Precise indices based on n-alkane distribution for quantifying sources of sedimentary organic matter in coastal systems
Precise indices based on n-alkane signatures were developed in order to determine the sources and composition of sedimentary organic matter (SOM) in coastal systems. The Arcachon Bay (France), a well-studied temperate lagoon, was used as an example of a complex coastal system sheltering a wide diversity of OM sources. Three main groups of sources were well discriminated from their n-alkane signatures: seagrass (Zostera sp.) produced mainly n-C17, n-C19, n-C21, n-C23 and n-C25 alkanes, algae (Rhodophyta, Chlorophyta) produced n-C15 and n-C17 and the terrigenous input [Quercus sp., Spartina sp. and river suspended particulate OM (SPOM)] was characterized by n-C25, n-C27, n-C29, n-C31 and n-C33. From the above and literature n-alkane fingerprints, we developed a set of indices (n-alkane ratios) to quantify the contribution of these three major sources of the SOM. At the Arcachon Bay scale, they indicated that SOM was composed mainly of seagrass (ca. 53 ± 19%) and terrestrial (ca. 41 ± 17%) material, followed by algae (ca. 6 ± 9%). Moreover, the new n-alkane indices exhibited more relevant spatial patterns than classical ones – the TAR (C27 + C29 + C31/C15 + C17 + C19; terrestrial to aquatic ratio) and the Paq (C23 + C25/C23 + C25 + C29 + C31; aquatic plant %) – with a greater contribution from marine sources in the central part of the lagoon where a high density of Zostera seagrass was observed. Therefore, the development of precise indices adapted to the local diversity of OM sources is needed when using n-alkanes for quantifying the source composition of SOM in complex coastal systems.
(Organic Geochemistry. vol. 88, n° 0146-6380, pp. 69-77, 01/11/2015)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
Using ecological models to assess ecosystem status in support of the European Marine Strategy Framework Directive
The European Union's Marine Strategy Framework Directive (MSFD) seeks to achieve, for all European seas, "Good Environmental Status" (GEnS), by 2020. Ecological models are currently one of the strongest approaches used to predicting and understanding the consequences of anthropogenic and climate-driven changes in the natural environment. We assess the most commonly used capabilities of the modelling community to provide information about indicators outlined in the MSFD, particularly on biodiversity, food webs, non-indigenous species and seafloor integrity descriptors. We built a catalogue of models and their derived indicators to assess which models were able to demonstrate: (1) the linkages between indicators and ecosystem structure and function and (2) the impact of pressures on ecosystem state through indicators. Our survey identified 44 ecological models being implemented in Europe, with a high prevalence of those that focus on links between hydrodynamics and biogeochemistry, followed by end-to-end, species distribution/habitat suitability, bio-optical (remote sensing) and multispecies models. Approximately 200 indicators could be derived from these models, the majority of which were biomass and physical/hydrological/chemical indicators. Biodiversity and food webs descriptors, with about 49% and about 43% respectively, were better addressed in the reviewed modelling approaches than the non-indigenous species (0.3%) and sea floor integrity (about 8%) descriptors. Out of 12 criteria and 21 MSFD indicators relevant to the abovementioned descriptors, currently only three indicators were not addressed by the 44 models reviewed. Modelling approaches showed also the potential to inform on the complex, integrative ecosystem dimensions while addressing ecosystem fundamental properties, such as interactions between structural components and ecosystems services provided, despite the fact that they are not part of the MSFD indicators set. The cataloguing of models and their derived indicators presented in this study, aim at helping the planning and integration of policies like the MSFD which require the assessment of all European Seas in relation to their ecosystem status and pressures associated and the establishment of environmental targets (through the use of indicators) to achieve GEnS by 2020.
(Ecological Indicators. vol. 58, n° 1470-160X, pp. 175-191, 01/11/2015)
IES, JRC, JRC, CEFAS, HCMR, UDELAR, SYKE, UC, MHI, NASU / НАН України, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, BOREA, UNICAEN, NU, MNHN, IRD, SU, CNRS, UA
Development and application of a multi-residue method for the determination of 53 pharmaceuticals in water, sediment, and suspended solids using liquid chromatography-tandem mass spectrometry
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.
