Application of confocal laser Raman spectroscopy on marine sediment microplastics -- Journal of Oceanology and Limnology,2020,38(5):1502-1516

	Cite this paper:
	LIU Jing, ZHANG Xin, DU Zengfeng, LUAN Zhendong, LI Lianfu, XI Shichuan, WANG Bing, CAO Lei, YAN Jun. Application of confocal laser Raman spectroscopy on marine sediment microplastics[J]. Journal of Oceanology and Limnology, 2020, 38(5): 1502-1516

Application of confocal laser Raman spectroscopy on marine sediment microplastics

LIU Jing^1,3,4, ZHANG Xin^1,2,3,4, DU Zengfeng^1,4, LUAN Zhendong^1,4, LI Lianfu^1,3,4, XI Shichuan^1,3,4, WANG Bing^1,4, CAO Lei^1,4, YAN Jun^1,4

1 Key Laboratory of Marine Geology and Environment&Center of Deep Sea Research, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China;
2 Laboratory for Marine Geology, Pilot National Laboratory for Marine Science and Technology(Qingdao), Qingdao 266237, China;
3 University of Chinese Academy of Sciences, Beijing 100049, China;
4 Center for Ocean Mega-Science, Chinese Academy of Sciences, Qingdao 266071, China

Abstract:

Marine sediment is the primary sink of microplastics and is an indicator of pollution levels. However, although there are well-developed detection methods, detection is rarely focused on lowmicrometer-sized particles, mainly due to technique limitations. In this study, a simplified process omitting digestion procedures was developed to pretreat microplastics obtained from marine sediment and was coupled with micro-Raman spectroscopy to identify microplastics. Based on the overall analysis of the characteristic peak assignments, a Raman spectral reference library was constructed for 18 types of plastic. In addition, the effects of the measurement parameters were systematically described. Field research was then conducted to validate the developed process and investigate microplastic contamination in Huiquan Bay, Qingdao, China. This simplified process could retain the original appearance of microparticles and accomplish the detection of <500 μm-sized microplastics in environmental samples. Microplastics in the size range of 10-150 μm accounted for 76% of all microplastics, and 56% of the total particles was particles smaller than 50 μm. Polypropylene (42%) and polyethylene (20%) were predominant components of the particles. In particular, polypropylene particles smaller than 10 μm were identified in marine sediment. This work demonstrates that Raman spectroscopy is not only an effective tool for detecting environmental particles but also highly applicable for identifying particles extracted from marine sediment.

