Is Zooplankton an Entry Point of Microplastics into the Marine Food Web?

Microplastics (MPs) overlap in size with phytoplankton and can be ingested by zooplankton, transferring them to higher trophic levels. Copepods are the most abundant metazoans among zooplankton and the main link between primary producers and higher trophic levels. Ingestion of MPs has been investigated in the laboratory, but we still know little about the ingestion of MPs by zooplankton in the natural environment. In this study, we determined the concentration and characteristics of MPs down to 10 µm in zooplankton samples, sorted calanoid copepods, and fecal pellets collected in the Kattegat/Skagerrak Sea (Denmark). We found a median concentration of 1.7 × 10-3 MPs ind-1 in the zooplankton samples, 2.9 × 10-3 MPs ind-1 in the sorted-copepods, and 3 × 10-3 MPs per fecal pellet. Most MPs in the zooplankton samples and fecal pellets were fragments smaller than 100 µm, whereas fibers dominated in the sorted copepods. Based on the collected data, we estimated a MP budget for the surface layer (0-18 m), where copepods contained only 3% of the MPs in the water, while 5% of the MPs were packed in fecal pellets. However, the number of MPs exported daily to the pycnocline via fecal pellets was estimated to be 1.4% of the total MPs in the surface layer. Our results indicate that zooplankton are an entry point of small MPs in the food web, but the number of MPs in zooplankton and their fecal pellets was low compared with the number of MPs found in the water column and the occurrence and/or ingestion of MPs reported for nekton. This suggests a low risk of MP transferring to higher trophic levels through zooplankton and a quantitatively low, but ecologically relevant, contribution of fecal pellets to the vertical exportation of MPs in the ocean.

Shapes of Hyperspectral Imaged Microplastics.

Shape matters for microplastics, but its definition, particularly for hyperspectral imaged microplastics, remains ambiguous and inexplicit, leading to incomparability across data. Hyperspectral imaging is a common approach for quantification, yet no unambiguous microplastic shape classification exists. We conducted an expert-based survey and proposed a set of clear and concise shapes (fiber, rod, ellipse, oval, sphere, quadrilateral, triangle, free-form, and unidentifiable). The categories were validated on images of 11,042 microplastics from four environmental compartments (seven matrices: indoor air; wastewater influent, effluent, and sludge; marine water; stormwater; and stormwater pond sediments), by inviting five experts to score each shape. We found that the proposed shapes were well defined, representative, and distinguishable to the human eye, especially for fiber and sphere. Ellipse, oval, and rod were though less distinguishable but dominated in all water and solid matrices. Indoor air held more unidentifiable, an abstract shape that appeared mostly for particles below 30 µm. This study highlights the need for assessing the recognizability of chosen shape categories prior to reporting data. Shapes with a clear and stringent definition would increase comparability and reproducibility across data and promote harmonization in microplastic research.

Can a Sediment Core Reveal the Plastic Age? Microplastic Preservation in a Coastal Sedimentary Record.

The seafloor is the major sink for microplastic (MP) pollutants. However, there is a lack of robust data on the historical evolution of MP pollution in the sediment compartment, particularly the sequestration and burial rate of small MPs. By combining a palaeoceanographic approach and state-of-the-art analytical methods for MP identification down to 11 µm in size, we present the first high-resolution reconstruction of MP pollution from an undisturbed sediment core collected in the NW Mediterranean Sea. Furthermore, we investigate the fate of MPs once buried in the sediments by evaluating the changes in the size distribution of the MPs and the weathering status of the polyolefins, polyethylene, and polypropylene. Our results indicate that the MP mass sequestered in the sediment compartment mimics the global plastic production from 1965 to 2016. We observed an increase in the weathering status of the polyolefins as the size decreased. However, the variability in the size and weathering status of the MPs throughout the sedimentary record indicated that these pollutants, once incorporated into sediments, remain preserved with no further degradation under conditions lacking remobilization.

