluorotelomer (FT) AFFFs, while unknown compounds still constituted a significant fraction (19-53 mol%) in most electrochemical fluorination (ECF) AFFFs. A fluorine mass balance was achieved by comparing the amounts of compounds identified by LC-HRMS with those detected by CIC, although LC-HRMS overestimated TOF with a recovery of 127 ± 36%.