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The overall objective of the 2018 survey campaign of contaminants of emerging concern in surface waters (continental and coastal) and sediments known as EMNAT 2018, is to provide monitoring data for the emerging contaminants prioritization exercise, which will allow the update of the list of relevant substances to be monitored (SPAS), as part of the future Water Framework Directive (WFD) monitoring programmes (2022). This campaign collected nearly 14,000 data regarding 49 contaminants of emerging concern (32 biocides and 17 surfactants) in surface waters and sediments on 98 sites in mainland France and in the French overseas regions. Linear Alkylbenzene Sulfonic acids (LAS) were the most frequently quantified surfactants and at the highest median concentrations in water and sediment samples, in metropolitan France and in the overseas regions. Fipronil was the most frequently quantified biocide in water samples in metropolitan France and in the overseas regions, but at lower median concentrations than other biocides. Methyl nonyl ketone was the most frequently quantified biocide and at high median concentrations in sediment samples from mainland France and in overseas regions. Based on the available predicted no effect concentrations (PNEC), several contaminants were identified as highly and moderately critical regarding the PNEC exceedance, and will be considered to be included in the SPAS list for the next WFD cycle.

Azoles represent the most used family of organic fungicides worldwide and they are used in agriculture to circumvent the detrimental impact of fungi on yields. Although it is known that these triazoles can contaminate the air, the soil, and the water, field data are currently and dramatically lacking to assess if, and to what extent, the use of triazoles could contaminate non-target wild vertebrate species, notably in agroecosystems. In this study, we aimed to document for the first time the degree of blood contamination of a generalist wild bird species by multiple azoles which are used for plant protection and fungi pest control in various habitats. We deployed passive air samplers and captured 118 Common blackbirds (Turdus merula) in an agroecosystem (vineyard), a protected forest, and a city in western France. We collected blood and analyzed the plasma levels of 13 triazoles and 2 imidazoles. We found that a significant percentage of blackbirds living in vineyards have extremely high plasma levels of multiple azoles (means (pg.g

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in aquatic environments and a recent shift toward emerging PFAS is calling for new data on their occurrence and fate. In particular, understanding the determinants of their bioaccumulation is fundamental for risk assessment purposes. However, very few studies have addressed the combined influence of potential ecological drivers of PFAS bioaccumulation in fish such as age, sex or trophic ecology. Thus, this work aimed to fill these knowledge gaps by performing a field study in the Seine River basin (France). Composite sediment and fish (European chub, Squalius Cephalus) samples were collected from four sites along a longitudinal transect to investigate the occurrence of 36 PFAS. Sediment molecular patterns were dominated by fluorotelomer sulfonamidoalkyl betaines (i.e. 6:2 and 8:2 FTAB, 46% of ∑PFAS on average), highlighting the non-negligible contribution of PFAS of emerging concern. C

International audience; The rivers of Guadeloupe and Martinique (French West Indies) show high levels of chlordecone (CLD) contamination. This persistent molecule has a dramatic impact on both aquatic ecosystems and human health. In these rivers, epilithic biofilms are the main endogenous primary producers and represent a central food source for fish and crustaceans. Recently, their viscoelastic properties have been shown to be effective in bio-assessing pollution in tropical environments. As these properties are closely related to the biochemical composition of the biofilms, biochemical (fatty acids, pigments, extracellular polymeric substances (EPS) monosaccharides) and molecular markers (T-RFLP fingerprints of bacteria, archaea and eukaryotes) were investigated. Strong links between CLD pollution and both biofilm biochemistry and microbial community composition were found. In particular, high levels of CLD were linked with modified exo-polysaccharides corresponding to carbohydrates with enhanced adsorption and adhesion properties. The observed change probably resulted from a preferential interaction between CLD and sugars and/or a differential microbial secretion of EPS in response to the pollutant. These changes were expected to impact viscoelastic properties of epilithic biofilms highlighting the effect of CLD pollution on biofilm EPS matrix. They also suggested that microorganisms implement a CLD scavenging strategy, providing new insights on the role of EPS in the adaptation of microorganisms to CLD-polluted environments.

The last remaining population of European sturgeon (Acipenser sturio) lives in the Gironde-Garonne-Dordogne (France) catchment (GGD). Captive young individuals are released into the GGD hydrosystem each year, as part of a restocking programme. This study aims to assess the health status of juveniles A. sturio to current conditions in the GGD hydrosystem, to evaluate their capacity to survive and grow in a moderately anthropized ecosystems. 3-month-old farmed sturgeons were exposed for one month in experimental conditions that mimic the environmental conditions in the Garonne and Dordogne rivers, followed by five months of depuration. After one month of exposure, fish exposed to Dordogne and Garonne waters bioaccumulated higher levels of metals and persistent organic pollutants, displayed a reduced hepato-somatic index, and had depleted levels of lipids and glycogen content in their liver, when compared with the Reference group. However, metabolic and swimming performance, as well as the costs of swimming were not impaired. After the 5 months depuration, a significant decrease of K was observed for all exposure conditions. HSI also decreased with time. The overall health status and adaptive capacity of juvenile A. sturio appeared to be maintained over the experimental 6 months' period. Juveniles of A. sturio seem to have the adaptive capacity to survive and grow in the GGD hydrosystem, after being released as part of a restocking programme.

