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International audience; Diazotrophs are ubiquitous in the surface (sub)tropical ocean, where they sustain most new primary produc-tion. Several recent studies also report the presence of diverse cyanobacterial diazotrophs in the mesopelagicand bathypelagic ocean, suggesting that they gravitationally sink, potentially supporting organic matter exportand the biological carbon pump. Yet, the mechanisms leading to their export are not elucidated. Here, we simu-lated the sinking of diazotrophs in the water column by using rolling tanks, and measured the aggregationcapacity and sinking velocities of four globally distributed strains having different sizes, shapes, and abilities toproduce transparent exopolymer particles (TEP): twofilamentous diazotrophs (Trichodesmium erythraeum,Calothrixsp.) and two unicellular cyanobacterial diazotrophs (UCYN-B,Crocosphaera watsonii) and (UCYN-C,Cyanothecesp.). All diazotrophs tested, regardless their size and shape, were capable of forming aggregates andsunk, albeit at different velocities depending on the aggregation capacity. Overall, UCYN formed aggregates aslarge as those formed by thefilamentous diazotrophs (7000–32,014μm ESD, equivalent spherical diameter), andsunk at 100–400 m d1, i.e., at the same velocity asfilamentous diazotrophs (92–400 m d1). Although TEP aregenerally considered as enhancers of aggregation, TEP did not clearly influence aggregation rates nor sinkingvelocities during our study. We conclude that diazotrophs may be important contributors to carbon export inthe ocean and need to be considered in future studies to improve the accuracy of current regional and globalestimates of export.

International audience; The ultramafic massifs of New Caledonia are mainly composed of regolites with lateritic soils rich in metals such as Co, Fe, Mg and Ni. The nickeliferous ore is exploited by opencast mines. After rainfalls, erosion and particle runoff cause the mobilization of metals and metalloids in surface waters. The objective of this study is (i) to determine the geochemical background of metals and metalloids in surface waters draining a mining ultramafic massif, (ii) to identify the geochemical markers influenced by the mining of nickeliferous ore (iii) and to define discriminant values of the mining impact. Hydrochemical monitoring was carried out on five streams draining the Koniambo massif over a 15-years period. Twenty-four elements were analyzed for their total concentration and 18 for their dissolved concentration (

The dispersion of micropollutants, especially from wastewater treatment plants (WWTP), has been a recurring topic for several years regarding the need of aquatic environments protection i.e. towards chemical quality and ecotoxicity considerations. The development of high-resolution mass spectrometry (UHPLC-HRMS) and the access to databases allowed the development of non-targeted analysis for environmental matrices such as WWTP water and surface water. The objectives of this PhD work were to develop a non-targeted analysis method and to apply it to water samples from wastewater treatment plants in order to characterize them. The possibly of tracing these waters close to river discharges has been studied. Relevant features and tracers of WWTP discharge were thus sought by the use of differential analyses.Two methods based on Mzmine 2 software (combined with the use of R 3.5.1 and Excel) and Compound Discoverer were developed. As a result of these developments, the use of Compound Discoverer software was favored for the rest of this work. The use of three injection replicas during the analyses by UHPLC-HRMS resulted in a reduction in the number of false positives. The matrix effect was also evaluated as well as the use of solid phase extraction which was generally positive. The application of non-targeted analysis on samples from WWTP influents and treated waters showed a decrease in the number of features detected in the treated water, especially in the case of features corresponding to apolar molecules and/or with a high molecular mass. However new features were also observed in these waters. From the differential analysis, 375 stable or increasing relevant features in treated waters were selected and a chemical structure was proposed for some of them. The study of the impact of the discharge of treated water highlighted the addition of new features in the river. Despite a decrease in the area values of the features immediately downstream, a return to the initial state of the upstream was not observed. 305 relevant features were selected on the basis of a downstream/upstream comparison whose a small number which were common with the relevant features list made from the analysis of WWTP samples. These results underline both the interest of the method and the difficulty of determining tracers that are really related to WWTP discharges. Analyses of suspects were also carried out in addition to the non-targeted analysis.; La diffusion des micropolluants et plus particulièrement de la diffusion par les rejets de stations d’épuration (STEP) est une problématique récurrente depuis de plusieurs années dans la nécessité de protéger les milieux aquatiques du point de vu de la qualité chimique et écotoxique. Le développement de la spectrométrie de masse haute résolution et de l’accès aux bases de données a permis l’essor de l’analyse non ciblée appliquée aux matrices environnementales dont les eaux de STEP et les eaux de surfaces. Les objectifs de ce travail de thèse ont été de développer une méthode d’analyse non ciblée, de l’appliquer sur des eaux de stations d’épuration afin de les caractériser et d’étudier l’impact du traitement des eaux usées et du rejet des eaux traitées dans la rivière Clain. Des signaux pertinents et traceurs du rejet de STEP ont également été recherchés par l’utilisation d’analyses différentielles.Deux méthodes se basant sur les logiciels Mzmine 2 (avec R 3.5.1 et Excel en complément) et Compound Discoverer ont été développées. À la suite de ces développements, le logiciel Compound Discoverer a été conservé pour le reste des travaux de thèse. L’usage de trois réplicas a montré une réduction du nombre de faux positifs. L’effet matrice a également été évaluée de même que l’utilisation de l’extraction sur phase solide qui s’est avérée globalement positive. L’application de l’analyse non ciblée sur des entrées et sortie de STEP a montré une diminution du nombre de signaux détectés en sortie, principalement des signaux plutôt apolaires et/ou de taille importante mais a montré aussi l’apparition de nouveaux signaux. À partir de l’analyse différentielle, 375 signaux pertinents stables ou augmentant en sortie ont été sélectionnés et l’annotation d’une partie d’entre eux a été effectuée. L’étude de l’impact du rejet des eaux traitées a mis en lumière l’apport de nouveaux signaux dans le Clain. Malgré une baisse des valeurs des aires en aval immédiat, il n’a pas été observé de retour à l’état initial en amont. Une sélection de 305 signaux pertinents a été effectuée donc un faible nombre sont communs avec la liste réalisée à partir des échantillons de STEP, témoignant à la fois de l’intérêt de la méthode mais également de la difficulté de déterminer des traceurs apparentés réellement aux rejets de STEP. Des analyses de suspects ont également été réalisées en complément de l’analyse non ciblée.

International audience; A robust method is provided to analyze 18 hydrophilic and hydrophobic biocides in both dissolved and particulate fractions of five types of urban and surface waters using high-performance liquid chromatography coupled to tandem mass spectrometry. The linearity, accuracy, and intermediate precision were validated. The target biocides were enriched by solid-phase extraction using Chromabond HR-X 200-mg cartridges and eluted with methanol, ethyl acetate, and dichloro-methane. Suspended matter was extracted by microwave-assisted extraction in methanol and dichlo-romethane. Recoveries and variability (respectively > 75% and < 30% for most of the target biocides and matrices) made it possible to quantify biocides at a trace level in all matrices. Limits of quantification were in the range of nanograms per liter in the dissolved fraction and in the range of nanograms per gram of dry weight in the particulate fraction for most of the biocides and matrices, and were generally lower than those reported in previous studies. The method was successfully applied to surface waters, treated and untreated wastewa-ter, combined sewer overflows, and stormwater, providing unique data in these matrices for some substances , in particular with respect to particle contamination. In urban waters, concentrations of most of the biocides ranged from 10 to 200 ng/L. Diuron, isothiazolinone, and benzalkonium concentrations could reach 0.9, 0.9, and 20 μg/L respectively. In rivers, most of the biocides were measured at less than 10 ng/L, but higher concentrations were observed for benzalkoniums (up to 200 ng/L) or after rain events, which indicates biocide transfer from urban surfaces into the aquatic environment during wet weather.

Every night across the world’s oceans, numerous marine animals arrive at the surface of the ocean to feed on plankton after an upward migration of hundreds of metres. Just before sunrise, this migration is reversed and the animals return to their daytime residence in the dark mesopelagic zone (at a depth of 200–1,000 m). This daily excursion, referred to as diel vertical migration (DVM), is thought of primarily as an adaptation to avoid visual predators in the sunlit surface layer1,2 and was first recorded using ship-net hauls nearly 200 years ago3. Nowadays, DVMs are routinely recorded by ship-mounted acoustic systems (for example, acoustic Doppler current profilers). These data show that night-time arrival and departure times are highly conserved across ocean regions4 and that daytime descent depths increase with water clarity4,5, indicating that animals have faster swimming speeds in clearer waters4. However, after decades of acoustic measurements, vast ocean areas remain unsampled and places for which data are available typically provide information for only a few months, resulting in an incomplete understanding of DVMs. Addressing this issue is important, because DVMs have a crucial role in global ocean biogeochemistry. Night-time feeding at the surface and daytime metabolism of this food at depth provide an efficient pathway for carbon and nutrient export6–8. Here we use observations from a satellite-mounted light-detection-and-ranging (lidar) instrument to describe global distributions of an optical signal from DVM animals that arrive in the surface ocean at night. Our findings reveal that these animals generally constitute a greater fraction of total plankton abundance in the clear subtropical gyres, consistent with the idea that the avoidance of visual predators is an important life strategy in these regions. Total DVM biomass, on the other hand, is higher in more productive regions in which the availability of food is increased. Furthermore, the 10-year satellite record reveals significant temporal trends in DVM biomass and correlated variations in DVM biomass and surface productivity. These results provide a detailed view of DVM activities globally and a path for refining the quantification of their biogeochemical importance. Satellite-derived analysis of daily vertical migrations of ocean animals shows that the relative abundance and total biomass of these animals differ between different regions globally, depending on the availability of food and necessity to avoid predators.

