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Environmental Science and Pollution Research

, Volume 26, Issue 8, pp 7364–7374 | Cite as

High-throughput NIR spectroscopic (NIRS) detection of microplastics in soil

  • Andrea PaulEmail author
  • Lukas Wander
  • Roland Becker
  • Caroline Goedecke
  • Ulrike Braun
Advancements in chemical methods for environmental research

Abstract

The increasing pollution of terrestrial and aquatic ecosystems with plastic debris leads to the accumulation of microscopic plastic particles of still unknown amount. To monitor the degree of contamination, analytical methods are urgently needed, which help to quantify microplastics (MP). Currently, time-costly purified materials enriched on filters are investigated both by micro-infrared spectroscopy and/or micro-Raman. Although yielding precise results, these techniques are time consuming, and are restricted to the analysis of a small part of the sample in the order of few micrograms. To overcome these problems, we tested a macroscopic dimensioned near-infrared (NIR) process-spectroscopic method in combination with chemometrics. For calibration, artificial MP/ soil mixtures containing defined ratios of polyethylene, polyethylene terephthalate, polypropylene, and polystyrene with diameters < 125 μm were prepared and measured by a process FT-NIR spectrometer equipped with a fiber-optic reflection probe. The resulting spectra were processed by chemometric models including support vector machine regression (SVR), and partial least squares discriminant analysis (PLS-DA). Validation of models by MP mixtures, MP-free soils, and real-world samples, e.g., fermenter residue, suggests a reliable detection and a possible classification of MP at levels above 0.5 to 1.0 mass% depending on the polymer. The benefit of the combined NIRS chemometric approach lies in the rapid assessment whether soil contains MP, without any chemical pretreatment. The method can be used with larger sample volumes and even allows for an online prediction and thus meets the demand of a high-throughput method.

Keywords

Microplastics Soil Chemometrics PLS-DA Support vector machines Near-infrared spectroscopy 

Notes

Acknowledgements

The authors kindly thank Dr. Markus Ostermann and Dr. Ute Kalbe for providing standard soils from their collections, Andreas Sauer for the cryo-milling of polymers, Dr. Thomas Schmid for kindly providing microphotographs, Dr. Claus Gerhard Bannick (Umweltbundesamt Berlin, Germany) for fermenter residue samples and washing machine filter material, BONARES for soil samples, and Yosri Hassanein for assistance with the preparation of samples. Many thanks to Dr. Michael Maiwald (BAM), the Focus area “Microplastics” at BAM, and the BMBF (MIWA, coordination Technische Universität Berlin, Prof. Martin Jekel) for the financial support of this project.

Supplementary material

11356_2018_2180_MOESM1_ESM.docx (1.7 mb)
ESM 1 (DOCX 1731 kb)

