Simultaneous determination of 21 trace perfluoroalkyl substances in fish by isotope dilution ultrahigh performance liquid chromatography tandem mass spectrometry

Abstract

Perfluoroalkyl substances (PFASs) have been identified as emerging environmental contaminants. In this study, an efficient and accurate ultrahigh performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method was developed for simultaneous determination of 21 PFASs in fish. Acetonitrile was used for sample extraction. Solid phase extraction (SPE) by WAX cartridges and then freezing at -30 °C were adopted as cleanup strategies. Strict measurements were performed to control background contamination during the whole procedure. Matrix effects were evaluated by external standard and isotope dilution mass spectrometry (IDMS) methods. IDMS can compensate the matrix effects to a large extent. The method detection limits (MDLs) ranged from 2 pg/g to 10 pg/g except for PFBA (120 pg/g). The method quantitation limits (MQLs) ranged from 5 pg/g to 30 pg/g except for PFBA (300 pg/g). The matrix spiked recoveries of three spiked levels were in the range of 79.6%-109%. The intra-day relative standard deviation (RSD) and inter-day RSD were from 0.94% to 13.9% and 0.36% to 11.2% respectively. Two fish tissue reference materials were analyzed by the developed method. The results of reference materials were within the uncertainty of the given value. The quantitative results of IDMS and standard addition (SA) - IDMS were comparable. The developed UHPLC-MS/MS method was applied for PFASs detection in 20 marine fish samples. 9 PFASs were detected in the samples with the ∑9 PFASs concentration range of 0.04 to 2.14 ng/g wet weight (ww).