Environmental Science and Pollution Research

, Volume 26, Issue 8, pp 7326–7336 | Cite as

Robust trace analysis of polar (C2-C8) perfluorinated carboxylic acids by liquid chromatography-tandem mass spectrometry: method development and application to surface water, groundwater and drinking water

  • Joachim JandaEmail author
  • Karsten Nödler
  • Heinz-Jürgen Brauch
  • Christian Zwiener
  • Frank T. Lange
Advancements in chemical methods for environmental research


A simple and robust analytical method for the determination of perfluorinated carboxylic acids (PFCAs) with C2 to C8 chains, based on solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS), was developed, validated and applied to tap water, groundwater and surface water. Two stationary phases for LC (Obelisc N and Kinetex C18) and two materials with weak anion-exchange properties for SPE (Strata X-AW and Oasis WAX) were evaluated. Robust separation and retention was achieved with the reversed phase column and an acidic eluent. Quantitative extraction recoveries were generally achieved for PFCAs with C > 3, but extraction efficiencies were different for the two shortest chained analytes: 36 to 114% of perfluoropropanoate (PFPrA) and 14 to 99% of trifluoroacetate (TFA) were recovered with Strata X-AW, while 93 to 103% of PFPrA and 40 to 103% of TFA were recovered with Oasis WAX. The sample pH was identified as a key parameter in the extraction process. One-step elution-filtration was introduced in the workflow, in order to remove sorbent particles and minimise sample preparation steps. Validation resulted in limits of quantification for all PFCAs between 0.6 and 26 ng/L. Precision was between 0.7 and 15% and mean recoveries ranged from 83 to 107%. In groundwater samples from sites impacted by per- and polyfluoroalkyl substances (PFASs), PFCA concentrations ranged from 0.056 to 2.2 μg/L. TFA and perfluorooctanoate were the predominant analytes. TFA, however, revealed a more ubiquitous occurrence and was found in concentrations between 0.045 and 17 μg/L in drinking water, groundwater and surface water, which were not impacted by PFASs.


Trifluoroacetate (TFA) PFAS PFCA Water analysis Solid-phase extraction Liquid chromatography-tandem mass spectrometry Water pollution Water quality 



We highly appreciate the analysis of inorganic anions, performed by Brigitte Raue, Franziska Klein and Alexander Heck as well as Raman spectroscopic measurements of SPE particles, performed by Marco Pittroff (all from TZW).


This work was financially supported by the German Association of Gas and Waterworks (Deutscher Verein des Gas- und Wasserfaches e.V., DVGW), project W 7-03-14.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11356_2018_1731_MOESM1_ESM.pdf (645 kb)
ESM 1 (PDF 645 kb)


