TY - JOUR
T1 - Sensitive and accurate determination of 32 PFAS in human serum using online SPE-UHPLC-HRMS
AU - Belay, Masho Hilawie
AU - Robotti, Elisa
AU - Ghignone, Arianna
AU - Fabbris, Alessia
AU - Brandi, Jessica
AU - Cecconi, Daniela
AU - Masini, Maria Angela
AU - Dondero, Francesco
AU - Marengo, Emilio
N1 - Publisher Copyright:
© 2024 The Authors
PY - 2025/3/5
Y1 - 2025/3/5
N2 - Per- and polyfluoroalkyl substances’ (PFAS) extreme persistence has been linked to many adverse effects on human health including increased risk of certain cancers. This study presents the development and validation of a new, highly sensitive method for the quantification of 32 PFAS in human serum using online solid-phase extraction (SPE) coupled with ultra-high performance liquid chromatography–high resolution mass spectrometry (UHPLC–HRMS). Legacy and emerging PFAS were targeted. Main steps of sample pretreatment include protein precipitation (PP), pellet rinsing, centrifugation, preconcentration through solvent evaporation, and online SPE using a weak anion-exchange polymeric sorbent. The PP and pellet-rinsing procedures were optimized through a comprehensive exploration of solvent combinations. Following this, a pretreatment that offers the best compromise for the targeted PFAS was identified using principal component analysis. The method demonstrated excellent linearity (R² = 0.977–0.997) with limits of quantification ranging from 8.9 to 27 ng/L, 5 to 15 times lower than previous methods. Precision (intraday 2.6–14.0 % and interday 1.3–11.0 % relative standard deviation) and accuracy (recoveries 72.7–106 %) were robust. The method was validated in accordance with ISO/IEC 17025 and successfully applied to five human serum samples, confirming its suitability for high-throughput profiling of PFAS in biomonitoring studies. This method is the first to use online SPE for the simultaneous determination of a broad range of PFAS, including ether congeners such as perfluoro(2-ethoxyethane) sulfonic acid and Nafion byproduct 2. Furthermore, control charts were employed to assess instrument performance during routine analysis and implement necessary actions.
AB - Per- and polyfluoroalkyl substances’ (PFAS) extreme persistence has been linked to many adverse effects on human health including increased risk of certain cancers. This study presents the development and validation of a new, highly sensitive method for the quantification of 32 PFAS in human serum using online solid-phase extraction (SPE) coupled with ultra-high performance liquid chromatography–high resolution mass spectrometry (UHPLC–HRMS). Legacy and emerging PFAS were targeted. Main steps of sample pretreatment include protein precipitation (PP), pellet rinsing, centrifugation, preconcentration through solvent evaporation, and online SPE using a weak anion-exchange polymeric sorbent. The PP and pellet-rinsing procedures were optimized through a comprehensive exploration of solvent combinations. Following this, a pretreatment that offers the best compromise for the targeted PFAS was identified using principal component analysis. The method demonstrated excellent linearity (R² = 0.977–0.997) with limits of quantification ranging from 8.9 to 27 ng/L, 5 to 15 times lower than previous methods. Precision (intraday 2.6–14.0 % and interday 1.3–11.0 % relative standard deviation) and accuracy (recoveries 72.7–106 %) were robust. The method was validated in accordance with ISO/IEC 17025 and successfully applied to five human serum samples, confirming its suitability for high-throughput profiling of PFAS in biomonitoring studies. This method is the first to use online SPE for the simultaneous determination of a broad range of PFAS, including ether congeners such as perfluoro(2-ethoxyethane) sulfonic acid and Nafion byproduct 2. Furthermore, control charts were employed to assess instrument performance during routine analysis and implement necessary actions.
KW - High resolution mass spectrometry
KW - Human biomonitoring
KW - Method development
KW - PFAS
KW - Serum pretreatment
UR - http://www.scopus.com/inward/record.url?scp=85211482401&partnerID=8YFLogxK
U2 - 10.1016/j.jhazmat.2024.136780
DO - 10.1016/j.jhazmat.2024.136780
M3 - Article
SN - 0304-3894
VL - 485
JO - Journal of Hazardous Materials
JF - Journal of Hazardous Materials
M1 - 136780
ER -