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Two different sample preparation protocols for the determination of 37 emerging and historical halogenated flame retardants (HFRs) in marine tissues were compared with regards to extraction recovery, lipid removal efficiency, repeatability, reproducibility, and ability to measure sub-ng g−1 (dry weight) concentrations in marine biota. One method involved a purification step using gel permeation chromatography (GPC) followed by a HPLC fractionation step on a Partisil amino-cyano normal phase (GPC-Partisil procedure) and the other more traditional method was based on sulphuric acid treatment followed by silica column fractionation (H2SO4-silica procedure). The samples were analysed by gas chromatography (GC) and liquid chromatography (LC) tandem mass spectrometry (MS/MS). Sample fractionation in both methods enabled unique sample preparation procedures to isolate the GC from the LC amenable compounds. Both methods could remove > 99% of the lipids which was necessary prior to GC- and LC-MS/MS analyses. The majority of the target compounds (70%) had acceptable recoveries between 60–120% for both methods. However, the sulphuric acid treatment resulted in the degradation of the TBP-AE and the silica column fractionation resulted in the loss of BEH-TEBP and the elution of PBB-Acr and TBBPA-BME in the unsuitable fraction. High recoveries of DBE-DBCH (α+β), EHTBB, BTBPE, BEH-TEBP, and PBB-Acr were attributed to matrix effects, suggesting the need to use isotope-labelled surrogate standards of the target compounds. The optimisation of the silica column chromatography, GPC, and Partisil fractionation is described and discussed to afford easy implementation of the method. The method using GPC followed by Partisil fractionation is more efficient and more reproducible than the sulphuric acid-silica procedure. The application of this method to marine biota reference materials revealed the presence of relatively high concentrations of DBE-DBCH isomers and BDE-47 in fish samples. The method detection limits comply with the recommendations of the European Commission. Electronic supplementary material The online version of this article (10.1007/s11356-020-10966-y) contains supplementary material, which is available to authorized users.

Concentrations, profiles and muscle-liver distribution of halogenated natural products (HNPs) and anthropogenic persistent organic pollutants (POPs) were investigated in five large pelagic fish species and one smaller planktivore fish species from the Western Indian Ocean. Analysis of swordfish muscle from the Seychelles revealed the predominance of HNPs, with the highest concentrations found for 2′-methoxy-2,3′,4,5′- tetraBDE (2′-MeO-BDE 68 or BC-2), 6-methoxy-2,2′,4,4′- tetraBDE (6-MeO-BDE 47 or BC-3) and 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1), along with varied contributions of further HNPs. The mean concentration of ∑HNPs (330 ng/g lw) was one or two orders of magnitude higher than ∑DDTs (60 ng/g lw) and ∑PCBs (6.8 ng/g lw). HNPs (BC-2, BC-3 and Q1) were also predominant in individual samples of three tropical tuna species from the Seychelles and from other regions of the Western Indian Ocean (Mozambique Channel, off Somalia and Chagos Archipelago). Non-targeted gas chromatography coupled with electron capture negative ion mass spectrometry operated in the selected ion monitoring mode (GC/ECNI-MS-SIM) analysis of one swordfish sample indicated low abundance of rarely reported HNPs (three hexachloro-1′-methyl-1,2′-bipyrrole (Cl6-MBP) isomers and pentabromo-1,1′-dimethyl-2,2′-bipyrroles (Br5-DBP)) but no further abundant unscreened polyhalogenated compounds. Supplementary Information The online version contains supplementary material available at 10.1007/s11356-021-14738-0.