International audience; Initiated by the CIESM and upgraded to the operational status within the HyMeX/MISTRALS program, the TRANSMEDinitiative aimed at developing an autonomous and low-cost thermosalinometer system to record SSS (Sea Surface Salinity) andSST (Sea Surface Temperature) while underway. The seven-year time series recorded from February 2012 till present betweenFrance (Marseille) and Algeria yield an unprecedented insight in the basin-wide seasonal evolution of the Western Basin, up tomesoscale features, and is used to validate the Copernicus Marine Service global operational system in the area.

Plastic is made of synthetic organic polymers of high molecular mass, which are usually produced through the polymerization of monomers derived from oil, gas or coal. In the second half of the 20th Century, its production expanded, which resulted in the elaboration of various products such as lightweight, versatile, durable, formable and corrosion- and flameresistant plastic types. Today, plastic products can be found in diverse fields, such as healthcare, energy generation and automotive industries, construction, electronics, packaging and textiles, as well as at the household level. In the last few decades, global production of plastic has increased by 500% (more than 322 million tons in 2016) and almost 10% of the annual production has ended up into the. Plastic waste is transported to landfills, and a part of it is carried away by winds. Together with carelessly discharged plastic (e.g. packaging and construction materials), plastic waste enters the environment continuously. Historically, floating plastic has been reported in the Northern Hemisphere subtropical gyres since the early 1970s in the North Atlantic, North Pacific and in the Southern Hemisphere. These gyres are formed by circular surface currents created by Ekman currents, driven by local wind, and the Coriolis force (spinning of the Earth). Across the globe, several monitoring campaigns are operating, such as the Tara expedition, which observed that 88% of surface waters presented microplastics even in the most remote places.

International audience; Slamming is a dynamic phenomenon in which a high magnitude pulse peak pressure occurs in a short time duration when the bottom structure of a ship impacted against the sea surface. This phenomenon can cause damage in the structure due to fluid-structure interaction (FSI) thus, plays a vital role in designing and manufacturing of ships for naval applications. In this paper, high performance sandwich structure, having many opportunities and challenges for the marine structural design, were studied experimentally using a high-speed shock test machine to examine the water entry problem. In addition, a velocity control system was used to calibrate and preserve the approximately uniform velocity throughout the slamming impact. Sandwich panels with different thicknesses i.e. 27 mm and 37 mm therefore, having different stiffness's were exposed under constant impact velocities of 6 and 8 m/s at the deadrise angle 10°. Experimental results were then compared and verified by the numerical investigation based on explicit Smoothed Particle Hydrodynamics (SPH) method. This study focuses on the overall structural response, deformation, and hydrodynamic response of the structure during the dynamic impact designed for naval applications.

Surface waters are important resources for the biosphere and the anthroposphere. Surface waters preserve diverse habitat, support biodiversity and provide ecosystem service by controlling nutrient cycles and global carbon. Surface waters are essential for human's everyday life, such as for irrigation, drinking-water and/or the production of energy (power plants, hydro-electricity). Further, surface waters through flooding can pose hazards to human, settlements and infrastructures. Monitoring the dynamic changes of surface waters is crucial for decision making process and policy. Remote sensing data can provide information on surface waters. Nowadays, satellite remote sensing has gone through a revolution with the launch of the Sentinel-1 SAR data and Sentinel-2 optical data with high revisit time at medium to high spatial resolution. Those data can provide time series and multi-source data which are essential in providing more information to upgrade ability in observing surface water. Analyzing such massive datasets is challenging in terms of knowledge extraction and processing as nearly fully automated processing chains are needed to enable systematic detection of water surfaces.In this context, the objectives of the work are to propose new (e.g. fully automated) approaches for surface water detection and flood extents detection by exploring the single and combined used of Sentinel-1 and Sentinel-2 data., Les eaux de surface sont des ressources importantes pour la biosphère et l'anthroposphère. Elles favorisent la préservation des habitats, le développement de la biodiversité et le maintien des services écosystémiques en contrôlant le cycle des nutriments et le carbone à l’échelle mondiale. Elles sont essentielles à la vie quotidienne de l’homme, notamment pour l'irrigation, la consommation d’eau potable, la production hydro-électrique, etc. Par ailleurs, lors des inondations, elles peuvent présenter des dangers pour l'homme, les habitations et les infrastructures. La surveillance des changements dynamiques des eaux de surface a donc un rôle primordial pour guider les choix des gestionnaires dans le processus d’aide à la décision. L’imagerie satellitaire constitue une source de données adaptée permettant de fournir des informations sur les eaux de surface. De nos jours, la télédétection satellitaire a connu une révolution avec le lancement des satellites Sentinel-1 (Radar) et Sentinel-2 (Optique) qui disposent d’une haute fréquence de revisite et d’une résolution spatiale moyenne à élevée. Ces données peuvent fournir des séries temporelles essentielles pour apporter davantage d'informations afin d'améliorer la capacité d'observation des eaux de surface. L’exploitation de telles données massives et multi-sources pose des défis en termes d’extraction de connaissances et de processus de traitement d’images car les chaines de traitement doivent être le plus automatiques possibles. Dans ce contexte, l'objectif de ce travail de thèse est de proposer de nouvelles approches permettant de cartographier l’extension spatiales des eaux de surface et des inondations, en explorant l'utilisation unique et combinée des données Sentinel-1 et Sentinel-2.

Surface waters are important resources for the biosphere and the anthroposphere. Surface waters preserve diverse habitat, support biodiversity and provide ecosystem service by controlling nutrient cycles and global carbon. Surface waters are essential for human's everyday life, such as for irrigation, drinking-water and/or the production of energy (power plants, hydro-electricity). Further, surface waters through flooding can pose hazards to human, settlements and infrastructures. Monitoring the dynamic changes of surface waters is crucial for decision making process and policy. Remote sensing data can provide information on surface waters. Nowadays, satellite remote sensing has gone through a revolution with the launch of the Sentinel-1 SAR data and Sentinel-2 optical data with high revisit time at medium to high spatial resolution. Those data can provide time series and multi-source data which are essential in providing more information to upgrade ability in observing surface water. Analyzing such massive datasets is challenging in terms of knowledge extraction and processing as nearly fully automated processing chains are needed to enable systematic detection of water surfaces.In this context, the objectives of the work are to propose new (e.g. fully automated) approaches for surface water detection and flood extents detection by exploring the single and combined used of Sentinel-1 and Sentinel-2 data.; Les eaux de surface sont des ressources importantes pour la biosphère et l'anthroposphère. Elles favorisent la préservation des habitats, le développement de la biodiversité et le maintien des services écosystémiques en contrôlant le cycle des nutriments et le carbone à l’échelle mondiale. Elles sont essentielles à la vie quotidienne de l’homme, notamment pour l'irrigation, la consommation d’eau potable, la production hydro-électrique, etc. Par ailleurs, lors des inondations, elles peuvent présenter des dangers pour l'homme, les habitations et les infrastructures. La surveillance des changements dynamiques des eaux de surface a donc un rôle primordial pour guider les choix des gestionnaires dans le processus d’aide à la décision. L’imagerie satellitaire constitue une source de données adaptée permettant de fournir des informations sur les eaux de surface. De nos jours, la télédétection satellitaire a connu une révolution avec le lancement des satellites Sentinel-1 (Radar) et Sentinel-2 (Optique) qui disposent d’une haute fréquence de revisite et d’une résolution spatiale moyenne à élevée. Ces données peuvent fournir des séries temporelles essentielles pour apporter davantage d'informations afin d'améliorer la capacité d'observation des eaux de surface. L’exploitation de telles données massives et multi-sources pose des défis en termes d’extraction de connaissances et de processus de traitement d’images car les chaines de traitement doivent être le plus automatiques possibles. Dans ce contexte, l'objectif de ce travail de thèse est de proposer de nouvelles approches permettant de cartographier l’extension spatiales des eaux de surface et des inondations, en explorant l'utilisation unique et combinée des données Sentinel-1 et Sentinel-2.