(Analytical and Bioanalytical Chemistry. vol. 407, n° 1618-2642, pp. 8585-8604, 01/11/2015)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, ARS
Implantation des échantillonneurs passifs pour le suivi des pesticides dans les milieux aquatiques libanais
Suite à l’utilisation massive et peu contrôlée des pesticides au LIBAN et conformément auxexigences des législations fixées par les réglementations nationales, européennes etinternationales sur la qualité de l’eau, des programmes de surveillances nationaux ont étéélaborés afin d’évaluer la qualité de l’eau dans les milieux aquatiques libanais et de jauger lesimpacts écologiques et sanitaires liés à la présence éventuelle de pesticides dansl’environnement au Liban.Dans le cadre de ces programmes de surveillance, des prélèvements périodiques ponctuelssont réalisés mais, le suivi permanant dans le temps d’une contamination étendue est trèsdifficile ce qui impose alors la multiplication des prélèvements dans le temps et dansl’espace. L’apparition récente des échantillonneurs intégratifs comme alternativesintéressantes aux techniques d’échantillonnage déjà existantes semblent relativement plusefficaces et mieux représentatifs du point de vue économique et environnemental. Ilspermettent d'effectuer un suivi moyenné sur de longues périodes d'observation allant dequelques jours à plusieurs semaines associé à une simplicité d'usage et une réduction descoûts.Le POCIS (Polar Organic Chemical Integrative Sampler) est le type d’échantillonneur adoptédurant nos travaux de thèse afin d’étudier l’applicabilité de ces POCIS au dosage des résidusde pesticides dans les milieux aquatiques libanais. Cent-neuf molécules appartenant àdifférentes familles de pesticides fréquemment utilisés par les agriculteurs libanais ont étéretenues pour l’étude. Les cinétiques d’adsorption des molécules sur les POCIS et celle de ladésorption des composés références de performance « PRC » ont été suivies par calibrationin-situ ou au laboratoire soit en flux statique ou en flux continu sous différentes conditionsayant une influence sur la rétention des pesticides.Le coefficient d’échantillonnage Rs (L.j-1) spécifique à chaque molécule, nécessaire au calculde la concentration moyenne dans le milieu d’exposition du POCIS, a été déterminé dans lesdivers milieux d’étude : Eau minérale, eau de robinet et eau de rivière. Les cinétiquesd’adsorption des molécules ont également été élaborées afin d’évaluer la durée optimaled’implantation dans les différents milieux aquatiques.Après validation du système d’échantillonnage au laboratoire, son efficacité a été vérifiée surle terrain, les POCIS ont été testés in-situ sur divers sites appartenant aux différentes régionsagricoles libanaises (Estuaire de la rivière Ibrahim, Lac Qaraoun, et Rivière Hasbani). Lesconcentrations moyennes de la totalité des pesticides ciblés ont été estimées et leurs valeursont été comparées avec celles obtenues par prélèvements actifs. Cependant, pour le futur, desétudes élaborées devraient être entreprises afin de couvrir la majorité des molécules activesde pesticides employés au Liban; il faudrait également essayer d’améliorer la reproductibilitédes POCIS pour les analyses quantitatives par l’incorporation de nouveaux composésréférences de Performance (PRC) ou par calibration in-situ systématique pour les différentssites étudiés.
(30/10/2015)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
Etude de la contamination par les pesticides des milieux eau, air et sols : développement de nouveaux outils et application à l’estuaire de la Gironde
Largement utilisés par l’agriculture intensive, les pesticides sont aujourd’hui présents dans les différents compartiments environnementaux et ce à un niveau mondial. Les recherches de ces travaux de thèse se sont plus particulièrement portées sur deux grandes thématiques, l’une liée à l’écodynamique des pesticides en Garonne estuarienne par la caractérisation des sources, la présence et le devenir des molécules, et l’autre sur leur transfert dans les compartiments eau, air et sols d’un château viticole. Des méthodes d’analyse simples et rapides à mettre en oeuvre ont été optimisées, tout en étant sensibles afin d’être compatibles avec l’étude des milieux faiblement contaminés.Les pesticides les plus fortement quantifiés dans les stations d’épuration (STEP) bordelaises sont le diuron, l’imidaclopride et le fipronil (≈ 50-100 ng.L-1). N’étant pas éliminés par les différents traitements, ils sont présents dans les rejets (apports de l’ordre du g.j-1) qui peuvent alors être une source de contamination pour le milieu. Si les pesticides majoritairement présents dans la Garonne sont le métolachlore et ses métabolites (≈ 10-800 ng.L-1), qui présentent des pics printaniers en lien avec l’application de la molécule, les pesticides caractéristiques de STEP sont également quantifiés. Les concentrations sont plus faibles (0,5-20 ng.L-1) et moins variables mais ne peuvent cependant pas être négligées, certaines molécules étant fortement toxiques même à faible concentration, comme le fipronil (PNEC = 0,77 ng.L-1).Les sols du château viticoles sont caractérisés par des pics printaniers (50-1000 ng.g-1) en pesticides en lien avec les applications, comme le boscalid ou l’azoxystrobine. Des molécules non utilisées depuis plusieurs années, comme le diuron, ont également été mis en évidence à plus faibles niveaux de concentrations (ng.g-1) et moins variables ce qui témoigne de la persistance de certaines molécules. Le compartiment atmosphérique est également caractérisé par des pics saisonniers en lien avec l’application et la volatilité des molécules, comme le folpel ou le chlorpyrifos-methyl. Des pesticides non utilisés par le château mais potentiellement appliqués par des exploitations voisines comme le métolachlore ont également été détectés, ce qui démontre bien du transport des molécules. Des pesticides interdits (diuron), non utilisés (métolachlore) et utilisés (boscalid) par le château ont été mis en évidence dans la nappe phréatique.
