A rapid UHPLC-MS/MS method for simultaneous quantitation of 23 perfluoroalkyl substances (PFAS) in estuarine water

Abstract

Per- and polyfluoroalkyl substances (PFAS) represent a large group of synthetic organic compounds which, as a result of their unique chemical properties, render them extremely recalcitrant to environmental degradation. Research concerning the environmental, ecological, and human health effects of PFAS has focused on long aliphatic chain (> C7) compounds having no ether bonds. For new, less studied, or previously unknown PFAS (≤ C7 with ether bonds), there is little to no information about their environmental behavior, transport, fate, exposure, and toxicological effects. LC-MS/MS has proven effective for detection and quantitation of some PFAS, however, straightforward analytical methods for simultaneous trace quantitation of broad mixtures of PFAS in varied complex environmental media, available to a wide range of researchers and also suitable for routine monitoring, remain critical needs. Here we describe a simple, rapid, sensitive, and reproducible quantitative analytical method for trace analysis and monitoring of 23 PFAS in estuarine water, using ultra-high performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-MS/MS). The developed MRM method allows simultaneous trace quantitation of a broad mixture of PFAS, including 13 perfluoroalkyl carboxylic acids, 8 perfluoroalkyl sulfonates, and 2 short-chain perfluoroethers. The method provides better peak resolution and peak separation, and shorter run times (method separation/total run time: 6/8 min) compared to those of existing analytical methods. Percent recoveries for the validated method ranged from 78.54 to 112.61. LOD and LOQ values ranged from 0.48 to 1.68 pg/injection and 1.71 to 5.40 pg/injection, respectively. The validated method was used for quantitative PFAS analysis of estuarine water samples collected from 16 locations within the Perdido Bay estuary in coastal Alabama.