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Quantitative analysis of PET microplastics in environmental model samples using quantitative 1H-NMR spectroscopy: validation of an optimized and consistent sample clean-up method

  • Nadine Peez
  • Jochen Becker
  • Sonja M. Ehlers
  • Melanie Fritz
  • Christian B. Fischer
  • Jochen H. E. Koop
  • Carola Winkelmann
  • Wolfgang ImhofEmail author
Research Paper
  • 103 Downloads

Abstract

Identification and quantification of microplastics (MP) in environmental samples is crucial for understanding the risk and distribution of MP in the environment. Currently, quantification of MP particles in environmental samples and the comparability of different matrices is a major research topic. Research also focusses on sample preparation, since environmental samples must be free of inorganic and organic matrix components for the MP analysis. Therefore, we would like to propose a new method that allows the comparison of the results of MP analysis from different environmental matrices and gives a MP concentration in mass of MP particles per gram of environmental sample. This is possible by developing and validating an optimized and consistent sample preparation scheme for quantitative analysis of MP particles in environmental model samples in conjunction with quantitative 1H-NMR spectroscopy (qNMR). We evaluated for the first time the effects of different environmental matrices on identification and quantification of polyethylene terephthalate (PET) fibers using the qNMR method. Furthermore, high recovery rates were obtained from spiked environmental model samples (without matrix ~ 90%, sediment ~ 97%, freshwater ~ 94%, aquatic biofilm ~ 95%, and invertebrate matrix ~ 72%), demonstrating the high analytical potential of the method.

Graphical abstract

Keywords

Microplastic Sample preparation Matrix effects qNMR PET fibers Quantification 

Notes

Acknowledgments

The authors thank Prof. Dr. B. Hahn and M. Albanna (University of Applied Science, RheinAhrCampus, Remagen, Germany) for SEM support. Furthermore, we thank Lana Vuleta for proofreading.

Funding information

The authors gratefully acknowledge the financial support of the Deutsche Forschungsgemeinschaft (INST 366/6-1) for the purchase of the NMR spectrometer. The authors also acknowledge financial support of the research fund of University Koblenz - Landau.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

Supplementary material

216_2019_2089_MOESM1_ESM.docx (2.9 mb)
ESM 1 (DOCX 2.94 kb)