This study investigates the spatiotemporal variability of major and trace elements, dissolved organic carbon (DOC), total dissolved solids (TDS), and suspended particulate matter (SPM) in surface waters of several hydrosystems of the Loire River watershed in France. In particular, this study aims to delineate the impact of the abovementioned water physicochemical parameters on natural iron and manganese physical speciation (homoaggregation/heteroaggregation) among fine colloidal and dissolved ( 10 nm), colloidal (10-450 nm) and particulate ( 450 nm) phases in Loire River watershed. Results show that the chemistry of the Loire River watershed is controlled by two end members: magmatic and metamorphic petrographic context on the upper part of the watershed; and sedimentary rocks for the middle and low part of the Loire. The percentage of particulate Fe and Mn increased downstream concurrent with the increase in SPM and major cations concentration, whereas the percentage of colloidal Fe and Mn decreased downstream. Transmission electron microscopy analyses of the colloidal and particulate fractions (from the non-filtered water sample) revealed that heteroaggregation of Fe and Mn rich natural nanoparticles and natural organic matter to the particulate phase is the dominant mechanism. The heteroaggregation controls the partitioning of Fe and Mn in the different fractions, potentially due to the increase in the ionic strength, and divalent cations concentration downstream, and SPM concentration. These findings imply that SPM concentration plays an important role in controlling the fate and behavior of Fe and Mn in various sized fractions. Graphical abstract Physical speciation by heteroaggregation of (Fe-Mn) compounds: high [SPM] → [Fe-Mn] particulate faction; low {SPM] → [Fe-Mn] colloid-dissolved fraction.

Atmospheric deposition is an important source of micronutrients to the ocean, but atmospheric deposition fluxes remain poorly constrained in most ocean regions due to the limited number of field observations of wet and dry atmospheric inputs. Here we present the distribution of dissolved aluminium (dAl), as a tracer of atmospheric inputs, in surface waters of the Atlantic Ocean along GEOTRACES sections GA01, GA06, GA08, and GA10. We used the surface mixed-layer concentrations of dAl to calculate atmospheric deposition fluxes using a simple steady state model. We have optimized the Al fractional aerosol solubility, the dAl residence time within the surface mixed layer and the depth of the surface mixed layer for each separate cruise to calculate the atmospheric deposition fluxes. We calculated the lowest deposition fluxes of 0.15±0.1 and 0.27±0.13 g m−2 yr−1 for the South and North Atlantic Ocean (>40∘ S and >40∘ N) respectively, and the highest fluxes of 1.8 and 3.09 g m−2 yr−1 for the south-east Atlantic and tropical Atlantic Ocean, respectively. Overall, our estimations are comparable to atmospheric dust deposition model estimates and reported field-based atmospheric deposition estimates. We note that our estimates diverge from atmospheric dust deposition model flux estimates in regions influenced by riverine Al inputs and in upwelling regions. As dAl is a key trace element in the GEOTRACES programme, the approach presented in this study allows calculations of atmospheric deposition fluxes at high spatial resolution for remote ocean regions.

Surface water is essential for all forms of life since it is involved in almost all processes of life on Earth. Quantifying and monitoring surface water and its variations are important because of the strong connections between surface water, other hydrological components (groundwater and soil moisture, for example), and the changing climate system. Satellite remote sensing of land surface hydrology has shown great potential in studying hydrology from space at regional and global scales. In this thesis, different techniques using several types of satellite estimates have been made to study the variation of surface water, as well as other hydrological components in the lower Mekong basin (located in Vietnam and Cambodia) over the last two decades. This thesis focuses on four aspects. First, the use of visible/infrared MODIS/Terra satellite observations to monitor surface water in the lower Mekong basin is investigated. Four different classification methods are applied, and their results of surface water maps show similar seasonality and dynamics. The most suitable classification method, that is specially designed for tropical regions, is chosen to produce regular surface water maps of the region at 500 m spatial resolution, from January 2001 to present time. Compared to reference data, the MODIS-derived surface water time series show the same amplitude, and very high temporal correlation for the 2001-2007 period (> 95%). Second, the use of SAR Sentinel-1 satellite observations for the same objective is studied. Optical satellite data are replaced by SAR satellite data to benefit the ability of their microwave wavelengths to pass through clouds. Free-cloud Landsat-8 satellite imagery are set as targets to train and optimize a Neural Network (NN). Predicted surface water maps (30 m spatial resolution) are built for the studied region from January 2015 to present time, by applying a threshold (0.85) to the output of the NN. Compared to reference free-cloud Landsat-8 surface water maps, results derived from the NN show high spatial correlation (_90%), as well as true positive detection of water pixels (_90%). Predicted SAR surface water maps are also compared to floodability maps derived from topography data, and results show high consistency between the two independent maps with 98% of SAR-derived water pixels located in areas with a high probability of inundation (>60%). Third, the surface water volume variation is calculated as the product of the surface water extent and the surface water height. The two components are validated with other hydrological products, and results show good consistencies. The surface water height are linearly interpolated over inundated areas to build monthly maps at 500 m spatial resolution, then are used to calculate changes in the surface water volume. Results show high correlations when compared to variation of the total land surface water volume derived from GRACE data (95%), and variation of the in situ discharge estimates (96%). Fourth, two monthly global multi-satellite surface water products (GIEMS & SWAMPS) are compared together over the 1993-2007 period at regional and global scales. Ancillary data are used to support the analyses when available. Similar temporal dynamics of global surface water are observed when compared GIEMS and SWAMPS, but _50% of the SWAMPS inundated surfaces are located along the coast line. Over the Amazon and Orinoco basins, GIEMS and SWAMPS have very high water surface time series correlations (95% and 99%, respectively), but SWAMPS maximum water extent is just a half of what observed from GIEMS and SAR estimates. SWAMPS fails to capture surface water dynamics over the Niger basin since its surface water seasonality is out of phase with both GIEMS- and MODIS-derived water extent estimates, as well as with in situ river discharge data.; Les eaux superficielles sont nécessaires à toute forme de vie en tant que parties intégrantes de tout processus de vie sur Terre. Quantifier les eaux de surface et suivre leurs variations est primordial en raison du lien direct qui existe entre les variables hydrologiques et le changement climatique. La télédétection par satellite, de l’hydrologie continental offre l’opportunité unique d’étudier, depuis l’espace, les processus hydrologiques à différentes échelles (régionale et globale). Dans cette thèse, différentes techniques ont été développées afin d’étudier les variations des eaux superficielles ainsi que d’autres variables hydrologiques, au niveau du bassin inférieur du Mékong (entre le Vietnam et le Cambodge) et ce en utilisant plusieurs estimations satellitaires différentes. Cette thèse s’articule autour de quatre points principaux. Premièrement, l’utilisation d’observations satellitaires dans le visible et dans l’infrarouge (MODIS) est étudiée et comparée afin d’évaluer les eaux de surface au niveau du bassin inférieur du Mékong. Quatre méthodes de classification ont été utilisées afin de différencier les types de surface (inondés ou pas) dans le bassin. Les différentes méthodes ont donné des cartes d’eaux de surface aux résultats semblables en terme de dynamique saisonnière. La classification la plus adaptée aux régions tropicales a été ensuite choisie pour produire une carte des eaux de surface à la résolution de 500 m entre janvier 2001 et aujourd’hui. La comparaison des séries temporelles issues de cette carte et de celles issues du produit de référence MODIS donne une forte corrélation temporelle (> 95%) pour la période 2001-2007. Deuxièmement, l’utilisation des observations issues du satellite SAR Sentinel-1 est examinée à des fins identiques. L’imagerie satellitaire optique est ici remplacée i par les images SAR qui grâce aux longueurs d’ondes utilisées dans le micro-ondes, permettent de « voir » à travers les nuages. Un jeu d’images Landsat-8-sans-nuage est alors utilisé pour entraîner un Réseau de Neurones (RN) afin de restituer des cartes d’eaux de surface par l’utilisation d’un seuillage sur les sorties du modèle RN. Les cartes sont à la résolution spatiale de 30 m et disponibles depuis janvier 2015. Comparées aux cartes de référence Landsat-8-sans-nuage, les sorties de modèles RN montre une très grande corrélation (90%) ainsi qu’une détection "vraie" à 90%. Les cartes restituées d’eaux de surface utilisant la technologie SAR sont enfin comparées aux cartes d’inondation issues de données topographiques. Les résultats montrent une fois encore une très grande consistance entres les deux cartes avec 98% des pixels considérés comme inondés dans cartes SAR se trouvant dans les régions de très grande probabilité d’inondation selon la topographie (>60%). Troisièmement, la variation volumique des eaux de surface est calculée comme le produit de l’étendue de la surface avec la hauteur d’eau. Ces deux variables sont validées à l’aide d’autres produits hydrologiques et montrent de bons résultats. La hauteur d’eau superficielle est linéairement interpolée aux régions non inondées afin de produire des cartes mensuelles à la résolution spatiale de 500 m. La hauteur d’eau est ensuite analysée pour estimer les variations volumiques. Ces résultats montrent une très bonne corrélation avec la variation volumique induite par la mesure du contenu en eau du satellite GRACE (95%) ainsi qu’avec la variation des mesures in situ de débit des rivières. Finalement, deux produits globaux et multi-satellites d’eaux superficielles sont comparés à l’échelle régionale et globale sur la période 1993-2007: GIEMS et SWAMPS. Lorsqu’elles existent, les données auxiliaires sont utilisées afin de renforcer l’analyse. Les deux produits montrent une dynamique similaire, mais 50% des pixels inondés dans SWAMPS se trouvent le long des côtes.