Corrigendum: Aquatic Toxicology, Volume 247, June 2022, Pages 106166 https://doi.org/10.1016/j.aquatox.2022.106166 WOS:000799284400001; International audience; Transgenic fish are powerful models that can provide mechanistic information regarding the endocrine activity of test chemicals. In this study, our objective was to use a newly developed transgenic zebrafish line expressing eGFP under the control of the cyp19a1a promoter in the OECD Fish Short Term Reproduction Assay (TG 229) to provide additional mechanistic information on tested substances. For this purpose, we exposed adult transgenic zebrafish to a reference substance of the TG 229, i.e. prochloraz (PCZ; 1.7, 17.2 and 172.6 μg/L). In addition to “classical” endpoints used in the TG 229 (reproductive outputs, vitellogenin), the fluorescence intensity of the ovaries was monitored at 4 different times of exposure using in vivo imaging. Our data revealed that 172.6 μg/L PCZ significantly decreased the number of eggs laid per female per day and the concentrations of vitellogenin in females, reflecting the decreasing E2 synthesis due to the inhibition of the ovarian aromatase activities. At 7 and 14 days, GFP intensities in ovaries were similar over the treatment groups but significantly increased after 21 days at 17.2 and 172.6 μg/L. A similar profile was observed for the endogenous cyp19a1a expression measured by qPCR thereby confirming the reliability of the GFP measurement for assessing aromatase gene expression. The overexpression of the cyp19a1a gene likely reflects a compensatory response to the inhibitory action of PCZ on aromatase enzymatic activities. Overall, this study illustrates the feasibility of using the cyp19a1a-eGFP transgenic line for assessing the effect of PCZ in an OECD test guideline while providing complementary information on the time- and concentration-dependent effects of the compound, without disturbing reproduction of fish. The acquisition of this additional mechanistic information on a key target gene through in vivo fluorescence imaging of the ovaries was realized without increasing the number of individuals.

International audience; Bed sediments and a dated sediment core were collected upstream and downstream from the city of Lyon (France) to assess the spatial and temporal trends of contamination by per- and polyfluoroalkyl substances (PFASs) in this section of the Rhône River. Upstream from Lyon, concentrations of total PFASs (ΣPFASs) in sediments are low (between 0.19 and 2.6 ng g−1 dry weight - dw), being characterized by a high proportion of perfluorooctane sulfonate (PFOS). Downstream from Lyon, and also from a fluoropolymer manufacturing plant, ΣPFASs concentrations reach 48.7 ng g−1 dw. A gradual decrease of concentrations is reported at the coring site further downstream (38 km). Based on a dated sediment core, the temporal evolution of PFASs is reconstructed from 1984 to 2013. Prior to 1987, ΣPFASs concentrations were low (≤2 ng g−1 dw), increasing to a maximum of 51 ng g−1 dw in the 1990s and then decreasing from 2002 to the present day (∼10 ng g−1 dw). In terms of the PFAS pattern, the proportion of perfluoroalkyl sulfonic acids (PFSAs) has remained stable since the 1980s (∼10%), whereas large variations are reported for carboxylic acids (PFCAs). Long chain- (C > 8) PFCAs characterized by an even number of perfluorinated carbons represent about 74% of the total PFAS load until 2005. However, from 2005 to 2013, the relative contribution of long chain- (C > 8) PFCAs with an odd number of perfluorinated carbons reaches 80%. Such changes in the PFAS pattern likely highlight a major shift in the industrial production process. This spatial and retrospective study provides valuable insights into the long-term contamination patterns of PFAS chemicals in river basins impacted by both urban and industrial activities.

International audience; Per- and poly-fluoroalkyl substances (PFAS) raised increasing concerns over the past years due to their persistence and global distribution. Understanding their occurrence in the environment and their disruptive effect on the physiology of humans and wildlife remains a major challenge in ecotoxicological studies. Here, we investigate the occurrence of several carboxylic and sulfonic PFAS in 105 individuals of three seabird species (27 great black-backed gull Larus marinus; 44 lesser black-backed gull Larus fuscus graellsii; and 34 European herring gull Larus argentatus) from South western France. We further estimated the relationship between plasma concentrations of PFAS and i) the body condition of the birds and ii) plasma concentrations of thyroid hormone triiodothyronine (TT3). We found that great and lesser black-backed gulls from South Western France are exposed to PFAS levels comparable to highly contaminated species from other geographical areas, although major emission sources (i.e. related to industrial activities) are absent in the region. We additionally found that PFAS are negatively associated with the body condition of the birds in two of the studied species, and that these results are sex-dependent. Finally, we found positive associations between exposure to PFAS and TT3 in the great black-backed gull, suggesting a potential disrupting mechanism of PFAS exposure. Although only three years of data have been collected, we investigated PFAS trend over the study period, and found that great black-backed gulls document an increasing trend of plasma PFAS concentration from 2016 to 2018. Because PFAS might have detrimental effects on birds, French seabird populations should be monitored since an increase of PFAS exposure may impact on population viability both in the short- and long-term.

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.

International audience; AbstractThis study addresses the spatio-temporal dynamics of per and polyfluoroalkyl substances (PFASs) in a highly urbanized freshwater hydrosystem, the Seine River (NW France). The distribution of PFASs between water, sediment, and periphytic biofilm was investigated at three sampling sites along a longitudinal gradient upstream and downstream from the Paris urban area. Seasonal variability was assessed through four sampling campaigns performed under contrasting hydrological conditions. In the dissolved phase, ∑PFASs fluctuated between 2 and 9 ng L−1 upstream and 6–105 ng L−1 downstream from Paris. Negative correlations between dissolved PFAS levels and river flow rate were generally observed, corroborating the predominance of point-source PFAS inputs at these sites. 18/19 target PFASs were detected, with a predominance of PFHxS and PFOS (20% of ∑PFASs each), except for the farthest downstream site where 6:2 FTSA was prevalent (35 ± 8% of ∑PFASs), likely reflecting industrial and urban inputs. In biofilms, ∑PFASs fell in the 4–32 ng g−1 dw range, and substantial bioconcentration factors (BCFs) were reported for PFNA, PFDA, and PFOS (log BCF 2.1–4.3), higher than those of PFHxS or PFOA. BCFs varied inversely with dissolved PFAS levels, potentially pointing to concentration-dependent bioaccumulation. Biofilm community characteristics (C/N ratio) may also be an influential determinant of PFAS bioaccumulation.

