Abstract
The contamination of aquatic ecosystems with microplastics has recently been reported through many studies, and negative impacts on the aquatic biota have been described. For the chemical identification of microplastics, mainly Fourier transform infrared (FTIR) and Raman spectroscopy are used. But up to now, a critical comparison and validation of both spectroscopic methods with respect to microplastics analysis is missing. To close this knowledge gap, we investigated environmental samples by both Raman and FTIR spectroscopy. Firstly, particles and fibres >500 μm extracted from beach sediment samples were analysed by Raman and FTIR microspectroscopic single measurements. Our results illustrate that both methods are in principle suitable to identify microplastics from the environment. However, in some cases, especially for coloured particles, a combination of both spectroscopic methods is necessary for a complete and reliable characterisation of the chemical composition. Secondly, a marine sample containing particles <400 μm was investigated by Raman imaging and FTIR transmission imaging. The results were compared regarding number, size and type of detectable microplastics as well as spectra quality, measurement time and handling. We show that FTIR imaging leads to significant underestimation (about 35 %) of microplastics compared to Raman imaging, especially in the size range <20 μm. However, the measurement time of Raman imaging is considerably higher compared to FTIR imaging. In summary, we propose a further size division within the smaller microplastics fraction into 500–50 μm (rapid and reliable analysis by FTIR imaging) and into 50–1 μm (detailed and more time-consuming analysis by Raman imaging).
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References
Andrady AL. Microplastics in the marine environment. Mar Pollut Bull. 2011;62:1596–605.
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.
Ivar do Sul JA, Costa MF. The present and future of microplastic pollution in the marine environment. Environ Pollut. 2014;185:352–64.
Dris R, Imhof HK, 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.
Colton JB, Knapp FD, Burns BR. Plastic particles in surface waters of the Northwestern Atlantic. Science. 1974;185:491–7.
Carpenter EJ, Anderson SJ, Harvey GR, Miklas HP, Peck BB. Polystyrene spherules in coastal waters. Science. 1972;178:749–50.
Carpenter EJ, Smith KL. Plastics on the Sargasso sea surface. Science. 1972;175:1240–1.
Frias JPGL, Otero V, Sobral P. Evidence of microplastics in samples of zooplankton from Portuguese coastal waters. Mar Environ Res. 2014;95:89–95.
Isobe A, Uchida K, Tokai T, Iwasaki S. East Asian seas: a hot spot of pelagic microplastics. Mar Pollut Bull. 2015;101:618–23.
Morét-Ferguson S, Law KL, Proskurowski G, Murphy EK, Peacock EE, Reddy CM. The size, mass, and composition of plastic debris in the western North Atlantic Ocean. Mar Pollut Bull. 2010;60:1873–8.
Song YK, Hong SH, Jang M, Kang J-H, Kwon OY, Han GM, et al. Large accumulation of micro-sized synthetic polymer particles in the sea surface microlayer. Environ Sci Technol. 2014;48:9014–21.
Enders K, Lenz R, Stedmon CA, Nielsen TG. Abundance, size and polymer composition of marine microplastics ≥10 μm in the Atlantic Ocean and their modelled vertical distribution. Mar Pollut Bull. 2015;100:70–81.
Lattin GL, Moore CJ, Zellers AF, Moore SL, Weisberg SB. A comparison of neustonic plastic and zooplankton at different depths near the southern California shore. Mar Pollut Bull. 2004;49:291–4.
Doyle MJ, Watson W, Bowlin NM, Sheavly SB. Plastic particles in coastal pelagic ecosystems of the Northeast Pacific ocean. Mar Environ Res. 2011;71:41–52.
Browne MA, Crump P, Niven SJ, Teuten E, Tonkin A, Galloway T, et al. Accumulation of microplastic on shorelines worldwide: sources and sinks. Environ Sci Technol. 2011;45:9175–9.
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.
Dekiff JH, Remy D, Klasmeier J, Fries E. Occurrence and spatial distribution of microplastics in sediments from Norderney. Environ Pollut. 2014;186:248–56.
Van Cauwenberghe L, Vanreusel A, Mees J, Janssen CR. Microplastic pollution in deep-sea sediments. Environ Pollut. 2013;182:495–9.