The distribution of dissolved aluminium (dAl) in the water column of the North Atlantic and Labrador Sea was studied along GEOTRACES section GA01 to unravel the sources and sinks of this element. Surface water dAl concentrations were low (median of 2.5 nM) due to low aerosol deposition and removal by biogenic particles (i.e. phytoplankton cells). However, surface water dAl concentrations were enhanced on the Iberian and Greenland shelves (up to 30.9 nM) due to continental inputs (rivers, glacial flour, and ice melt). Dissolved Al in surface waters scaled negatively with chlorophyll a and biogenic silica (opal) concentrations. The abundance of diatoms exerted a significant (p) control on the surface particulate Al (pAl) to dAl ratios by decreasing dAl levels and increasing pAl levels. Dissolved Al concentrations generally increased with depth and correlated strongly with silicic acid (R2>0.76) west of the Iberian Basin, suggesting net release of dAl at depth during remineralization of sinking opal-containing particles. Enrichment of dAl at near-bottom depths was observed due to the resuspension of sediments. The highest dAl concentrations (up to 38.7 nM) were observed in Mediterranean Outflow Waters, which act as a major source of dAl to mid-depth waters of the eastern North Atlantic. This study clearly shows that the vertical and lateral distributions of dAl in the North Atlantic differ when compared to other regions of the Atlantic and global oceans. Responsible for these large inter- and intra-basin differences are the large spatial variabilities in the main Al source, atmospheric deposition, and the main Al sink, particle scavenging by biogenic particles.

Surface water is essential for all forms of life since it is involved in almost all processes of life on Earth. Quantifying and monitoring surface water and its variations are important because of the strong connections between surface water, other hydrological components (groundwater and soil moisture, for example), and the changing climate system. Satellite remote sensing of land surface hydrology has shown great potential in studying hydrology from space at regional and global scales. In this thesis, different techniques using several types of satellite estimates have been made to study the variation of surface water, as well as other hydrological components in the lower Mekong basin (located in Vietnam and Cambodia) over the last two decades. This thesis focuses on four aspects. First, the use of visible/infrared MODIS/Terra satellite observations to monitor surface water in the lower Mekong basin is investigated. Four different classification methods are applied, and their results of surface water maps show similar seasonality and dynamics. The most suitable classification method, that is specially designed for tropical regions, is chosen to produce regular surface water maps of the region at 500 m spatial resolution, from January 2001 to present time. Compared to reference data, the MODIS-derived surface water time series show the same amplitude, and very high temporal correlation for the 2001-2007 period (> 95%). Second, the use of SAR Sentinel-1 satellite observations for the same objective is studied. Optical satellite data are replaced by SAR satellite data to benefit the ability of their microwave wavelengths to pass through clouds. Free-cloud Landsat-8 satellite imagery are set as targets to train and optimize a Neural Network (NN). Predicted surface water maps (30 m spatial resolution) are built for the studied region from January 2015 to present time, by applying a threshold (0.85) to the output of the NN. Compared to reference free-cloud Landsat-8 surface water maps, results derived from the NN show high spatial correlation (_90%), as well as true positive detection of water pixels (_90%). Predicted SAR surface water maps are also compared to floodability maps derived from topography data, and results show high consistency between the two independent maps with 98% of SAR-derived water pixels located in areas with a high probability of inundation (>60%). Third, the surface water volume variation is calculated as the product of the surface water extent and the surface water height. The two components are validated with other hydrological products, and results show good consistencies. The surface water height are linearly interpolated over inundated areas to build monthly maps at 500 m spatial resolution, then are used to calculate changes in the surface water volume. Results show high correlations when compared to variation of the total land surface water volume derived from GRACE data (95%), and variation of the in situ discharge estimates (96%). Fourth, two monthly global multi-satellite surface water products (GIEMS & SWAMPS) are compared together over the 1993-2007 period at regional and global scales. Ancillary data are used to support the analyses when available. Similar temporal dynamics of global surface water are observed when compared GIEMS and SWAMPS, but _50% of the SWAMPS inundated surfaces are located along the coast line. Over the Amazon and Orinoco basins, GIEMS and SWAMPS have very high water surface time series correlations (95% and 99%, respectively), but SWAMPS maximum water extent is just a half of what observed from GIEMS and SAR estimates. SWAMPS fails to capture surface water dynamics over the Niger basin since its surface water seasonality is out of phase with both GIEMS- and MODIS-derived water extent estimates, as well as with in situ river discharge data., Les eaux superficielles sont nécessaires à toute forme de vie en tant que parties intégrantes de tout processus de vie sur Terre. Quantifier les eaux de surface et suivre leurs variations est primordial en raison du lien direct qui existe entre les variables hydrologiques et le changement climatique. La télédétection par satellite, de l’hydrologie continental offre l’opportunité unique d’étudier, depuis l’espace, les processus hydrologiques à différentes échelles (régionale et globale). Dans cette thèse, différentes techniques ont été développées afin d’étudier les variations des eaux superficielles ainsi que d’autres variables hydrologiques, au niveau du bassin inférieur du Mékong (entre le Vietnam et le Cambodge) et ce en utilisant plusieurs estimations satellitaires différentes. Cette thèse s’articule autour de quatre points principaux. Premièrement, l’utilisation d’observations satellitaires dans le visible et dans l’infrarouge (MODIS) est étudiée et comparée afin d’évaluer les eaux de surface au niveau du bassin inférieur du Mékong. Quatre méthodes de classification ont été utilisées afin de différencier les types de surface (inondés ou pas) dans le bassin. Les différentes méthodes ont donné des cartes d’eaux de surface aux résultats semblables en terme de dynamique saisonnière. La classification la plus adaptée aux régions tropicales a été ensuite choisie pour produire une carte des eaux de surface à la résolution de 500 m entre janvier 2001 et aujourd’hui. La comparaison des séries temporelles issues de cette carte et de celles issues du produit de référence MODIS donne une forte corrélation temporelle (> 95%) pour la période 2001-2007. Deuxièmement, l’utilisation des observations issues du satellite SAR Sentinel-1 est examinée à des fins identiques. L’imagerie satellitaire optique est ici remplacée i par les images SAR qui grâce aux longueurs d’ondes utilisées dans le micro-ondes, permettent de « voir » à travers les nuages. Un jeu d’images Landsat-8-sans-nuage est alors utilisé pour entraîner un Réseau de Neurones (RN) afin de restituer des cartes d’eaux de surface par l’utilisation d’un seuillage sur les sorties du modèle RN. Les cartes sont à la résolution spatiale de 30 m et disponibles depuis janvier 2015. Comparées aux cartes de référence Landsat-8-sans-nuage, les sorties de modèles RN montre une très grande corrélation (90%) ainsi qu’une détection "vraie" à 90%. Les cartes restituées d’eaux de surface utilisant la technologie SAR sont enfin comparées aux cartes d’inondation issues de données topographiques. Les résultats montrent une fois encore une très grande consistance entres les deux cartes avec 98% des pixels considérés comme inondés dans cartes SAR se trouvant dans les régions de très grande probabilité d’inondation selon la topographie (>60%). Troisièmement, la variation volumique des eaux de surface est calculée comme le produit de l’étendue de la surface avec la hauteur d’eau. Ces deux variables sont validées à l’aide d’autres produits hydrologiques et montrent de bons résultats. La hauteur d’eau superficielle est linéairement interpolée aux régions non inondées afin de produire des cartes mensuelles à la résolution spatiale de 500 m. La hauteur d’eau est ensuite analysée pour estimer les variations volumiques. Ces résultats montrent une très bonne corrélation avec la variation volumique induite par la mesure du contenu en eau du satellite GRACE (95%) ainsi qu’avec la variation des mesures in situ de débit des rivières. Finalement, deux produits globaux et multi-satellites d’eaux superficielles sont comparés à l’échelle régionale et globale sur la période 1993-2007: GIEMS et SWAMPS. Lorsqu’elles existent, les données auxiliaires sont utilisées afin de renforcer l’analyse. Les deux produits montrent une dynamique similaire, mais 50% des pixels inondés dans SWAMPS se trouvent le long des côtes.

International audience; This study aimed to investigate the degradation of triclosan (TCS) in the presence of p-aminobenzoic acid (PABA) under simulated sunlight irradiation (lambda >= 290 nm). The effect of PABA concentration, pH, dissolved organic matter (DOM), and DOM-hydrolytic Fe(III) species complexes on the photodegradation of TCS in the presence of PABA (TCS-PABA) was also studied. The photolysis of TCS-PABA obeyed pseudo-first-order kinetics well, and the degradation of TCS-PABA enhanced with increasing solution pH (from 3.0 to 11.0). The presence of PABA inhibited the degradation of TCS-PABA, and the weakest inhibitory effect was observed while the concentration of PABA was 5 mg L-1. The addition of DOM (Suwannee River fulvic acid standard I [SRFA], Suwannee River HA standard II [SRHA], and Suwannee River natural organic matter [SRNOM]) showed different inhibition effects on TCS-PABA degradation. However, higher Fe(III) concentration at the DOM concentration of 5 mg L-1 could favor the formation of DOM-hydrolytic Fe(III) species complexes, further accelerating the degradation of TCS-PABA. In comparison with deionized water (DI water), TCS-PABA could be better photodegraded in river water nearby the effluent of a wastewater treatment plant. This study provides useful information for understanding the natural behavior of TCS in the presence of other organic contaminants.

