Skip to main content
SpringerLink
Log in

A single analytical method for the determination of 53 legacy and emerging per- and polyfluoroalkyl substances (PFAS) in aqueous matrices

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

A quantitative method for the determination of per- and polyfluoroalkyl substances (PFAS) using liquid chromatography (LC) tandem mass spectrometry (MS/MS) was developed and applied to aqueous wastewater, surface water, and drinking water samples. Fifty-three PFAS from 14 compound classes (including many contaminants of emerging concern) were measured using a single analytical method. After solid-phase extraction using weak anion exchange cartridges, method detection limits in water ranged from 0.28 to 18 ng/L and method quantitation limits ranged from 0.35 to 26 ng/L. Method accuracy ranged from 70 to 127% for 49 of the 53 extracted PFAS, with the remaining four between 66 and 138%. Method precision ranged from 2 to 28% RSD, with 49 out of the 53 PFAS being below < 20%. In addition to quantifying > 50 PFAS, many of which are currently unregulated in the environment and not included in typical analytical lists, this method has efficiency advantages over other similar methods as it utilizes a single chromatographic separation with a shorter runtime (14 min), while maintaining method accuracy and stability and the separation of branched and linear PFAS isomers. The method was applied to wastewater influent and effluent; surface water from a river, wetland, and lake; and drinking water samples to survey PFAS contamination in Australian aqueous matrices. The compound classes FTCAs, FOSAAs, PFPAs, and diPAPs were detected for the first time in Australian WWTPs and the method was used to quantify PFAS concentrations from 0.60 to 193 ng/L. The range of compound classes detected and different PFAS signatures between sample locations demonstrate the need for expanded quantitation lists when investigating PFAS, especially newer classes in aqueous environmental samples.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2

Similar content being viewed by others

References

  1. Houde M, Bujas TAD, Small J, Wells RS, Fair PA, Bossart GD, et al. Biomagnification of perfluoroalkyl compounds in the bottlenose dolphin (Tursiops truncatus) food web. Environ Sci Technol. 2006;40(13):4138–44.

    Article  CAS  PubMed  Google Scholar 

  2. Ahrens L, Bundschuh M. Fate and effects of poly- and perfluoroalkyl substances in the aquatic environment: a review. Environ Toxicol Chem. 2014;33:1921–9.

    Article  CAS  PubMed  Google Scholar 

  3. Giesy JP, Kannan K. Global distribution of perfluorooctane sulfonate in wildlife. Environ Sci Technol. 2001;35(7):1339–42.

    Article  CAS  PubMed  Google Scholar 

  4. Buck RC, Franklin J, Berger U, Conder JM, Cousins IT, de Voogt P, et al. Perfluoroalkyl and polyfluoroalkyl substances in the environment: terminology, classification, and origins. Integr Environ Assess Manag. 2011;7(4):513–41.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Wang Z, DeWitt JC, Higgins CP, Cousins IT. A never-ending story of per- and polyfluoroalkyl substances (PFASs)? Environ Sci Technol. 2017.

  6. UNEP UEP. Governments unite to step-up reduction on global DDT reliance and add nine new chemicals under international treaty. 2009. Available from: http://chm.pops.int/Convention/Media/Pressreleases/COP4Geneva9May2009/tabid/542/lan. Accessed 29 Mar 2016.

  7. UNEP UEP. Chemicals proposed for listing under the convention: Dicofol; Perfluorooctanoic acid (PFOA), its salts and PFOA-related compounds; Perfluorohexane sulfonic acid (PFHxS), its salts and PFHxS-related compounds. 2018 . Available from: http://chm.pops.int/TheConvention/ThePOPs/ChemicalsProposedforListing/tabid/2510/Default.aspx. Accessed 17 Nov 2018.

  8. US EPA. Lifetime Health Advisories and Health Effects Support Documents for Perfluorooctanoic Acid and Perfluorooctane Sulfonate. Washington DC; 2016.

  9. HEPA HotEAaNZ. PFAS National Environmental Management Plan. Australia; 2018 January 2018.

  10. Wang ZY, Cousins IT, Scheringer M, Hungerbuhler K. Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their potential precursors. Environ Int. 2013;60.

  11. OECD. Toward a new comprehensive global database of per- and polyfluoroalkyl substances (PFASs): summary report on updating the OECD 2007 List of per- and polyfluoroalkyl substances (PFASs). Paris; 2018. Contract No.: JT03431231.

  12. Arvaniti OS, Stasinakis AS. Review on the occurrence, fate and removal of perfluorinated compounds during wastewater treatment. Sci Total Environ. 2015;524–525:81–92.