  1. Ahrens L (2011) Polyfluoroalkyl compounds in the aquatic environment: a review of their occurrence and fate. J Environ Monit 13:20–31. CrossRefGoogle Scholar
  2. Ahrens L, Taniyasu S, Yeung LWY, Yamashita N, Lam PKS, Ebinghaus R (2010) Distribution of polyfluoroalkyl compounds in water, suspended particulate matter and sediment from Tokyo Bay, Japan. Chemosphere 79:266–272. CrossRefGoogle Scholar
  3. Alder AC, van der Voet J (2015) Occurrence and point source characterization of perfluoroalkyl acids in sewage sludge. Chemosphere 129:62–73. CrossRefGoogle Scholar
  4. Backe WJ, Day TC, Field JA (2013) Zwitterionic, cationic, and anionic fluorinated chemicals in aqueous film forming foam formulations and groundwater from U.S. military bases by nonaqueous large-volume injection HPLC-MS/MS. Environ Sci Technol 47:5226–5234. CrossRefGoogle Scholar
  5. Berger U, Kaiser MA, Kärrman A, Barber JL, van Leeuwen, Stefan P J (2011) Recent developments in trace analysis of poly- and perfluoroalkyl substances. Anal Bioanal Chem 400:1625–1635Google Scholar
  6. Chen S, Jiao X-C, Gai N, Li X-J, Wang X-C, Lu G-H, Piao H-T, Rao Z, Yang Y-L (2016) Perfluorinated compounds in soil, surface water, and groundwater from rural areas in eastern China. Environ Pollut 211:124–131. CrossRefGoogle Scholar
  7. Commission of the European Communities (2006) Directive 2006/122/EC of the European parliament and of the council amending for the 30th time council directive 76/769/EEC on the approximation of the laws, regulations and administrative provisions on the member states relating to restrictions on the marketing and use of certain dangerous substances and preparations (perfluorooctane sulfonates). Off J Eur Union L372:32–34Google Scholar
  8. Deutsches Institut für Normung e.V (DIN) (2011) German standard methods for the examination of water, waste water and sludge—jointly determinable substances (group F)—part 42: determination of selected polyfluorinated compounds (PFC) in water—method using high performance liquid chromatography and mass spectrometric detection (HPLC/MS-MS) after solid-liquid extraction (F 42)(38407-42) (in German)Google Scholar
  9. Ding G, Peijnenburg WJGM (2013) Physicochemical properties and aquatic toxicity of poly- and perfluorinated compounds. Crit Rev Environ Sci Technol 43:598–678. CrossRefGoogle Scholar
  10. Dinglasan-Panlilio MJA, Mabury SA (2006) Significant residual fluorinated alcohols present in various fluorinated materials. Environ Sci Technol 40:1447–1453. CrossRefGoogle Scholar
  11. Eschauzier C, Voogt P de, Brauch H-J, Lange FT (2012) Polyfluorinated chemicals in European surface waters, ground- and drinking waters. In: Knepper TP, Lange FT (eds) Polyfluorinated chemicals and transformation products. Springer, Berlin, Heidelberg, pp 73–102Google Scholar
  12. Gawor A, Shunthirasingham C, Hayward SJ, Lei YD, Gouin T, Mmereki BT, Masamba W, Ruepert C, Castillo LE, Shoeib M, Lee SC, Harner T, Wania F (2014) Neutral polyfluoroalkyl substances in the global atmosphere. Environ Sci: Processes Impacts 16:404–413. Google Scholar
  13. Gellrich V, Stahl T, Knepper TP (2012) Behavior of perfluorinated compounds in soils during leaching experiments. Chemosphere 87:1052–1056CrossRefGoogle Scholar
  14. Giesy JP, Kannan K (2001) Global distribution of perfluorooctane sulfonate in wildlife. Environ Sci Technol 35:1339–1342. CrossRefGoogle Scholar
  15. Houde M, De Silva AO, Muir DCG, Letcher RJ (2011) Monitoring of perfluorinated compounds in aquatic biota: an updated review. Environ Sci Technol 45:7962–7973. CrossRefGoogle Scholar
  16. Hu XC, Andrews DQ, Lindstrom AB, Bruton TA, Schaider LA, Grandjean P, Lohmann R, Carignan CC, Blum A, Balan SA, Higgins CP, Sunderland EM (2016) Detection of poly- and perfluoroalkyl substances (PFASs) in U.S. drinking water linked to industrial sites, military fire training areas, and wastewater treatment plants. Environ Sci Technol Lett 3:344–350. CrossRefGoogle Scholar
  17. Jahnke A, Berger U (2009) Trace analysis of per- and polyfluorinated alkyl substances in various matrices-how do current methods perform? J Chromatogr A 1216:410–421. CrossRefGoogle Scholar
  18. Jordan A, Frank H (1999) Trifluoroacetate in the environment. Evidence for sources other than HFC/HCFCs. Environ Sci Technol 33:522–527. CrossRefGoogle Scholar
  19. Kissa E (2001) Fluorinated surfactants and repellents, 2nd edn. Surfactant science series, vol 97. Marcel Dekker, New YorkGoogle Scholar
  20. Lee H, Mabury SA (2014) Global distribution of polyfluoroalkyl and perfluoroalkyl substances and their transformation products in environmental solids. In: Nollet LML, Lambropoulou DA (eds) Transformation products of emerging contaminants in the environment. Analysis, processes, occurrence, effects and risks. John Wiley & Sons, Chichester, pp 797–826Google Scholar
  21. Lewis KA, Tzilivakis J, Warner DJ, Green A (2016) An international database for pesticide risk assessments and management. Hum Ecol Risk Assess 22:1050–1064. CrossRefGoogle Scholar