Cavity-enhanced non-destructive detection of atoms for an optical lattice clock.

We demonstrate a new method of cavity-enhanced non-destructive detection of atoms for a strontium optical lattice clock. The detection scheme is shown to be linear in atom number up to at least 2×104 atoms, to reject technical noise sources, to achieve signal to noise ratio close to the photon shot noise limit, to provide spatially uniform atom-cavity coupling, and to minimize inhomogeneous ac Stark shifts. These features enable detection of atoms with minimal perturbation to the atomic state, a critical step towards realizing an ultra-high-stability, quantum-enhanced optical lattice clock.

Detecting small microplastics down to 1.3 µm using large area ATR-FTIR.

Large area attenuated total reflectance-Fourier transform infrared spectroscopy (LAATR-FTIR) is introduced as a novel technique for detecting small microplastics (MPs) down to 1.3 µm. Two different LAATR units, one with a zinc selenide (ZnSe) and one with a germanium (Ge) crystal, were used to detect reference MPs < 20 µm, and MPs in marine water samples, and compared with µ-FTIR in transmission mode. The LAATR units performed well in identifying small MPs down to 1.3 µm. However, they were poorly suited for large MPs as uneven particle thickness resulted in uneven contact between crystal and particle, misinterpreting large MPs as many small MPs. However, for more homogeneous matrices, the technique was promising. Further assessment indicated that there was little difference in spectra quality between transmission mode and LAATR mode. All in all, while LAATR units struggle to substitute transmission mode, it provides additional information and valuable information on small MPs.

Downward migrating microplastics in lake sediments are a tricky indicator for the onset of the Anthropocene.

Plastics are a recent particulate material in Earth's history. Because of plastics persistence and wide-range presence, it has a great potential of being a global age marker and correlation tool between sedimentary profiles. In this research, we query whether microplastics can be considered among the array of proxies to delimit the Anthropocene Epoch (starting from the year 1950 and above). We present a study of microplastics deposition history inferred from sediment profiles of lakes in northeastern Europe. The sediments were dated with independent proxies from the present back to the first half of the 18th century. Regardless of the sediment layer age, microplastic particles were found throughout the cores in all sites. Depending on particles' aspect ratio, less elongated particles were found deeper, while more elongated particles and fibers have reduced mobility. We conclude that interpretation of microplastics distribution in the studied sediment profiles is ambiguous and does not strictly indicate the beginning of the Anthropocene Epoch.

Spatial distribution of small microplastics in the Norwegian Coastal Current.

High concentrations of microplastic (MP) particles have been reported in the Arctic Ocean. However, studies on the high-resolution lateral and vertical transport of MPs from the European waters to the Arctic are still scarce. Here, we provide information about the concentrations and compositions of MPs in surface, subsurface, and deeper waters (< 1 m, ∼ 4 m, and 17-1679 m) collected at 18 stations on six transects along the Norwegian Coastal Current (NCC) using an improved Neuston Catamaran, the COntinuos MicroPlastic Automatic Sampling System (COMPASS), and in situ pumps, respectively. FTIR microscopy and spectroscopy were applied to measure MP concentration, polymer composition, and size distribution. Results indicate that the concentrations of small microplastics (SMPs, <300 µm) varied considerably (0-1240 MP m-3) within the water column, with significantly higher concentrations in the surface (189 MP m-3) and subsurface (38 MP m-3) waters compared to deeper waters (16 MP m-3). Furthermore, the average concentration of SMPs in surface water samples was four orders of magnitude higher than the abundance of large microplastics (LMPs, >300 µm), and overall, SMPs <50 µm account for >80 % of all detected MPs. However, no statistically significant geographical patterns were observed in SMP concentrations in surface/subsurface seawaters between the six sampling transects, suggesting a relatively homogeneous horizontal distribution of SMPs in the upper ocean within the NCC/Norwegian Atlantic Current (NwAC) interface. The Lagrangian particle dispersal simulation model further enabled us to assess the large-scale transport of MPs from the Northern European waters to the Arctic.