Key words: microplastics|confocal|Raman spectroscopy|marine sediment

Received: 2020-03-17 Revised: 2020-05-07

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References:
Andrady A L. 2011. Microplastics in the marine environment.Marine Pollution Bulletin, 62(8):1 596-1 605, https://doi.org/10.1016/j.marpolbul.2011.05.030.
Andrady A L. 2017. The plastic in microplastics:a review.Marine Pollution Bulletin, 119(1):12-22, https://doi.org/10.1016/j.marpolbul.2017.01.082.
Andreassen E. 1999. Infrared and Raman spectroscopy of polypropylene. In:Karger-Kocsis J ed. Polypropylene.Springer, Dordrecht, https://doi.org/10.1007/978-94-011-4421-6_46.
Anger P M, von der Esch E, Baumann T, Elsner M, Niessner R, Ivleva N P. 2018. Raman microspectroscopy as a tool for microplastic particle analysis. TrAC Trends in Analytical Chemistry, 109:214-226, https://doi.org/10.1016/j.trac.2018.10.010.
Araujo C F, Nolasco M M, Ribeiro A M P, Ribeiro-Claro P J A. 2018. Identification of microplastics using Raman spectroscopy:latest developments and future prospects.Water Research, 142:426-440, https://doi.org/10.1016/j.watres.2018.05.060.
Browne M A, Galloway T, Thompson R. 2007. Microplastican emerging contaminant of potential concern? Integrated Environmental Assessment and Management, 3(4):559-561, https://doi.org/10.1002/ieam.5630030412.
Carbery M, O'Connor W, Palanisami T. 2018. Trophic transfer of microplastics and mixed contaminants in the marine food web and implications for human health. Environment International, 115:400-409, https://doi.org/10.1016/j.envint.2018.03.007.
Carpenter E J, Smith Jr K L. 1972. Plastics on the Sargasso Sea surface. Science, 175(4027):1 240-1 241, https://doi.org/10.1126/science.175.4027.1240.
Chiba S, Saito H, Fletcher R, Yogi T, Kayo M, Miyagi S, Ogido M, Fujikura K. 2018. Human footprint in the abyss:30 year records of deep-sea plastic debris. Marine Policy, 96:204-212.
Choy C A, Robison B H, Gagne T O, Erwin B, Firl E, Halden R U, Hamilton J A, Katija K, Lisin S E, Rolsky C, Van Houtan K S. 2019. The vertical distribution and biological transport of marine microplastics across the epipelagic and mesopelagic water column. Scientific Reports, 9(1):7843, https://doi.org/10.1038/s41598-019-44117-2.
Claessens M, Van Cauwenberghe L, Vandegehuchte M B, Janssen C R. 2013. New techniques for the detection of microplastics in sediments and field collected organisms.Marine Pollution Bulletin, 70(1-2):227-233, https://doi.org/10.1016/j.marpolbul.2013.03.009.
Cole M, Lindeque P, Halsband C, Galloway T S. 2011.Microplastics as contaminants in the marine environment:a review. Marine Pollution Bulletin, 62(12):2 588-2 597, https://doi.org/10.1016/j.marpolbul.2011.09.025.
Cole M, Webb H, Lindeque P K, Fileman E S, Halsband C, Galloway T S. 2014. Isolation of microplastics in biotarich seawater samples and marine organisms. Scientific Reports, 4:4 528, https://doi.org/10.1038/srep04528.
Colthup N B, Daly L H, Wiberley S E. 1990. Aromatic and heteroaromatic rings. In:Colthup N B, Daly L H, Wiberley S E eds. Introduction to Infrared and Raman Spectroscopy. 3rd edn. Academic Press, London.
Cózar A, Echevarría F, González-Gordillo J I, Irigoien X, Úbeda B, Hernández-León S, Palma A T, Navarro S, García-de-Lomas J, Ruiz A, Fernández-de-Puelles M L, Duarte C M. 2014. Plastic debris in the open ocean.
Proceedings of the National Academy of Sciences of the United States of America, 111(28):10 239-10 244, https://doi.org/10.1073/pnas.1314705111.
Elert A M, 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? Environmental Pollution, 231:1 256-1 264, https://doi.org/10.1016/j.envpol.2017.08.074.
Engler R E. 2012. The complex interaction between marine debris and toxic chemicals in the ocean. Environmental Science & Technology, 46(22):12 302-12 315, https://doi.org/10.1021/es3027105.
Eo S, Hong S H, Song Y K, Lee J, Lee J, Shim W J. 2018.Abundance, composition, and distribution of microplastics larger than 20 μm in sand beaches of South Korea.Environmental Pollution, 238:894-902, https://doi.org/10.1016/j.envpol.2018.03.096.