  22. Mak YL, Taniyasu S, Yeung LWY, Lu G, Jin L, Yang Y, Lam PKS, Kannan K, Yamashita N (2009) Perfluorinated compounds in tap water from China and several other countries. Environ Sci Technol 43:4824–4829. CrossRefGoogle Scholar
  23. Mallet CR, Lu Z, Mazzeo JR (2004) A study of ion suppression effects in electrospray ionization from mobile phase additives and solid-phase extracts. Rapid Commun Mass Spectrom 18:49–58. CrossRefGoogle Scholar
  24. Matuszewski BK, Constanzer ML, Chavez-Eng CM (2003) Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC−MS/MS. Anal Chem 75:3019–3030. CrossRefGoogle Scholar
  25. Miyake Y, Yamashita N, Rostkowski P, So MK, Taniyasu S, Lam PKS, Kannan K (2007) Determination of trace levels of total fluorine in water using combustion ion chromatography for fluorine: a mass balance approach to determine individual perfluorinated chemicals in water. J Chromatogr A 1143:98–104. CrossRefGoogle Scholar
  26. NA 119-01-03-02-19 AK PFC in Wasser, Klärschlamm und Boden (2011) Validierungsdokument zu DIN 38407-42. Accessed 29 Jan 2018 (in German)
  27. O'Neil MJ (2013) The Merck index. An encyclopedia of chemicals, drugs, and biologicals, 15th edn. Royal Society of Chemistry, CambridgeGoogle Scholar
  28. Place BJ, Field JA (2012) Identification of novel fluorochemicals in aqueous film-forming foams used by the US military. Environ Sci Technol 46:7120–7127. CrossRefGoogle Scholar
  29. Scheurer M, Nödler K, Freeling F, Janda J, Happel O, Riegel M, Müller U, Storck FR, Fleig M, Lange FT, Brunsch A, Brauch H-J (2017) Small, mobile, persistent: trifluoroacetate in the water cycle—overlooked sources, pathways, and consequences for drinking water supply. Water Res 126:460–471. CrossRefGoogle Scholar
  30. Scott BF, Mehran A (1998) Determination of haloacetic acids from aqueous samples collected from the Canadian environment using an in situ derivatization technique. Water Qual Res J Canada 33:279–293CrossRefGoogle Scholar
  31. Scott BF, Moody CA, Spencer C, Small JM, Muir DCG, Mabury SA (2006) Analysis for perfluorocarboxylic acids/anions in surface waters and precipitation using GC−MS and analysis of PFOA from large-volume samples. Environ Sci Technol 40:6405–6410. CrossRefGoogle Scholar
  32. Skutlarek D, Exner M, Färber H (2006) Perfluorinated surfactants in surface and drinking waters. Environ Sci Pollut Res 13:299–307. CrossRefGoogle Scholar
  33. Solomon KR, Velders GJM, Wilson SR, Madronich S, Longstreth J, Aucamp PJ, Bornman JF (2016) Sources, fates, toxicity, and risks of trifluoroacetic acid and its salts: relevance to substances regulated under the Montreal and Kyoto protocols. J Toxicol Environ Health, Part B 19:1–16. CrossRefGoogle Scholar
  34. Stahl T, Mattern D, Brunn H (2011) Toxicology of perfluorinated compounds. Environ Sci Eur 23:38. CrossRefGoogle Scholar
  35. Taniyasu S, Kannan K, Yeung LWY, Kwok KY, Lam PKS, Yamashita N (2008) Analysis of trifluoroacetic acid and other short-chain perfluorinated acids (C2-C4) in precipitation by liquid chromatography-tandem mass spectrometry: comparison to patterns of long-chain perfluorinated acids (C5-C18). Anal Chim Acta 619:221–230CrossRefGoogle Scholar
  36. Trier X, Granby K, Christensen JH (2011) Polyfluorinated surfactants (PFS) in paper and board coatings for food packaging. Environ Sci Pollut Res 18:1108–1120CrossRefGoogle Scholar
  37. United Nations Environment Programme (2010) Stockholm convention on persistent organic pollutants (POPs) as amended in 2009. Stockholm Convention. Accessed 29 Jan 2018
  38. Vierke L, Möller A, Klitzke S (2014) Transport of perfluoroalkyl acids in a water-saturated sediment column investigated under near-natural conditions. Environ Pollut 186:7–13. CrossRefGoogle Scholar
  39. Villagrasa M, López de Alda M, Barceló D (2006) Environmental analysis of fluorinated alkyl substances by liquid chromatography-(tandem) mass spectrometry: a review. Anal Bioanal Chem 386:953–972. CrossRefGoogle Scholar
  40. Wang Z, Cousins IT, Scheringer M, Hungerbühler K (2013) Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their potential precursors. Environ Int 60:242–248. CrossRefGoogle Scholar
  41. Zhai Z, Wu J, Hu X, Li L, Guo J, Zhang B, Hu J, Zhang J (2015) A 17-fold increase of trifluoroacetic acid in landscape waters of Beijing, China during the last decade. Chemosphere 129:110–117. CrossRefGoogle Scholar
  42. Zhang W, Zhang Y, Taniyasu S, Yeung LWY, Lam PKS, Wang J, Li X, Yamashita N, Dai J (2013) Distribution and fate of perfluoroalkyl substances in municipal wastewater treatment plants in economically developed areas of China. Environ Pollut 176:10–17. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.DVGW-Technologiezentrum Wasser (TZW)KarlsruheGermany
  2. 2.Environmental Analytical ChemistryUniversity of TübingenTübingenGermany

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