Fire debris analysis and scene reconstruction.

During the summer of 2010 near a little village in the south of Italy, a fire destroyed a piece of brushland without any apparent economic importance. The remains of a fire-setting tool were found at the point of origin of the fire. It was started using a well-planned and methodical approach. The analytical results demonstrated a sophisticated and effective incendiary tool designed to leave little evidence that could identify the offender. The action and the purpose of the arsonist were clear but the basic motivation was unpredictable. The burned area was without any relevant economical interest. It was burnt during the past and has not been used for any cultivation or sheep farming but in the region there was evidence of bushfires that had been lit to stimulate the growth of forest fruits to be harvested for sale.

Exploration of occurrence and sources of microplastics (>10 µm) in Danish marine waters.

Microplastics (MPs) were quantified in Danish marine waters of the Kattegat and the southernmost part of Skagerrak bordering to it. Kattegat is a waterbody between Denmark and Sweden that receives inflow from the Baltic Sea and direct urban runoff from the metropolitan area of Copenhagen and Malmö. MPs were measured in 14 continuous transects while steaming between monitoring stations. MP levels tended to be highest close to the Copenhagen-Malmö area, albeit this was more obvious from the abundance of particles rather than mass. The outcome of the measurements allowed a rough MP budget in the Danish Straits region, suggesting that urban waste- and stormwater discharges could not be neglected as potential MP source in these waters. The marine samples were collected by pumping and filtering water over 10 µm steel filters, hereby sampling a total of 19.3 m3. They were prepared and analyzed by FPA-µFTIR imaging, and the scans interpreted to yield MP size, shape, polymer type, and estimated mass. The average concentration was 103 ± 86 items m-3, corresponding to 23.3 ± 28.3 µg m-3 (17-286 items m-3; 0.6-84.1 µg m-3). Most MPs were smaller than 100 µm and fragments dominated the samples. The carbonyl index was assessed for polyolefins, showing that oxidation increased with decreasing MP size, but did not correlate with distance to urban areas. A rough budget of MP in the Danish Straits region suggested that MPs discharged from urban waste- and stormwaters were an import source of MPs.

Searching for hotspots of neustonic microplastics in the Canary Islands.

In this study, we investigated the concentration, distribution, and characteristics of neustonic MPs in the Canary Islands, with a particular focus on the island leeward zones, where a high accumulation of floating marine microplastics is expected. Samples were collected with a manta net at 15 different sites from Alegranza to La Gomera during the IMPLAMAC expedition. The microplastic concentration in surface waters ranged from 0.27 MPs/m3 in Alegranza to 136.7 MPs/m3 in the south of Gran Canaria. The highest concentration of MPs found was due to the presence of a sea-surface slick, also called "marine litter windrow", formed in the south of Gran Canaria. The most abundant zooplankton group in the neuston was copepods, except at the marine litter windrow where fish larvae and eggs predominated. This indicates that coastal areas where marine litter windrows are formed have a high risk of MP ingestion and potential adverse effects on biota.

Abundance and distribution of microplastics in surface waters of the Kattegat/ Skagerrak (Denmark).

Microplastics (MPs) are ubiquitous pollutants in the ocean, and there is a general concern about their persistence and potential effects on marine ecosystems. We still know little about the smaller size-fraction of marine MPs (MPs <300 µm), which are not collected with standard nets for MPs monitoring (e.g., Manta net). This study aims to determine the concentration, composition, and size distribution of MPs down to 10 µm in the Kattegat/Skagerrak area. Surface water samples were collected at fourteen stations using a plastic-free pump-filter device (UFO sampler) in October 2020. The samples were treated with an enzymatic-oxidative method and analyzed using FPA-µFTIR imaging. MPs concentrations ranged between 11 and 87 MP m-3, with 88% of the MPs being smaller than 300 µm. The most abundant shape of MPs were fragments (56%), and polyester, polypropylene, and polyethylene were the dominant synthetic polymer types. The concentration of MPs shows a significant positive correlation to the seawater density. Furthermore, there was a tendency towards higher MPs concentrations in the Northern and the Southern parts of the study area. The concentration of MPs collected with the UFO sampler was several orders of magnitude higher than those commonly found in samples collected with the Manta net due to the dominance of MP smaller size fractions. Despite the multiple potential sources of MPs in the study area, the level of MPs pollution in the surface waters was low compared (<100 MP m-3) to other regions. The concentrations of MPs found in the studied surface waters were six orders of magnitude lower than those causing negative effects on pelagic organisms based on laboratory exposure studies, thus is not expected to cause any impact on the pelagic food web.