Kinetics of photodegradation of novel oral anticoagulants dabigatran, rivaroxaban, and apixaban were studied under simulated solar light irradiation in purified, mineral, and river waters. Dabigatran and rivaroxaban underwent direct photolysis with polychromatic quantum yields of 2.2 x 10(-4) and 4.4 x 10(-2), respectively. The direct photodegradation of apixaban was not observed after 19 h of irradiation. Kinetics of degradation of rivaroxaban was not impacted by the nature of the aqueous matrix while photosensitization from nitrate ions was observed for dabigatran and apixaban dissolved in a mineral water. The photosensitized reactions were limited in the tested river water (Isle River, Perigueux, France) certainly due to the hydroxyl radical scavenging effect of the dissolved organic matter. The study of photoproduct structures allowed to identify two compounds for dabigatran. One of them is the 4-aminobenzamidine while the second one is a cyclization product. In the case of rivaroxaban, as studied by very high field NMR, only one photoproduct was observed i.e. a photoisomer. Finally, seven photoproducts were clearly identified from the degradation of apixaban under simulated solar light. (C) 2017 Elsevier Ltd. All rights reserved.

Microalgae, which are the foundation of aquatic food webs, may be the indirect target of herbicides used for agricultural and urban applications. Microalgae also interact with other compounds from their environment, such as natural dissolved organic matter (DOM), which can itself interact with herbicides. This study aimed to evaluate the influence of natural DOM on the toxicity of three herbicides (diuron, irgarol and S-metolachlor), singly and in ternary mixtures, to two marine microalgae, Chaetoceros calcitrans and Tetraselmis suecica, in monospecific, non-axenic cultures. Effects on growth, photosynthetic efficiency (?\textquoterightM) and relative lipid content were evaluated. The chemical environment (herbicide and nutrient concentrations, dissolved organic carbon and DOM optical properties) was also monitored to assess any changes during the experiments. The results show that, without DOM, the highest irgarol concentration (I0.5: 0.5 mg.L-1) and the strongest mixture (M2: irgarol 0.5 μg.L-1 + diuron 0.5 μg.L-1 + S-metolachlor 5.0 μg.L-1) significantly decreased all parameters for both species. Similar impacts were induced by I0.5 and M2 in C. calcitrans (around -56% for growth, -50% for relative lipid content and -28% for ?\textquoterightM), but a significantly higher toxicity of M2 was observed in T. suecica (-56% and -62% with I0.5 and M2 for growth, respectively), suggesting a possible interaction between molecules. With DOM added to the culture media, a significant inhibition of these three parameters was also observed with I0.5 and M2 for both species. Furthermore, DOM modulated herbicide toxicity, which was decreased for C. calcitrans (-51% growth at I0.5 and M2) and increased for T. suecica (-64% and -75% growth at I0.5 and M2, respectively). In addition to the direct and/or indirect (via their associated bacteria) use of molecules present in natural DOM, the characterization of the chemical environment showed that the toxic effects observed on microalgae were accompanied by modifications of DOM composition and the quantity of dissolved organic carbon excreted and/or secreted by microorganisms. This toxicity modulation in presence of DOM could be explained by (i) the modification of herbicide bioavailability, (ii) a difference in cell wall composition between the two species, and/or (iii) a higher detoxification capacity of C. calcitrans by the use of molecules contained in DOM. This study therefore demonstrated, for the first time, the major modulating role of natural DOM on the toxicity of herbicides to marine microalgae. \textcopyright 2018 Elsevier B.V.

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.

International audience; We report on a fast, accurate and rugged analytical procedure to determine a wide span of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in seabird plasma. The 26 investigated compounds included perfluoroalkyl carboxylates (C5–C14 PFCAs), perfluoroalkyl sulfonates (C4, C6, C7, C8, C10 PFSAs), perfluorooctane sulfonamide (FOSA) and N-alkyl derivatives (MeFOSA, EtFOSA), N-alkyl perfluorooctane sulfonamido acetic acids (MeFOSAA, EtFOSAA), fluorotelomer sulfonates (4:2 FTSA, 6:2 FTSA, 8:2 FTSA), polyfluoroalkyl phosphate diesters (diPAPs) and perfluorooctane sulfonamide phosphate diester (diSAmPAP). The method described herein requires a reduced sample amount (25 μL) and involves rapid and simple sample preparation (protein precipitation with acetonitrile but without acidification) prior to analysis by on-line solid phase extraction (Oasis HLB sorbent) coupled to high performance liquid chromatography negative electrospray ionization tandem mass spectrometry. The optimization was conducted using experimental designs to account for potential interactions between variables. Out of the 26 target analytes, 23 compounds showed excellent accuracy (± 25% of the expected values). Intermediate precision and matrix effects remained acceptable for most analytes thanks to efficient internal standardization. A human serum standard reference material (NIST SRM 1957) was included in the validation scheme to evaluate method trueness, which proved satisfactory (│Z-scores│54% of ΣPFASs on average). The reduced plasma amount required implies that the present method could also be applied to the analysis of PFASs in the plasma of smaller biological models

