Less is More: a Methodological Assessment of Extraction Techniques for Per- and Polyfluoroalkyl Substances (PFAS) Analysis in Mammalian Tissues

Overview

Journal Anal Bioanal Chem

Specialty Chemistry

Date 2023 Aug 22

PMID 37606646

Authors

Helena Mertens

Benedikt Noll

Tanja Schwerdtle

Klaus Abraham

Bernhard H Monien

Affiliations

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Abstract

Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants. Studying the bioaccumulation in mammalian tissues requires a considerable effort for the PFAS extraction from complex biological matrices. The aim of the current work was to select and optimize the most efficient among common extraction strategies for eleven perfluoroalkyl acids (PFAA). Primary extractions from wild boar tissues (liver, kidney, and lung) were performed with methanol at neutral, acidic, or alkaline conditions, or with methyl-tert-butyl ether (MTBE) after ion-pairing with tetrabutylammonium (TBA) ions. A second purification step was chosen after comparing different solid-phase extraction (SPE) cartridges (Oasis WAX, ENVI-Carb, HybridSPE Phospholipid) and various combinations thereof or dispersive SPE with C18 and ENVI-Carb material. The best extraction efficiencies of the liquid PFAA extraction from tissue homogenates were achieved with methanol alone (recoveries from liver 86.6-114.4%). Further purification of the methanolic extracts using dispersive SPE or Oasis WAX columns decreased recoveries of most PFAA, whereas using pairs of two SPE columns connected in series proved to be more efficient albeit laborious. Highest recoveries for ten out of eleven PFAA were achieved using ENVI-Carb columns (80.3-110.6%). In summary, the simplest extraction methods using methanol and ENVI-Carb columns were also the most efficient. The technique was validated and applied in a proof of principle analysis in human tissue samples.

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References

Kurwadkar S, Dane J, Kanel S, Nadagouda M, Cawdrey R, Ambade B . Per- and polyfluoroalkyl substances in water and wastewater: A critical review of their global occurrence and distribution. Sci Total Environ. 2021; 809:151003. PMC: 10184764. DOI: 10.1016/j.scitotenv.2021.151003. View

Nassazzi W, Lai F, Ahrens L . A novel method for extraction, clean-up and analysis of per- and polyfluoroalkyl substances (PFAS) in different plant matrices using LC-MS/MS. J Chromatogr B Analyt Technol Biomed Life Sci. 2022; 1212:123514. DOI: 10.1016/j.jchromb.2022.123514. View

R Powley C, George S, Ryan T, Buck R . Matrix effect-free analytical methods for determination of perfluorinated carboxylic acids in environmental matrixes. Anal Chem. 2005; 77(19):6353-8. DOI: 10.1021/ac0508090. View

Wang T, Lu Y, Chen C, Naile J, Khim J, Park J . Perfluorinated compounds in estuarine and coastal areas of north Bohai Sea, China. Mar Pollut Bull. 2011; 62(8):1905-14. DOI: 10.1016/j.marpolbul.2011.05.029. View

Yoo H, Washington J, Jenkins T, Libelo E . Analysis of perfluorinated chemicals in sludge: method development and initial results. J Chromatogr A. 2009; 1216(45):7831-9. DOI: 10.1016/j.chroma.2009.09.051. View

Brase R, Mullin E, Spink D . Legacy and Emerging Per- and Polyfluoroalkyl Substances: Analytical Techniques, Environmental Fate, and Health Effects. Int J Mol Sci. 2021; 22(3). PMC: 7863963. DOI: 10.3390/ijms22030995. View

Faust J . PFAS on atmospheric aerosol particles: a review. Environ Sci Process Impacts. 2022; 25(2):133-150. DOI: 10.1039/d2em00002d. View

Keller J, Calafat A, Kato K, Ellefson M, Reagen W, Strynar M . Determination of perfluorinated alkyl acid concentrations in human serum and milk standard reference materials. Anal Bioanal Chem. 2009; 397(2):439-51. DOI: 10.1007/s00216-009-3222-x. View

Robuck A, McCord J, Strynar M, Cantwell M, Wiley D, Lohmann R . Tissue-specific distribution of legacy and novel per- and polyfluoroalkyl substances in juvenile seabirds. Environ Sci Technol Lett. 2021; 8(6):457-462. PMC: 8437152. DOI: 10.1021/acs.estlett.1c00222. View

10.