International audience; The interactions between carbon-based engineered nanoparticles (ENPs) and organic pollutants might enhance the uptake of contaminants into biota. The present integrated study aimed to assess this potential ‘Trojan Horse’, probing the interactive effects of purpose-made multi-walled carbon nanotubes (MWCNTs), a representative ENP, and benzo[a]pyrene (BaP), a ubiquitous polycyclic aromatic hydrocarbon (PAH) pollutant, on the marine mussel Mytilus galloprovincialis. Mussels were exposed to MWCNTs and BaP either alone or in various combinations. The co-exposure of BaP with MWCNTs revealed that the presence of MWCNTs enhanced the aqueous concentrations of BaP, thereby reducing the uptake of this pollutant by mussels as evidenced by lowering BaP concentrations in the tissues. Determination of DNA damage (comet assay) showed a concentration-dependent response for BaP alone which was absent when MWCNTs were present. Global gene expression using microarray analyses indicated that BaP and MWCNTs, in combination, differentially activated those genes which are involved in DNA metabolism compared to the exposures of BaP or MWCNTs alone, and the gene expression response was tissue-specific. Mechanisms to explain these results are discussed and relate primarily to the adsorption of BaP on MWCNTs, mediated potentially by van der Waals interactions. The use of a novel approach based on gold-labeled MWCNTs to track their uptake in tissues improved the traceability of nanotubes in biological samples. Overall, our results did not indicate the ‘Trojan Horse’ effects following co-exposure to the contaminants and clearly showed that the adsorption of BaP to MWCNTs modified the uptake of the pollutant in marine mussels.

Chemical contaminants are one of the causes of the ongoing degradation of coastal and estuarine nurseries, key functional habitats in which the juveniles of many marine species grow. As chemical contaminants can cause a decrease in the energy available and induce defence mechanisms reducing the amount of energy allocated to life history traits, quantifying their effect on the fitness of juvenile fish is key to understand their population-level consequences. However, these effects are primarily estimated experimentally or in the wild but on a limited number of contaminants or congeners that do not reflect the wide variety of chemical contaminants to which juvenile fish are exposed. To address this issue, we measured concentrations of 14 trace metal elements (TMEs) and bioaccumulative organic contaminants (OCs) in European sea bass juveniles (1-year-old) from three major French nurseries (Seine, Loire and Gironde estuaries). We tested the hypotheses that (i) levels and profiles of contaminants differed among studied nurseries, and ii) fish growth and body condition (based on morphometric measurements and muscle C:N ratio) were lower in individuals with higher contaminant concentrations. Multivariate analyses showed that each nursery had distinct contaminant profiles for both TMEs and OCs, confirming the specific contamination of each estuary, and the large array of contaminants accumulated by sea bass juveniles. Increasing concentrations in some TMEs were associated to decreased growth, and TMEs were consistently related to lower fish body condition. The effect of OCs was more difficult to pinpoint possibly due to operational constraints (i.e., analyses on pooled fish) with contrasting results (i.e., higher growth and decreased body condition). Overall, this study shows that chemical contaminants are related to lower fish growth and body condition at an early life stage in the wild, an effect that can have major consequences if sustained in subsequent ages and associated with a decline in survival and/or reproductive success.

The Mytilus mussels are spread all over the world and many related species coexist in several areas and can produce hybrid offspring. Mussels have been used for decades in national and international programs to monitor chemical contamination in the environment. Differences in bioaccumulation and biotransformation abilities between species and their hybrids should be evaluated to assess the comparability of the results obtained within the international biomonitoring programs. The objective of this study was to characterize bioaccumulation abilities and biomarker responses in Mytilus edulis, Mytilus galloprovincialis and their hybrids via an in situ transplantation experimentation on their progenies. Four mussel groups (M. edulis, M. galloprovincialis and two hybrids batches) issued from genetically characterized parents were transplanted for one year in Charente Maritime (France) to ensure their exposure to identical sources of contamination. The bioaccumulation of several families of contaminants (trace metals, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers, polychlorinated biphenyls), the response of several biomarkers (DNA strand breaks level, lysosomal membrane stability, metallothionein content, acetylcholine esterase activity) and some physiological parameters (growth, mortality, gonadal development), were analyzed. Differences were observed between species, however they were contaminant-specific. Variations in contaminants levels were observed between progenies, with higher levels of Cu, PBDE, PCB in M. edulis, and higher levels of Cd, Hg, Zn in M galloprovincialis. This study demonstrated that variations in contaminant bioaccumulation and different biomarker responses exist between Mytilus species in the field. Data on species or the presence of hybrid individuals (or introgression) is an important additional parameter to add to biomonitoring programs databases.

