Stable Isotope Insights into Microplastic Contamination within Freshwater Food Webs.

Microplastic pollution and ingestion are ubiquitous phenomena in freshwater ecosystems. However, our understanding of the role of trophic niche in microplastic ingestion is still limited. Here, we quantified the level of microplastic (700 µm to 5 mm) contamination for macroinvertebrates and fish within the Garonne river. We then used stable isotope analyses (δ13C and δ15N) to quantify trophic niches. We first demonstrated that the abundance of ingested microplastics differed between macroinvertebrates and fish and was not significantly related to microplastic pollution. We then found that microplastic characteristics (shape, color, size, and polymer composition) differ between the abiotic (surface waters and sediments) and biotic (ingested by macroinvertebrates and fish) compartments. The abundance of ingested microplastics increased with the size of organisms in both fish and macroinvertebrates and tended to increase with trophic position in macroinvertebrates only. Finally, the origin of the resources consumed by fish significantly affected the abundance of microplastics ingested. Altogether, these results suggest the absence of microplastic bioaccumulation in freshwater food webs and the dominance of direct consumption, most likely accidentally. The use of stable isotope analyses is therefore crucial to improve our understanding of microplastic ingestion by wild organisms.

Molecular-Scale Understanding of the Embrittlement in Polyethylene Ocean Debris.

The fate of plastic waste is a pressing issue since it forms a visible and long-lived reminder of the environmental impact of consumer habits. In this study, we examine the structural changes in the lamellar arrangements of semicrystalline polyethylene (PE) packaging waste with the aim of understanding the physical mechanisms of embrittlement in PE exposed to the marine environment. PE microplastics and macroplastics from identifiable PE packaging were collected in the Atlantic Ocean and compared to new PE boxes. Several experimental techniques interrogate the effects of environmental exposure on their bulk and surface properties. Size exclusion chromatography determines the molecular weight distribution of the PE polymer chains and differential scanning calorimetry gives the crystallinity. Small- and wide-angle X-ray scattering examines the packing of PE chains into semicrystalline lamellae. Longitudinal acoustic mode Raman spectroscopy provides a complementary measurement of the length of PE polymer chains extending through the crystalline lamellar domains. While there is a high degree of uncertainty in the time scale for the changes, the overall picture at the molecular scale is that although PE becomes more crystalline with environmental exposure, the lamellar order present in new packing boxes is disrupted by the weathering process. This process has important implications for embrittlement and subsequent degradation.

Small Microplastics As a Main Contributor to Plastic Mass Balance in the North Atlantic Subtropical Gyre.

Estimates of cumulative plastic inputs into the oceans are expressed in hundred million tons, whereas the total mass of microplastics afloat at sea is 3 orders of magnitude below this. This large gap is evidence of our ignorance about the fate of plastics, as well as transformations and sinks in the oceans. One of the current challenges consists of identifying and quantifying plastic particles at the microscale, the small microplastics (SMP, 25-1000 µm). The aim of the present study is to investigate SMP concentration in count and in mass at the sea surface in the North Atlantic subtropical gyre during the sea campaign Expedition 7 th Continent. After isolation, SMP were characterized by micro-Fourier-transform infrared spectroscopy. Microplastic distribution was modeled by a wind-driven vertical mixing correction model taking into account individual particle properties (dimension, shape and density). We demonstrate that SMP buoyancy is significantly decreased compared to the large microplastics (LMP, 1-5 mm) and consequently more susceptible to vertical transport. The uncorrected LMP concentration in count was between 13 000 and 174 000 pieces km-2, and was between 5 and 170 times more abundant for SMP. With a wind-driven vertical mixing correction, we estimated that SMP were 300 to 70 000 times more abundant than LMP. When discussing this in terms of weight after correction, LMP concentrations were between 50 and 1000 g km-2, and SMP concentrations were between 5 and 14 000 g km-2.

Nanoplastic in the North Atlantic Subtropical Gyre.