Polymer composition assessment suggests prevalence of single-use plastics among items ingested by loggerhead sea turtles in the western mediterranean sub-region.

The ingestion of plastic is becoming a major concern for various species and particularly for marine turtles across the globe. The loggerhead sea turtle (Caretta caretta) was recently chosen by the European Commission as a bio-indicator for plastic pollution within the Mediterranean basin. We further investigated which items this key species is more prone to ingest, following the standardised Marine Strategy Framework Directive protocols. Moreover, we integrated to this protocol the Fourier Transform Infrared Spectroscopy, which allowed us to determine the polymer type of each item. We analysed samples from 226 sea turtles from 2008 to 2017 in two areas of the western Mediterranean sub-region (sensu MSFD). In the Lazio area we found a frequency of occurrence of plastic ingestion of 78.33%, while in Sardinia 41.79%. The analysis of the litter categories, among all individuals, highlights a prevalence of user-sheet (Use-She; 69.13%) and user-fragment plastics (Use-Fra; 20.84%). In addition, the polymer analysis showed a dominance of polyethylene (65.98%) and polypropylene (26.23%). As a result, by looking at other works that have investigated polymer types and items sources, we are able to infer that 77.25% of the objects ingested by the C. caretta individuals are attributable to disposable daily-life objects managed in an improper way. Therefore, C. caretta apart from being an efficient bio-indicator for plastic pollution, highlighting spatial and temporal concentration differences, it could also be used to verify the effectiveness of the Single-use Plastic Directive (EU 2019/904).

Accelerated weathering affects the chemical and physical properties of marine antifouling paint microplastics and their identification by ATR-FTIR spectroscopy.

Microplastics prepared from commercial marine antifouling paints were weathered by UV-C irradiation representing between 25 and 101 days of real-time, outdoor exposure. Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy of the degraded paint particles showed that weathering induced chemical changes in the material, including the release of volatile components and the formation of hydrophilic groups. The chemical changes and increased reactivity of the paint binder were associated with alterations in their physical properties and increased leaching of metals in freshwater conditions. Changes in the spectra obtained from weathered paint samples reduced their match with spectra of unaged materials, resulting in a poorer similarity index, the Score when using automatic identification tools for microplastics. The results suggest that spectra of weathered, as well as pristine paint microplastics, should be consulted when applying analytical pipelines to identify microplastics extracted from natural matrices.

A novel approach based on multiple fish species and water column compartments in assessing vertical microlitter distribution and composition.

The assessment of the distribution and composition of microlitter in the sea is a great challenge. Biological indicators can be an irreplaceable tool since they measure microlitter levels in their environments in a way that is virtually impossible to replicate by direct physical measurements. Furthermore, trends can provide policymakers with statistically robust analysis. We looked into the capacity of multiple fish species to describe the distribution and composition of microlitter vertically across different compartments of the water column. A total of 502 individuals from six selected species (Scomber scombrus, Oblada melanura, Spicara smaris, Boops boops, Merluccius merluccius and Mullus barbatus) were collected on the western side of Sardinia island and allocated to three compartments: surface, mid-water and bottom. The species of the surface exhibited a higher frequency of occurrence (41.89%) of microlitter ingestion, compared to those of the mid-water and bottom (19.60%; 22.58%). A significant difference in the average number of ingested microlitter was found between the surface and the bottom compartment. All the microlitter fragments found were analysed through Fourier Transform Infrared Spectroscopy (FTIR). The comparison of the expected buoyancies of the polymers identified puth faith in the allocation of the species to the respective compartments. Therefore, considering the Marine Strategy Framework Directive objective, this approach could be useful in assessing microlitter distribution and composition vertically across the water column.