Obbard RW, Sadri S, Wong YQ, Khitun AA, Baker I, Thompson RC. Global warming releases microplastic legacy frozen in Arctic Sea ice. Earth’s Futur. 2014;2:315–20.
Free CM, Jensen OP, Mason SA, Eriksen M, Williamson NJ, Boldgiv B. High-levels of microplastic pollution in a large, remote, mountain lake. Mar Pollut Bull. 2014;85:156–63.
Eriksen M, Mason S, Wilson S, Box C, Zellers A, Edwards W, et al. Microplastic pollution in the surface waters of the Laurentian Great Lakes. Mar Pollut Bull. 2013;77:177–82.
Zbyszewski M, Corcoran PL. Distribution and degradation of fresh water plastic particles along the beaches of Lake Huron, Canada. Water Air Soil Pollut. 2011;220:365–72.
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.
Lechner A, Keckeis H, Lumesberger-Loisl F, Zens B, Krusch R, Tritthart M, et al. The Danube so colourful: a potpourri of plastic litter outnumbers fish larvae in Europe’s second largest river. Environ Pollut. 2014;188:177–81.
Gasperi J, Dris R, Bonin T, Rocher V, Tassin B. Assessment of floating plastic debris in surface water along the Seine River. Environ Pollut. 2014;195:163–6.
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.
Besseling E, Foekema EM, Van Franeker JA, Leopold MF, Kühn S, Bravo Rebolledo EL, et al. Microplastic in a macro filter feeder: humpback whale Megaptera novaeangliae. Mar Pollut Bull. 2015;95:248–52.
Rummel CD, Löder MGJ, Fricke NF, Lang T, Griebeler EM, Janke M, et al. Plastic ingestion by pelagic and demersal fish from the North Sea and Baltic Sea. Mar Pollut Bull. 2016;102:134–41.
Van Cauwenberghe L, Janssen CR. Microplastics in bivalves cultured for human consumption. Environ Pollut. 2014;193:65–70.
Neves D, Sobral P, Ferreira JL, Pereira T. Ingestion of microplastics by commercial fish off the Portuguese coast. Mar Pollut Bull. 2015;101:119–26.
Devriese LI, van der Meulen MD, Maes T, Bekaert K, Paul-Pont I, Frère L, et al. Microplastic contamination in brown shrimp (Crangon crangon, Linnaeus 1758) from coastal waters of the Southern North Sea and Channel area. Mar Pollut Bull. 2015;98:179–87.
De Witte B, Devriese L, Bekaert K, Hoffman S, Vandermeersch G, Cooreman K, et al. Quality assessment of the blue mussel (Mytilus edulis): comparison between commercial and wild types. Mar Pollut Bull. 2014;85:146–55.
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.
Yang D, Shi H, Li L, Li J, Jabeen K, Kolandhasamy P. Microplastic pollution in table salts from China. Environ Sci Technol. 2015;49:13622–7.
Galgani F, Hanke G, Werner S, Oosterbaan L, Nilsson P, Fleet D, et al. Guidance on monitoring of marine litter in European seas. JRC Scientific and Policy Reports. 2013;1–128.
Wagner M, Scherer C, Alvarez-Muñoz D, Brennholt N, Bourrain X, Buchinger S, et al. Microplastics in freshwater ecosystems: what we know and what we need to know. Environ Sci Eur. 2014;26:12.
Van Cauwenberghe L, Devriese L, Galgani F, Robbens J, Janssen CR. Microplastics in sediments: a review of techniques, occurrence and effects. Mar Environ Res. 2015;111:5–17.
Liebezeit G, Dubaish F. Microplastics in beaches of the East Frisian islands Spiekeroog and Kachelotplate. Bull Environ Contam Toxicol. 2012;89:213–7.
Lenz R, Enders K, Stedmon CA, Mackenzie DMA, Nielsen TG. A critical assessment of visual identification of marine microplastic using Raman spectroscopy for analysis improvement. Mar Pollut Bull. 2015;100:82–91.
Song YK, Hong SH, Jang M, Han GM, Rani M, Lee J, et al. A comparison of microscopic and spectroscopic identification methods for analysis of microplastics in environmental samples. Mar Pollut Bull. 2015;93:202–9.