Plastics can be found in all ecosystems across the globe. This type of environmental pollution is important, even if its impact is not fully understood. The presence of small plastic particles at the micro- and nanoscales is of growing concern, but nanoplastic has not yet been observed in natural samples. In this study, we examined four size fractions (meso-, large micro-, small micro-, and nanoplastics) of debris collected in the North Atlantic subtropical gyre. To obtain the nanoplastic portion, we isolated the colloidal fraction of seawater. After ultrafiltration, the occurrence of nanoscale particles was demonstrated using dynamic light scattering experiments. The chemical fingerprint of the colloids was obtained by pyrolysis coupled with gas chromatography-mass spectrometry. We demonstrated that the signal was anthropogenic and attributed to a combination of plastics. The polymer composition varied among the size classes. At the micro- and nanoscales, polyvinyl chloride, polyethylene terephthalate, polystyrene and polyethylene were observed. We also observed changes in the pyrolytic signals of polyethylene with decreasing debris size, which could be related to the structural modification of this plastic as a consequence of weathering.

Understanding the Fragmentation Pattern of Marine Plastic Debris.

The global estimation of microplastic afloat in the ocean is only approximately 1% of annual global plastic inputs. This reflects fundamental knowledge gaps in the transformation, fragmentation, and fates of microplastics in the ocean. In order to better understand microplastic fragmentation we proceeded to a thorough physicochemical characterization of samples collected from the North Artlantic subtropical gyre during the sea campaign Expedition seventh Continent in May 2014. The results were confronted with a mathematical approach. The introduction of mass distribution in opposition to the size distribution commonly proposed in this area clarify the fragmentation pattern. The mathematical analysis of the mass distribution points out a lack of debris with mass lighter than 1 mg. Characterization by means of microscopy, microtomography, and infrared microscopy gives a better understanding of the behavior of microplastic at sea. Flat pieces of debris (2 to 5 mm in length) typically have one face that is more photodegraded (due to exposure to the sun) and the other with more biofilm, suggesting that they float in a preferred orientation. Smaller debris, with a cubic shape (below 2 mm), seems to roll at sea. All faces are evenly photodegraded and they are less colonized. The breakpoint in the mathematical model and the experimental observation around 2 mm leads to the conclusion that there is a discontinuity in the rate of fragmentation: we hypothesized that the smaller microplastics, the cubic ones mostly, are fragmented much faster than the parallelepipeds.

Niche partitioning and plastisphere core microbiomes in the two most plastic polluted zones of the world ocean.

Plastics are offering a new niche for microorganisms colonizing their surface, the so-called "plastisphere," in which diversity and community structure remain to be characterized and compared across ocean pelagic regions. Here, we compared the bacterial diversity of microorganisms living on plastic marine debris (PMD) and the surrounding free-living (FL) and organic particle-attached (PA) lifestyles sampled during the Tara expeditions in two of the most plastic polluted zones in the world ocean, i.e., the North Pacific gyre and the Mediterranean Sea. The 16S rRNA gene sequencing analysis confirmed that PMD are a new anthropogenic ocean habitat for marine microbes at the ocean-basin-scale, with clear niche partitioning compared to FL and PA lifestyles. At an ocean-basin-scale, the composition of the plastisphere communities was mainly driven by environmental selection, rather than polymer types or dispersal effect. A plastisphere "core microbiome" could be identified, mainly dominated by Rhodobacteraceae and Cyanobacteria. Predicted functions indicated the dominance of carbon, nitrogen and sulfur metabolisms on PMD that open new questions on the role of the plastisphere in a large number of important ecological processes in the marine ecosystem.

Among-colony variation in plastic ingestion by Yellow-legged gulls (Larus michahellis) across the western Mediterranean basin.

The Mediterranean region is both a hotspot for biodiversity and for the accumulation of plastic pollution. Many species are exposed to this pollution while feeding, including a wide diversity of seabirds. Our objective was to investigate spatial variation in the quantity and types of plastic ingested by Yellow-legged gulls using information obtained from regurgitated pellets collected in 11 colonies. Anthropogenic debris, and particularly plastic, was found in pellets from all colonies, but the amount varied considerably. This among-colony difference was stable over the two years of study. The presence of marine prey and the proportion of agricultural area around the colonies significantly influenced the number of ingested plastics. As landfills close and garbage management improves, the availability of anthropogenic waste should decline. Following the response of gulls to these changes will be particularly useful for monitoring plastic pollution and for understanding the response of opportunistic wildlife to environmental modifications.