Erni-Cassola G, Gibson M I, Thompson R C, Christie-Oleza J A. 2017. Lost, but found with Nile red:a novel method for detecting and quantifying small microplastics (1 mm to 20 μm) in environmental samples. Environmental Science & Technology, 51(23):13 641-13 648, https://doi.org/10.1021/acs.est.7b04512.
Fischer E R, Hansen B T, Nair V, Hoyt F H, Dorward D W. 2012. Scanning electron microscopy. Current Protocols in Microbiology, 25(1):2B.2.1-2B.2.47, https://doi.org/10.1002/9780471729259.mc02b02s25.
Foekema E M, De Gruijter C, Mergia M T, van Franeker J A, Murk A J, Koelmans A A. 2013. Plastic in North Sea fish.Environmental Science & Technology, 47(15):8 818-8 824, https://doi.org/10.1021/es400931b.
Fortin S, Song B, Burbage C. 2019. Quantifying and identifying microplastics in the effluent of advanced wastewater treatment systems using Raman microspectroscopy.Marine Pollution Bulletin, 149:110579, https://doi.org/10.1016/j.marpolbul.2019.110579.
Frias J P G L, Otero V, Sobral P. 2014. Evidence of microplastics in samples of zooplankton from Portuguese coastal waters. Marine Environmental Research, 95:89-95, https://doi.org/10.1016/j.marenvres.2014.01.001.
Gerrard D L, Maddam W F. 1986. Polymer characterization by Raman spectroscopy. Applied Spectroscopy Reviews, 22(2-3):251-334, https://doi.org/10.1080/05704928608070179.
Hanvey J S, Lewis P J, Lavers J L, Crosbie N D, Pozo K, Clarke B O. 2017. A review of analytical techniques for quantifying microplastics in sediments. Analytical Methods, 9(9):1 369-1 383, https://doi.org/10.1039/c6ay02707e.
Harrison J P, Schratzberger M, Sapp M, Osborn A M. 2014.Rapid bacterial colonization of low-density polyethylene microplastics in coastal sediment microcosms. BMC Microbiology, 14:232, https://doi.org/10.1186/s12866-014-0232-4.
Hidalgo-Ruz V, Gutow L, Thompson R C, Thiel M. 2012.Microplastics in the marine environment:a review of the methods used for identification and quantification.Environmental Science & Technology, 46(6):3 060-3 075, https://doi.org/10.1021/es2031505.
Imhof H K, Laforsch C, Wiesheu A C, Schmid J, Anger P M, Niessner R, Ivleva N P. 2016. Pigments and plastic in limnetic ecosystems:a qualitative and quantitative study on microparticles of different size classes. Water Research, 98:64-74, https://doi.org/10.1016/j.watres.2016.03.015.
Ivar do Sul J A, Costa M F. 2014. The present and future of microplastic pollution in the marine environment.Environmental Pollution, 185:352-364, https://doi.org/10.1016/j.envpol.2013.10.036.
Jahan S, Strezov V, Weldekidan H, Kumar R, Kan T, Sarkodie S A, He J, Dastjerdi B, Wilson S P. 2019. Interrelationship of microplastic pollution in sediments and oysters in a seaport environment of the eastern coast of Australia.Science of the Total Environment, 695:133924, https://doi.org/10.1016/j.scitotenv.2019.133924.
Kach D J, Ward J E. 2008. The role of marine aggregates in the ingestion of picoplankton-size particles by suspensionfeeding molluscs. Marine Biology, 153(5):797-805, https://doi.org/10.1007/s00227-007-0852-4.
Kanhai L D K, Johansson C, Frias J P G L, Gardfeldt K, Thompson R C, O'Connor I. 2019. Deep sea sediments of the Arctic Central Basin:a potential sink for microplastics.Deep Sea Research Part I:Oceanographic Research Papers, 145:137-142, https://doi.org/10.1016/j.dsr.2019.03.003.
Käppler 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? Analytical and Bioanalytical Chemistry, 408(29):8 377-8 391, https://doi.org/10.1007/s00216-016-9956-3.
Koelmans A A, Mohamed Nor N H, Hermsen E, Kooi M, Mintenig S M, De France J. 2019. Microplastics in freshwaters and drinking water:critical review and assessment of data quality. Water Research, 155:410-422, https://doi.org/10.1016/j.watres.2019.02.054.
Koenig J L. 1971. Raman scattering of synthetic polymers-a review. Applied Spectroscopy Reviews, 4(2):233-305, https://doi.org/10.1080/05704927108082605.
