HS-SPME-Arrow-GC-MS/MS Method for Quality Control of Neutral Per- and Polyfluoroalkyl Substances in Drinking Water: Contamination Profiles in Commercial Bottled and Sparkling Waters for Food Safety Assessment

Neutral per- and polyfluoroalkyl substances (PFAS), including volatile precursors to persistent perfluoroalkyl acids, are analytically challenging to quantify in aqueous matrices due to their trace concentrations and the limitations of conventional methods. In this study, we developed a highly sensitive and robust method for simultaneous quantification of 12 neutral PFAS—fluorotelomer alcohols, fluorotelomer olefins, and perfluoroalkane sulfonamides/sulfonamidoethanols—in water. A headspace solid-phase microextraction-Arrow (HS-SPME-Arrow) method was developed and coupled with gas chromatography–tandem mass spectrometry (GC–MS/MS) using electron ionization (EI) in selected reaction monitoring mode. Systematic optimization of extraction parameters maximized extraction efficiency across analytes spanning a wide range of volatilities and polarities. The validated method demonstrated excellent analytical performance, with sub-ng·L −1 detection limits, high recoveries, and robust precision. Application to tap, bottled, and sparkling water samples from Jeonju City, South Korea, revealed distinct contamination profiles, with consistent detection of specific neutral PFAS in all commercial water products. • HS-SPME-Arrow-GC-MS/MS method was developed for 12 neutral PFAS in water • Ultra-low detection limits were achieved with high accuracy and precision • Extraction was optimized using the DVB/CWR/PDMS fiber at 60 °C with 10% NaCl • N-EtFOSA and N-EtFOSE were consistently detected in bottled and sparkling waters • A solvent-free robust protocol was established for PFAS monitoring