References

  1. 1.
    World Economic Forum. The New Plastics Economy: Rethinking the future of plastics. 2016. https://www.ellenmacarthurfoundation.org/publications/the-new-plastics-economy-rethinking-the-future-of-plastics. Accessed 6 Mar 2019.
  2. 2.
    Geyer R, Jambeck JR, Law KL. Production, use, and fate of all plastics ever made. Sci Adv. 2017;3:e1700782.CrossRefGoogle Scholar
  3. 3.
    Moore CJ, Moore SL, Leecaster MK, Weisberg SB. A comparison of plastic and plankton in the North Pacific central gyre. Mar Pollut Bull. 2001;42:1297–300.CrossRefGoogle Scholar
  4. 4.
    Wagner M, Scherer C, Alvarez-Munoz D, Brennholt N, Bourrain X, Buchinger S, et al. Microplastic in freshwater ecosystems: what we know and what we need to know. Environ Sci Eur. 2014;26:12.CrossRefGoogle Scholar
  5. 5.
    Thompson RC, Olsen Y, Mitchell RP, Davis A, Rowland SJ, John Anthony WG, et al. Lost at sea: where is all the plastic? Science. 2004;304:838.CrossRefGoogle Scholar
  6. 6.
    Thompson RC, Moore CJ, Vom Saal FS, Swan SH. Plastics, the environment and human health: current consensus and future trends. Philos Trans R Soc B. 2009;364:2153–66.CrossRefGoogle Scholar
  7. 7.
    Wagner M, Lambert S, editors. Freshwater microplastics: emerging environmental contaminants? SpringerOpen. 2018.Google Scholar
  8. 8.
    Wright SL, Thompson RC, Galloway TS. The physical impacts of microplastics on marine organisms: a review. Environ Pollut. 2013;178:483–92.CrossRefGoogle Scholar
  9. 9.
    Klein S, Worch E, Knepper TP. Occurrence and spatial distribution of microplastics in river shore sediments of the Rhine-Main area in Germany. Environ Sci Technol. 2015;49:6070–6.CrossRefGoogle Scholar
  10. 10.
    Eerkes-Medrano D, Thompson RC, Aldridge DC. Microplastics in freshwater systems: a review of the emerging threats, identification of knowledge gaps and prioritisation of research needs. Water Res. 2015;75:63–82.CrossRefGoogle Scholar
  11. 11.
    Derraik JGB. The pollution of the marine environment by plastic debris: a review. Mar Pollut Bull. 2002;44:842–52.CrossRefGoogle Scholar
  12. 12.
    Ziajahromi S, Kumar A, Neale PA, Leusch FDL. Impact of microplastic beads and fibers on waterflea (Ceriodaphnia dubia) survival, growth, and reproduction: implications of single and mixture exposures. Environ Sci Technol. 2017;51:13397–406.CrossRefGoogle Scholar
  13. 13.
    Wendt-Potthoff K, Imhof HK, Wagner M, Primpke S, Fischer D, Scholz-Böttcher BM, Laforsch C. Mikroplastik in Binnengewässern. Handbuch Angewandte Limnologie. 2017.Google Scholar
  14. 14.
    Käppler A, Fischer D, Oberbeckmann S, Schernewski G, Labrenz M, Eichhorn K-J, et al. Analysis of environmental microplastics by vibrational microspectroscopy: FTIR, Raman or both? Anal Bioanal Chem. 2016;408:8377–91.CrossRefGoogle Scholar
  15. 15.
    Mai L, Bao L-J, Shi L, Wong CS, Zeng EY. A review of methods for measuring microplastics in aquatic environments. Environ Sci Pollut Res Int. 2018;25:11319–32.CrossRefGoogle Scholar
  16. 16.
    Sanchez W, Bender C, Porcher J-M. Wild gudgeons (Gobio gobio) from French rivers are contaminated by microplastics: preliminary study and first evidence. Environ Res. 2014;128:98–100.CrossRefGoogle Scholar
  17. 17.
    Ivleva NP, Wiesheu AC, Niessner R. Microplastic in aquatic ecosystems. Angew Chem Int Ed. 2017;56:1720–39.CrossRefGoogle Scholar
  18. 18.
    Hidalgo-Ruz V, Gutow L, Thompson RC, Thiel M. Microplastics in the marine environment: a review of the methods used for identification and quantification. Environ Sci Technol. 2012;46:3060–75.CrossRefGoogle Scholar
  19. 19.
    Imhof HK, Schmid J, Niessner R, Ivleva NP, Laforsch C. A novel, highly efficient method for the separation and quantification of plastic particles in sediments of aquatic environments. Limnol Oceanogr Methods. 2012;10:524–37.CrossRefGoogle Scholar
  20. 20.
    Dris R, Imhof H, Sanchez W, Gasperi J, Galgani F, Tassin B, et al. Beyond the ocean: contamination of freshwater ecosystems with (micro-) plastic particles. Environ Chem. 2015;12:539–50.CrossRefGoogle Scholar
  21. 21.
    Vandermeersch G, van Cauwenberghe L, Janssen CR, Marques A, Granby K, Fait G, et al. A critical view on microplastic quantification in aquatic organisms. Environ Res. 2015;143:46–55.CrossRefGoogle Scholar
  22. 22.
    Löder MGJ, Imhof HK, Ladehoff M. Enzymatic purification of microplastics in environmental samples. Environ Sci Technol. 2017;51:14283–92.CrossRefGoogle Scholar
  23. 23.
    Peez N, Janiska M-C, Imhof W. The first application of quantitative 1H-NMR-spectroscopy as a simple and fast method of identification and quantification of microplastic particles (PE, PET and PS). Anal Bioanal Chem. 2019;411:823–33.CrossRefGoogle Scholar
  24. 24.
    Alves Filho EG, Silva LMA, Araújo NVP, Alves EG, Lião LM, Alcantara GB. Qualitative and quantitative control of pediatric syrups using nuclear magnetic resonance and chemometrics. J Pharm Biomed Anal. 2018;153:29–36.CrossRefGoogle Scholar
  25. 25.