International audience; The occurrence and spatial distribution of 22 selected perfluoroalkyl and polyfluoroalkyl substances (PFASs) in surface water (n=75), groundwater (n=80) and surficial sediment (n=15) were investigated for the first time in the tropical areas constituted by the French Overseas Territories (French Guiana, Guadeloupe, Martinique, Mayotte and Reunion). Descriptive statistics and correlations between PFASs were evaluated through the use of specific statistical treatments to handle left-censored data ("non-detects"). PFASs were ubiquitous in these samples and detection frequencies as high as 79% for perfluorooctane sulfonate (PFOS) and 65% for perfluorooctanoate (PFOA) were reported in surface waters. Sigma PFASs was in the range

The aim of the present study, one of the most complete ever performed in France, was to carry out an extensive survey on the potential presence of a large amount of emerging contaminants in 40 French bottled waters, including parent compounds and metabolites. The studied samples represented 70% of the French bottled water market in volume. Six classes of compounds were investigated, most of them being unregulated in bottled waters: pesticides and their transformation products (118), pharmaceutical substances (172), hormones (11), alkylphenols (APs) (8), phthalates (11) and perfluoroalkyl substances (PFAS) (10). One of the objectives of this work was to achieve low and reliable limits of quantification (LOQs) (87% of the LOQs were below 10 ng/L) using advanced analytical technologies and reliable sample preparation methodologies, including stringent quality controls. Among the 14,000 analyses performed, 99.7% of the results were below the LOQs. None of the hormones, pharmaceutical substances and phthalates were quantified. Nineteen compounds out of the 330 investigated were quantified in 11 samples. Eleven were pesticides including 7 metabolites, 6 were PFAS and 2 were APs. As regards pesticides, their sum was at least twice lower than the quality standards applicable for bottled waters in France. The presence of a majority of pesticide metabolites suggested a former use in the recharge areas of the exploited aquifers. The quantification of a few unregulated emerging compounds at the nano-trace level, such as PFAS, raised the issue of their potential sources, including long-range atmospheric transport and deposition. This study confirmed that the groundwater aquifers exploited for bottling were well-preserved from chemicals, as compared to less geologically protected groundwaters, and also underlined the need to pursue the protection policies implemented in recharge areas in order to limit the anthropogenic pressure.

Metolachlor is one of the most intensively used chloroacetanilide herbicides in agriculture. Consequently, it has been frequently detected in coastal waters as well as its major degradation products, metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOA) which are encountered at higher concentrations than metolachlor. Although a few studies of metolachlor toxicity have been conducted on marine organisms, little is known about the environmental toxicity of metolachlor degradation products. In this study, the deleterious effects of metolachlor and its degradation products on spermatozoa and embryos of Crassostrea gigas have been compared using biomarkers of developmental defects, DNA damage and gene transcription levels. After 24h exposure, significant increases in the percentage of abnormal D-larvae and DNA damage were observed from 0.01 μg L(-1) for S-metolachlor and 0.1 μg L(-1) for MESA and MOA. Results showed that S-metolachlor was more embryotoxic and genotoxic than its degradation products. Oyster sperm was also very sensitive to metolachlor exposure and followed the pattern: metolachlor (0.01 μg L(-1))>MOA (0.1 μg L(-1))>MESA (1 μg L(-1)). Metolachlor and MESA mainly triggered variations in the transcription level of genes encoding proteins involved in oxidative stress responses (mitochondrial superoxide dismutase and catalase). Overall, no significant variation in transcription levels could be detected in C. gigas embryos exposed to MOA. This study demonstrates that metolachlor and its main degradation products have the potential to impact several steps of oyster development and therefore recruitment in coastal areas exposed to chronic inputs of pesticides.

The purpose of the Water Framework Directive is to ensure the quality of the natural water across Europe. In this context, passive samplers have shown interesting capacities for the monitoring of contaminants in aqueous ecosystems. They allow the measurement of time-weighted average concentrations, overcoming many drawbacks of the spot-sampling techniques known to be expensive and time consuming. However, application of passive samplers such as polar organic chemical integrative samplers (POCIS) for the monitoring of hydrophilic contaminants requires calibration to define compound sampling rates; key parameters to deduce the pollutant water concentrations from the amounts of pollutants accumulated by the device. Unfortunately, sampling rates are influenced by a range of environmental factors; in that respect, a question remains: is it not evident to know to what extent the sampling rates obtained in laboratory experiments can be used in field conditions? The problem can be solved for hydrophobic samplers by using performance reference compounds (PRCs), and an ongoing challenge for POCIS is focused on the improvement of the quantitative aspect of this family of samplers. In this study, potential PRCs have been selected during a specific experiment and their performance was tested in the laboratory under two hydrodynamic conditions. Results revealed a good proportionality between elimination rates of PRCs and sampling rates of chemicals. Afterwards, the application of the approach under environmental conditions was assessed by deploying POCIS in the Arcachon Bay (France) where POCIS-PRC-derived water concentrations appear to be close to the simultaneous grab-sampling results.

POCIS (polar organic chemical integrative samplers) are increasingly used for sampling polar compounds. Although very efficient for a wide range of pollutants, the classic configuration of the device has a number of limitations, in particular for the sampling of highly polar analytes and hydrophobic compounds. This study presents a new version of the POCIS passive sampler which uses a highly porous Nylon membrane of 30 μm pore size, enabling the sampling of hydrophobic pollutants and improving the accumulation rate of other pollutants. This newly designed tool and the classic POCIS were both tested during a laboratory experiment to evaluate the accumulation kinetics of a selection of pesticides and pharmaceuticals. The observed results show unexpected accumulation kinetics for the new version of POCIS. To explain the data, the use of an intraparticulate diffusion model was required, which also enabled us to propose another explanation of the burst effect observed with the classic POCIS, primarily related to the potential wetting of the device as the first step in the accumulation of compounds.