Ce numéro comprend les articles issus du colloque de restitution Ecophyto Recherche « Des outils et des dispositifs pour éclairer les décisions, explorer les possibles et accompagner la transition vers des systèmes économes et multi-performants », qui s’est tenu à Saint-Malo, du 22 au 24 mars 2017.; The EQUIPE project aims to assess the predictive quality of pesticide indicators addressing transfers tosurface and underground water. The project is structured in three actions. In action 1 the output of 26indicators and a mechanistic model are compared to measure pesticide transfers at plot and catchmentlevels at four sites (included one watershed) with different climate and soil conditions, and, transferpathways for a broad range of active ingredients. Action 2 consists in designing indicator chains by datamining on a database containing cultural practices, soil and climate data and measured pesticidetransfers. In action 3 the validity and use of the indicators is defined by the experts of the project.; Le projet EQUIPE vise à évaluer la qualité prédictive d’indicateurs pesticides traitant des transferts versles eaux de surface ou souterraines Le projet est structuré en trois actions. Dans l’action 1, il s’agit decomparer à l’échelle parcellaire et du bassin versant les sorties de 26 indicateurs pesticides decomplexité croissante et du modèle MACRO à des mesures de terrain sur quatre sites (dont un bassinversant) présentant des voies de transfert et des conditions pédoclimatiques différentes pour une largegamme de molécules. L’action 2 consiste en la construction d’une chaîne d’indicateurs par uneméthode de fouille de données sur une base de données incluant pratiques culturales, variables dumilieu et données de transfert observées. L’action 3 porte sur une expertise du groupe sur le domainede validité et d’utilisation des indicateurs.

International audience; The occurrence of endocrine-disrupting chemicals (EDCs) in the aquatic environment has brought increasing concern due to their potential adverse impacts on ecosystems and humans. These compounds are generally present in complex water matrices, such as surface waters at trace levels (ng L−1) making their analysis difficult. In this work, an analytical method for the simultaneous determination of 13 EDCs, including 5 steroid estrogens, 1 progestogen, 1 androgen, and 6 endocrine-disrupting phenols in water, was developed using solid phase extraction (SPE), derivatization, and gas chromatography-mass spectrometry (GC-MS). The method was validated by spiking the 13 EDCs to the interest matrix. The recovery was in the range of 52–71% with an average of 62%. The limits of quantification were 1 and 5–10 ng L−1 for phenolic compounds and hormones, respectively. The validated method was applied to assess the contamination level of the targeted EDCs in 15 sites collected from six rivers located at the cross-border area of Northern France and Belgium. The majority of the considered compounds were detected in the sampling sites and among them, bisphenol A (BPA) was found at the highest level which can be up to 286 ng L−1. However, NP was the most frequently detected, followed by BPA and PG.

International audience; Silicone rubber (SR) has been successfully implemented as a receiving phase in various passive samplers (MESCO, Passive SBSE and silicone rod/sheet). Indeed, SR is mechanically resistant, insoluble in common solvents used for compound desorption, and enable a thermal desorption at high temperature. Nevertheless, SR is an hydrophobic material which permit mainly enrichment of apolar organic compounds (log Kow > 3) from water (organochlorine pesticides, PAHs, PCBs, etc.). To remedy this lack of measurement representativity, the use of an other passive sampler in co-deployement for polar organics, as Polar Organic Chemical Integrative Sampler (POCIS), is the stategy preferred. This work aimed at testing the affinity of an innovative material for more polar organic compounds using passive samplers with a single receiving phase. In this way, a Polar/Apolar Composite Silicone Rubber (PACSiR) was developed for sorption of a wide range of organics compounds. First, this innovative composite material was assessed in laboratory for pesticides sorption whith a large range of physico-chemical properties. Then, PACSiR was shaped and calibrated as a passive sampler in laboratory, to be finally applied for the monitoring of several pesticides in surface waters. Extraction recoveries determined experimentally for 22 pesticides were similar or higher for all pesticides than for SR. The enhancement of extraction performances is the highest for polar pesticides, with log Kow below 3, which are poorly sorbed on SR. Kinetics of uptake of pesticides in calibration system were mainly described by a pseudo-linear equation model for 14 days exposure. Sampling rate and partition coeficient were determined for calculation of time weighted average concentration (TWAC). Sampling rates for PACSiR passive sampler were 1.3 to 12.5 higher than for SR depending on the pesticide. Consequently, PACSiR enable to reach lower LOQ than SR for polar pesticides. Finally, results of field exposition of passive samplers in rivers were compared with grab sampling to access the occurrence of pesticides and to estimate the TWACs during field exposition. This study demonstrated that the PACSiR is a sensitive receiving phase for pesticides which can greatly improved sorption properties comparared to SR and permitted to reach lower LOQ for polar pesticides. Further experimental investigations on accumulation of other organic compounds will be carried out (hormones, pharmaceuticals, PAHs and PCBs).

International audience; In this paper, the well-known Ament model is generalized to multiple rebounds (reflections) from rough sea surfaces in a stratified medium. To solve this propagation-scattering problem in the radar microwave domain, the physical optics (PO) approximation is applied to determine the currents on the rough sea surface. Next, to solve the propagation problem, i.e., to calculate the scattered field in the duct, an appropriate Green function of the duct (which is a stratified medium with linear-square refraction index profile) is used to radiate the currents from Huygens' principle. Due to refraction phenomenon, this field induces new currents on the surface (second rebound), which are again evaluated by PO. The process is iterated. Then, for each rebound, the coherent components of the surface currents and the scattered field are calculated and compared with those of a flat surface in order to derive the generalized Ament model. In addition, this model is compared with the results computed by the rigorous method of moments and accelerated by the multilevel subdomain decomposition iterative method combined with the adaptive cross approximation. © 2016 IEEE.

International audience; Due to industrialization and the use of chemical products in everyday life, various types of drugs and pesticides are present in our environment, which threaten and cause negative impacts on aquatic ecosystems. The consequences of these pollutants are gradually becoming visible. Recent evidence confirms that long term exposure to environmental pharmaceutical concentrations can induce adverse effects in aquatic vertebrates and invertebrates such as reproductive impairments and collapse wild populations. Consequently, one of the challenges of environmental science is to evaluate the associated risks.In this context, a new methodology has been developed using nano-LC-nano-ESI MS/MS to quantify traces of two pharmaceuticals (a neuropharmaceutical drug, fluoxetine, and an anticonvulsant drug, carbamazepine) in two molluscs. Potamopyrgus antipodarum and Valvata piscinalis, which are both prosobranch gastropods. A simple and quick extraction method was developed based on a modified and miniaturized version of the QuEChERS method. The procedure involves the extraction of approximately 10 mg of wet mollusc tissue by 500 mu L of a mixture of acetonitrile/water/hexane (50/20/30) and 100 mg of buffer salt. Thus, the extraction step was carried out on an individual scale.The sensitivity of this method allowed for the detection of levels as low as 18 ng/g and 128 ng/g for carbamazepine and fluoxetine, respectively, with recoveries of greater than 85% for the two targeted compounds. This method was then applied to both gastropod species exposed to fluoxetine under laboratory conditions. The results provide evidence of bioaccumulation in both P. antipodarum and V. piscinalis and reveal the inter-species differences.

Environmental quality monitoring of water resources is challenged with providing the basis for safeguarding the environment against adverse biological effects of anthropogenic chemical contamination from diffuse and point sources. While current regulatory efforts focus on monitoring and assessing a few legacy chemicals, many more anthropogenic chemicals can be detected simultaneously in our aquatic resources. However, exposure to chemical mixtures does not necessarily translate into adverse biological effects nor clearly shows whether mitigation measures are needed. Thus, the question which mixtures are present and which have associated combined effects becomes central for defining adequate monitoring and assessment strategies. Here we describe the vision of the international, EU-funded project SOLUTIONS, where three routes are explored to link the occurrence of chemical mixtures at specific sites to the assessment of adverse biological combination effects. First of all, multi-residue target and non-target screening techniques covering a broader range of anticipated chemicals co-occurring in the environment are being developed. By improving sensitivity and detection limits for known bioactive compounds of concern, new analytical chemistry data for multiple components can be obtained and used to characterise priority mixtures. This information on chemical occurrence will be used to predict mixture toxicity and to derive combined effect estimates suitable for advancing environmental quality standards. Secondly, bioanalytical tools will be explored to provide aggregate bioactivity measures integrating all components that produce common (adverse) outcomes even for mixtures of varying compositions. The ambition is to provide comprehensive arrays of effect-based tools and trait-based field observations that link multiple chemical exposures to various environmental protection goals more directly and to provide improved in situ observations for impact assessment of mixtures. Thirdly, effect-directed analysis (EDA) will be applied to identify major drivers of mixture toxicity. Refinements of EDA include the use of statistical approaches with monitoring information for guidance of experimental EDA studies. These three approaches will be explored using case studies at the Danube and Rhine river basins as well as rivers of the Iberian Peninsula. The synthesis of findings will be organised to provide guidance for future solution-oriented environmental monitoring and explore more systematic ways to assess mixture exposures and combination effects in future water quality monitoring. The SOLUTIONS Project is supported by the Seventh Framework Programme (FP7-ENV-2013) of the European Union under grant agreement no. 603437.

