Abstract
The quantification of microplastics (MP) in environmental samples is currently a challenging task. To enable low quantification limits, an analytical method has been developed combining pressurized liquid extraction (PLE) and pyrolysis GC-MS. The automated extraction includes a pre-extraction step via methanol followed by a subsequent PLE using tetrahydrofuran. For the most frequently used synthetic polymers polyethylene (PE), polypropylene (PP), and polystyrene (PS), limits of quantification were achieved down to 0.007 mg/g. Recoveries above 80% were attained for solid matrices such as soil and sediments. The developed method was applied for MP quantification in environmental samples such as sediment, suspended matter, soil, and sewage sludge. In all these matrices, PE and PP were detected with concentrations ranging from 0.03 to 3.3 mg/g. In sewage sludge samples, all three polymers were present with concentration levels ranging between 0.08 ± 0.02 mg/g (PP) and 3.3 ± 0.3 mg/g (PE). However, especially for solid samples, the analysis of triplicates revealed elevated statistical uncertainties due to the inhomogeneous distribution of MP particles. Thus, care has to be taken when milling and homogenizing the samples due to the formation of agglomerates.
Similar content being viewed by others
References
Mani T, Hauk A, Walter U, Burkhardt-Holm P. Microplastics profile along the Rhine River. Sci Rep. 2015;5:17988. https://doi.org/10.1038/srep17988.
Blettler MCM, Ulla MA, Rabuffetti AP, Garello N. Plastic pollution in freshwater ecosystems: macro-, meso-, and microplastic debris in a floodplain lake. Environ Monit Assess. 2017;189(11):581. https://doi.org/10.1007/s10661-017-6305-8.
Chae Y, An Y-J. Current research trends on plastic pollution and ecological impacts on the soil ecosystem: a review. Environ Pollut. 2018;240:387–95. https://doi.org/10.1016/j.envpol.2018.05.008.
Dekiff JH, Remy D, Klasmeier J, Fries E. Occurrence and spatial distribution of microplastics in sediments from Norderney. Environ Pollut. 2014;186. https://doi.org/10.1016/j.envpol.2013.11.019.
Imhof HK, Laforsch C, Wiesheu AC, Schmid J, Anger PM, Niessner R, et al. Pigments and plastic in limnetic ecosystems: a qualitative and quantitative study on microparticles of different size classes. Water Res. 2016;98:64–74. https://doi.org/10.1016/j.watres.2016.03.015.
Peters CA, Hendrickson E, Minor EC, Schreiner K, Halbur J, Bratton SP. Pyr-GC/MS analysis of microplastics extracted from the stomach content of benthivore fish from the Texas Gulf Coast. Mar Pollut Bull. 2018;137:91–5. https://doi.org/10.1016/j.marpolbul.2018.09.049.
Vidyasakar A, Neelavannan K, Krishnakumar S, Prabaharan G, Sathiyabama Alias Priyanka T, Magesh NS, et al. Macrodebris and microplastic distribution in the beaches of Rameswaram Coral Island, Gulf of Mannar, Southeast coast of India: a first report. Mar Pollut Bull. 2018;137:610–6. https://doi.org/10.1016/j.marpolbul.2018.11.007.
Piehl S, Leibner A, Löder MGJ, Dris R, Bogner C, Laforsch C. Identification and quantification of macro- and microplastics on an agricultural farmland. Sci Rep. 2018;8(1):17950. https://doi.org/10.1038/s41598-018-36172-y.
Haave M, Lorenz C, Primpke S, Gerdts G. Different stories told by small and large microplastics in sediment - first report of microplastic concentrations in an urban recipient in Norway. Mar Pollut Bull. 2019;141:501–13. https://doi.org/10.1016/j.marpolbul.2019.02.015.
Mani T, Primpke S, Lorenz C, Gerdts G, Burkhardt-Holm P. Microplastic pollution in benthic midstream sediments of the Rhine River. Environ Sci Technol. 2019. https://doi.org/10.1021/acs.est.9b01363.
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(Part 2):1256–64. https://doi.org/10.1016/j.envpol.2017.08.074.
Renner G, Schmidt TC, Schram J. Analytical methodologies for monitoring micro(nano)plastics: which are fit for purpose? Curr Opin Environ Sci Health. 2018;1:55–61. https://doi.org/10.1016/j.coesh.2017.11.001.
Huppertsberg S, Knepper TP. Instrumental analysis of microplastics—benefits and challenges. Anal Bioanal Chem. 2018. https://doi.org/10.1007/s00216-018-1210-8.
Zarfl C. Promising techniques and open challenges for microplastic identification and quantification in environmental matrices. Anal Bioanal Chem. 2019. https://doi.org/10.1007/s00216-019-01763-9.
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(29):8377–91. https://doi.org/10.1007/s00216-016-9956-3.