Lenz R, Enders K, Stedmon C A, Mackenzie D M A, Nielsen T G. 2015. A critical assessment of visual identification of marine microplastic using Raman spectroscopy for analysis improvement. Marine Pollution Bulletin, 100(1):82-91, https://doi.org/10.1016/j.marpolbul.2015.09.026.
Lewis P A. 2003. Organic colorants. In:Charvat R A ed.Coloring of Plastics:Fundamentals. John Wiley & Sons, Hoboken.
Li Q L, Wu J T, Zhao X P, Gu X Y, Ji R. 2019. Separation and identification of microplastics from soil and sewage sludge. Environmental Pollution, 254:113076, https://doi.org/10.1016/j.envpol.2019.113076.
Liebezeit G, Dubaish F. 2012. Microplastics in beaches of the East Frisian Islands Spiekeroog and Kachelotplate.Bulletin of Environmental Contamination and Toxicology, 89(1):213-217, https://doi.org/10.1007/s00128-012-0642-7.
Löder M G J, Kuczera M, Mintenig S, Lorenz C, Gerdts G. 2015. Focal plane array detector-based micro-Fouriertransform infrared imaging for the analysis of microplastics in environmental samples. Environmental Chemistry, 12(5):563-581, https://doi.org/10.1071/en14205.
Luo Y D, Lin Q H, Jia F L, Xu G D, Li F M. 2019. Distribution characteristics of microplastics in Qingdao coastal beaches. Environmental Science, 40(6):2 631-2 638, https://doi.org/10.13227/j.hjkx.201810074. (in Chinese with English abstract)
Nuelle M T, Dekiff J H, Remy D, Fries E. 2014. A new analytical approach for monitoring microplastics in marine sediments. Environmental Pollution, 184:161-169, https://doi.org/10.1016/j.envpol.2013.07.027.
Qiu Q X, Tan Z, Wang J D, Peng J P, Li M M, Zhan Z W. 2016.Extraction, enumeration and identification methods for monitoring microplastics in the environment. Estuarine, Coastal and Shelf Science, 176:102-109, https://doi.org/10.1016/j.ecss.2016.04.012.
Schymanski D, Goldbeck C, Humpf H U, Fürst P. 2018.Analysis of microplastics in water by micro-Raman spectroscopy:release of plastic particles from different packaging into mineral water. Water Research, 129:154-162, https://doi.org/10.1016/j.watres.2017.11.011.
Sobhani Z, Zhang X, Gibson C, Naidu R, Mallavarapu M, Fang C. 2020. Identification and visualisation of microplastics/nanoplastics by Raman imaging (i):down to 100 nm. Water Research, 174:115658, https://doi.org/10.1016/j.watres.2020.115658.
Song Y K, Hong S H, Jang M, Han G M, Rani M, Lee J, Shim W J. 2015. A comparison of microscopic and spectroscopic identification methods for analysis of microplastics in environmental samples. Marine Pollution Bulletin, 93(1-2):202-209, https://doi.org/10.1016/j.marpolbul.2015.01.015.
Sui Q, Zhang L J, Xia B, Chen B J, Sun X M, Zhu L, Wang R Y, Qu K M. 2020. Spatiotemporal distribution, source identification and inventory of microplastics in surface sediments from Sanggou Bay, China. Science of the Total Environment, 723:138064, https://doi.org/10.1016/j.scitotenv.2020.138064.
Sun C J, Jiang F H, Li J X, Zheng L. 2016. The research progress in source, distribution, ecological and environmental effects of marine microplastics. Advances in Marine Science, 34(4):449-461, https://doi.org/10.3969/j.issn.1671-6647.2016.04.001. (in Chinese with English abstract)
Sun X X, Liang J H, Zhu M L, Zhao Y F, Zhang B. 2018.Microplastics in seawater and zooplankton from the Yellow Sea. Environmental Pollution, 242:585-595, https://doi.org/10.1016/j.envpol.2018.07.014.
Tagg A S, Sapp M, Harrison J P, Ojeda J J. 2015. Identification and quantification of microplastics in wastewater using focal plane array-based reflectance micro-FT-IR imaging.Analytical Chemistry, 87(12):6 032-6 040, https://doi.org/10.1021/acs.analchem.5b00495.
Tang G W, Liu M Y, Zhou Q, He H X, Chen K, Zhang H B, Hu J H, Huang Q H, Luo Y M, Ke H W, Chen B, Xu X R, Cai M G. 2018. Microplastics and polycyclic aromatic hydrocarbons (PAHs) in Xiamen coastal areas:implications for anthropogenic impacts. Science of the Total Environment, 634:811-820, https://doi.org/10.1016/j.scitotenv.2018.03.336.
