Optimization, performance, and application of a pyrolysis-GC/MS method for the identification of microplastics

Plastics are found to be major debris composing marine litter; microplastics (MP, < 5 mm) are found in all marine compartments. The amount of MPs tends to increase with decreasing size leading to a potential misidentification when only visual identification is performed. These last years, pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS) has been used to get information on the composition of polymers with some applications on MP identification. The purpose of this work was to optimize and then validate a Py-GC/MS method, determine limit of detection (LOD) for eight common polymers, and apply this method on environmental MP. Optimization on multiple GC parameters was carried out using polyethylene (PE) and polystyrene (PS) microspheres. The optimized Py-GC/MS method require a pyrolysis temperature of 700 °C, a split ratio of 5 and 300 °C as injector temperature. Performance assessment was accomplished by performing repeatability and intermediate precision tests and calculating limit of detection (LOD) for common polymers. LODs were all below 1 μg. For performance assessment, identification remains accurate despite a decrease in signal over time. A comparison between identifications performed with Raman micro spectroscopy and with Py-GC/MS was assessed. Finally, the optimized method was applied to environmental samples, including plastics isolated from sea water surface, beach sediments, and organisms collected in the marine environment. The present method is complementary to μ-Raman spectroscopy as Py-GC/MS identified pigment containing particles as plastic. Moreover, some fibers and all particles from sediment and sea surface were identified as plastic.

Ludovic Hermabessiere, Charlotte Himber, Béatrice Boricaud, Maria Kazour, Rachid Amara, Anne-Laure Cassone, Michel Laurentie, Ika Paul-Pont, Philippe Soudant, Alexandre Dehaut, Guillaume Duflos, Analytical and Bioanalytical Chemistry, , Volume 410, Issue 25, pp 6663–6676

The article

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Single contaminant and combined exposures of polyethylene microplastics and fluoranthene: accumulation and oxidative stress response in the blue mussel, Mytilus edulis

The microplastic “vector effect” has received increasing attention. The aim of this study was to investigate the influence of polyethylene microplastic beads (PE MP) on accumulation and associated oxidative stress responses attributed to fluoranthene (Flu) in blue mussels, Mytilus edulis. Blue mussels were exposed for 96 h to four treatment groups: Flu-only, MP-only, Flu and MP coexposure, and Flu-incubated MP. Treatments were conducted at a low and high concentration (50 μg/L and 100  Flu μg/L and 100, and 1000 MP/mL). Results demonstrated that in both the gill and digestive gland, coexposure did not markedly affect Flu uptake, but this treatment significantly decreased tissue Flu concentrations. Antioxidant responses including activities of superoxide dismutase (SOD), catalase (CAT), glutathione peroxidases (GPx), and levels of total glutathione (GSH) in both gills and digestive glands were significantly altered suggesting a perturbation of redox state induced by the exposure conditions. Although individual biomarkers varied, the biomarker profile enabled certain generalizations to be made. Antioxidant responses occurred more likely in gill tissue than in digestive gland. Individual contaminant exposures to Flu or MP led to varying responses, but coexposures and incubated exposures did not result in additive or synergistic effects. Exposure concentrations (i.e., low or high treatments) were not a consistent a predictor of response; and the internal Flu dose did not consistently predict outcome of various biomarkers. Importantly, MP-only exposure appeared to be capable of eliciting direct effects on the oxidative stress system as demonstrated by the activities of CAT and GPx. These findings warrant further investigation.

Gabriele Magara, Antonia Concetta Elia, Kristian Syberg & Farhan R. Khan, Journal of Toxicology and Environmental Health, Part A, Volume 81 (16), Pages 761-773, 2018

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Distribution of Microplastics and Nanoplastics in Aquatic Ecosystems and Their Impacts on Aquatic Organisms, with Emphasis on Microalgae

Plastics, with their many useful physical and chemical properties, are widely used in various industries and activities of daily living. Yet, the insidious effects of plastics, particularly long-term effects on aquatic organisms, are not properly understood. Plastics have been shown to degrade to micro- and nanosize particles known as microplastics and nanoplastics, respectively. These minute particles have been shown to cause various adverse effects on aquatic organisms, ranging from growth inhibition, developmental delay and altered feeding behaviour in aquatic animals to decrease of photosynthetic efficiency and induction of oxidative stress in microalgae. This review paper covers the distribution of microplastics and nanoplastics in aquatic ecosystems, focusing on their effects on microalgae as well as co-toxicity of microplastics and nanoplastics with other pollutants. Besides that, this review paper also discusses future research directions which could be taken to gain a better understanding of the impacts of microplastics and nanoplastics on aquatic ecosystems.