References

  1. Bajer K, Braun U (2014) Different aspects of the accelerated oxidation of polypropylene at increased pressure in an autoclave with regard to temperature, pretreatment and exposure media. Polym Test 37:102–111CrossRefGoogle Scholar
  2. Barej JAM, Pätzold S, Perkons U, Amelung W (2014) Phosphorus fractions in bulk subsoil and its biopore systems. Eur J Soil Sci 65:553–561.  https://doi.org/10.1111/ejss.12124 CrossRefGoogle Scholar
  3. Blaesing M, Amelung W (2018) Plastics in soil: analytical methods and possible sources. Sci Total Environ 612:422–435CrossRefGoogle Scholar
  4. Boucher J, Friot D (2017) Primary Microplastics in the Oceans: A Global Evaluation of Sources Imprint: Gland: IUCN, ISBN: 978-2-8317-1827-9. https://portals.iucn.org/library/node/46622, Accessed 17 Nov 2017
  5. Chen W, Ouyang Z-Y, Qian C, Yu H-Q (2018) Induced structural changes of humic acid by exposure of polystyrene microplastics: a spectroscopic insight. Environ Pollut 233:1–7CrossRefGoogle Scholar
  6. Cortes C, Vapnik V (1995) Support-vector networks. Mach Learn 20:273–297Google Scholar
  7. De Boves Harrington P (2015) Support vector machine classification trees. Anal Chem 87:11065–11071CrossRefGoogle Scholar
  8. Duemichen E, Eisentraut P, Bannick CG, Barthel A-K, Senz R, Braun U (2017) Fast identification of microplastics in complex environmental samples by a thermal degradation method. Chemosphere 174:572–584CrossRefGoogle Scholar
  9. Eide I, Neverdal G, Westad F (2010) Detection of 5 ppm fatty acid methyl ester (FAME) in jet fuel using electrospray ionization mass spectrometry and Chemometrics. Energy Fuel 24:3661–3664CrossRefGoogle Scholar
  10. Elert AM, Becker R, Duemichen E, Eisentraut P, Falkenhagen J, Sturm H, Braun U (2017) Comparison of different methods for MP detection: what can we learn from them, and why asking the right question before measurements matters? Environ Pollut 231:1256–1264CrossRefGoogle Scholar
  11. Fabbri D (2001) Use of pyrolysis-gas chromatography/mass spectrometry to study environmental pollution caused by synthetic polymers. A case study: the Ravenna lagoon. J Anal Appl Pyrolysis 58–59:361–370CrossRefGoogle Scholar
  12. Fischer M, Scholz-Bottcher BM (2017) Simultaneous trace identification and quantification of common types of microplastics in environmental samples by pyrolysis-gas chromatography-mass spectrometry. Environ Sci Technol 51:5052–5060CrossRefGoogle Scholar
  13. Fries E, Dekiff JH, Willmeyer J, Nuelle M-T, Ebert M, Remy D (2013) Identification of polymer types and additives in marine microplastic particles using pyrolysis-GC/MS and scanning electron microscopy. Environ Sci Process Impacts 15:1949–1956CrossRefGoogle Scholar
  14. Fuller S, Gautam A (2016) A procedure for measuring microplastics using pressurized fluid extraction. Environ Sci Technol 50:5774–5780CrossRefGoogle Scholar
  15. Heggemann T, Welp G, Amelung W, Angst G, Franz SO, Koszinski S, Schmidt S, Pätzold S (2017) Proximal gamma-ray spectrometry for site-independent in situ prediction of soil texture on ten heterogeneous fields in Germany using support vector machines. Soil Tillage Res 168:99–109CrossRefGoogle Scholar
  16. Herzke D, Anker-Nilssen T, Nøst TH, Götsch A, Christensen-Dalsgaard S, Langset M, Fangel K, Koelmans AA (2016) Negligible impact of ingested microplastics on tissue concentrations of persistent organic pollutants in northern fulmars off coastal Norway. Environ Sci Technol 50:1924–1933CrossRefGoogle Scholar
  17. Hidalgo-Ruz V, Gutow L, Thompson RC, Thiel M (2012) Microplastics in the marine environment: a review of the methods used for identification and quantification. Environ Sci Technol 46:3060–3075CrossRefGoogle Scholar
  18. Imhof HK, Laforsch C, Wiesheu AC, Schmid J, Anger PM, Niessner R, Ivleva NP (2016) Pigments and plastic in limnetic ecosystems: a qualitative and quantitative study on microparticles of different size classes. Water Res 98:64–74CrossRefGoogle Scholar