The levels and trends of four bioaccumulative synthetic musks (galaxolide - HHCB, tonalide - AHTN, musk xylene - MX and musk ketone - MK) were investigated in filter-feeding bivalves collected yearly since 2010 at sites of contrasted pressure along the French coasts. Quantification rates were high for all 4 compounds (85–99%), indicating their geographical and temporal extensive occurrence in the French coastal environment. The polycyclic musks HHCB and AHTN prevailed, with median concentrations of 2.27 ng g−1 dw and of 0.724 ng g−1 dw, whilst nitromusks were found 1 to 2 orders of magnitude lower. These levels were in the high range of those encountered for various other CEC families at the same sites and comparable to those from other locations on European coasts. Unlike for the other musks, the accumulation of HHCB was evidenced to be species-specific, with significantly lower levels found in oysters in comparison with mussels, possibly suggesting a higher metabolization in oysters. Geographical differences in musk distribution highlighted the sites under strong anthropogenic pressures and these differences were found to be consistent between years. The HHCB/AHTN ratio proved to be discriminant to explain the relative occurrence of polycyclic musks. The 8-year time series showed that only the now-banned compound MX displayed a significant decrease in most sites, whilst stable concentrations of the other musks suggested consistency in their usage over the last decade. These results provide reference data for future studies of the occurrence of personal care products on European coasts.

International audience; The hypothesis that C fullerene nanoparticles (C) exert an antagonistic interactive effect on the toxicity of benzo[a]pyrene (BaP) has been supported by this investigation. Mussels were exposed to BaP (5, 50 & 100μg/L) and C (C-1mg/L) separately and in combination. Both BaP and C were shown to co-localize in the secondary lysosomes of the hepatopancreatic digestive cells in the digestive gland where they reduced lysosomal membrane stability (LMS) or increased membrane permeability, while BaP also induced increased lysosomal lipid and lipofuscin, indicative of oxidative cell injury and autophagic dysfunction. Combinations of BaP and C showed antagonistic effects for lysosomal stability, mTORC1 (mechanistic target of rapamycin complex 1) inhibition and intralysosomal lipid (5 & 50μg/L BaP). The biomarker data (i.e., LMS, lysosomal lipidosis and lipofuscin accumulation; lysosomal/cell volume and dephosphorylation of mTORC1) were further analysed using multivariate statistics. Principal component and cluster analysis clearly indicated that BaP on its own was more injurious than in combination with C. Use of a network model that integrated the biomarker data for the cell pathophysiological processes, indicated that there were significant antagonistic interactions in network complexity (% connectance) at all BaP concentrations for the combined treatments. Loss of lysosomal membrane stability probably causes the release of intralysosomal iron and hydrolases into the cytosol, where iron can generate harmful reactive oxygen species (ROS). It was inferred that this adverse oxidative reaction induced by BaP was ameliorated in the combination treatments by the ROS scavenging property of intralysosomal C, thus limiting the injury to the lysosomal membrane; and reducing the oxidative damage in the cytosol and to the nuclear DNA. The ROS scavenging by C, in combination with enhanced autophagic turnover of damaged cell constituents, appeared to have a cytoprotective effect against the toxic reaction to BaP in the combined treatments.

The hypothesis that C

Marine pollution has been increasing as a consequence of anthropogenic activities. The preservation of marine ecosystems, as well as the safety of harvested seafood, are nowadays a global concern. Here, we report for the first time the contamination levels of a large set of 99 emerging and persistent organic contaminants (butyltins (BTs), polycyclic aromatic hydrocarbons (PAHs), pesticides including pyrethroids, pharmaceuticals and personal care products (PCPs) and flame retardants) in roe/gonads of sea urchin Paracentrotus lividus. Sea urchins are a highly prized worldwide delicacy, and the harvesting of this seafood has increased over the last decades, particularly in South West Atlantic coast, where this organism is harvested mainly for exportation. Sampling was performed in three harvesting sites of the NW Portuguese coast subjected to distinct anthropogenic pressures: Carreço, Praia Norte and Vila Chã, with sea urchins being collected in the north and south areas of each site. Butyltins and pharmaceuticals were not found at measurable levels. Several PAHs, four pyrethroids insecticides, four PCPs and eleven flame retardants were found in roe/gonads of sea urchins, though in general at low levels. Differences among harvesting sites and between areas within each site were found, the lowest levels of contaminants being registered in Carreço. The accumulation of contaminants in sea urchins’ roe/gonads seemed to reflect the low anthropogenic pressure felt in the sampling sites. Nevertheless, taking into account the low accumulated levels of chemicals, results indicate that sea urchins collected in South West Atlantic coast are safe for human consumption. © 2017 Elsevier Inc. Authors acknowledge INSEAFOOD colleagues that carried out sea urchin samplings. This work has been financially supported by the European project ‘Real time monitoring of SEA contaminants by an autonomous lab-on-a-chip biosensor ( SEA-on-a-CHIP ; No. 614168 ) and the research line INSEAFOOD within the Structured Program of R&D&I INNOVMAR – Innovation and Sustainability in the Management and Exploitation of Marine Resources (Reference NORTE-01–145-FEDER-000035 ) is funded by the Northern Regional Operational Programme ( NORTE2020 ) through the European Regional Development Fund (ERDF). António Marques acknowledge FCT for the IF2014 contract. Carolina Camacho acknowledges MARINALGAE4aqua Project ( ERA-NETCOFASP/004/2015 ) for the research grant. Part of this work was conducted in the Unit of Environmental, Organic and Biochemical high resolution analysis-Orbitrap-LC-MS analysis of the University of Ioannina, Greece and the authors would like to thank the Unit for providing access to the facilities.

