Raman Imaging and Spectrometers
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By Alina Maltseva, Market Application Scientist, HORIBA France
Microplastics are tiny particles of synthetic polymers, insoluble in water, ranging in size between 1 µm and 5 mm. They have been found in the environment, as well as in drinking water and food, and are therefore recognized as emerging particulate anthropogenic pollutants. They are persistent in nature and raise public concern due to their potentially harmful effects on the health of living organisms and the environment. These harmful effects may be caused not only by the physical presence and/or accumulation of foreign particles in the organism but also by their role in transporting other chemical substances adsorbed on the surface of microplastics or containing toxic substances. In this context, smaller particles pose a greater risk due to their increased probability of penetrating biological organisms and their larger specific surface area, which enhances their capacity for toxic chemicals adsorption.
Current efforts by the scientific community and standardization bodies are focused on risk assessment and the collection of knowledge on real exposure to microplastics, as well as the evaluation of their effects on living organisms. Robust methods and comprehensive monitoring of microplastic concentrations in the environment and food are key to achieving a global understanding of the problem.
Raman micro-spectroscopy is recognized as a reference method for microplastics analysis, providing chemical identification, size measurements, and particle counting.Raman micro-spectroscopy covers all particle size ranges and remains the only technique providing reliable information about the smallest particles, down to 1 micron.
In this edition of the Raman XPerience, we suggest that you take a glance at three recent publications and gain practical insights into the application of Raman spectroscopy for microplastics analysis in various matrices. This includes information on sample preparation and quality control, which are crucial points for microplastics analysis.
L. Maurizi, L. Simon-Sanchez, A. Vianello, A.H. Nielsen, J. Vollertsen [1]
Inhalation is the most evident source of exposure to microplastics. The smallest, low-weight particles that tend to float in the air have a higher probability of being inhaled. In this very recent publication (June 2024), Raman micro-spectroscopy was employed to assess the concentration of indoor airborne microplastics >1 μm in indoor environments under different levels of human activity.
Sampling was conducted by actively pumping air through a Si membrane, which was then analyzed using Raman spectroscopy. A XploRA Nano confocal Raman microscope and ParticleFinder™ software were used for automated particle analysis. This publication provides detailed infomation about the instrumental settings and explains the functionality of ParticleFinder™, which allowed for the automatic characterization of thousands of particles on the filter.
The results revealed a concentration of microplastics between 58 and 684 MPs per cubic meter, depending not only on the type and level of human activity but also on the surface area and air circulation of the investigated locations. The authors estimated a human microplastics (MPs) intake from indoor air of 3,415 ± 2,881 MPs per day. A total of 15 polymers were identified, with polyamide (PA) clearly dominating the polymer composition.
It should be noted that this work presents a good example of quality control that must be applied while performing microplastics analysis. The authors presented the limit of quantification (LOQ) for each type of polymer based on multiple procedural blanks analyses. This approach is crucial to distinguish between microplastics contamination due to sample preparation (consumables, clothing, etc.) and microplastics collected from the sample itself.
O. Hagelskjær, F. Hagelskjær, H. Margenat, N. Yakovenko, J.E. Sonke, G. Le Roux [2]
In this publication, the authors studied the presence of microplastic particles down to 1 micron in bottled and tap water. First, 4.5 L of the tested sample was subjected to chemical digestion with H2O2 and HCl to reduce the quantity of organic matter and mineral deposits and then filtered on a filter suitable for Raman analysis.
LabRAM Soleil Raman microscope and ParticleFinder™ software were used for automatic particle detection and analysis. The ViewSharp™ option, which permits precise optical focus for each particle, was applied, guaranteeing high precision in Raman analysis.
Even though the authors mention some perspectives for improving sample preparation and quality control procedures, they demonstrated that Raman µspectroscopy is a reliable tool for detecting the smallest particles.
According to the findings, the majority of particles identified as microplastics were in the range of 1-20 μm. Thus, authors suggest an amendment to the guidance published in the EU directive 2020/2184 regarding water intended for human consumption. More precisely, the authors recommend including the fraction of particles below 20 microns in systematic monitoring and explain that the minimum sampling volume should be reduced from 1 m3 to several litres. This suggestion is in accordance with both realistic human daily/weekly consumption and the sensitivity of the methodology for particle detection and analysis.
P. A. Da Costa Filho, D. Andrey, B. Eriksen, R. P. Peixoto, B. M. Carreres, M. E. Ambühl, J. B. Descarrega, S. Dubascoux, P. Zbinden, A.Panchaud, E. Poitevin [3]
To understand potential exposure to microplastic pollution via ingestion, monitoring drinking water alone is not enough. Measuring the concentration of microplastics in different food products, especially those subjected to industrial production, is essential.
In this article published in 2021, the authors used Raman microscopy to study the presence of microplastic particles in milk-based products. Enzymatic and chemical digestion were used to dissolve the organic matrix and have been validated for 5 types of polymers. The liquid phase was then filtered through a Si filter and analyzed with a confocal micro-Raman LabRAM HR Evolution (now proposed as LabRAM Odyssey.) Instead of a particle-by-particle approach, Raman imaging was used to scan the surface of the filter and identify polymeric particles. This approach overcomes the difficulties related to the agglomeration of particles of different natures and thus offers high precision in terms of particle counting in complex matrices.
[1] Maurizi, L., Simon-Sánchez, L., Vianello, A., Nielsen, A. H., & Vollertsen, J. (2024). Every breath you take: high concentration of breathable microplastics in indoor environments. Chemosphere, 142553.
[2] Hagelskjær, O., Hagelskjær, F., Margenat, H., Yakovenko, N., Sonke, J., & Le Roux, G. (2024). Majority of potable water microplastics are smaller than the 20 µm EU methodology limit for consumable water quality.
[3] Da Costa Filho, P. A., Andrey, D., Eriksen, B., Peixoto, R. P., Carreres, B. M., Ambühl, M. E., ... & Poitevin, E. (2021). Detection and characterization of small-sized microplastics (≥ 5 µm) in milk products. Scientific reports, 11(1), 24046.
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