Sonne C, Vorkamp K, Galatius A, Kyhn L, Teilmann J, Bossi R . Human exposure to PFOS and mercury through meat from baltic harbour seals (Phoca vitulina). Environ Res. 2019; 175:376-383. DOI: 10.1016/j.envres.2019.05.026. View

11.

Tian Y, Yao Y, Chang S, Zhao Z, Zhao Y, Yuan X . Occurrence and Phase Distribution of Neutral and Ionizable Per- and Polyfluoroalkyl Substances (PFASs) in the Atmosphere and Plant Leaves around Landfills: A Case Study in Tianjin, China. Environ Sci Technol. 2018; 52(3):1301-1310. DOI: 10.1021/acs.est.7b05385. View

12.

Kaiser A, Aro R, Karrman A, Weiss S, Hartmann C, Uhl M . Comparison of extraction methods for per- and polyfluoroalkyl substances (PFAS) in human serum and placenta samples-insights into extractable organic fluorine (EOF). Anal Bioanal Chem. 2020; 413(3):865-876. PMC: 7809006. DOI: 10.1007/s00216-020-03041-5. View

13.

Yeung L, Guruge K, Taniyasu S, Yamashita N, Angus P, Herath C . Profiles of perfluoroalkyl substances in the liver and serum of patients with liver cancer and cirrhosis in Australia. Ecotoxicol Environ Saf. 2013; 96:139-46. DOI: 10.1016/j.ecoenv.2013.06.006. View

14.

Schrenk D, Bignami M, Bodin L, Chipman J, Del Mazo J, Grasl-Kraupp B . Risk to human health related to the presence of perfluoroalkyl substances in food. EFSA J. 2020; 18(9):e06223. PMC: 7507523. DOI: 10.2903/j.efsa.2020.6223. View

15.

So M, Taniyasu S, Lam P, Zheng G, Giesy J, Yamashita N . Alkaline digestion and solid phase extraction method for perfluorinated compounds in mussels and oysters from South China and Japan. Arch Environ Contam Toxicol. 2005; 50(2):240-8. DOI: 10.1007/s00244-005-7058-x. View

16.

Abraham K, El-Khatib A, Schwerdtle T, Monien B . Perfluorobutanoic acid (PFBA): No high-level accumulation in human lung and kidney tissue. Int J Hyg Environ Health. 2021; 237:113830. DOI: 10.1016/j.ijheh.2021.113830. View

17.

Gallen C, Eaglesham G, Drage D, Nguyen T, Mueller J . A mass estimate of perfluoroalkyl substance (PFAS) release from Australian wastewater treatment plants. Chemosphere. 2018; 208:975-983. DOI: 10.1016/j.chemosphere.2018.06.024. View

18.

Zhang B, He Y, Yang G, Chen B, Yao Y, Sun H . Legacy and Emerging Poly- and Perfluoroalkyl Substances in Finless Porpoises from East China Sea: Temporal Trends and Tissue-Specific Accumulation. Environ Sci Technol. 2021; 56(10):6113-6122. DOI: 10.1021/acs.est.1c00062. View

19.

Taniyasu S, Kannan K, So M, Gulkowska A, Sinclair E, Okazawa T . Analysis of fluorotelomer alcohols, fluorotelomer acids, and short- and long-chain perfluorinated acids in water and biota. J Chromatogr A. 2005; 1093(1-2):89-97. DOI: 10.1016/j.chroma.2005.07.053. View

20.

Dodds J, Alexander N, Kirkwood K, Foster M, Hopkins Z, Knappe D . From Pesticides to Per- and Polyfluoroalkyl Substances: An Evaluation of Recent Targeted and Untargeted Mass Spectrometry Methods for Xenobiotics. Anal Chem. 2020; 93(1):641-656. PMC: 7855838. DOI: 10.1021/acs.analchem.0c04359. View