A passive sampler inspired from previous devices was developed for the integrative sampling of a broad range of contaminants in the water column. Our primary objective was to improve the performance of the device to provide accurate and averaged pollutant water concentrations. For this purpose, an agarose diffusive gel was used as the boundary layer that drives the analyte uptake rate. Contrary to conventional passive samplers, the developed device does not require the sampling rates to be corrected for exposure conditions (e.g. hydrodynamic flow) because the diffusive gel boundary layer selected was sufficiently large to control the pollutant diffusion rate from the aqueous phase. The compounds diffusion coefficients in agarose gel and the gel thickness are the only required data to accurately calculate the time weighted averaged water concentration of pollutants. The performance of the developed sampler was evaluated in the laboratory under two contamination scenarios and in the field in 8 contrasting exposure sites for a selection of 16 emerging pollutants and pesticides. The results show that detection limits of this method are environmentally relevant and allow the determination of the averaged pollutant concentrations. Additionally, the ability of the device to sense very short contamination pulses (5-320min) was evaluated through a theoretical approach and laboratory tests. Results show that the device is suitable for sampling contamination pulses as short as 5min without deviation from the actual average concentrations of pollutants.

This study aimed to assess the ecotoxicological effects of the interaction of fullerene (C60) and benzo[a]pyrene (B[a]P) on the marine mussel, Mytilus galloprovincialis. The uptake of nC60, B[a]P and mixtures of nC60 and B[a]P into tissues was confirmed by GC-MS, LC-HRMS and ICP-MS. Biomarkers of DNA damage as well as proteomics analysis were applied to unravel the toxic effect of B[a]P and C60. Antagonistic responses were observed at the genotoxic and proteomic level. Differentially expressed proteins (DEPs) were only identified in the B[a]P single exposure and the B[a]P mixture exposure groups containing 1 mg/L of C60, the majority of which were down-regulated (~52%). No DEPs were identified at any of the concentrations of nC60 (p < 0.05, 1% FDR). Using DEPs identified at a threshold of (p < 0.05; B[a]P and B[a]P mixture with nC60), gene ontology (GO) and Kyoto encyclopedia of genes and genomes (KEGG) pathway analysis indicated that these proteins were enriched with a broad spectrum of biological processes and pathways, including those broadly associated with protein processing, cellular processes and environmental information processing. Among those significantly enriched pathways, the ribosome was consistently the top enriched term irrespective of treatment or concentration and plays an important role as the site of biological protein synthesis and translation. Our results demonstrate the complex multi-modal response to environmental stressors in M. galloprovincialis.