Drinking plastics? - Quantification and qualification of microplastics in drinking water distribution systems by µFTIR and Py-GCMS.

While it seems indisputable that potable water contains microplastics (MP), the actual concentrations are much debated and reported numbers vary many orders of magnitude. It is difficult to pinpoint the cause of these differences, but it might be variation between waters, variation between quantification methods, and that some studies did not live up to rigorous analytical standards. Despite the urgent need to understand human exposure by drinking water, there is a lack of trustable methods generating reliable data. Essentially, proper MP assessment requires that quality assurance is in place and demonstrated, that an adequate volume of drinking water is assessed, and that differences in analytical methods are understood. This study presents a systematic and robust approach where MP down to 6.6 µm were assessed in potable water distribution systems in terms of quantity, size, shape, and material. For the first time, sub-samples were analysed by two of the most validated and complementary analytical techniques: µFTIR imaging and Py-GCMS. Both methods successfully determined low contents in drinking water. However, µFTIR and Py-GCMS identified different polymer types in samples with overall low MP content. With increasing concentration of a given polymer type, the values determined by the techniques became more comparable. Most detected MPs were smaller than 150 µm, and 32% were smaller than 20 µm. Our results indicate a potential annual uptake of less than one MP per person, suggesting that drinking potable water produced at a high-performance drinking water treatment plant represents a low risk for human health.

Single-Pot Method for the Collection and Preparation of Natural Water for Microplastic Analyses: Microplastics in the Mississippi River System during and after Historic Flooding.

We describe a simple single-pot method for collection and preparation of natural water for microplastic analyses. The method prepares samples in the same vessel (mason jars) that they are collected in right up until the microplastics are transferred onto filters or spectroscopic windows for analyses. The method minimized contamination, degradation, and losses, while increasing recoveries and throughput when compared with conventional sieving. We applied it to surface grab samples collected from the Mississippi River and its major tributaries during and after historic flooding in 2019. Microplastics (>~30 µm) were quantified using Nile red fluorescence detection, and a small subset of samples were identified by micro-Fourier transform infrared imaging spectroscopy. Concentrations were lower during the flooding, likely due to dilution. Concentrations ranged from approximately 14 microplastics/L in the Tennessee River during flooding to approximately 83 microplastics/L in the Ohio River during low-flow (summer) conditions. Loads of microplastics tended to increase downriver and ranged from approximately 87 to approximately 129 trillion microplastics/d near New Orleans. Most of the microplastics (>60%) were in the lower size fraction (~30-90 µm) and consisted primarily of fragments (~85%), followed by fibers (~8%) and beads (~7%), with polyester, polyethylene, polypropylene, and polyacrylate as the primary microplastic types. Overall, we demonstrate that the single-pot method is effective and versatile and, because it uses relatively inexpensive and easily assembled materials, can be adapted for microplastic surveys worldwide, especially those involving sample collection by volunteers from the community and schools. Environ Toxicol Chem 2020;39:986-995. © 2020 SETAC.

Quantification of plankton-sized microplastics in a productive coastal Arctic marine ecosystem.