The response of the phytoplanktonic community (primary production and algal biomass) to contrasted Saharan dust events (wet and dry deposition) was studied in the framework of the DUNE ("a DUst experiment in a low-Nutrient, low-chlorophyll Ecosystem") project. We simulated realistic dust deposition events (10 g m−2) into large mesocosms (52 m3). Three distinct dust addition experiments were conducted in June 2008 (DUNE-1-P: simulation of a wet deposition; DUNE-1-Q: simulation of a dry deposition) and 2010 (DUNE-2-R1 and DUNE-2-R2: simulation of two successive wet depositions) in the northwestern oligotrophic Mediterranean Sea. No changes in primary production (PP) and chlorophyll a concentrations (Chl a) were observed after a dry deposition event, while a wet deposition event resulted in a rapid (24 h after dust addition), strong (up to 2.4-fold) and long (at least a week in duration) increase in PP and Chl a. We show that, in addition to being a source of dissolved inorganic phosphorus (DIP), simulated wet deposition events were also a significant source of nitrate (NO3−) (net increases up to +9.8 μM NO3− at 0.1 m in depth) to the nutrient-depleted surface waters, due to cloud processes and mixing with anthropogenic species such as HNO3. The dry deposition event was shown to be a negligible source of NO3−. By transiently increasing DIP and NO3- concentrations in N–P starved surface waters, wet deposition of Saharan dust was able to relieve the potential N or NP co-limitation of the phytoplanktonic activity. Due to the higher input of NO3− relative to DIP, and taking into account the stimulation of the biological activity, a wet deposition event resulted in a strong increase in the NO3−/DIP ratio, from initially less than 6, to over 150 at the end of the DUNE-2-R1 experiment, suggesting a switch from an initial N or NP co-limitation towards a severe P limitation. We also show that the contribution of new production to PP strongly increased after wet dust deposition events, from initially 15% to 60–70% 24 h after seeding, indicating a switch from a regenerated-production based system to a new-production based system. DUNE experiments show that wet and dry dust deposition events induce contrasting responses of the phytoplanktonic community due to differences in the atmospheric supply of bioavailable new nutrients. Our results from original mesocosm experiments demonstrate that atmospheric dust wet deposition greatly influences primary productivity and algal biomass in LNLC environments through changes in the nutrient stocks, and alters the NO3−/DIP ratio, leading to a switch in the nutrient limitation of the phytoplanktonic activity.

The distribution of dissolved aluminium in the West Atlantic Ocean shows a mirror image with that of dissolved silicic acid, hinting at intricate interactions between the ocean cycling of Al and Si. The marine biogeochemistry of Al is of interest because of its potential impact on diatom opal remineralisation, hence Si availability. Furthermore, the dissolved Al concentration at the surface ocean has been used as a tracer for dust input, dust being the most important source of the bio-essential trace element iron to the ocean. Previously, the dissolved concentration of Al was simulated reasonably well with only a dust source, and scavenging by adsorption on settling biogenic debris as the only removal process. Here we explore the impacts of (i) a sediment source of Al in the Northern Hemisphere (especially north of ~ 40° N), (ii) the imposed velocity field, and (iii) biological incorporation of Al on the modelled Al distribution in the ocean. The sediment source clearly improves the model results, and using a different velocity field shows the importance of advection on the simulated Al distribution. Biological incorporation appears to be a potentially important removal process. However, conclusive independent data to constrain the Al / Si incorporation ratio by growing diatoms are missing. Therefore, this study does not provide a definitive answer to the question of the relative importance of Al removal by incorporation compared to removal by adsorptive scavenging.

Five marine sediment cores distributed along the Norwegian, western Barents Sea, and Svalbard continental margins have been investigated in order to reconstruct late Holocene changes in the poleward flow of the Norwegian Atlantic Current (NwAC) and West Spitsbergen Current (WSC) and the nature of the upper surface water masses within the eastern Nordic Seas. This research project is based on the use of dinocyst and coccolith assemblages for qualitative and quantitative reconstructions of surface water conditions from high resolution sediment cores, and involve upstream investigations on proxy reliabilities. The investigated area (66 to 77°N) was affected by an overall increase in the strength of the AW flow from 3000 cal. yrs BP to the Present. The long-term modulation of westerlies strength and location which are essentially driven by the dominant mode of the North Atlantic Oscillation (NAO), is thought to explain the observed dynamics of the AW flow. The same mechanism also reconciles the recorded opposite zonal shifts in the location of the Arctic Front between the area off western Norway and the western Barents Sea-eastern Fram Strait region. Submillenial changes in AW flow are organised according to known pre-Anthropocene warm (RWP, MCA and the Modern period: strong poleward flow) and cold (LIA, DA: weak poleward flow) climatic spells. A sudden short pulse of resumed high WSC flow interrupted the LIA in the eastern Nordic Seas from 330 to 410 cal. yrs BP. Our results are indicative of a major impact of AW flow dynamics on the Arctic sea ice distribution during the last millenium, when changes in reconstructed sea-ice extent are negatively correlated with the strength of the WSC flow off western Barents Sea and western Svalbard. The extensive decrease in sea ice extent during the last century is synchronous with an exceptional increase in AW flow. The previously reconstructed high amplitude warming of surface waters in eastern Fram Strait at the turn of the 19th century was therefore primarily induced by an excess flow of AW which stands as unprecedented over the last 3000 years., La variabilité de l’intensité du flux d’eaux atlantiques et de la nature des masses d’eau de surface le long des marges occidentales de la Norvège, de la mer de Barents et du Svalbard a été reconstituée sur la base des assemblages de coccolithes et dinokystes présents dans cinq carottes sédimentaires marines représentatives de l’Holocène terminal. Les résultats sont présentés sous la forme de reconstructions qualitatives et quantitatives (fonctions de transfert MAT) à haute résolution temporelle (échelle décennale à sub-séculaire). Un travail visantà valider les traceurs micropaléontologiques utilisés a été réalisé en parallèle à l’objectif principal, et s’est en particulier nourri de la collecte et de l’examen de populations vivantes distribuées le long de plusieurs transectszonaux en mer de Norvège, mer d’Islande et à travers le détroit de Fram.Nos résultats indiquent que la partie orientale des mers Nordiques (66 à 77°N) a été sujette à une tendance globale à l’augmentation du flux d’eaux atlantiques (AW) au cours des derniers 3000 ans. La dynamique récente de ce flux méridien est supposée répondre à la modulation long-terme de la force et de la localisation de la ceinture des vents d’ouest qui est essentiellement pilotée par l’Oscillation Nord Atlantique. Ce même mécanisme atmosphérique réconcilie le déplacement zonal et contradictoire du front arctique entre le domaine ouest-norvégien, et les façades occidentales de la mer de Barents et du détroit de Fram. La variabilité rapide du flux d’AW reproduit la succession des phases climatiques historiques classiques chaudes (Période Chaude Romaine, Période Chaude Médiévale, Période Moderne : flux accentué d’AW) et froides (Période Sombre, Petit Age Glaciaire : flux réduit d’AW) des derniers 2500 ans. Un événènement rapide de renforcement du flux d’AW en mers Nordiques a été identifié pendant le Petit Age Glaciaire entre 330 et 410 ans BP (cal.). Nos résultats indiquent que les variations d’intensité du flux d’AW vers l’Océan Arctique ont eu un impact majeur sur la distribution de la glace de mer arctique au cours du dernier millier d’années, les variations reconstruites de l’extension du couvert de glace à l’echelle de l’océan arctique étant parfaitement corrélées (échelle subséculaire) avec nos reconstructions qualitatives de la dynamique de l’AW au large du Svalbard et de la mer de Barents. La diminution importante de l’extension de la banquise durant le 20ème siècle est synchrone d’un flux record d’AW à travers le détroit de Fram, flux qui, d’après nos données, est sans précédent pour les derniers 3000 ans.