The contamination of marine ecosystems by contaminants of emerging concern such as personal care products or per- and polyfluoroalkyl substances is of increasing concern. This work assessed the concentrations of selected contaminants of emerging concern in water and sediment of European aquaculture areas, to evaluate their co-variation with legacy contaminants (polycyclic aromatic hydrocarbons) and faecal biomarkers, and estimate the risks associated with their occurrence. The 9 study sites were selected in 7 European countries to be representative of the aquaculture activities of their region: 4 sites in the Atlantic Ocean and 5 in the Mediterranean Sea. Musks, UV filters, preservatives, per- and polyfluoroalkyl substances and polycyclic aromatic hydrocarbons were detected in at least one of the sites with regional differences. While personal care products appear to be the main component of the water contamination, polycyclic aromatic hydrocarbons were mostly found in sediments. As expected, generally higher levels of personal care products were found in sewage impacted sites, urbanised coasts and estuaries. The risk assessment for water and sediment revealed a potential risk for the local aquatic environment from contaminants of both legacy and emerging concern, with a significant contribution of the UV filter octocrylene. Despite marginal contributions of per- and polyfluoroalkyl substances to the total concentrations, PFOS (perfluorooctane sulfonate) aqueous concentrations combined to its low ecotoxicity thresholds produced significant hazard quotients indicating a potential risk to the ecosystems., This study was financially supported by the SEA-on-a-CHIP project, funded from European Union Seventh Framework Programme (FP7-OCEAN-2013) under grant agreement No. 614168. Antonio Marques is supported through the FCT Investigator program (IF).

International audience; Pharmaceuticals were screened in the estuarine Garonne River to investigate the role of estuaries as passive or active transfer compartments in the removal of these compounds. Monthly monitoring of 53 pharmaceuticals from various therapeutic classes at 6 sampling points over 18 months showed that most compounds were frequently detected with median concentrations in the low ng L− 1 range. Saline intrusion was responsible of an overall dilution but an enrichment from the treated urban effluents of Bordeaux city was also observed with increases resulting from this input being compound dependent. An average cumulated load of 10 kg of the monitored pharmaceuticals was found to enter the estuary daily from the catchment area. After normalization to the persistent marker carbamazepine, a large majority of the compounds were found to exhibit in-stream attenuation during summer while this removal was enhanced farther down the estuary, indicating a likely effect of residence time, temperature and suspended solid concentration on the stability of the pharmaceuticals.

Marine plastic debris can act as a reservoir of chemical additives that can pose a potential threat to sensitive ecosystems such as coral reefs. A survey of foam macrodebris collected on beaches indeed revealed high concentrations of hexabromocyclododecanes (ΣHBCDD) in polystyrene (PS) samples (up to 1940 μg g−1). Results also showed that PS fragments can still leach over 150 ng g−1 d−1 of ΣHBCDD (primarily as the α-isomer) for relatively long durations, and that these additives are readily bioaccumulated and well-retained by corals. Despite significant HBCDD bioaccumulation in coral tissue, short-term exposure to HBCDD or PS leachate had no considerable effect on coral photosynthetic activity, symbiont concentration and chlorophyll content. Exposure to the PS leachate did however cause consistent polyp retraction in nubbins over the 5-day exposure. This response was not observed in animals exposed to HBCDD alone, suggesting that another constituent of the leachate stressed corals.

The study aim was to determine a range of relevant persistent and emerging pollutants in oysters produced in an aquaculture facility located in an important production area, to assure their safety for human consumption. Pollutants, including 16 PAHs, 3 butyltins (BTs), 29 flame retardants (FRs, including organophosphate and halogenated FRs), 35 pesticides (including 9 pyrethroid insecticides) and 13 personal care products (PCPs, including musks and UV filters), were determined in oysters' tissues collected during one year in four seasonal sampling surveys. The seasonal environmental pollution on the production site was evaluated by water and sediment analysis. Furthermore, oysters' nutritional quality was also assessed and related with the consumption of healthy seafood, showing that oysters are a rich source of protein with low fat content and with a high quality index all year around. Results showed that most analysed pollutants were not detected either in oyster tissues or in environmental matrixes (water and sediments). The few pollutants detected in oyster tissues, including both regulated and non-legislated pollutants, such as a few PAHs (fluorene, phenanthrene, anthracene, fluoranthene, pyrene and indenopyrene), FRs (TPPO, TDCPP, DCP, BDE-47, BDE-209 and Dec 602) and PCPs (galaxolide, galaxolidone, homosalate and octocrylene), were present at low levels (in the ng/g dw range) and did not represent a significant health risk to humans. The observed seasonal variations related to human activities (e.g. tourism in summer) highlights the need for environmental protection and sustainable resource exploration for safe seafood production. © 2019 Elsevier B.V., This work was supported by the Structured R&D&I Project INNOVMAR – “Innovation and Sustainability in the Management and Exploitation of Marine Resources” (ref. NORTE-01-0145-FEDER-000035) within the research line “INSEAFOOD - Innovation and valorization of seafood products: meeting local challenges and opportunities”, founded by the Northern Regional Operational Programme (NORTE2020) through the European Regional Development Fund (ERDF). This study was also supported by the SEA-on-a-CHIP project, funded from European Union Seventh Framework Programme (FP7-OCEAN-2013) under grant agreement No. 614168. This work has been also financially supported by the Generalitat de Catalunya (Consolidated Research Group 2017 SGR 01404 – Water and Soil Quality Unit). Biotage is acknowledged for providing SPE cartridges. Authors acknowledge Carlos R. Gomes for helping on multivariated analysis.

