Integrating total oxidizable precursor assay data to evaluate fate and transport of PFASs

Fate and transport of per‐ and polyfluoroalkyl substances (PFASs) are complex and are not well understood. Among this class of emerging contaminants, perfluoroalkyl acids (PFAAs) comprising perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs) are being studied more frequently than polyfluorinated compounds. PFAAs are persistent in the environment, recalcitrant to biological degradation, and, therefore, widespread. Previous studies have indicated that some PFASs bioaccumulate. The fate and transport of PFAAs can be complicated by the presence of PFAA precursors. The PFAA precursors are defined in this article as those fluorinated chemicals that can be potentially transformed abiotically or biotically into terminal PFCA or PFSA products. Due to potential biotransformation in the environment, PFAA precursors can influence the temporal and lateral distribution of PFAAs in the environment. Presently, only a very small number of PFAA precursors can be quantitatively analyzed by commercial laboratories. For instance, N‐ethyl perfluorooctanesulfonamidoacetic acid and N‐methyl perfluorooctanesulfonamidoacetic acid are the only two precursors included in the most commonly applied PFAS analytical method, U.S. Environmental Protection Agency Method 537. The current commercial laboratory methodologies primarily quantify between 14 and 31 PFASs. As an alternative, a total oxidizable precursor assay (TOPA) was developed to quantify the measurable PFSA and PFCA concentrations after aggressive oxidation converting PFAA precursors abiotically into PFCAs. The difference between PFAA concentrations before and after oxidation can be used to estimate the amount of oxidizable PFAA precursors in the sample. This is one of the first articles that utilized TOPA data to help interpret PFAS fate and transport in the environment.