Determination of perfluorinated compounds in fish fillet homogenates: Method validation and application to fillet homogenates from the Mississippi River

• Published in: Analytica chimica acta 2011-01, Vol.683 (2), p.248-257
• Main Authors: Malinsky, Michelle Duval, Jacoby, Cliffton B., Reagen, William K.
• Format: Article
• Language: English
• Subjects: accuracy; Analytical chemistry; Animals; Calibration; Caprylates - analysis; Caprylates - standards; carboxylic acids; chemical analysis; chemical precipitation; Chemistry; Chromatographic methods and physical methods associated with chromatography; Chromatography, High Pressure Liquid - methods; Chromatography, High Pressure Liquid - standards; Exact sciences and technology; filleting; Fillets; Fish; fish fillets; Fish tissues; Fluorocarbons - analysis; Fluorocarbons - standards; food analysis; food contamination; Freshwater; high performance liquid chromatography; homogenization; Homogenizing; Hydrocarbons, Fluorinated - analysis; Hydrocarbons, Fluorinated - standards; Isomerism; Isomers; Lepomis macrochirus; Liquid chromatography–tandem mass spectrometry (LC/MS/MS); Matrix-matched calibration; Method validation; Mississippi; Other chromatographic methods; Perciformes; Perfluorinated compounds; perfluorocarbons; Perfluorooctanesulfonate; Perfluorooctanoic acid; PFOA; PFOS; pollutants; Precipitation; precision; Proteins; quantitative analysis; Rivers; solid phase extraction; Spectrometric and optical methods; stable isotopes; Sulfonamides - analysis; Sulfonamides - standards; sulfonic acid; tandem mass spectrometry; Tandem Mass Spectrometry - methods; Tandem Mass Spectrometry - standards; Water Pollutants, Chemical - analysis; Water Pollutants, Chemical - standards; water pollution
• ISSN: 0003-2670; 1873-4324
• DOI: 10.1016/j.aca.2010.10.028

We report herein a simple protein precipitation extraction-liquid chromatography tandem mass spectrometry (LC/MS/MS) method, validation, and application for the analysis of perfluorinated carboxylic acids (C7–C12), perfluorinated sulfonic acids (C4, C6, and C8), and perfluorooctane sulfonamide (FOSA) in fish fillet tissue. The method combines a rapid homogenization and protein precipitation tissue extraction procedure using stable-isotope internal standard (IS) calibration. Method validation in bluegill ( Lepomis macrochirus) fillet tissue evaluated the following: (1) method accuracy and precision in both extracted matrix-matched calibration and solvent (unextracted) calibration, (2) quantitation of mixed branched and linear isomers of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) with linear isomer calibration, (3) quantitation of low level (ppb) perfluorinated compounds (PFCs) in the presence of high level (ppm) PFOS, and (4) specificity from matrix interferences. Both calibration techniques produced method accuracy of at least 100 ± 13% with a precision (%RSD) ≤18% for all target analytes. Method accuracy and precision results for fillet samples from nine different fish species taken from the Mississippi River in 2008 and 2009 are also presented.