International audience; Phthalate acid esters (PAEs) which are mainly anthropogenic molecules with endocrine disrupting effects in animals and humans, have been detected in terrestrial and aquatic environments. However, little is known about their distribution in the Mediterranean Sea, mainly because of analytical difficulties and the high possibility of ambient sample contamination. Here, we report the optimization of an existing protocol for the determination of PAEs in seawater and freshwater samples, as well as the first estimation of the source and distribution of phthalates acid esters (PAEs) in coastal waters from the NW Mediterranean Sea. By passing 1 L of sample through glass cartridges packed with 200 mg of Oasis HLB and eluted with 6 mL of ethyl acetate followed by gas chromatography and mass spectrometry (GC/ MS) analyses, the recoveries for DMP, DEP, DPP, DiBP, DnBP, BzBP, DEHP and DnOP were 101, 98, 115, 110, 99, 98, 103 and 95%, respectively, with acceptable blank values (below 0.4–4.0% of the masses mea- sured in different seawater samples). By using this method, we detected PAEs in the Marseilles coastal area, offshore (2000 m depth) and in the Rhone River with total concentrations ranging from 75.3 ng/L offshore in surface water to 1207.1 ng/L a few meters above the bottom of the Marseilles Bay. High con- centrations were also observed in deep waters offshore (310.2 ng/L) as well as in the Rhone River (615.1 ng/L). These results suggest that Marseilles urban area, Rhone River and sediment are potential sources of PAEs in the areas studied.In the Rhone River, DEHP was the most abundant PAE (66.1%) followed by DiBP (20.5%) and DnBP (6.6%), whereas a gradual change was observed in the plume of the river with increasing salinity. In the Marseilles Bay, DiBP was the most abundant PAE at the surface (47.3% of total PAEs) followed by DEHP (22.7%) and DnBP (19.1%), whereas DnBP was predominant (38.6%) a few meters above the bottom. By contrast, DEHP was the dominant species in the first 50 m (66.9–76.7%) offshore followed by DnBP (10.9–15.2%), whereas DnBP was the most abundant (57.0–72.6%) followed by DEHP (20.1–33.1%) in the deepest waters. This study suggests that in addition to direct PAEs injection in marine waters, differ- ent processes regulate PAE distribution in Mediterranean Sea including photochemical oxidation reac- tions, bacterial degradation and possible diffusion following release from marine litter near the bottom.

The occurrence, fate and behaviour of carbon nanomaterials in the aquatic environment are dominated by their functionalization, association with organic material and aggregation behaviour. In particular, the degradation of fullerene aggregates in the aquatic environment is a primary influence on their mobility, sorption potential and toxicity. However, the degradation and kinetics of water suspensions of fullerenes remain poorly understood. In the present work, first, an analytical method based on liquid chromatography and high-resolution mass spectrometry (LC-HRMS) for the determination of C60 fullerene and their environmental transformation products was developed. Secondly, a series of C60 fullerene water suspensions were degraded under relevant environmental conditions, controlling the salinity, the humic substances content, the pH and the sunlight irradiation. Up to ten transformation products were tentatively identified, including epoxides and dimers with two C60 units linked via one or two adjacent furane-like rings. Fullerenols were not observed under these environmentally relevant conditions. The kinetics of generation of each transformation product were studied with and without simulated sunlight conditions. The ionic strength of the media, its pH and the humic substances content were observed to modulate the kinetics of generation.

