Selective Quantification of Charged and Neutral Polyfluoroalkyl Substances Using the Total Oxidizable Precursor (TOP) Assay

Perfluoroalkyl acid (PFAA) precursors are a diverse subclass of per- and polyfluoroalkyl substances (PFASs) that can be transformed into PFAAs of public health concern. Unlike strongly acidic PFAAs, precursors can be anionic, cationic, neutral, or zwitterionic. Precursor charge affects the environmental fate, but existing quantification techniques struggle to ascertain the abundance of compounds within each charge group. To fill this gap, we developed and validated a solid-phase extraction procedure that separates precursors by charge and quantifies the sum of the precursors in each fraction with the total oxidizable precursor (TOP) assay. Method performance was demonstrated by spiking known concentrations of ten precursors into aqueous film-forming foam (AFFF)-impacted groundwater, municipal wastewater, and soil samples. Precursor fractionation and recovery were greater in groundwater and soil samples than in wastewater. Use of the method provided results that were consistent with expectations based on precursor transport properties. In surficial soils near an AFFF source zone, anionic precursors with five or fewer perfluorinated carbons accounted for about 95% of PFASs, but less than half of PFASs in the underlying groundwater. In municipal wastewater influent, the sum of precursors exceeded the sum of PFAAs and was approximately equally distributed among all charge fractions.