    Imhof HK, Ivleva NP, Schmid J, Niessner R, Laforsch C. Contamination of beach sediments of a subalpine lake with microplastic particles. Curr Biol. 2013;23:R867–8.CrossRefGoogle Scholar
  26. 26.
    Monakhova Y, Diehl B. Practical guide for selection of 1H qNMR acquisition and processing parameters confirmed by automated spectra evaluation. Magn Reson Chem. 2017:996–1005.Google Scholar
  27. 27.
    Bharti SK, Roy R. Quantitative 1H NMR spectroscopy. TrAC. 2012;35:5–26.Google Scholar
  28. 28.
    Barding G, Salditos R, Larive C. Quantitative NMR for bioanalysis and metabolomics. Anal Bioanal Chem. 2012;404:1165–79.CrossRefGoogle Scholar
  29. 29.
    Elert AM, Becker R, Duemichen E, Eisentraut P, Falkenhagen J, Sturm H, et al. Comparison of different methods for MP detection: what can we learn from them, and why asking the right question before measurements matters? Environ Pollut. 2017;231:1256–64.CrossRefGoogle Scholar
  30. 30.
    Fischer M, Scholz-Böttcher BM. Simultaneous trace identification and quantification of common types of microplastics in environmental samples by pyrolysis-gas chromatography–mass spectrometry. Environ Sci Technol. 2017;51:5052–60.CrossRefGoogle Scholar
  31. 31.
    Dümichen E, Barthel A-K, Braun U, Bannick CG, Brand K, Jekel M, et al. Analysis of polyethylene microplastics in environmental samples, using a thermal decomposition method. Water Res. 2015;85:451–7.CrossRefGoogle Scholar
  32. 32.
    Silva AB, Bastos AS, Justino CIL, da Costa JP, Duarte AC, Rocha-Santos TAP. Microplastics in the environment: challenges in analytical chemistry - a review. Anal Chim Acta. 2018;1017:1–19.CrossRefGoogle Scholar
  33. 33.
    Catarino AI, Thompson R, Sanderson W, Henry TB. Development and optimization of a standard method for extraction of microplastics in mussels by enzyme digestion of soft tissues. Environ Toxicol Chem. 2017;36:947–51.CrossRefGoogle Scholar
  34. 34.
    Caron AGM, Thomas CR, Berry KLE, Motti CA, Ariel E, Brodie JE. Validation of an optimised protocol for quantification of microplastics in heterogenous samples: a case study using green turtle chyme. MethodsX. 2018;5:812–23.CrossRefGoogle Scholar
  35. 35.
    Ceccarini A, Corti A, Erba F, Modugno F, La Nasa J, Bianchi S, et al. The hidden microplastics: new insights and figures from the thorough separation and characterization of microplastics and of their degradation byproducts in coastal sediments. Environ Sci Technol. 2018;52:5634–43.CrossRefGoogle Scholar
  36. 36.
    Avio CG, Gorbi S, Regoli F. Experimental development of a new protocol for extraction and characterization of microplastics in fish tissues: first observations in commercial species from Adriatic Sea. Mar Environ Res. 2015;111:18–26.CrossRefGoogle Scholar
  37. 37.
    Claessens M, van Cauwenberghe L, Vandegehuchte MB, Janssen CR. New techniques for the detection of microplastics in sediments and field collected organisms. Mar Pollut Bull. 2013;70:227–33.CrossRefGoogle Scholar
  38. 38.
    Zhao S, Zhu L, Gao L, Li D (eds). Limitations for microplastic quantification in the ocean and recommendations for improvement and standardization. Microplatic Contamination in Aquatic Environments: Elsevier Inc. 2018.Google Scholar
  39. 39.
    Nuelle M-T, Dekiff JH, Remy D, Fries E. A new analytical approach for monitoring micrplastics in marine sediments. Environ Pollut. 2014;184:161–9.CrossRefGoogle Scholar
  40. 40.
    Fries E, Dekiff JH, Willmeyer J, Nuelle M-T, Ebert M, Remy D. Identification of polymer types and additives in marine microplastic particles using pyrolysis-GC/MS and scanning electron microscopy. Environ Sci: Processes Impacts. 2013;15:1949–56.Google Scholar
  41. 41.
    Nor NHM, Obbard JP. Microplastics in Singapore's coastal mangrove ecosystems. Mar Pollut Bull. 2014;79:278–83.CrossRefGoogle Scholar
  42. 42.
    Stolte A, Forster S, Gerdts G, Schubert H. Microplastic concentrations in beach sediments along the German Baltic coast. Mar Pollut Bull. 2015;99:216–29.CrossRefGoogle Scholar
  43. 43.
    Hurley RR, Lusher AL, Olsen M, Nizzetto L. Validation of a method for extracting microplastics from complex, organic-rich, environmental matrices. Environ Sci Technol. 2018;52:7409–17.CrossRefGoogle Scholar
  44. 44.
    Hanvey JS, Lewis PJ, Lavers JL, Crosbie ND, Pozo K, Clarke BO. A review of analytical techniques for quantifying microplastics in sediments. Anal Methods. 2017;9:1369–83.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Nadine Peez
    • 1
  • Jochen Becker
    • 1
  • Sonja M. Ehlers
    • 1
    • 2
  • Melanie Fritz
    • 1
  • Christian B. Fischer
    • 1
    • 3
  • Jochen H. E. Koop
    • 2
  • Carola Winkelmann
    • 1
  • Wolfgang Imhof
    • 1
    Email author
  1. 1.Institute of Integrated Natural SciencesUniversity Koblenz-LandauKoblenzGermany
  2. 2.Department of Animal EcologyFederal Institute of HydrologyKoblenzGermany
  3. 3.Materials Science and Nano-engineering DepartmentMohammed VI Polytechnic UniversityBen GuerirMorocco

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