Small microplastics have much higher mass concentrations than large microplastics at the surface of nine major European rivers.

Understanding the fates and impacts of microplastics requires information on their sizes, polymer types, concentrations, and spatial and temporal distributions. Here, we focused on large (LMPs, 500 µm to 5 mm) and small (SMPs, 25 to 500 µm) microplastics sampled with the exact same protocol in nine of the major European rivers during the seven months of the Tara Microplastic Expedition. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC-MS) analyses were used to determine the microplastics contents by number and mass. The median LMP concentration was 6.7 particles m-3, which was lower than those in other regions of the world (America and Asia). The SMP mass concentration was much higher to the LMP concentrations, with SMP/LMP ratios up to 1000 in some rivers. We did not observe a systematic positive effect of urban areas for the two size classes or polymers; this could be explained by the fact that the transport of microplastic is highly heterogeneous in rivers. We believe that this study has important implications for predictive models of plastics distribution and fate in aquatic environments.

Untargeted metabolomic insights into plastisphere communities in European rivers.

Every year, rivers introduce a staggering amount of hundred kilotons of plastic into the Oceans. This plastic is inhabited by microorganisms known as the plastisphere, which can be transferred between different ecosystems through the transport of microplastics. Here, we simulated the microbial colonization of polyethylene-based plastic pellets that are classically used to manufacture large-scale plastic products. The pellets were immersed for 1 month in four to five sampling stations along the river-to-sea continuum of nine of the major European rivers. This study presents the first untargeted metabolomics analysis of the plastisphere, by using ultra high-performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS). The plastisphere metabolomes were similar in the Rhine and Rhone rivers, while being different from the Tiber and Loire rivers, which showed greater similarity to the Thames and Seine rivers. Interestingly, we found a clear distinction between plastisphere metabolomes from freshwater and marine water in most of the river-to-sea continuum, thus suggesting a complete segregation in plastisphere metabolites that is not consistent with a major transfer of microorganisms between the two contrasted ecosystems. Putative annotations of 189 discriminating metabolites suggested that lipid metabolism was significantly modulated. These results enlightened the relevance of using environmental metabolomic as complementary analysis to the current OMICs analysis.

Barau's petrel, Pterodroma baraui, as a bioindicator of plastic pollution in the South-West Indian Ocean: A multifaceted approach.

Marine plastic pollution is well described by bioindicator species in temperate and polar regions but remains understudied in tropical oceans. We addressed this gap by evaluating the seabird Barau's petrel as bioindicator of plastic pollution in the South-West Indian Ocean. We conducted a multifaceted approach including necropsies of birds to quantify plastic ingestion; GPS tracking of breeding adults to identify their foraging areas; manta trawling of plastic debris to measure plastic pollution at sea and modelling of plastic dispersal. We developed a spatial risk index of seabird exposure to plastic ingestion. Seventy-one percent of the analysed birds had ingested plastic. GPS tracking coupled with manta trawling and dispersal modelling show that adults consistently foraged at places with high level of plastic concentration. The highest ingestion risk occurred in the northwest of Reunion Island and at latitude 30°S. Our findings confirm that Barau's petrel is a reliable bioindicator of plastic pollution in the region.

Phototransformation of azoxystrobin fungicide in organic solvents. Photoisomerization vs. photodegradation.

Azoxystrobin is a systemic fungicide that has a tendency to accumulate at the surface of crop leaves or inside their cuticle where it undergoes photodegradation. Its photochemistry was investigated in n-heptane and isopropanol to mimic the polarity of wax leaves. Using analytical and kinetic data, we demonstrate that azoxystrobin (isomer E) undergoes efficient photoisomerization into the isomer Z with a quantum yield of 0.75 ± 0.08. This value is 30-fold higher than that reported in aqueous solution. The photoisomerization of isomer Z into azoxystrobin is more efficient with a chemical yield of 0.95 ± 0.1. In addition, a pseudo photostationary equilibrium is reached when the ratio [azoxystrobin]/[isomer Z] is 2.0 ± 0.1. Photodegradation also takes place from azoxystrobin (quantum yield = 0.073 ± 0.008). Photoproducts mainly arise from bond cleavage between rings and from demethylation of the ether with or without saturation of the acrylate double bond. Theoretical calculations were undertaken to investigate the photoisomerization mechanism and the solvent effect. These data show that the photochemical reactivity of azoxystrobin is enhanced when the solvent polarity decreases and thus should be significant in leaf waxes.