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 Process Impacts. 2013;15:1949–56.
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.
Hintersteiner I, Himmelsbach M, Buchberger WW. Characterization and quantitation of polyolefin microplastics in personal-care products using high-temperature gel-permeation chromatography. Anal Bioanal Chem. 2015;407:1253–9.
Everall NJ, Chalmer JM, Griffiths PR. Vibrational spectroscopy of polymers: principles and practice. Weinheim: Wiley-VCH; 2007.
Koenig JL. Spectroscopy of polymers, ACS Professional Reference Book. Washington, DC: American Chemical Society; 1992.
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.
Löder MGJ, Kuczera M, Mintenig S, Lorenz C, Gerdts G. FPA-based micro-FTIR imaging for the analysis of microplastics in environmental samples. Environ Chem. 2015;12:563–581.
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;87:6032–40.
Käppler A, Windrich F, Löder MGJ, Malanin M, Fischer D, Labrenz M, et al. Identification of microplastics by FTIR and Raman microscopy: a novel silicon filter substrate opens the important spectral range below 1300 cm−1 for FTIR transmission measurements. Anal Bioanal Chem. 2015;407:6791–801.
Fischer D, Käppler A, Eichhorn K-J. Identification of microplastics in the marine environment by Raman microspectroscopy and imaging. Am Lab. 2015;47:32–4.
Horiba Jobin Yvon, Palaiseau. Raman ParticleFinder—automated particle location and Raman analysis with LabSpec 6. 2012. http://www.horiba.com/fileadmin/uploads/Scientific/Documents/Raman/SO-TN05_-_ParticleFinder_with_LabSpec6.pdf. Accessed 4 Jul 2016.
rap.ID particle systems GmbH, Berlin. Single particle explorer. http://www.rap-id.com/media/files/SPE_raman_LIBS_ENG_web.pdf. Accessed 4 Jul 2016.
Robertson I. Detection and identification of microplastic particles in cosmetic formulations using IR microscopy. PerkinElmer, Waltham. 2015. http://www.perkinelmer.de/lab-solutions/resources/docs/APP_Detection-Identification-Microplastic-Particles-Cosmetics-012079_01.pdf. Accessed 5 Jul 2016.
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. Limnol Oceanogr Methods. 2012;10:524–37.
Mark JE. Polymer data handbook. Oxford: Oxford University Press; 1999.
Balachandran U, Eror NG. Raman spectra of titanium dioxide. J Solid State Chem. 1982;42:276–82.
Gall MJ, Hendra PJ, Peacock CJ, Cudby MEA, Willis HA. The laser-Raman spectrum of polyethylene. The assignment of the spectrum to fundamental modes of vibration. Spectrochim Acta. 1972;28:1485–96.
Schulte F, Brzezinka K-W, Lutzenberger K, Stege H, Panne U. Raman spectroscopy of synthetic organic pigments used in 20th century works of art. J Raman Spectrosc. 2008;39:1455–63.
Stromberg RR, Straus S, Achhammer BG. Infrared spectra of thermally degraded poly(vinyl-chloride). J Res Natl Bur Stand. 1958;60:147–52.
Siesler HW, Salzer R. Infrared and Raman spectroscopic imaging. Wiley: Weinheim; 2009.
Acknowledgments
The authors would like to thank Leonie Buschbeck (University Rostock) and Rica Wegner (Leibniz-Institut für Ostseeforschung Warnemünde (IOW)) for their support during sampling, sample extraction and purification. Special thanks to Falk Pollehne (IOW) for providing sediment trap samples. We also thank Julia Muche (Leibniz-Institut für Polymerforschung Dresden (IPF)) for technical assistance during Raman measurements and Dr. Cordelia Zimmerer (IPF) for helpful discussion regarding FTIR imaging. We are grateful to the Leibniz Association for financial support of the SAW project ‘MikrOMIK’ (SAW-2014-IOW-2).
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Käppler, A., Fischer, D., Oberbeckmann, S. et al. Analysis of environmental microplastics by vibrational microspectroscopy: FTIR, Raman or both?. Anal Bioanal Chem 408, 8377–8391 (2016). https://doi.org/10.1007/s00216-016-9956-3
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DOI: https://doi.org/10.1007/s00216-016-9956-3