WOS:000380385800017; International audience; The Serotonin/Norepinephrine Reuptake Inhibitor (SNRI) antidepressant venlafaxine (VEN, Effexor (R)) has become one of the most common antidepressants detected in North American and European streams. Mammalian research has established that VEN exposure is associated with a range of structural, neurochemical, and functional alterations of the brain in adults and newborns. However, the neurodevelopmental effects of VEN on non-target organisms have never been investigated. The aim of our research was to decrease this gap in knowledge by characterizing the effects of VEN exposure on a cephalopod mollusk, the common cuttlefish Sepia officinalis. This species inhabits VEN-contaminated waters and possesses an unusually sophisticated brain. These characteristics render it a unique invertebrate species for studying the neurodevelopmental effects of VEN. Cuttlefish were exposed to environmentally-relevant concentrations of VEN (Measured concentrations approximate to 5 and 100 ng L-1) or to filtered natural seawater (control) in a closed-loop system with regular water changes during the first 20 days after hatching. We evaluated brain maturation as well as neurochemical changes and behavioral performances during this critical period of development. Our results show that both VEN-exposed groups exhibited a decrease in norepinephrine levels, along with a reduction in the relative number of glutamate NMDA-like receptors binding sites in the group exposed to 5 ng L-1 of VEN after 20 days of exposure. Brain regional changes in cellular proliferation were observed in VEN-exposed groups in the vertical lobe (i.e. a key structure involved in cognitive processes) and in the optic lobes (i.e. main visual processing centers) in the absence of significant change in their volume. Along with these neurodevelopmental changes, 20 days of exposure to 100 ng L-1 of VEN was associated with a decrease in camouflage ability. Overall, our study suggests that VEN is a neurodevelopmental toxicant in non-target aquatic organisms at environmentally-relevant concentrations. (C) 2016 Elsevier B.V. All rights reserved.

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.

Cent dix-neuf pesticides ont été recherchés dans des eaux naturelles de la Jalle d’Eysines, un cours d’eau aquitain, et dans des effluents de zones industrielles bordelaises, au cours de deux campagnes de prélèvement. Les molécules ont été quantifiées à partir de prélèvements moyennés sur 24 h. En parallèle, des échantillonneurs passifs de type POCIS (Polar Organic Chemicals Integrative Sampler) ont permis d’établir un suivi qualitatif. Les profils moléculaires au sein d’un même type de masse d’eaux sont identiques, mais diffèrent entre une eau naturelle et un effluent de zone industrielle. L’approche qualitative via les POCIS a permis de quantifier des molécules non détectées lors des prélèvements moyennés, tant pour les eaux de la Jalle d’Eysines que pour celles des zones industrielles. Les échantillonneurs passifs semblent donc prometteurs pour la caractérisation de masses d’eaux de différentes origines, en ce qui concerne les pesticides dont le log KOW est compris entre un et quatre. Il est cependant nécessaire de développer la démarche PRC (Performance Reference Compounds) afin d’y ajouter une visée quantitative., One hundred and nineteen pesticides were investigated in the Aquitaine river “la Jalle d’Eysines”, and in industrial-zone sewage waters from Bordeaux in France, for two sampling campaigns. Compounds were quantified with average grab sampling and Polar Organic Chemical Integrative Samplers (POCIS) were used at these sampling points for screening purposes. Waters of the same origin had similar contamination profiles. However these profiles were different in structure and concentration between waters of different origins. The qualitative approach with passive samplers demonstrates that some compounds are not quantified in grab samples for both natural and sewage waters. POCIS seem to be interesting for pesticide analysis for the different kinds of water, provided that the targeted compounds have a log KOW value between one and four. The development of Performance Reference Compounds appears to be necessary to implement a quantitative approach based on passive sampling.

The global phenolic content of argan oil and press cake samples (alimentary and cosmetic) was evaluated using the Folin-Ciocalteu colorimetric method and the phenolic composition of argan oil (alimentary and cosmetic) and press cake (alimentary) samples were analyzed by GC-MS after extraction with 80:20 (v/v) methanol:water and silylation. Identification of chromatographic peaks was made by mass selective detection. Nineteen simple phenols were detected, 16 in press cake, 6 in the alimentary oil, and 7 in the cosmetic oil, among which 15 compounds [3-hydroxypyridine (3-pyridinol), 6-methyl-3-hydroxypyridine, catechol, resorcinol, 4-hydroxybenzyl alcohol, vanillin, 4-hydroxyphenylacetic acid, vanillyl alcohol, 3,4-dihydroxybenzyl alcohol, 4-hydroxy-3-methoxyphenethyl alcohol, methyl 3,4-dihydroxybenzoate, hydroxytyrosol, protocatechuic acid, epicatechin, and catechin] were identified for the first time in such materials.

To prepare composite films from biopolymers with anti-listerial activity and moisture barrier properties, the antimicrobial efficiency of chitosan-hydroxy propyl methyl cellulose (HPMC) films, chitosan-HPMC films associated with lipid, and chitosan-HPMC films chemically modified by cross-linking were evaluated. In addition, the physicochemical properties of composite films were evaluated to determine their potential for food applications. The incorporation of stearic acid into the composite chitosan-HPMC film formulation decreased water sensitivity such as initial solubility in water and water drop angle. Thus, cross-linking of composite chitosan-HPMC, using citric acid as the cross-linking agent, led to a 40% reduction in solubility in water. The water vapor transfer rate of HPMC film, approximately 270 g x m(-2) x day(-1) x atm(-1), was improved by incorporating chitosan and was further reduced 40% by the addition of stearic acid and/or cross-linking. Anti-listerial activity of films was determined on solid medium by a numeration technique. Chitosan-HPMC-based films, with and without stearic acid, inhibited the growth of Listeria monocytogenes completely. On the other hand, a loss of antimicrobial activity after chemical cross-linking modification was observed. FTIR and 13C NMR analyses were then conducted in order to study a potential chemical modification of biopolymers such as a chemical reaction with the amino group of chitosan. To complete the study, the mechanical properties of composite films were determined from tensile strength assays.