  19. Kaeppler A, Fischer D, Oberbeckmann S, Schernewski G, Labrenz M, Eichhorn K-J, Voit B (2016) Analysis of environmental microplastics by vibrational microspectroscopy: FTIR, Raman or both? Anal Bioanal Chem 408:8377–8391Google Scholar
  20. Karlsson TM, Grahn H, van Bavel B, Geladi P (2016) Hyperspectral imaging and data analysis for detecting and determining plastic contamination in seawater filtrates. J Near Infrared Spectrosc 24:141–149CrossRefGoogle Scholar
  21. Kooi M, EHv N, Scheffer M, Koelmans AA (2017) Ups and downs in the ocean: effects of biofouling on vertical transport of microplastics. Environ Sci Technol 51:7963–7971CrossRefGoogle Scholar
  22. Kostamovaara J, Tenhunen J, Kögler M, Nissinen I, Nissinen J, Keränen P (2013) Fluorescence suppression in Raman spectroscopy using a time-gated CMOS SPAD. Opt Express 21:31632–31645CrossRefGoogle Scholar
  23. Miller CE, Eichinger BE (1990) Determination of crystallinity and morphology of fibrous and bulk poly(ethylene terephthalate) by near-infrared diffuse reflectance spectroscopy. Appl Spectrosc 44:496–504CrossRefGoogle Scholar
  24. Mizushima M, Kawamura T, Takahashi K, Nitta KH (2012) In situ near-infrared spectroscopic studies of the structural changes of polyethylene during melting. Polym J 44:162–166CrossRefGoogle Scholar
  25. Moroni M, Mei A, Leonardi A, Lupo E, La Marca F (2015) PET and PVC separation with hyperspectral imagery. Sensors 15:2205–2227.  https://doi.org/10.3390/s150102205 CrossRefGoogle Scholar
  26. Nizetto et al. (2016) Are agricultural soils dumps for microplastics of urban origin? Environ Sci Technol 50:10777–10779CrossRefGoogle Scholar
  27. Paul A, Breitfeld S, Sauer A, Becker R, Kalbe U, Bremser W, Braun U (2016) A Raman spectroscopic method for the monitoring of microplastic in soil, 12. Kolloquium Prozessanalytik, BerlinGoogle Scholar
  28. Paul A, Becker R, Wander L, Breitfeld S, Koegler M, Sauer A, Braun U (2017) An alternative spectroscopic approach for the monitoring of microplastics in environmental samples, 16th International Conference on chemistry and the environment, Oslo Norwegen, http://www.mn.uio.no/kjemi/english/research/projects/ICCE2017/monday-19.06/helga-eng-auditorium-1/Hr.-11%3A00/. Accessed 20 Nov 2017
  29. Primpke S, Lorenz C, Rascher-Friesenhausen R, Gerdts G (2017) An automated approach for microplastics analysis using focal plane array (FPA) FTIR microscopy and image analyst. Anal Methods 9:1499–1511CrossRefGoogle Scholar
  30. Renner G, Schmidt TC, Schram J (2017) A new chemometric approach for automatic identification of microplastics from environmental compartments based on FT-IR spectroscopy. Anal Chem 89:12045–12053.  https://doi.org/10.1021/acs.analchem.7b02472 CrossRefGoogle Scholar
  31. Roberts JJ, Cozzolino D (2016) Wet or dry? The effect of sample characteristics on the determination of soil properties by near infrared spectroscopy. Trends Anal Chem 83:25–30CrossRefGoogle Scholar
  32. Szczendzina G et al (2009) DCC-Ringversuche fester Brennstoffe, Probenahme und Analytik. GIT Laborfachzeitschrift 3:163–165Google Scholar
  33. van den Broek WHAM, Wienke D, Melssen DJ, Buydens LMC (1998) Plastic material identification with spectroscopic near infrared imaging and articial neural networks. Anal Chim Acta 361:161–176CrossRefGoogle Scholar
  34. Vianello A, Boldrin A, Guerriero P, Da Ros L (2013) Microplastic particles in sediments of lagoon of Venice, Italy: first observations on occurrence, spatial patterns and identification. Estuar Coast Shelf Sci 130:54–61CrossRefGoogle Scholar
  35. Wang L, Zhang J, Hou S, Sun H (2017) A simple method for quantifying polycarbonate and polyethylene terephthalate microplastics in environmental samples by liquid chromatography–tandem mass spectrometry. Environ Sci Technol Lett 4:530–534CrossRefGoogle Scholar
  36. Workman J Jr, Weyer L (2012) Practical guide and spectral atlas for interpretive near-infrared spectroscopy. CRC Press Taylor & Francis Group, Boca RatonGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Bundesanstalt für Materialforschung und –prüfungBerlinGermany

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