International audience

This study focuses on the fate of pharmaceuticals discharged into an estuarine environment, particularly into the Turbidity Maximum Zone (TMZ). Batch experiments were set up to investigate the factors regulating the degradation of 53 selected pharmaceuticals. Treated effluents from Bordeaux city (France) were mixed with water from the estuarine Garonne River during 4 weeks under 6 characterized conditions in order to assess the influence of suspended particulates, sterilization, untreated wastewater input and dilution on the degradation kinetics. Of the 53 pharmaceuticals monitored, 43 were quantified at the initial time. Only 7 exhibited a persistent behavior (e.g. carbamazepine, meprobamate) while biotic degradation was shown to be the main attenuation process for 38 molecules (e.g. abacavir, ibuprofen highly degradable). Degradation was significantly enhanced by increasing concentrations of suspended solids. A persistence index based on the half-lives of the compounds has been calculated for each of the 43 pharmaceuticals to provide a practical estimate of their relative stability. The stability of pharmaceuticals in estuarine environments is likely to be highly variable and attenuated primarily by changes in suspended solid concentration.

We report a novel and inexpensive method to provide high resolution vertical measurements of temporally integrated organic contaminants in surface and sub-surface waters in polluted coastal environments. It employs a strip of polyethylene deployed as a passive sampler. Verifications are confirmed via conventional spot sample analyses and against Performance Reference Compound (PRC) calibration methods. Analytes targeted include 16 Polycyclic Aromatic Hydrocarbons, 15 personal care products, 8 organophosphorus flame retardants, 4 antifouling ‘booster’ biocides and 15 n-alkanes. Whilst all contaminants typically revealed homogeneous concentrations from 10 cm to 3 m depth in the selected harbour (

We used the marine bivalve (Mytilus galloprovincialis) to assess a range of biological or biomarker responses following exposure to a model-engineered nanoparticle, C60 fullerene, either alone or in combination with a model polycyclic aromatic hydrocarbon, benzo(α)pyrene [B(α)P]. An integrated biomarker approach was used that included: (i) determination of 'clearance rates' (a physiological indicator at individual level), (ii) histopathological alterations (at tissue level), (iii) DNA strand breaks using the comet assay (at cellular level) and (iv) transcriptional alterations of p53 (anti-oncogene) and ras (oncogene) determined by real-time quantitative polymerase chain reaction (at the molecular/genetic level). In addition, total glutathione in the digestive gland was measured as a proxy for oxidative stress. Here, we report that mussels showed no significant changes in 'clearance rates' after 1 day exposure, however significant increases in 'clearance rates' were found following exposure for 3 days. Histopathology on selected organs (i.e. gills, digestive glands, adductor muscles and mantles) showed increased occurrence of abnormalities in all tissues types, although not all the exposed organisms showed these abnormalities. Significantly, increased levels of DNA strand breaks were found after exposure for 3-days in most individuals tested. In addition, a significant induction for p53 and ras expression was observed in a tissue and chemical-specific pattern, although large amounts of inter-individual variability, compared with other biomarkers, were clearly apparent. Overall, biological responses at different levels showed variable sensitivity, with DNA strand breaks and gene expression alterations exhibiting higher sensitivities. Furthermore, the observed genotoxic responses were reversible after a recovery period, suggesting the ability of mussels to cope with the toxicants C60 and/or B(α)P under our experimental conditions. Overall, in this comprehensive study, we have demonstrated mussels as a suitable model marine invertebrate species to study the potential detrimental effects induced by possible genotoxicants and toxicants, either alone or in combinations at different levels of biological organisation (i.e. molecular to individual levels).

International audience; Comprehensive source and fate studies of pharmaceuticals in the environment require analytical methods able to quantify a wide range of molecules over various therapeutic classes, in aqueous and solid matrices. Considering this need, the development of an analytical method to determine 53 pharmaceuticals in aqueous phase and in solid matrices using a combination of microwave-assisted extraction, solid phase extraction, and liquid chromatography coupled with tandem mass spectrometry is reported. Method was successfully validated regarding linearity, repeatability, and overall protocol recovery. Method detection limits (MDLs) do not exceed 1 ng L−1 for 40 molecules in aqueous matrices (6 ng L−1 for the 13 remaining), while subnanogram per gram MDLs were reached for 38 molecules in solid phase (29 ng g−1 for the 15 remaining). Losses due to preparative steps were assessed for the 32 analytes associated to their labeled homologue, revealing an average loss of 40 % during reconcentration, the most altering step. Presence of analytes in wastewater treatment plant (WWTP) effluent aqueous phase and suspended solids (SS) as well as in river water, SS, and sediments was then investigated on a periurban river located in the suburbs of Bordeaux, France, revealing a major contribution of WWTP effluent to the river contamination. Sorption on river SS exceeded 5 % of total concentration for amitriptyline, fluoxetine, imipramine, ritonavir, sildenafil, and propranolol and appeared to be submitted to a seasonal influence. Sediment contamination was lower than the one of SS, organic carbon content, and sediment fine element proportion was accountable for the highest measured concentrations.

