Advancing PFAS characterization: Development and optimization of a UV-H2O2-TOP assay for improved PFCA chain length preservation and organic matter tolerance.

ABSTRACT

As per- and polyfluoroalkyl substances (PFAS) infiltrate the environment via industrial, commercial, and domestic sources, the demand for robust, cost-effective, and straightforward analytical assays intensifies to enhance PFAS characterization and quantification. To address this demand, this study introduces a novel UV-H2O2-TOP assay, identifying optimal parameters such as pH (5-9), oxidant concentration (500 mM H2O2), activation rate (63 mM H2O2 h-1), and an acceptable total organic carbon (TOC) limit (~1000 mg/L TOC) to achieve maximum PFAA precursor conversion. Additional work was performed further optimizing the UV-TOP assay, by confirming its superiority to heat activation, identifying the effectiveness of different persulfate salts, and investigating different concentrations of sodium persulfate and sodium hydroxide at a 12.5 ratio on PFCA yield. Our investigation concluded by applying the UV-H2O2-TOP assay, using sodium persulfate as the TOP assay oxidant, to 62 FTS and five different AFFF samples. High-resolution mass spectrometry and an expanded analytical suite support sample analysis, facilitating direct quantification of ultra-short chain perfluoroalkyl carboxylates (PFCAs) and common fluorotelomer compounds including 53/512 fluorotelomer betaine and 62 fluorotelomer sulfonamido betaine. Results highlight several advantages of this tandem UV-activated method, including enhanced preservation of perfluoroalkyl chains (post-oxidation of 62 fluorotelomer sulfonate resulted in 28 % PFHpA, 47 % PFHxA, 25 % C3-C5 PFCA), capacity to handle high TOC limits (1000 mg/L TOC), and ability to incorporate higher persulfate concentrations in a single oxidation cycle.