The ability of eelgrass (Zostera noltii (ZN)) to retain cupric ions from dilute aqueous solutions was studied as a function of pH, contact time and initial metal/sorbent ratio. Copper removal increased with pH, the optimum efficiency being attained between pH 5.5 and 6. When compared with other local lignocellulosic materials such as wood and corncob, Z. noltii appeared to be three times more effective than maritime pine and twice more than corncob. The presence of carboxyl groups in eelgrass was evidenced by infrared spectroscopy and photometric titration. These groups were found to participate in the adsorption process through cation exchange mechanisms, though other active binding sites were shown to be also involved. The metal and eelgrass relative concentrations appeared to influence the sorption capacity: the adsorption capacity of Z. noltii increased from 0.31 to 0.76 mmol Cu per gram as the metal/sorbent ratio increased. This behavior was partly explained by a change in the stoichiometry of a number of complexes as the metal and eelgrass relative concentrations varied.

In order to decrease water sensitivity of packaging materials based on water-soluble cellulose derivatives, and especially to avoid partial solubilisation of films into food products, crosslinking of hydroxy propyl methyl cellulose (HPMC) with citric acid was carried out using different contents of polycarboxylic acid and catalyst. To determine reticulation rate or ester bond rate in crosslinked cellulosic derivatives, FTIR in transmittance, based on of the ester band (1735 cm −1 ) was compared to acid–base titration. Infra-red spectroscopy had advantages over time consuming titration. Crosslinking of the hydrophilic polymers induced a strong influence on water solubility and an improvement in the water vapor barrier of about 34%.

Wastes produced during fermentation and distillation of crude sugarcane juice in rum factories were evaluated as a new source of waxes. The chemical composition of the crude wax extracted from adsorbat of the wastes on fuller's earth was studied by GC–mass spectrometry. Series of linear alkanes (C19–C33), and wax esters constitute the main components. In addition, phytosterols, triterpene methyl ethers, ethyl and methyl esters of fatty acids, and free fatty acids were found as minor components. Acid (predominance of C16 and C18) and alcohol portions (C26–C32) of the wax esters were analysed after saponification.

The chemical composition of cooperage oak wood is highly variable, depending upon the tree species (Quercus robur L. versus Quercus petraea Liebl.), its geographic location, and the single-tree effect. In the process of cask-making, natural seasoning and toasting contribute strongly to the modification of the oak wood chemical composition and therefore influence wine cooperaging. HPLC and GC quantification of ellagitannins and volatile compounds such as whiskey-lactones, eugenol, and vanillin over a sample set of 61 pedunculate oaks and 72 sessile oaks originating from six different forests showed that natural drying leads to a decrease of the ellagitannins and total extractives content level and a quasi constant level of the volatile compounds. Toasting (medium type) drastically enhanced the loss of ellagitannins and the gain in volatile compounds. Statistical treatment showed that the species effect remained significant throughout the process of drying and toasting, but not the provenance. The poor correlation with ring width of extractives levels measured on fresh timber remained unchanged as did the single-tree effect, with high variability found for all chemical parameters. These results provide further evidence that cooperage oak selection should not be based solely on the wood grain or the provenance but rather on a species-provenance combination.

The Echinacea-derived immunostimulator and HIV-1 integrase inhibitor (−)-chicoric acid (=2,3-bis{[3-(3,4-dihydroxyphenyl)-1-oxoprop-2-enyl]oxy}butanedioic acid; 1a) was conveniently prepared via a silane-promoted Pd-mediated chemoselective hydrogenolysis of its perbenzylated derivative 12a, which was generated from an efficient and reliable carbodiimide-mediated coupling reaction between the caffeic acid dibenzyl ether derivative 7 and commercially available (+)-dibenzyl L-tartrate (9a). The other naturally occurring dextrorotatory chicoric acid (1b) can be similarly prepared.

The changes in volatile flavor components and lipoxygenase and peroxidase enzymatic activity of Cilady strawberry puree during high pressure processing (400 MPa/20 °C/20 min) and storage at 4 °C were evaluated. High pressure processing maintains the original aromatic distribution, but after thirty days of storage an increase in some volatile compounds was observed. After high pressure treatment and storage, a residual lipoxygenase activity was observed, which could explain some slight changes of volatile compounds. On the other hand, the peroxidase was clearly inactivated by high pressure treatment.

A bioanalytical approach was used to identify chemical contaminants at river sites located downstream from a pharmaceutical factory, where reproductive alterations in wild fish have been previously observed. By using polar organic compound integrative samplers (POCIS) at upstream and downstream sites, biological activity profiles based on in vitro bioassays revealed the occurrence of xenobiotic and steroid-like activities, including very high glucocorticoid, antimineralocorticoid, progestogenic and pregnane X receptor (PXR)-like activities (mu g standard-EQ/g of sorbent range), and weak estrogenic activity (ng E2-EQ/g of sorbent range). Chemical analyses detected up to 60 out of 118 targeted steroid and pharmaceutical compounds in the extracts. In vitro profiling of occurring individual chemicals revealed the ability of several ones to act as agonist and/or antagonist of different steroids receptors. Mass balance calculation identified dexamethasone, spironolactone, and 6-alpha-methylprednisolone as major contributors to corticosteroid activities and levonorgestrel as the main contributor to progestogenic activities. Finally, RP-HPLC based fractionation of POCIS extracts and testing activity of fractions confirmed identified compounds and further revealed the presence of other unknown active chemicals. This study is one of the first to report environmental contamination by such chemicals; their possible contribution to in situ effects on fish at the same site is suggested.