Tagg AS, Sapp M, Harrison JP, Ojeda JJ. Identification and quantification of microplastics in wastewater using focal plane array-based reflectance micro-FT-IR imaging. Anal Chem. 2015;87(12):6032–40. https://doi.org/10.1021/acs.analchem.5b00495.
Primpke S, Lorenz C, Rascher-Friesenhausen R, Gerdts G. An automated approach for microplastics analysis using focal plane array (FPA) FTIR microscopy and image analysis. Anal Methods. 2017;9(9):1499–511. https://doi.org/10.1039/C6AY02476A.
Araujo CF, Nolasco MM, Ribeiro AMP, Ribeiro-Claro PJA. Identification of microplastics using Raman spectroscopy: latest developments and future prospects. Water Res. 2018;142:426–40. https://doi.org/10.1016/j.watres.2018.05.060.
Simon M, van Alst N, Vollertsen J. Quantification of microplastic mass and removal rates at wastewater treatment plants applying focal plane array (FPA)-based Fourier transform infrared (FT-IR) imaging. Water Res. 2018;142:1–9. https://doi.org/10.1016/j.watres.2018.05.019.
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. 2018;25(12):11319–32. https://doi.org/10.1007/s11356-018-1692-0.
Unice KM, Kreider ML, Panko JM. Use of a deuterated internal standard with pyrolysis-GC/MS dimeric marker analysis to quantify tire tread particles in the environment. Int J Environ Res Public Health. 2012;9(11):4033–55. https://doi.org/10.3390/ijerph9114033.
Duemichen E, Braun U, Senz R, Fabian G, Sturm H. Assessment of a new method for the analysis of decomposition gases of polymers by a combining thermogravimetric solid-phase extraction and thermal desorption gas chromatography mass spectrometry. J Chromatogr A. 2014;1354:117–28. https://doi.org/10.1016/j.chroma.2014.05.057.
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(9):5052–60. https://doi.org/10.1021/acs.est.6b06362.
Fuller S, Gautam A. A procedure for measuring microplastics using pressurized fluid extraction. Environ Sci Technol. 2016. https://doi.org/10.1021/acs.est.6b00816.
Eisentraut P, Dümichen E, Ruhl AS, Jekel M, Albrecht M, Gehde M, et al. Two birds with one stone—fast and simultaneous analysis of microplastics: microparticles derived from thermoplastics and tire wear. Environ Sci Technol Lett. 2018;5(10):608–13. https://doi.org/10.1021/acs.estlett.8b00446.
David J, Steinmetz Z, Kučerík J, Schaumann GE. Quantitative analysis of poly(ethylene terephthalate) microplastics in soil via thermogravimetry–mass spectrometry. Anal Chem. 2018. https://doi.org/10.1021/acs.analchem.8b00355.
Brand S, Schlüsener MP, Albrecht D, Kunkel U, Strobel C, Grummt T, et al. Quaternary (triphenyl-) phosphonium compounds: environmental behavior and toxicity. Water Res. 2018;136:207–19. https://doi.org/10.1016/j.watres.2018.02.032.
Wick A, Jacobs B, Kunkel U, Heininger P, Ternes TA. Benzotriazole UV stabilizers in sediments, suspended particulate matter and fish of German rivers: new insights into occurrence, time trends and persistency. Environ Pollut. 2016;212:401–12. https://doi.org/10.1016/j.envpol.2016.01.024.
García MT, Gracia I, Duque G, Lucas A, Rodríguez JF. Study of the solubility and stability of polystyrene wastes in a dissolution recycling process. Waste Manag. 2009;29(6):1814–8. https://doi.org/10.1016/j.wasman.2009.01.001.
Scholz-Böttcher BM, Nissenbaum A, Rullkötter J. An 18th century medication “Mumia vera aegyptica” – fake or authentic? Org Geochem. 2013;65:1–18. https://doi.org/10.1016/j.orggeochem.2013.09.011.
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. https://doi.org/10.1016/j.watres.2015.09.002.
Bergmann M, Wirzberger V, Krumpen T, Lorenz C, Primpke S, Tekman MB, et al. High quantities of microplastic in Arctic deep-sea sediments from the HAUSGARTEN observatory. Environ Sci Technol. 2017;51(19):11000–10. https://doi.org/10.1021/acs.est.7b03331.
Acknowledgments
This work was part of the FONA project “Microplastics in Inland Waters - Investigation and Modeling of Entries and whereabouts in the Danube Area as a Basis for Action Planning (MicBin)” funded by the German Federal Ministry of Education and Research (BMBF).
Funding
Funding by the Federal Ministry of Transport and Digital Infrastructure (BMVI) is acknowledged. Tim Lauschke is thankful for financial support by University of Koblenz.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no competing interests.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Dierkes, G., Lauschke, T., Becher, S. et al. Quantification of microplastics in environmental samples via pressurized liquid extraction and pyrolysis-gas chromatography. Anal Bioanal Chem 411, 6959–6968 (2019). https://doi.org/10.1007/s00216-019-02066-9
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-019-02066-9