Tata T, Belabed B E, Bououdina M, Bellucci S. 2020.Occurrence and characterization of surface sediment microplastics and litter from North African coasts of Mediterranean Sea:preliminary research and first evidence. Science of the Total Environment, 713:136664, https://doi.org/10.1016/j.scitotenv.2020.136664.
Thompson R C, Olsen Y, Mitchell R P, Davis A, Rowland S J, John A W G, McGonigle D, Russell A E. 2004. Lost at sea:where is all the plastic? Science, 304(5672):838, https://doi.org/10.1126/science.1094559.
Uddin S, Fowler S W, Saeed T. 2020. Microplastic particles in the Persian/Arabian Gulf-a review on sampling and identification. Marine Pollution Bulletin, 154:111100, https://doi.org/10.1016/j.marpolbul.2020.111100.
Van Cauwenberghe L, Devriese L, Galgani F, Robbens J, Janssen C R. 2015. Microplastics in sediments:a review of techniques, occurrence and effects. Marine Environmental Research, 111:5-17, https://doi.org/10.1016/j.marenvres.2015.06.007.
Van Cauwenberghe L, Vanreusel A, Mees J, Janssen C R. 2013. Microplastic pollution in deep-sea sediments.Environmental Pollution, 182:495-499, https://doi.org/10.1016/j.envpol.2013.08.013.
Vandermeersch G, Van Cauwenberghe L, Janssen C R, Marques A, Granby K, Fait G, Kotterman M J, Diogène J, Bekaert K, Robbens J, Devriese L. 2015. A critical view on microplastic quantification in aquatic organisms. Environmental Research, 143:46-55, https://doi.org/10.1016/j.envres.2015.07.016.
Vianello A, Boldrin A, Guerriero P, Moschino V, Rella R, Sturaro A, Da Ros L. 2013. Microplastic particles in sediments of Lagoon of Venice, Italy:first observations on occurrence, spatial patterns and identification.Estuarine, Coastal and Shelf Science, 130:54-61, https://doi.org/10.1016/j.ecss.2013.03.022.
Waller C L, Griffiths H J, Waluda C M, Thorpe S E, Loaiza I, Moreno B, Pacherres C O, Hughes K A. 2017.Microplastics in the Antarctic marine system:an emerging area of research. Science of the Total Environment, 598:220-227, https://doi.org/10.1016/j.scitotenv.2017.03.283.
Wang J D, Tan Z, Peng J P, Qiu Q X, Li M M. 2016. The behaviors of microplastics in the marine environment.Marine Environmental Research, 113:7-17, https://doi.org/10.1016/j.marenvres.2015.10.014.
Wang Q, Shan E C, Zhang B, Teng J, Wu D, Yang X, Zhang C, Zhang W J, Sun X Y, Zhao J M. 2020. Microplastic pollution in intertidal sediments along the coastline of China. Environmental Pollution, 263:114428, https://doi.org/10.1016/j.envpol.2020.114428.
Wright S L, Thompson R C, Galloway T S. 2013. The physical impacts of microplastics on marine organisms:a review.Environmental Pollution, 178:483-492, https://doi.org/10.1016/j.envpol.2013.02.031.
Xi S C, Zhang X, Luan Z D, Du Z F, Li L F, Liang Z W, Lian C, Yan J. 2019. Micro-Raman study of thermal transformations of sulfide and oxysalt minerals based on the heat induced by laser. Minerals, 9(12):751, https://doi.org/10.3390/min9120751.
Xu J L, Thomas K V, Luo Z S, Gowen A A. 2019. FTIR and Raman imaging for microplastics analysis:state of the art, challenges and prospects. TrAC Trends in Analytical Chemistry, 119:115629, https://doi.org/10.1016/j.trac.2019.115629.
Yao P, Zhou B, Lu Y H, Yin Y, Zong Y Q, Chen M T, O'Donnell Z. 2019. A review of microplastics in sediments:spatial and temporal occurrences, biological effects, and analytic methods. Quaternary International, 519:274-281, https://doi.org/10.1016/j.quaint.2019.03.028.
You S X, Tu H H, Zhao Y B, Liu Y, Chaney E J, Marjanovic M, Boppart S A. 2016. Raman spectroscopic analysis reveals abnormal fatty acid composition in tumor micro-and macroenvironments in human breast and rat mammary cancer. Scientific Reports, 6:32922, https://doi.org/10.1038/srep32922.
Zhang K, Su J, Xiong X, Wu X, Wu C X, Liu J T. 2016.Microplastic pollution of lakeshore sediments from remote lakes in Tibet plateau, China. Environmental Pollution, 219:450-455, https://doi.org/10.1016/j.envpol.2016.05.048.
Zhao S Y, Zhu L X, Li D J. 2015. Characterization of small plastic debris on tourism beaches around the South China Sea. Regional Studies in Marine Science, 1:55-62, https://doi.org/10.1016/j.rsma.2015.04.001.