Incorporating ultrashort-chain compounds into the comprehensive analysis of per- and polyfluorinated substances in potable and non-potable waters by LC-MS/MS

• A novel method to incorporate ultrashort-chain compounds into PFAS analysis. • Implementing an inert polar-embedded LC column for accurate and sensitive quantification. • A simple workflow to ensure low contamination and accurate results. Ultrashort-chain (USC) per- and polyfluoroalkyl substances (PFAS) are small and very polar compounds with carbon chain lengths shorter than C4. Their ubiquitous and high levels of occurrence in environmental aquatic systems are emerging as a significant concern, rivaling the well-established issues associated with long-chain PFAS contamination. Therefore, it is important to analyze both USC and long-chain PFAS together in water samples to comprehensively assess and address the full spectrum of PFAS contamination. The high polarity of USC PFAS poses a challenge for standard chromatographic practices in PFAS analysis, primarily due to insufficient chromatographic retention. In this study, a simple and reliable workflow was developed for the simultaneous analysis of C1 to C14 perfluoroalkyl carboxylic and sulfonic acids, along with other groups of PFAS, in both potable and non-potable waters. The chromatographic separation was conducted using a polar-embedded reversed-phase LC column with an inert coating on the hardware. Three different water matrices (tap water, bottled water, sewage treatment wastewater) were chosen for method evaluation to demonstrate the applicability of the developed workflow for measuring 45 PFAS compounds in diverse water samples. A dilute-and-shoot workflow was evaluated by accuracy and precision analysis at five fortification levels, ranging from 2 to 250 ng/L. Eighteen isotopically labeled PFAS, serving as extracted internal standards, were added to the samples at 100 ng/L to validate the accuracy of the entire workflow. Calibration standards were prepared in reverse osmosis water due to its cleanliness for all analytes. The calibration ranges varied among different analytes, spanning from 1 – 1000 ng/L. All analytes and extracted internal standards exhibited recovery values ranging from 70% to 130% of the nominal concentration across all fortification levels. Satisfactory method precision was demonstrated with %RSD values below 20%. Additional potable and non-potable waters collected from various source waters were tested to further demonstrate that the established workflow is suitable for the accurate quantification of targeted PFAS in a wide range of water matrices.