Edible cellulosic films made with hydroxypropylmethylcellulose (HPMC) have proven to be inadequate moisture barriers. To improve its water vapor barrier properties, different hydrophobic compounds were incorporated into the HPMC matrix. Some fatty acids and derivatives were included into the film-forming solution prior to film formation. Stearic acid was chosen because of its high capacity to reduce significantly the water vapor transmission rate. Antimicrobial activity of edible HPMC film was obtained by the incorporation of nisin into the film-forming solution. Nisin is an antimicrobial peptide effective against gram-positive bacteria. The inhibitory activity of this bacteriocin was tested for inhibition of Listeria innocua and Staphylococcus aureus. The use of stearic acid was observed to reduce the inhibitory activity of active HPMC film against both selected strains. This phenomenon may be explained by electrostatic interactions between the cationic nisin and the anionic stearic acid. Further studies showed that antimicrobial activity of film varied with the nature of the hydrophobic compound incorporated, in decreasing order: film without lipid, methylstearate film, and stearic acid film. This corroborated the idea of electrostatic interactions.

Dry extract, ellagitanins, free ellagic acid, whisky-lactone, eugenol and vanillin have been quantified for a sample set of 61 pedunculate oaks (Quercus robur L.) and 72 sessile oaks (Quercus petraea Liebl.) originating from 6 different forests. Despite a very high interindividual variability, pedunculate oak shows higher level of dry extract, ellagitanins and free ellagic acid but lower level in volatil compounds compared to sessile oak. Inside a same species, differences between forests are less marked . Extractible compounds level is poorly correlated to the grain (ring width). Regarding cambial age, it might have its significanc e but lack of scientific data could not permit to conclude in that sense. Our results suggest that cooperage oak selection should be based on a species-provenance combination rather than on the grain or the provenance solely.

Irgarol and diuron are the most representative "organic booster biocides" that replace organotin compounds in antifouling paints, and metolachlor is one of the most extensively used chloroacetamide herbicides in agriculture. The toxicity of S-metolachlor, irgarol and diuron was evaluated in Pacific oyster (Crassostrea gigas) gametes or embryos exposed to concentrations of pesticides ranging from 0.1× to 1000×, with 1× corresponding to environmental concentrations of the three studied pesticides in Arcachon Bay (France). Exposures were performed on (1) spermatozoa alone (2) oocytes alone and (3) both spermatozoa and oocytes, and adverse effects on fertilization success and offspring development were recorded. The results showed that the fertilizing capacity of spermatozoa was significantly affected after gamete exposure to pesticide concentrations as low as 1× of irgarol and diuron and 10× of metolachlor. The offspring obtained from pesticide-exposed spermatozoa displayed a dose-dependent increase in developmental abnormalities. In contrast, treating oocytes with pesticide concentrations up to 10× did not alter fertilization rate and offspring quality. However, a significant decline in fertilization success and increase in abnormal D-larvae prevalence were observed at higher concentrations 10× (0.1 μg L(-1)) for S-metolachlor and 100× for irgarol (1.0 μg L(-1)) and diuron (4.0 μg L(-1)). Irgarol, diuron and S-metolachlor also induced a dose-dependent increase in abnormal D-larvae prevalence when freshly fertilized embryos were treated with pesticide concentrations as low as concentration of 1× (0.01 μg L(-1) for irgarol or S-metolachlor, and 0.04 μg L(-1) for diuron). The two bioassays on C. gigas spermatozoa and embryos displayed similar sensitivities to the studied pesticides while oocytes were less sensitive. Diuron, irgarol and S-metolachlor induced spermiotoxicity and embryotoxicity at environmentally relevant concentrations and therefore might be a threat to oyster recruitment in coastal areas facing chronic inputs of pesticides.

In the context of massive summer mortality events of the Pacific oyster Crassostrea gigas, the aim of this study was to investigate the early effects on genes, enzymes and haemocyte parameters implicated in immune defence mechanisms in C. gigas oysters exposed to a potentially hostile environment, i.e. to an herbicide alone or within a mixture. Following 2 h of exposure to the herbicide diuron at 1 mu g L-1 the repression of different genes implicated in immune defence mechanisms in the haemocytes and the inhibition of enzyme activities, such as laccase-type phenoloxidase (PO) in the plasma, were observed. The inhibition of superoxide dismutase (SOD) activity in the plasma was also observed after 6 and 24 h of exposure. In the mixture with the herbicides diuron and isoproturon, and the pharmaceutical ibuprofen, catecholase-type PO activity in the plasma and the percentage of phagocytosis in the haemocytes were reduced after 6 h of exposure. Our results showed that early effects on molecular, biochemical and cellular parameters can be detected in the presence of diuron alone or within a mixture, giving an insight of its potential effect in situations that can be found in natural environments, i.e. relatively high concentrations for short periods of time. (C) 2012 Elsevier Ltd. All rights reserved.