Jun-Kit Wan, Wan-Loy Chu, Yih-Yih Kok, Choy-Sin Lee, Chapter, Part of the Reviews of Environmental Contamination and Toxicology book series, Springer

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Microplastic contamination in benthic organisms from the Arctic and sub-Arctic regions

The seafloor is recognized as one of the major sinks for microplastics (MPs). However, to date there have been no studies reported the MP contamination in benthic organisms from the Arctic and sub-Arctic regions. Therefore, this study provided the first data on the abundances and characteristics of MPs in a total of 413 dominant benthic organisms representing 11 different species inhabiting in the shelf of Bering and Chukchi Seas. The mean abundances of MP uptake by the benthos from all sites ranged from 0.02 to 0.46 items g−1 wet weight (ww) or 0.04–1.67 items individual−1, which were lower values than those found in other regions worldwide. The highest value appeared at the northernmost site, implying that the sea ice and the cold current represent possible transport mediums. Interestingly, the predator A. rubens ingested the maximum quantities of MPs, suggesting that the trophic transfer of MPs through benthic food webs may play a critical role. Fibers constituted the major type (87%) in each species, followed by film (13%). The colors of fibers were classified as red (46%) and transparent (41%), and the film was all gray. The predominant composition was polyamide (PA) (46%), followed by polyethylene (PE) (23%), polyester (PET) (18%) and cellophane (CP) (13%). The most common sizes of MPs concentrated in the interval from 0.10 to 1.50 mm, and the mean size was 1.45 ± 0.13 mm. Further studies about the temporal trends and detrimental effects of MPs remain to be carried out in benthic organisms from the Arctic and sub-Arctic regions.

Chao Fang, Ronghui Zheng, Yusheng Zhang and al., Chemosphere, Volume 209, October 2018, Pages 298–306

The article

Abundance and characterization of microplastics in the coastal waters of Tuscany (Italy): The application of the MSFD monitoring protocol in the Mediterranean Sea

Monitoring efforts are required to understand the sources, distribution and abundance of microplastic pollution. To verify the abundance of microplastics along the Tuscan coastal waters (Italy), water-column and surface samples were collected in two seasons across four transects at different distances to the coast (0.5, 5, 10 and 20 km), within the implementation of the European Marine Strategy Framework Directive. The results show an average concentration of 0.26 items/m3 in the water-column samples and 41.1 g/km2 and 69,161.3 items/km2 of floating microplastics, with an increase with the distance to the coast The seasonality and the sampling area do not affect the abundance of microplastics. The most abundant size class is 1–2.5 mm as fragments and sheets suggesting that fragmentation of larger polyethylene and polypropylene items could be the main source of microplastics. These data represent the application of a harmonized protocol to make the data on microplastics comparable and reliable.

Matteo Baini, Maria Cristina Fossi, Matteo Galli, Ilaria Caliani, Tommaso Campani, Maria Grazia Finoia, Cristina Panti, Marine Pollution Bulletin, Volume 133, August 2018, Pages 543–552

The article

Microplastic pollution in North Yellow Sea, China: Observations on occurrence, distribution and identification

Microplastics are emerging contaminants and have attracted widespread environmental concerns about their negative effects on the marine ecosystems. In this study, we investigated the abundances, distributions and characteristics of microplastics in surface seawater and sediments from the North Yellow Sea. The results showed that the abundance of microplastics was 545 ± 282 items/m3 in surface seawater and 37.1 ± 42.7 items/kg dry weight in sediments, representing a medium microplastic pollution level compared with other sea areas. Small microplastics (<1 mm) made up >70% of the total microplastic numbers. Films and fibers were the dominant shapes of microplastics in both the surface seawater and sediments. Transparent microplastics were generally more common than microplastics of other colors. Based on the identification by a Fourier transform infrared microscope, polyethylene (PE) was the dominant composition of microplastics in surface seawater, while polypropylene (PP) was the most common polymer type in sediments. These results will improve our understanding of the environmental risks posed by microplastics to marine ecosystems.

Lin Zhu, Huaiyu Bai, Bijuan Chen and al., Science of The Total Environment, Volume 636, 15 September 2018, Pages 20-29

The article

Abundance, composition, and distribution of microplastics larger than 20 μm in sand beaches of South Korea

To support microplastic management, the abundance, composition, and spatial distribution of microplastics on a national scale must be known. Hence, we studied the baseline level of microplastic pollution at 20 sandy beaches along the South Korean coast. All microplastic particles extracted from the sand samples were identified down to 20 μm in size using Fourier transform infrared spectroscopy. The abundances of large microplastics (L-MPs; 1–5 mm) and small microplastics (S-MPs; 0.02–1 mm) were in the range of 0–2088 n/m2 and 1400–62800 n/m2, respectively. Maximum microplastic abundance was in the size range of 100–150 μm, and particles smaller than 300 μm accounted for 81% of the total abundance. Expanded polystyrene (EPS) accounted for 95% of L-MPs, whereas S-MPs were predominantly composed of polyethylene (49%) and polypropylene (38%). The spatial distribution of L-MPs, excluding EPS, was significantly related to population, precipitation, proximity to a river mouth and abundance of macroplastic debris on beach. However, there were no relationships between S-MPs and other environmental and source-related factors, except for macroplastic debris and L-MPs excluding EPS. These results imply that S-MPs are mainly produced on beaches by weathering, whereas L-MPs other than EPS are mainly introduced from land-based sources and are also partly produced on beaches.

Soeun Eo, Sang Hee Hong, Young Kyoung Song and al., Environmental Pollution, Volume 238, July 2018, Pages 894-902

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