Robust Matrix Effect-Free Method for Simultaneous Determination of Legacy and Emerging Per- and Polyfluoroalkyl Substances in Crop and Soil Matrices.

Summary Increasing use of emerging per- and polyfluoroalkyl substances (PFASs) has caused extensive concerns around the world. Effective detection methods to trace their pollution characteristics and environmental behaviors in complex soil-crop systems are urgently needed. In this study, a reliable and matrix effect (ME)-free method was developed for simultaneous determination of 14 legacy and emerging PFASs, including perfluorooctanoic acid, perfluorooctane sulfonate, 6 hydrogenous PFASs, 3 chlorinated PFASs, and 3 hexafluoropropylene oxide homologues, in 6 crop (the edible parts) and 5 soil matrices using ultrasonic extraction combined with solid-phase extraction and ultraperformance liquid chromatography-mass spectrometry (MS)/MS. The varieties of extractants and cleanup cartridges, the dosage of ammonia hydroxide, and the ME were studied to obtain an optimal pretreatment procedure. The developed method had high sensitivity and accuracy with satisfactory method detection limits (2.40-83.03 pg/g dry weight) and recoveries (72-117%) of all target analytes in matrices at five concentrations, that is, 0.1, 1, 10, 100, and 1000 ng/g. In addition, the ME of this method (0.82-1.15) was negligible for all PFASs, even considering 11 different matrices. The successful application of the ME-free method to simultaneously determine the legacy and emerging PFASs in crop and soil samples has demonstrated its excellent practicability for monitoring emerging PFASs in soil-crop systems.