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
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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.
KeywordsTrifluoroacetate (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.
- 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. https://doi.org/10.1021/es3034999 CrossRefGoogle Scholar
- 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
- 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
- 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
- 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
- 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. https://doi.org/10.1039/c3em00499f Google Scholar
- 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. https://doi.org/10.1021/acs.estlett.6b00260 CrossRefGoogle Scholar
- Kissa E (2001) Fluorinated surfactants and repellents, 2nd edn. Surfactant science series, vol 97. Marcel Dekker, New YorkGoogle Scholar
- 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
- 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. https://doi.org/10.1016/j.chroma.2006.12.071 CrossRefGoogle Scholar
- NA 119-01-03-02-19 AK PFC in Wasser, Klärschlamm und Boden (2011) Validierungsdokument zu DIN 38407-42. http://www.wasserchemische-gesellschaft.de/dev/validierungsdokumente?download=33:f42-din-38407-42-2011-03&lang=de. Accessed 29 Jan 2018 (in German)
- O'Neil MJ (2013) The Merck index. An encyclopedia of chemicals, drugs, and biologicals, 15th edn. Royal Society of Chemistry, CambridgeGoogle Scholar
- 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. https://doi.org/10.1016/j.watres.2017.09.045 CrossRefGoogle Scholar
- 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. https://doi.org/10.1021/es061131o CrossRefGoogle Scholar
- 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. https://doi.org/10.1080/10937404.2016.1175981 CrossRefGoogle Scholar
- 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
- United Nations Environment Programme (2010) Stockholm convention on persistent organic pollutants (POPs) as amended in 2009. Stockholm Convention. http://chm.pops.int/TheConvention/ThePOPs/TheNewPOPs/tabid/2511/Default.aspx. Accessed 29 Jan 2018
- US EPA (2006) 2010/2015 PFOA Stewardship Program. https://www.epa.gov/assessing-and-managing-chemicals-under-tsca/risk-management-and-polyfluoroalkyl-substances-pfass. Accessed 29 Jan 2018
- 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. https://doi.org/10.1016/j.envpol.2012.12.019 CrossRefGoogle Scholar