title: High throughput online solid phase extraction-ultra high performance liquid chromatography-tandem mass spectrometry method for polyfluoroalkyl phosphate esters, perfluoroalkyl phosphonates, and other perfluoroalkyl substances in human serum, plasma, and whole blood.
abstract: A rapid, sensitive and reliable method was developed for the determination of a broad range of poly- and perfluoroalkyl substances (PFASs) in various blood matrices (serum, plasma, and whole blood), and uses only 50 μL of sample material. The method consists of a rapid protein precipitation by methanol followed by high throughput online solid phase extraction (SPE), ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS), and negative electrospray ionization detection. The method was developed for simultaneous determination of twenty-five PFASs, including polyfluoroalkyl phosphate esters (PAPs; 6:2, 8:2, 6:2/6:2, and 8:2/8:2), perfluoroalkyl phosphonates (PFPAs; C6, C8, and C10), perfluoroalkyl sulfonates (PFSAs; C4, C6, C7, C8, and C10), perfluoroalkyl carboxylates (PFCAs; C5C14), and perfluoroalkyl sulfonamides (FOSAs; C8, N-methyl, and N-ethyl). High linearity of matrix-matched calibration standards (correlation coefficients, R = 0.99-0.999) were obtained in the range of 0.006-45 ng mL-1blood. Excellent sensitivity was achieved with method detection limits (MDLs) between 0.0018 and 0.09 ng mL-1, depending on the compound and matrix. The method was validated for serum, plasma, and whole blood (n = 5 + 5) at six levels in the range 0.0180-30 ng mL-1. The accuracy (n = 5) was on average 102± 12%. The intermediate precision (n = 10) ranged from 2 to 40% with an average between-batch of analyses difference of 10± 10%. Two human serum samples from a former interlaboratory comparison were analyzed and the differences between the applied method and the consensus values were below ≤22% (n = 5). The method was also successfully applied to samples of human plasma and whole blood with coefficients of variation in the range 0.8-15.2% (n = 5).
authors.affiliation: Domain for Infection Control and Environmental Health, Norwegian Institute of Public Health, P.O. Box 4404, Nydalen, NO-0403, Oslo, Norway; Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, NO-0315, Oslo, Norway. Electronic address: somrutai.poothong@fhi.no.
authors.forename: Somrutai
authors.initials: S
authors.lastname: Poothong
authors.affiliation: Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, NO-0315, Oslo, Norway.
authors.forename: Elsa
authors.initials: E
authors.lastname: Lundanes
authors.affiliation: Domain for Infection Control and Environmental Health, Norwegian Institute of Public Health, P.O. Box 4404, Nydalen, NO-0403, Oslo, Norway.
authors.forename: Cathrine
authors.initials: C
authors.lastname: Thomsen
authors.affiliation: Domain for Infection Control and Environmental Health, Norwegian Institute of Public Health, P.O. Box 4404, Nydalen, NO-0403, Oslo, Norway.
authors.forename: Line Småstuen
authors.initials: LS
authors.lastname: Haug
mesh_terms: D002851:Chromatography, High Pressure Liquid; D004952:Esters; D005466:Fluorocarbons / Q000032:analysis* / Q000097:blood; D006801:Humans; D063065:Organophosphonates / Q000032:analysis* / Q000097:blood; D010710:Phosphates; D010949:Plasma / Q000737:chemistry; D044967:Serum / Q000737:chemistry; D052616:Solid Phase Extraction; D053719:Tandem Mass Spectrometry
chemical_list: D004952:Esters; D005466:Fluorocarbons; D063065:Organophosphonates; D010710:Phosphates
keywords: Human blood; Liquid chromatography; Online solid phase extraction; Perfluoroalkyl phosphonates; Perfluoroalkyl substances; Polyfluoroalkyl phosphate esters