International audience; The occurrence of endocrine disrupting chemicals such as estrogens in raw urban sewage is well documented. By contrast, the presence of other steroidal activities in wastewater has been poorly studied, although they can cause undesirable biological responses in the environment. In this work, extracts of raw wastewater were tested for agonist and antagonist activities on estrogen, androgen, progesterone, mineralocorticoid and glucocorticoid receptors. We detected strong estrogenic activities that correlated well with the concentration of natural estrogens (estrone, estriol and 17 beta-estradiol) measured by chemical analysis. We also measured strong androgenic activities which were not due to estrogen receptor ligands based on the use of recombinant estrogen receptor a affinity columns. Several molecules with androgenic activities were identified in wastewater samples, testosterone, dihydrotestosterone and epiandrosterone being the most abundant. However, they explain only a small part of the detected androgenic activity, as indicated by the comparison of the detected biological responses with the results of the targeted chemical analysis. Finally, we found that our samples also contained strong antagonist activities on progesterone, glucocorticoid and mineralocorticoid receptors. Very interestingly, we identified pregnenolone (the precursor to all steroid hormones in humans) as a major endocrine disrupting chemical which accounts for most of the anti-mineralocorticoid activities present in raw wastewater. In conclusion, this study demonstrates the occurrence of androgen agonists as well as other steroid receptor antagonists such as pregnenolone in raw wastewater. Further research is needed to assess the fate of such compounds during sewage treatment and their potential effect on living organisms. (C) 2012 Elsevier Ltd. All rights reserved.

Antiherpetic evaluation of five nonahydroxyterphenoyl-containing C-glycosidic ellagitannins, castalagin (1), vescalagin (2), grandinin (3), roburin B (5), and roburin D (7), was performed in cultured cells against four HSV-1 and HSV-2 strains, two of which were resistant to Acyclovir. All five ellagitannins displayed significant anti-HSV activities against the Acyclovir-resistant mutants, but the monomeric structures 1-3 were more active than the dimers 5 and 7. Vescalagin (2) stands out among the five congeners tested as the most potent and selective inhibitor, with an IC50 value in the subfemtomolar range and a selectivity index 5x10(5) times higher than that of Acyclovir. Molecular modeling was used to provide a rationale for the surprisingly lower activity profile of its epimer castalagin (1). These ellagitannins have promising potential as novel inhibitors in the search for non-nucleoside drugs active against Acyclovir-resistant herpes viruses.

International audience; Polyphenolic nonahydroxyterphenoyl-containing C-glycosidic oak ellagitannins are found in wine as a result of the aging of this beverage in oak-made barrels. Once in the slightly acidic wine (pH approximately 3-4), some of these complex natural products such as (-)-vescalagin (1), but not its C-1 epimer (-)-castalagin (2), can capture grape-derived nucleophilic entities such as ethanol, the flavanols catechin (10a) and epicatechin (10b), the anthocyanin oenin (13b), and the thiolic glutathione (16) to furnish condensation products with retention of configuration at the C-1 locus. A computer-aided rationale of this high diastereoselectivity is given. These condensation products can contribute to the modulation of organoleptic properties of the wine, as evidenced by the 23 nm bathochromic shift color absorbance observed with the novel oenin-based anthocyano-ellagitannin (15b). Hydrolysis of 1 under solvolytic conditions furnished another novel compound that we refer to as vescalene (21), in addition to the known (-)-vescalin (18). Of pharmacological importance is the fact that most of these found-in-wine water-soluble ellagitannin derivatives are much more potent than etoposide (VP-16) at inhibiting top2-mediated DNA decatenation in vitro (top2=topoisomerase II)). The known (-)-vescalin (18) and the novel vescalene (21) fully inhibited top2 at 10 microM concentration!

International audience; PURPOSE: According to the development in the last decade of industrial processes using high hydrostatic pressure (HHP) for preservation of several commercial food products, novel sterilization or decontamination processes for pharmaceutical products could be conceivable. The aim of this work is to evaluate the effects of HHP on the integrity of insulin and heparin solutions, suspension of monoclonal antibodies and Spherulites. METHODS: High performance liquid chromatography, thin layer chromatography, capillary electrophoresis assays, ELISA tests, laser granulometry and spectrophotometry analyses have been performed to compare HHP treated drugs (in a domain of pressure and temperature ranging respectively from 20 up to 500 MPa and from 20 degrees C up to 37 degrees C) vs. untreated ones. RESULTS: No difference has been detected except for monoclonal antibodies that are altered above 500 MPa. CONCLUSIONS: The structure integrity of sensitive molecule due to the small energy involved by HHP and the development of industrial plants (intended for the decontamination of food products) confer to this technology the potential of a new method for sterilization of fragile drugs and an original alternative to aseptic processes and sterilizing filtration.

The pressure treatment (400 MPa / 20°C / 20 min) was carried out on fresh Cilady strawberry puree. High pressure processing maintained the original aromatic distribution and after thirty days of storage, some volatile compounds were slightly modified. In similar conditions, a residual lipoxygenase activity was observed which increased during storage. On the other hand, the peroxidase activity and bacterial growth were clearly inactivated by high pressure treatment and after thirty days of storage at 4°C.

The effects of high hydrostatic pressure (HHP), at 4°C or -18°C, on black truffle flavour compounds, alteration enzymes (lipoxigenase (LOX), peroxidase (POD) and polyphenoloxidase (PPO)) and microbiological qualities were evaluated. The choosen analytes for this study are six alcohols, three aldehydes, one ketone and on sulfur component. The highest flavour stability was observed when samples were pressurized at 300 MPa / 4°C / 10 min. All the treatments induced a drastic decrease of LOX activity and a slight decrease of POD activity. On the other hand, the PPO was not inactivated by pressurization at sub-zero (200 MPa / -18°C / 10 min) and was strongly increased after the 300 MPa / 4°C / 10 min treatment. Pressurization at 300 and 550 MPa lead to an almost complete Pseudomonas fluorescens reduction (6 and 6.5 log destruction, respectively) whereas pressurization at -18°C (200MPa) allowed to obtain only 3 log reduction.