Per- and polyfluoroalkyl substances (PFAS) are a large class of synthetic aliphatic organofluorine compounds that are ubiquitious, recalcitrant, and linked to a growing number of toxicological effects. A large majority of PFAS cannot be quantified using standard liquid chromatography-mass spectrometry methods. To address this issue, the total oxidizable precursor (TOP) assay was developed by Houtz and Sedlak (2012) to convert unquantifiable PFAS into quantifiable PFAS end-products. However, this thermal-activated method is time-intensive, and can result in over-oxidation of precursor PFAS. This study focuses on the development of a rapid UV-activated TOP assay to allow for gentle conversion of PFAS precursors. The recovery and conversion of 6:2 fluorotelomer sulfonate (6:2 FTS) was examined following either heat or UV-activated TOP assay. The UV-activated TOP assay resulted in the complete oxidation of 6:2 FTS in 7.5 minutes with 99% molar recovery of generated PFCAs. For comparison, the thermal-activated TOP assay resulted in the complete oxidation of 6:2 FTS in 120 minutes with 62% molar recovery of PFCAs. The UV-activated TOP assay was then applied to 3M aqueous film-forming foam, identifying a total of 43.7 mM PFAS (compared to 20.9 mM PFAS measured without oxidation). Overall, the UV-activated TOP method proved to be faster and resulted in higher recoveries compared to a standard thermal-activated TOP assay contributing to a more comprehensive understanding of total PFAS load in aqueous matrices.

Development of a rapid UV-activated total oxidizable precursor (TOP) assay for improved quantification of Per- and Polyfluoroalkyl Substances (PFAS)

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ACS Fall 2022

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