    Article  CAS  PubMed  Google Scholar 

  13. Chen H, Peng H, Yang M, Hu J, Zhang Y. Detection, occurrence, and fate of fluorotelomer alcohols in municipal wastewater treatment plants. Environ Sci Technol. 2017;51(16):8953–61.

    Article  CAS  PubMed  Google Scholar 

  14. Eriksson U, Haglund P, Kärrman A. Contribution of precursor compounds to the release of per- and polyfluoroalkyl substances (PFASs) from waste water treatment plants (WWTPs). J Environ Sci. 2017;61(Supplement C):80–90.

    Article  Google Scholar 

  15. Wang N, Liu J, Buck RC, Korzeniowski SH, Wolstenholme BW, Folsom PW, et al. 6:2 Fluorotelomer sulfonate aerobic biotransformation in activated sludge of waste water treatment plants. Chemosphere. 2011;82(6):853–8.

    Article  CAS  PubMed  Google Scholar 

  16. Zhao L, McCausland PK, Folsom PW, Wolstenholme BW, Sun H, Wang N, et al. 6:2 Fluorotelomer alcohol aerobic biotransformation in activated sludge from two domestic wastewater treatment plants. Chemosphere. 2013;92(4):464–70.

    Article  CAS  PubMed  Google Scholar 

  17. Lee H, D’eon J, Mabury SA. Biodegradation of polyfluoroalkyl phosphates as a source of perfluorinated acids to the environment. Environ Sci Technol. 2010;44(9):3305–10.

    Article  CAS  PubMed  Google Scholar 

  18. Wang S, Huang J, Yang Y, Hui Y, Ge Y, Larssen T, et al. First report of a Chinese PFOS alternative overlooked for 30 years: its toxicity, persistence, and presence in the environment. Environ Sci Technol. 2013;47(18):10163–70.

    Article  CAS  PubMed  Google Scholar 

  19. Ruan T, Lin Y, Wang T, Liu R, Jiang G. Identification of novel Polyfluorinated ether sulfonates as PFOS alternatives in municipal sewage sludge in China. Environ Sci Technol. 2015;49(11):6519–27.

    Article  CAS  PubMed  Google Scholar 

  20. Sun M, Arevalo E, Strynar M, Lindstrom A, Richardson M, Kearns B, et al. Legacy and emerging perfluoroalkyl substances are important drinking water contaminants in the cape fear river watershed of North Carolina. Environ Sci Technol Lett. 2016;3(12):415–9.

    Article  CAS  Google Scholar 

  21. US EPA. Method 537. Determination of selected perfluorinated alkyl acids in drinking water by solid phase extraction and liquid chromatography/tandem mass spectrometry (LC/MS/MS). Ohio; 2009.

  22. Boiteux V, Bach C, Sagres V, Hemard J, Colin A, Rosin C, et al. Analysis of 29 per- and polyfluorinated compounds in water, sediment, soil and sludge by liquid chromatography–tandem mass spectrometry. Int J Environ Anal Chem. 2016;96(8):705–28.

    Article  CAS  Google Scholar 

  23. Gremmel C, Frömel T, Knepper TP. HPLC–MS/MS methods for the determination of 52 perfluoroalkyl and polyfluoroalkyl substances in aqueous samples. Anal Bioanal Chem. 2016:1–13.

  24. US EPA. Definition and Procedure for the Determination of the Method Detection Limit, Revision 2. 2016. Contract No.: EPA 821-R-16-006.

  25. Anumol T, Moshin SB, Woodman M, Abrahamsson P. Recommended plumbing configurations for reduction in per/polyfluoroalkyl substance background with Agilent 1260/1290 Infinity (II) LC Systems. USA: Agilent Technologies; 2017.

  26. Xiao F. Emerging poly- and perfluoroalkyl substances in the aquatic environment: a review of current literature. Water Res. 2017;124:482–95.

    Article  CAS  PubMed  Google Scholar 

  27. Liu J, Mejia Avendaño S. Microbial degradation of polyfluoroalkyl chemicals in the environment: a review. Environ Int. 2013;61(0):98–114.

    Article  CAS  PubMed  Google Scholar 

  28. Ruan T, Lin Y, Wang T, Jiang G, Wang N. Methodology for studying biotransformation of polyfluoroalkyl precursors in the environment. Trends Anal Chem. 2015;67:167–78.

    Article  CAS  Google Scholar 

  29. R Core Team. R: a language and environment for statistical computing Vienna, Austria 2017. Available from: https://www.R-project.org/.