Microplastics (MPs) are polluting the Arctic, but our understanding of their abundance, distribution, and sources is limited. This study quantified MPs down to 10 µm in marine waters of the most populated region in Greenland. A new plastic-free pump-filter system was used to collect MPs from surface waters in the fjord Nuup Kangerlua close to Nuuk. Additionally, we took samples by horizontal tows with a bongo net (300 µm mesh-size). The median concentrations were 142 MPs m-3 and 0.12 MPs m-3 in the pump and bongo samples, respectively. The most abundant polymer was polyester across stations and sampling types. Fibers were the dominant shape in the bongo samples, while non-fibrous particles dominated in the pump samples. MP abundance was lower in the fjord and increased close to Nuuk and towards the open ocean, indicating that Nuuk is an important point source for MPs. In both samples, concentrations of MPs increased with decreasing size, illustrating the importance of quantifying the smallest fraction of MPs. Thus, the use of methods allowing for a quantification of the smallest MPs is vital to reduce the underestimation of MP concentrations in the environment. The smallest size fraction is also most available to plankton-feeding marine invertebrates and an important entry point for MPs into marine food webs. At the found concentrations, immediate adverse effects on the pelagic food webs are unlikely. However, growing anthropogenic activities could increase the risk of MPs to affect the sensitive Arctic ecosystem.

Toward the Systematic Identification of Microplastics in the Environment: Evaluation of a New Independent Software Tool (siMPle) for Spectroscopic Analysis.

Microplastics (MP) are ubiquitous within the environment, but the approaches to analysis of this contaminant are currently quite diverse, with a number of analytical methods available. The comparability of results is hindered as even for a single analytical method such as Fourier transform infrared spectroscopy (FT-IR) the different instruments currently available do not allow a harmonized analysis. To overcome this limitation, a new free of charge software tool, allowing the systematic identification of MP in the environment (siMPle) was developed. This software tool allows a rapid and harmonized analysis of MP across FT-IR systems from different manufacturers (Bruker Hyperion 3000, Agilent Cary 620/670, PerkinElmer Spotlight 400, and Thermo Fischer Scientific Nicolet iN10). Using the same database and the automated analysis pipeline in siMPle, MP were identified in samples that were analyzed with instruments with different detector systems as well as optical resolutions and the results discussed.

Retention of microplastics in sediments of urban and highway stormwater retention ponds.

Urban and highway surfaces discharge polluted runoff during storm events. To mitigate environmental risks, stormwater retention ponds are commonly constructed to treat the runoff water. This study is the first to quantify the retention of microplastics in the sediments of such ponds. It applied state-of-art FTIR-methods to analyse the composition, size, shape, and mass of microplastics in the range 10-2000 µm. Seven ponds serving four land uses were investigated, and the results are related to catchment characteristics, sediment organic matter content, and hydraulic loading. We have not found a correlation between the microplastics abundance, polymer composition, size distribution and the land use in the catchment, as well as the sediment organic matter content. Both the highest (127,986 items kg-1; 28,732 µg kg-1) and the lowest (1511 items kg-1; 115 µg kg-1) accumulation of microplastics were found in the sediments of ponds serving industrial areas. There was, however, a correlation to the hydraulic loading of the ponds, where the sediments of the highest-loaded ponds held the most microplastics. This study shows that sediments in stormwater retention ponds can trap some of the microplastics and prevent them from being transported downstream. These systems need to be considered when assessing the fate of microplastics from urban and highway areas.

Simulating human exposure to indoor airborne microplastics using a Breathing Thermal Manikin.

Humans are potentially exposed to microplastics through food, drink, and air. The first two pathways have received quite some scientific attention, while little is known about the latter. We address the exposure of humans to indoor airborne microplastics using a Breathing Thermal Manikin. Three apartments were investigated, and samples analysed through FPA-µFTIR-Imaging spectroscopy followed by automatic analyses down to 11 µm particle size. All samples were contaminated with microplastics, with concentrations between 1.7 and 16.2 particles m-3. Synthetic fragments and fibres accounted, on average, for 4% of the total identified particles, while nonsynthetic particles of protein and cellulose constituted 91% and 4%, respectively. Polyester was the predominant synthetic polymer in all samples (81%), followed by polyethylene (5%), and nylon (3%). Microplastics were typically of smaller size than nonsynthetic particles. As the identified microplastics can be inhaled, these results highlight the potential direct human exposure to microplastic contamination via indoor air.