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Moreno, Victoria Garcia-Solsona, Ester Masque, Pere Masque, Pere/B-7379-2008 Masque, Pere/0000-0002-1789-320X Spanish Government project EDASMAR [CGL2006-09274/HID]; Consejo de Seguridad Nuclear project [2686-SRA]; MICINN (Spain) [AP2008-03044]; ICREA Academia; Generalitat de Catalunya The authors would like to thank the assistance in field and laboratory work from our colleagues at the Laboratori de Radioactivitat Ambiental (Universitat de Barcelona). This project has been funded partially by the Spanish Government project EDASMAR (Ref. CGL2006-09274/HID) and the Consejo de Seguridad Nuclear project (Ref. 2686-SRA). V.R. acknowledges financial support through a PhD fellowship (AP2008-03044) from MICINN (Spain). Support for the research of PM was received through the prize ICREA Academia, funded by the Generalitat de Catalunya. We also want to thank the collaboration of Anna Cherta, Maribel Forner (Hotel Marina), Camping Eden, FACSA, School "Jaume Sainz" and the Peniscola Municipality. We want also to thank Gerard Carmona and Lluis Benejam for their support during fish sampling. 1 ELSEVIER SCIENCE BV AMSTERDAM MAR CHEM SI; Submarine groundwater discharge (SGD) has attracted the interest from the scientific community over the past decade for its impact on biogeochemical cycles of coastal ecosystems and/or management of water resources. SGD is associated with a flow of natural radionuclides (Ra isotopes and Rn-222), which are often used as SGD tracers that can significantly increase the natural background radiation. Although in many circumstances the discharge is produced directly to the sea and therefore the increase of natural radioactivity levels can generally be considered negligible due to a dilution processes, the discharge into coastal wetlands (marshes, coastal lagoons or ponds), with somewhat restricted exchange with the open sea, may require a detailed study of the distribution of natural radionuclides and their effects on the coastal ecosystem. The Peniscola marsh is a Mediterranean coastal wetland where such studies may be of special interest because it is fed exclusively by groundwater, mainly discharging from a deep aquifer with high natural radioactivity content. In the Peniscola marsh, brackish groundwater discharging through the wetland sediments is enriched in radionuclides to maximum values of 2.8 and 616 kBq m(-3) of Ra-226 and Rn-222, respectively. These high dissolved concentrations result in high levels of Rn-222 in air (up to 36 Bq m(-3)) and Pb-210 and Po-210 dissolved in water (20 and 5.7 Bq m(-3), respectively). These elevated levels of natural radionuclides in the Peniscola marsh are also responsible of the significant increase in Po-210 and Pb-210 contents in both fish and plants. (C) 2013 Elsevier B.V. All rights reserved.

In this work, the low cost synthesis of polydimethylsiloxane (PDMS) rods is described, and the performances of this new passive sampling device (in laboratory and in situ) are compared to the passive stir bar sorptive extraction (SBSE) for the monitoring of pesticides from different classes (herbicides, insecticides and fungicides) in surface waters. The influence of synthesis parameters of PDMS rods (i.e., heating temperature, heating time and relative amount of curing agent) were assessed regarding their efficiency for the extraction of the target pesticides through a Hadamard's experimental design. This allowed the determination of the effect of the three parameters on the sorption of pesticides within four experiments. Thus, specific conditions were selected for the synthesis of the PDMS rods (heating at 80 °C for 2 h with 10% of curing agent). Laboratory experiments led to similar to lower extraction recovery in the PDMS rods in comparison with passive SBSE, depending on the pesticide. The in situ application demonstrated the efficiency of the PDMS rods for the passive sampling of the target pesticides in river water, although lower amounts of pesticides were recovered in comparison with passive SBSE. So, these very low cost PDMS rods could be used as an alternative to passive SBSE for large-scale monitoring campaigns.

According to Article 5 of the Directive 2008/105/EC on Environmental Quality Standards in the Field of Water Policy, Member States have to establish an inventory of emissions, discharges and losses of all priority substances and pollutants listed in Part A of Annex I to this Directive. This paper aims at describing the french approach used to review of the impact of human activity on the status of surface waters through : the general working shem of the methodology and few definitions ; the input data needed for the french approach ; some exemples of calculations carried out on French river basins ; the data compilation process. Methodology definition was guided by the following key ideas : a state-of-the-art methodology in agrement with reglementory requirments, and EU guidance ; a non substance specific methodology. The approach is based on effluent discharges data, in their absence some explicit estimation formulas are proposed ; a single methodology applicable at different spatial scales ; a methodology that will work despite scarcity of information and data, and uncertainties ; future use of emission inventory as a management tool for designing strategies for the reduction of the impacts of chemical pollution in watersheds ; a methodology which can easily deals with data from different years. All available information which are representative of a given year to draw a coherent picture of the micro pollutants releases in surface waters during this year must be used. After a bibliographical study, a pragmatic approach has also presided over the construction of the methodology developed in this paper in terms of work efficiency.

International audience; The chemical signature of stream water is influenced by several factors: atmospheric input, weathering of bedrock and soils, biological uptake, soil storage, and decomposition of organic matter. The importance of weathering and biological activity, according to season, can be assessed by subtracting atmospheric input. In the upper Iskar Reka watershed, Bulgaria, results show that Na and Ca are mainly exported out of the basin (weathering is dominant), while nitrate and sulphate are consumed/stored. The behaviour of K suggests that biological activity is dominated by vegetation uptake in spring and by bacterial activity in autumn. In summer, the weathering load of Mg is compensated by reactions with clays. The low nutrient input from weathering due to low reserves in the soil may lead to a biomass production closely linked to a rapid internal cycle and also to a relative sensitivity of the ecosystem to any change in vegetation cover and atmospheric input.; Plusieurs facteurs interviennent dans la chimie des eaux de rivières: les apports atmosphériques, l'altération des roches et des sols, la consommation biologique, le stockage dans les sols, la décomposition de la matière organique. La soustraction des apports atmosphériques permet d'estimer l'importance de l'altération et de l'activité biologique. Dans le bassin versant supérieur de l'Iskar Reka, Bulgarie, les résultats montrent que Na et Ca sont surtout exportés du bassin (l'altération domine), alors que nitrates et sulfates sont consommés/stockés. Le comportement du K suggère que l'activité biologique est dominée par la consommation végétale au printemps et par l'activité bactérienne à l'automne. En été, le Mg issu de l'altération est compensé par les réactions avec les argiles. Le faible apport en nutriments par altération des sols, dû aux faibles réserves des sols, peut entraîner une production de biomasse étroitement liée à un cycle interne rapide et aussi une relative sensibilité de l'écosystème à tout changement dans le couvert végétal et les apports atmosphériques.

We reconstructed a high-resolution, alkenone-based sea surface temperature (SST) record spanning the last ca. 150 years, from a sediment core retrieved within the main upwelling zone off Peru. A conspicuous SST decline is evidenced since the 1950s despite interdecadal SST variability. Instrumental SST data and reanalysis of ECMWF ERA 40 winds suggest that the recent coastal cooling corresponds mainly to an intensification of alongshore winds and associated increase of upwelling in spring. Consistently, both proxy and instrumental data evidence increased productivity in phase with the SST cooling. Our data expand on previous reports on recent SST cooling in other Eastern Boundary upwelling systems and support scenarios that relate coastal upwelling intensification to global warming. Yet, further investigations are needed to assess the role of different mechanisms and forcings (enhanced local winds vs. spin-up of the South Pacific High Pressure cell). Citation: Gutierrez, D., et al. (2011), Coastal cooling and increased productivity in the main upwelling zone off Peru since the mid-twentieth century, Geophys. Res. Lett., 38, L07603, doi:10.1029/2010GL046324.

Aerobic anoxygenic phototrophic (AAP) bacteria are photoheterotrophic prokaryotes able to use both light and organic substrates for energy production. They are widely distributed in coastal and oceanic environments and may contribute significantly to the carbon cycle in the upper ocean. To better understand questions regarding links between the ecology of these photoheterotrophic bacteria and the trophic status of water masses, we examined their horizontal and vertical distribution and the effects of nutrient additions on their growth along an oligotrophic gradient in the Mediterranean Sea. Concentrations of bacteriochlorophyll-a (BChl-a) and AAP bacterial abundance decreased from the western to the eastern basin of the Mediterranean Sea and were linked with concentrations of chlorophyll-a, nutrient and dissolved organic carbon. Inorganic nutrient and glucose additions to surface seawater samples along the oligotrophic gradient revealed that AAP bacteria were nitrogen- and carbon-limited in the ultraoligotrophic eastern basin. The intensity of the AAP bacterial growth response generally differed from that of the total bacterial growth response. BChl-a quota of AAP bacterial communities was significantly higher in the eastern basin than in the western basin, suggesting that reliance on phototrophy varied along the oligotrophic gradient and that nutrient and/or carbon limitation favors BChl-a synthesis.

International audience; Spatial and temporal variations of water quality were investigated at four sites of an urbanized river in Algeria during a period of low water level in the years 2002, 2003, and 2004. Physical-chemical parameters (temperature, pH, conductivity, dissolved oxygen, suspended matter, chemical oxygen demand [COD], and 5-day biochemical oxygen demand [BOD5]) were measured. The Soummam River showed a strong pollutant load, which was organic in origin and expressed by mean concentrations in suspended matter, COD and BOD5 exceeding 150, 100, and 50 mg/L, respectively. The spatial variation highlighted two areas--(1) the first one gathers the upstream and central sites of the river, and (2) the second one is found downstream. In the downstream area, the pollutant load is almost twice as high as in the first area and, the percent saturation of dissolved oxygen is relatively weak (< 55%). This load is the result of the significant volume of urban and industrial emissions in the river, the high temperature during low-water-level periods, and flood events, which occurred just before the period of low water level. The Soummam River was classified according to the criteria of appreciation of surface water and was found to be extremely polluted. This work is one of the first studies on the quality of rivers in Algeria. This research will be useful as a first step for future works in North Africa and will add to knowledge on the water quality in the Mediterranean Basin.