Inferring microplastics origins in the Mediterranean Sea by coupling modelling and in-situ measurements.

This work focuses on the dynamics and retention of microplastics (MP) in the Mediterranean. MP manta-net trawls were performed in autumn 2019 north of the Balearic Islands and along the Balearic Front (BF). Lagrangian modelling was used to find the MP collected origin during the campaign. These combined results show that North of Mallorca is a temporary retention zone of 3 months variability, with MP origin being the Northern Current (NC) and the Gulf of Lion (GOL). Retention processes were less clear along the BF, due to frontal dynamics together with the strong northerly winds. However, it appears that the origin can differ between the North (i.e. the large North-Westerly basin, including the GOL and the NC path) and the South (short distances around the zone) of this front. In both areas, the wind and the current variability are strongly conditioning the existence and position of the MP concentration zones.

Changes in plastic ingestion by yellow-legged gulls (Larus michahellis) over the breeding season.

Gulls can be particularly vulnerable to ingesting plastics when using anthropogenic food sources, with potential consequences for survival and reproductive success. Although birds are known to switch foraging habitats over the breeding season to provide higher quality food for chick provisioning, it is unclear what this means regarding the ingestion of plastics. Here, we tested whether breeding gulls decrease the amount of plastic ingested during reproduction by collecting pellets from a series of monitored nests at a large yellow-legged gull (Larus michahellis) colony in southern France. We found at least one plastic item in 83.9 % of the analyzed pellets, with the most abundant plastic type being polyethylene-based sheet plastic. As predicted, we found a slight decrease in the number of plastic items in pellets at chick hatching. These results suggest that gulls, like other birds, may adjust foraging habits to provide more digestible, less risky, food to chicks.

Discussion about suitable applications for biodegradable plastics regarding their sources, uses and end of life.

This opinion paper offers a scientific view on the current debate of the place of biodegradable plastics as part of the solution to deal with the growing plastic pollution in the world's soil, aquatic, and marine compartments. Based on the current scientific literature, we focus on the current limits to prove plastic biodegradability and to assess the toxicity of commercially used biobased and biodegradable plastics in natural environments. We also discuss the relevance of biodegradable plastics for selected applications with respect to their use and end of life. In particular, we underlined that there is no universal biodegradability of plastics in any ecosystem, that considering the environment as a waste treatment system is not acceptable, and that the use of compostable plastics requires adaptation of existing organic waste collection and treatment channels.

Impacts of microplastics and the associated plastisphere on physiological, biochemical, genetic expression and gut microbiota of the filter-feeder amphioxus.

Oceanic plastic pollution is of major concern to marine organisms, especially filter feeders. However, limited is known about the toxic effects of the weathered microplastics instead of the pristine ones. This study evaluates the effects of weathered polystyrene microplastic on a filter-feeder amphioxus under starvation conditions via its exposure to the microplastics previously deployed in the natural seawater allowing for the development of a mature biofilm (so-called plastisphere). The study focused on the integration of physiological, histological, biochemical, molecular, and microbiota impacts on amphioxus. Overall, specific alterations in gene expression of marker genes were observed to be associated with oxidative stresses and immune systems. Negligible impacts were observed on antioxidant biochemical activities and gut microbiota of amphioxus, while we highlighted the potential transfer of 12 bacterial taxa from the plastisphere to the amphioxus gut microbiota. Moreover, the classical perturbation of body shape detected in control animals under starvation conditions (a slim and curved body) but not for amphioxus exposed to microplastic, indicates that the microorganisms colonizing plastics could serve as a nutrient source for this filter-feeder, commitment with the elevated proportions of goblet cell-like structures after the microplastic exposure. The multidisciplinary approach developed in this study underlined the trait of microplastics that acted as vectors for transporting microorganisms from the plastisphere to amphioxus.

A critical review on the evaluation of toxicity and ecological risk assessment of plastics in the marine environment.

