TY - JOUR
T1 - Development and validation of an LC–MS/MS method for the quantitation of 30 legacy and emerging per- and polyfluoroalkyl substances (PFASs) in human plasma, including HFPO-DA, DONA, and cC6O4
AU - Frigerio, Gianfranco
AU - Cafagna, Simone
AU - Polledri, Elisa
AU - Mercadante, Rosa
AU - Fustinoni, Silvia
N1 - Funding Information:
We acknowledge Thomas G?en, Moritz Sch?fer, and Barbara Schaller (Institute and Outpatient Clinic of Occupational, Social and Environmental Medicine, Friedrich-Alexander-Universit?t Erlangen-N?rnberg) for providing us with the leftover samples from the external quality assurance schemes (ICI-EQUAS) carried out in the frame of the HBM4EU project.
Publisher Copyright:
© 2021, Springer-Verlag GmbH Germany, part of Springer Nature.
PY - 2022/1
Y1 - 2022/1
N2 - Per- and polyfluoroalkyl substances (PFASs) include persistent organic pollutants whose spread is still ubiquitous. Efforts to substitute substances of high concern with fluorinated alternatives, such as HFPO-DA (GenX), DONA (ADONA), and cC6O4, have been made. The aim of this work was to develop and validate an isotopic dilution liquid chromatography-tandem mass spectrometry (LC–MS/MS) method suitable to quantify 30 PFASs in human plasma. Analytes included legacy PFASs (PFOA, PFOS, and PFHxS), fluorinated alternatives (PFBA, PFBS, 6:2 FTSA, HFPO-DA, DONA, and cC6O4), and newly identified compounds (F-53B and PFECHS). The sample preparation was rapid and consisted of simple protein precipitation and centrifugation. Calibration standards and quality control solutions were prepared with a human pooled plasma containing relatively low background levels of the considered analytes. A complete validation was carried out: the lower limits of quantitation (LLOQs) ranged from 0.009 to 0.245 µg/L; suitable linearity (determination coefficients, R2 0.989–0.999), precision (2.0–19.5%, relative standard deviation), and accuracy (87.9–113.1% of theoretical) were obtained for considered concentration ranges. No significant variations of analyte responses were recorded under investigated storage conditions and during matrix effect tests. The external verification confirmed the accuracy of the method, although limited to 12 analytes. The method was also applied to 38 human plasma samples to confirm its applicability. The developed assay is suitable for large-scale analyses of a wide range of legacy and emerging PFASs in human plasma. To our knowledge, this is the first published method including cC6O4 for human biomonitoring. Graphical abstract: [Figure not available: see fulltext.].
AB - Per- and polyfluoroalkyl substances (PFASs) include persistent organic pollutants whose spread is still ubiquitous. Efforts to substitute substances of high concern with fluorinated alternatives, such as HFPO-DA (GenX), DONA (ADONA), and cC6O4, have been made. The aim of this work was to develop and validate an isotopic dilution liquid chromatography-tandem mass spectrometry (LC–MS/MS) method suitable to quantify 30 PFASs in human plasma. Analytes included legacy PFASs (PFOA, PFOS, and PFHxS), fluorinated alternatives (PFBA, PFBS, 6:2 FTSA, HFPO-DA, DONA, and cC6O4), and newly identified compounds (F-53B and PFECHS). The sample preparation was rapid and consisted of simple protein precipitation and centrifugation. Calibration standards and quality control solutions were prepared with a human pooled plasma containing relatively low background levels of the considered analytes. A complete validation was carried out: the lower limits of quantitation (LLOQs) ranged from 0.009 to 0.245 µg/L; suitable linearity (determination coefficients, R2 0.989–0.999), precision (2.0–19.5%, relative standard deviation), and accuracy (87.9–113.1% of theoretical) were obtained for considered concentration ranges. No significant variations of analyte responses were recorded under investigated storage conditions and during matrix effect tests. The external verification confirmed the accuracy of the method, although limited to 12 analytes. The method was also applied to 38 human plasma samples to confirm its applicability. The developed assay is suitable for large-scale analyses of a wide range of legacy and emerging PFASs in human plasma. To our knowledge, this is the first published method including cC6O4 for human biomonitoring. Graphical abstract: [Figure not available: see fulltext.].
KW - Emerging PFAS
KW - Fluorinated alternatives
KW - LC-MS/MS
KW - Per-/polyfluoroalkyl substances
KW - Per/polyfluoroalkyl acids
KW - PFAS
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U2 - 10.1007/s00216-021-03762-1
DO - 10.1007/s00216-021-03762-1
M3 - Article
AN - SCOPUS:85121292446
VL - 414
SP - 1259
EP - 1278
JO - Fresenius Journal of Analytical Chemistry
JF - Fresenius Journal of Analytical Chemistry
SN - 0016-1152
IS - 3
ER -