International audience; A multi residue analysis was developed for screening, quantification and confirmation of 36 priority organic compounds included in the 2000/60/EC European Water Framework Directive. The compounds analyzed included 19 pesticides, 8 PAH, 5 endocrine-disruptors and 4 organochlorine compounds. The method was developed in three steps. First, automated off-line solid-phase extraction using Strata X cartridges was optimized to trap simultaneously the 36 studied compounds. Second, the more volatile compounds were analysed by gas chromatography coupled to mass spectrometry with electron impact ionisation in selected ion monitoring mode (SIM). Third, the last 20 compounds were detected and quantified, in one run, by liquid chromatography coupled to fluorescence detector and tandem mass spectrometry. The excellent selectivity and sensitivity allowed us satisfactory quantification and confirmation at levels as low as 0.2-67 ng L(-1) with recoveries between 59 and 105%. Such methodology was then applied to French surface waters: all the waters present organic contaminants, and their concentration varied according to the origin and nature of substances.

International audience; Within the framework of the project AMPERES « Analyse de Micropolluants Prioritaires et émergents dans les Rejets et les Eaux Superficielles », studies were conducted on different wastewater treatment plants (WWTPs) to measure the concentrations of organic micropollutants in wastewaters and treated waters. Nevertheless the screening of surface water by grab sampling is difficult to interpret due to heterogeneity and variability. Thus compared with the grab sampling, the passive sampling has been studied to show its relevance for monitoring micropollutants in wastewater and aquatic systems impacted by these WWTP effluents. For this, two kinds of passive samplers were selected: the Semi Permeable Membrane Device (SPMD) and the Polar Organic Compound Integrative Sampler (POCIS). The first part of this study was the determination of the POCIS sampling rates (Rs) for Alkylphenol Polyethoxylates (APnEO) and Pharmaceutical Substances (PhACs). The second part consisted in a field validation of POCIS.

We studied estrogenic disrupting potency in rivers and wastewaters in the Orge catchment area near Paris, using analytical and biological approaches simultaneously. The MELN test was applied to surface-water samples, urban storm run-off and wastewater-treatment plant (WWTP) effluent in parallel with analytical determinations of natural estrogens and synthetic estrogen (ethinylestradiol) using liquid chromatography and tandem mass spectrometry. We quantified estrone in all samples in the range 0.1–15.7 ng/L. We also quantified β-estradiol in all samples, but at a lower level (0.1–2.3 ng/L), but we never detected α-estradiol. We quantified ethinylestradiol only in WWTP effluent (0.2 ng/L); we measured estriol in WWTP effluent (12.1 ng/L) and downstream effluent (4.9 ng/L). The biological responses using the MELN test closely followed the chemical responses. Analytical quantification of estrogens appears to be a simple way to trace estrogenic disruption in surface waters of urban areas, as these hormones are mainly responsible for biological effects.

Heavy metal contamination has been investigated in the Milluni Valley (Bolivia, High Plateau, 4800 m asl) combining geochemical, mineralogical and hydrochemical approaches. For each metal, the mineral source was determined, as well as the geochemical process leading to the weathering of primary minerals into tertiary minerals. The knowledge of the ongoing geochemical processes and of the hydrochemical budgets allowed to determining the origin, the transport pathways and the control parameters of the metals in this environment. Finally, the cores in lake sediments and in peat-bogs of the valley allowed assessing the historical behaviour of heavy metal contamination, especially during the last century.; Sur le site minier de Milluni (Bolivie, Altiplano, 4800 m asl), la contamination des eaux de surface et des sédiments par les métaux lourds a été étudiée en combinant des approches géochimiques, minéralogiques et hydrochimiques. Pour les différents métaux, les sources minérales de la contamination ont été établies, ainsi que les processus géochimiques d'altération des minéraux primaires en minéraux tertiaires. La compréhension des mécanismes géochimiques en jeu et les bilans réalisés ont permis de déterminer les origines et les modes de transport et de contrôle des métaux dans cet environnement. Enfin, les carottages des sédiments lacustres et des tourbières ont permis d'évaluer l'évolution historique de la contamination en métaux lourds, notamment au cours du siècle dernier.

The organic matter cycle at the continental scale still remains partly misunderstood. Thus, DOC has been mostly studied under indistinct chemical aspect. Isotopic studies and the use of biomarkers allowed the clarification of certain aspects of its cycle. The present study is part of this research perspective. Two types of environments, the St. Lawrence River and the Astien's aquifer (France), were examined. For the St. Lawrence study, we were interested in the terrigenous organic carbon (TOC) cycle from 13C and 14C measurements on DOC and a refractory fraction of DOC to understand the origin and evolution of TOC during its export towards the ocean. In the Astien study, similar approaches were used to determine the nature, sources, degradation state and temporal evolution of DOC in groundwater. Results show that we keep a predominantly terrigenous origin and a globally recent age for DOC from the St. Lawrence hydrological system. However, a small fraction of this DOC appeared to be much more ancient. The present study indicates that total DOC in the St. Lawrence hydrological system is constituted of organic compounds easily biomineralizable and thus potentially large consumers of dissolved oxygen. TOC could play a more important role than previously estimated in the apparition of hypoxic conditions in the world's estuaries and costal areas. In the Astien's aquifer system, relative kinetics of degradation of organic compounds product by lignin macromolecule could be used for geochronometrical applications., Le cycle de la matière organique à l'échelle continentale reste encore en partie méconnu. Ainsi, le COD a surtout été étudié sous un aspect chimique indifférencié. Des études isotopiques et l'utilisation de biomarqueurs ont permis d'élucider certains aspects de son cycle. La présente étude s'inscrit dans cette perspective. Deux types de milieux distincts, le fleuve Saint-Laurent et l'aquifère de l'Astien (France), ont été examinés. Dans le volet "Saint-Laurent", nous nous sommes intéressés au cycle du carbone organique terrigène (COT) à partir de mesures 13C et 14C du COD et d'une composante réfractaire du COD afin de comprendre l'origine et l'évolution du COT lors de son transit vers l'océan. Dans le second volet, les mêmes approches ont été retenues afin de déterminer la nature, les sources, l'état de dégradation et l'évolution temporelle du COD dans une nappe d'eau souterraine. Nous retenons une origine majoritairement terrigène pour le COD du Saint-Laurent, ainsi que son âge globalement très récent. Cependant, une fraction de ce COD est apparue beaucoup plus ancienne. La présente étude indique que le COD total du système hydrologique du fleuve Saint-Laurent est en majorité constitué de composés organiques facilement biominéralisables et donc potentiellement grands consommateurs d'oxygène dissous. Le COT pourrait donc jouer un rôle plus important qu'estimé aujourd'hui dans l'apparition de conditions hypoxiques dans les estuaires et zones côtières du globe. Dans le système de l'aquifère de l'Astien, les cinétiques relatives de dégradation des composés organiques issus de la macromolécule ligneuse pourraient donner lieu à des applications géochronométriques.

International audience; We present here an improved and reliable method for measuring the concentration of dissolved inorganic carbon (DIC) and its isotope composition (delta C-13(DIC) in natural water samples. Our apparatus, a gas chromatograph coupled to an isotope ratio mass spectrometer (GCIRMS), runs in a quasi-automated mode and is able to analyze about 50 water samples per day. The whole procedure (sample preparation, CO2(g)-CO2(aq) equilibration time and GCIRMS analysis) requires 2 days. It consists of injecting an aliquot of water into a H3PO4-loaded and He-flushed 12 mL glass tube. The H3PO4 reacts with the water and converts the DIC into aqueous and gaseous CO2. After a CO2(g)-CO2(aq) equilibration time of between 15 and 24 h, a portion of the headspace gas (mainly CO2+He) is introduced into the GCIRMS, to measure the carbon isotope ratio of the released CO2(g), from which the delta C-13(DIC) is determined via a calibration procedure. For standard solutions with DIC concentrations ranging from 1 to 25 mmol (.) L-1 and solution volume of 1 mL (high DIC concentration samples) or 5 mL (low DIC concentration samples), delta C-13(DIC) Values are determined with a precision (1 sigma) better than 0.1 parts per thousand. Compared with previously published headspace equilibration methods, the major improvement presented here is the development of a calibration procedure which takes the carbon isotope fractionation associated with the CO2(g)-CO2(aq) partition into account: the set of standard solutions and samples has to be prepared and analyzed with the same 'gas/liquid' and 'H3PO4/water' volume ratios. A set of natural water samples (lake, river and hydrothermal springs) was analyzed to demonstrate the utility of this new method. Copyright