The increasing production of plastics together with the insufficient waste management has led to massive pollution by plastic debris in the marine environment. Contrary to other known pollutants, plastic has the potential to induce three types of toxic effects: physical (e.g intestinal injuries), chemical (e.g leaching of toxic additives) and biological (e.g transfer of pathogenic microorganisms). This critical review questions our capability to give an effective ecological risk assessment, based on an ever-growing number of scientific articles in the last two decades acknowledging toxic effects at all levels of biological integration, from the molecular to the population level. Numerous biases in terms of concentration, size, shape, composition and microbial colonization revealed how toxicity and ecotoxicity tests are still not adapted to this peculiar pollutant. Suggestions to improve the relevance of plastic toxicity studies and standards are disclosed with a view to support future appropriate legislation.

Mission Tara Microplastics: a holistic set of protocols and data resources for the field investigation of plastic pollution along the land-sea continuum in Europe.

The Tara Microplastics mission was conducted for 7 months to investigate plastic pollution along nine major rivers in Europe-Thames, Elbe, Rhine, Seine, Loire, Garonne, Ebro, Rhone, and Tiber. An extensive suite of sampling protocols was applied at four to five sites on each river along a salinity gradient from the sea and the outer estuary to downstream and upstream of the first heavily populated city. Biophysicochemical parameters including salinity, temperature, irradiance, particulate matter, large and small microplastics (MPs) concentration and composition, prokaryote and microeukaryote richness, and diversity on MPs and in the surrounding waters were routinely measured onboard the French research vessel Tara or from a semi-rigid boat in shallow waters. In addition, macroplastic and microplastic concentrations and composition were determined on river banks and beaches. Finally, cages containing either pristine pieces of plastics in the form of films or granules, and others containing mussels were immersed at each sampling site, 1 month prior to sampling in order to study the metabolic activity of the plastisphere by meta-OMICS and to run toxicity tests and pollutants analyses. Here, we fully described the holistic set of protocols designed for the Mission Tara Microplastics and promoted standard procedures to achieve its ambitious goals: (1) compare traits of plastic pollution among European rivers, (2) provide a baseline of the state of plastic pollution in the Anthropocene, (3) predict their evolution in the frame of the current European initiatives, (4) shed light on the toxicological effects of plastic on aquatic life, (5) model the transport of microplastics from land towards the sea, and (6) investigate the potential impact of pathogen or invasive species rafting on drifting plastics from the land to the sea through riverine systems.

Do loggerhead sea turtle (Caretta caretta) gut contents reflect the types, colors and sources of plastic pollution in the Southwest Indian Ocean?

We analyzed plastic debris ingested by loggerheads from bycatch between 2007 and 2021 in the Southwest Indian Ocean (SWIO). We also analyzed plastic debris accumulated on beaches of the east coast of Madagascar as a proxy for ocean plastics to compare the characteristics of beached plastics and plastic ingested by turtles. We conducted a "brand audit" of the plastics to determine their country of origin. An oceanic circulation model was used to identify the most likely sources of plastics in the SWIO. In total, 202 of the 266 loggerheads analyzed had ingested plastics. Plastics categorized as "hard" and "white" were equally dominant in loggerheads and on beaches, suggesting no diet selectivity. Both the brand audit and circulation modeling demonstrated that Southeast Asia is the main source of plastic pollution in the region. This study demonstrates that loggerheads can be used as bioindicators of plastic pollution in the SWIO.

Grape marc extract acts as elicitor of plant defence responses.

Plant protection based on novel alternative strategies is a major concern in agriculture to sustain pest management. The marc extract of red grape cultivars reveals plant defence inducer properties. Treatment with grape marc extract efficiently induced hypersensitive reaction-like lesions with cell death evidenced by Evans Blue staining of tobacco leaves. Examination of the infiltration zone and the surrounding areas under UV light revealed the accumulation of autofluorescent compounds. Both leaf infiltration and a foliar spray of the red grape extract on tobacco leaves induced defence gene expression. The PR1 and PR2 target genes were upregulated locally and systemically in tobacco plants following grape marc extract treatment. The grape extract elicited an array of plant defence responses making this natural compound a potential phytosanitary product with a challenging issue and a rather attractive option for sustainable agriculture and environmentally friendly practices.