  30. Barreca S, Busetto M, Vitelli M, Colzani L, Clerici L, Dellavedova P. Online solid-phase extraction LC-MS/MS: a rapid and valid method for the determination of perfluorinated compounds at sub ng·L-1 level in natural water. J Chem. 2018. https://doi.org/10.1155/2018/3780825.

  31. Szabo D, Coggan TL, Robson TC, Currell M, Clarke BO. Investigating recycled water use as a diffuse source of per- and polyfluoroalkyl substances (PFASs) to groundwater in Melbourne, Australia. Sci Total Environ. 2018;644:1409–17.

    Article  CAS  PubMed  Google Scholar 

  32. Chandramouli B, Benskin JP, Hamilton MC, Cosgrove JR. Sorption of per- and polyfluoroalkyl substances (PFASs) on filter media: implications for phase partitioning studies. Environ Toxicol Chem. 2015;34(1):30–6.

    Article  CAS  PubMed  Google Scholar 

  33. DoD, DOE. Department of Defence (DoD) and Department of Energy (DOE) consolidated Quality Systems Manual (QSM) for Environmental Laboratories Based on ISO/IEC 17025:2005(E) and The NELAC Institute (TNI) Standards, Volume 1, (September 2009). United States; 2017.

  34. Gros M, Blum KM, Jernstedt H, Renman G, Rodríguez-Mozaz S, Haglund P, et al. Screening and prioritization of micropollutants in wastewaters from on-site sewage treatment facilities. J Hazard Mater. 2017;328:37–45.

    Article  CAS  PubMed  Google Scholar 

  35. Procopio NA, Karl R, Goodrow SM, Maggio J, Louis JB, Atherholt TB. Occurrence and source identification of perfluoroalkyl acids (PFAAs) in the Metedeconk River Watershed, New Jersey. Environ Sci Pollut Res Int. 2017;24(35):27125–35.

    Article  CAS  PubMed  Google Scholar 

  36. Zabaleta I, Bizkarguenaga E, Izagirre U, Negreira N, Covaci A, Benskin JP, et al. Biotransformation of 8:2 polyfluoroalkyl phosphate diester in gilthead bream (Sparus aurata). Sci Total Environ. 2017;609(Supplement C):1085–92.

    Article  CAS  PubMed  Google Scholar 

  37. Lange C. The aerobic biodegradation of N-EtFOSE alcohol by the microbial activity present in municipal wastewater treatment sludge. St. Paul, MN: 3M Environmental Laboratory; 2000.

  38. Thompson J, Eaglesham G, Mueller J. Concentrations of PFOS, PFOA and other perfluorinated alkyl acids in Australian drinking water. Chemosphere. 2011;83(10):1320–5.

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgments

We acknowledge the traditional owners of the land on which this research was conducted. This research was supported by an Australian Government Research Training Program (RTP) Scholarship. The Authors acknowledge the reviewers and editors for improving the manuscript. T Coggan acknowledges Agilent Technologies and Water Research Australia Limited for supporting this project. The authors acknowledge the following individuals for advice on the manuscript: Raymond Harvey, Thomas McGrath, Phoebe Lewis, and Courtney Milner. The authors thank Raymond Harvey for production of the icons used in the graphical abstract. T Coggan thanks Phoebe Lewis for assistance in collecting environmental samples.

Author information

Authors and Affiliations

  1. Centre for Environmental Sustainability and Remediation, School of Science, RMIT University, GPO Box 2476, Melbourne, VIC, 3001, Australia

    Timothy L. Coggan, Jeff Shimeta & Bradley O. Clarke

  2. Agilent Technologies Inc, Wilmington, DE, 19808, USA

    Tarun Anumol & James Pyke

Authors
  1. Timothy L. Coggan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tarun Anumol
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. James Pyke
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jeff Shimeta
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Bradley O. Clarke
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Timothy L. Coggan.

Ethics declarations

Conflict of interest

T. Anumol and J. Pyke are employees of Agilent Technologies Inc, who supplied the instrumentation used for LC-MS/MS analysis. B. Clarke has an LC-MS/MS demonstration instrument from Agilent Technologies Inc operating within his laboratory. T. Coggan receives scholarship funding from the Australian government Research Training Program and Water Research Australia. J. Shimeta declares that he has no conflicts of interest.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(PDF 361 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Coggan, T.L., Anumol, T., Pyke, J. et al. A single analytical method for the determination of 53 legacy and emerging per- and polyfluoroalkyl substances (PFAS) in aqueous matrices. Anal Bioanal Chem 411, 3507–3520 (2019). https://doi.org/10.1007/s00216-019-01829-8

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-019-01829-8

Keywords

Search

Navigation