Dans le cadre du Réseau de Surveillance Prospective, un volet littoral est décliné en 2019, avec l’objectif de proposer un dispositif de recherche des substances d’intérêt émergent (contaminants of emerging concern - CEC) en milieu marin qui permettre in fine d’alimenter la liste des substances pertinentes candidates aux PSEE (Polluants Spécifiques de l’Etat Ecologique). Cela se traduit par l’élaboration en 2019 d’une stratégie d’acquisition de données (substances, matrices, points d’échantillonnage, fréquence et période) et sa déclinaison opérationnelle pour une acquisition de données en 2020-2022. Le principe est d’assurer la pérennité et l’évolutivité de ce dispositif. L’élaboration de cette stratégie s’appuie sur les travaux engagés depuis plus de 10 années par l’Ifremer sur les échantillonneurs passifs en lien avec l’AFB et Aquaref et sur l’expertise et la mise en œuvre de la surveillance environnementale opérées via le ROCCH et le projet de recherche Veille-POP.

Le dispositif « SELI » est mis en place depuis 2016 pour acquérir des données sur les effets biologiques intégrateurs de la contamination chimique chez des organismes marins (poissons et bivalves) et ainsi renseigner le critère 2 du descripteur 8 de la DCSMM (Le niveau de concentration des contaminants ne provoque pas d’effets dus à la pollution). Le présent rapport concerne le volet SELIseine. Des poissons plats (194 soles, flets et limandes) ont été prélevés en septembre 2018 sur le N/O Antéa, et des moules ont été prélevées en février 2019 sur 6 stations dans le cadre du suivi ROCCH MV suivant le protocole de la convention OSPAR (2012). Les biomarqueurs suivis chez ces organismes couvrent plusieurs types d’effets toxiques (reprotoxicité, génotoxicité, neurotoxicité) et incluent des mesures de la santé générale de l'organisme (pathologies, indices somatiques (e.g. RGS, RHS), stabilité de la membrane lysosomale). Les contaminants listés dans les Arrêtés du 17 décembre 2012 relatif à la définition du bon état écologique des eaux marines et du 28 avril 2015 relatif aux critères et méthodes pour l'élaboration et la mise en œuvre du programme de surveillance du plan d'action pour le milieu marin sont suivis. Ils concernent des éléments traces métalliques et des contaminants organiques hydrophobes (historiques et émergents) susceptibles de s’accumuler dans les organismes et/ou de s’amplifier dans les réseaux trophiques. L’ensemble de ces analyses permet de répondre aux questions : 1) Quelles sont les réponses biologiques observées chez les organismes marins (poissons plats, bivalves) ? 2) Quel est le niveau d’imprégnation des organismes marins (poissons plats, bivalves) à la contamination chimique ? et 3) Les réponses biologiques observées peuvent-elles être associées à l’exposition à un stress chimique dans des zones de pressions anthropiques variées ? De plus, les analyses de biomarqueurs et contaminants chez les soles, flets et limandes prélevés lors de la même campagne sur le N/O Antéa ont permis : 1) D’évaluer les différences entre les réponses biologiques (biomarqueurs) et les niveaux d’imprégnation chez ces trois espèces de poissons plats : sole, flet et limande 2) D’évaluer l’applicabilité des seuils (EAC) développés au niveau du CIEM aux poissons plats suivis dans le cadre des SELI Atlantique : sole et flet. Le présent rapport est organisé selon un niveau d’intégration croissant, il commence par décrire chaque biomarqueur et chaque famille de contaminants individuellement, puis des représentations intégrées sont ensuite proposées pour avoir une vision de plus en plus globale, et donc de moins en moins détaillée, de la contamination chimique et de ses effets en Baie de Seine. Chaque niveau d’intégration est lié, et il est donc possible de passer d’une vision globale à une vision détaillée selon l’objectif recherché.