Analysis of hydrophilic per- and polyfluorinated sulfonates including trifluoromethanesulfonate using solid phase extraction and mixed-mode liquid chromatography-tandem mass spectrometry

Ultra-hydrophilic per- and polyfluorinated sulfonates (PFSA) are increasingly scrutinized in recent years due to their ubiquitous occurrence, persistence, and aqueous mobility in the environment, yet analysis remains a challenge. This study developed methods for the analysis of trifluoromethanesulfonate, perfluorobutanesulfonate, 10-camphorsulfonate, and a di-fluorinated sulfonate utilizing mixed-mode liquid chromatography, where all analytes were adequately retained and separated. Chromatography and electrospray ionization parameters were optimized; instrumental limits of quantification for the anionic target analytes were in the range of 4.3 - 16.1 ng L⁻¹. Solid phase extraction (SPE) methods were developed using Oasis WAX cartridges; SPE recoveries for the analytes ranged from 86% to 125%. Salinity and total organic carbon both impaired the SPE performance to different extents, depending on the respective analyte. Utilizing widely accessible instrumentation and materials, this is a single method to simultaneously analyze conceivably the most hydrophilic PFAS chemical, i.e., trifluoromethanesulfonate, and moderately hydrophobic PFSAs.