(26/10/2015)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
Zebrafish Models for Human Acute Organophosphorus Poisoning
Terrorist use of organophosphorus-based nerve agents and toxic industrial chemicals against civilian populations constitutes a real threat, as demonstrated by the terrorist attacks in Japan in the 1990 s or, even more recently, in the Syrian civil war. Thus, development of more effective countermeasures against acute organophosphorus poisoning is urgently needed. Here, we have generated and validated zebrafish models for mild, moderate and severe acute organophosphorus poisoning by exposing zebrafish larvae to different concentrations of the prototypic organophosphorus compound chlorpyrifos-oxon. Our results show that zebrafish models mimic most of the pathophysiological mechanisms behind this toxidrome in humans, including acetylcholinesterase inhibition, N-methyl-D-aspartate receptor activation and calcium dysregulation as well as inflammatory and immune responses. The suitability of the zebrafish larvae to in vivo high-throughput screenings of small molecule libraries makes these models a valuable tool for identifying new drugs for multifunctional drug therapy against acute organophosphorus poisoning.
(Scientific Reports. vol. 5, n° 2045-2322, pp. 15591, 22/10/2015)
CESAM, IDAEA, CSIC, UAB, U1211 INSERM/MRGM, UB, INSERM, CIBERDEM, ISCIII, IRB, UB, BIST, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, CID-CSIC, CSIC, CSIC, CSIC
Infragravity-wave modulation of short-wave celerity in the surf zone
The cross-shore evolution of individual wave celerity is investigated using two high-resolution laboratory experiments on bichromatic waves. Individual waves are tracked during their onshore propagation and their characteristics, including celerity, are estimated. The intrawave variability in celerity is low in the shoaling zone but increases strongly after breaking. It is maximum when the infragravity-wave height to water depth ratio is the largest, that is to say close to the shoreline. There the observed range of individual wave celerity can be as large as the mean celerity value. This variability can be largely explained by the variations in water depth and velocity induced by the infragravity waves. The differences in celerity are such that they lead to the merging of the waves in the inner surf zone for most of the wave conditions considered. Again, the location at which the first waves start merging strongly correlates with the infragravity-wave height to water depth ratio. The consequences of these findings for celerity-based depth-inversion techniques are finally discussed. Surprisingly, accounting for the infragravity-wave modulation of the velocity field in the celerity estimate does not significantly improve depth estimation in the surf zone. However, it is shown that the occurrence of bore merging decreases significantly the coherence of the wavefield in the surf zone. This loss of coherence could hamper celerity estimation from pixel intensity time series and explain, at least partly, the relatively poor performance of depth-inversion techniques in the inner surf zone.
(Journal of Geophysical Research. Oceans, n° 2169-9275, 20/10/2015)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, LEGI, UJF, Grenoble INP, CNRS
Etude de la pollution marine par les hydrocarbures et caractérisation de leurs effets biochimiques et moléculaires sur la palourde de Ruditapes sp.
Dans notre étude, la biosurveillance de la lagune de Tunis a été réalisée durant une année enemployant une approche combinant les analyses chimiques et biologiques et en utilisant lapalourde Ruditapes decussatus comme espèce bioindicatrice. Cette approche a permis demettre en évidence la forte contamination de la lagune de Tunis par les métaux traces et leshydrocarbures aromatiques polycycliques (HAPs). La variation saisonnière des niveaux debioaccumulation de ces contaminant par la palourde s’avère être fortement associée auxchangements des paramètres physico-chimiques du milieu et aux processus physiologiques del’animal. L’étude de la réponse biologique basée sur l’utilisation d’une batterie debiomarqueurs d’exposition et d’effet situés à différents niveaux de l’organisation biologique :moléculaire (l’expression de cinq gènes d’intérêt), biochimique (les activités benzo(a)pyrènehydroxylase, glutathion S-transférase, acétylcholinestérase, catalase et taux demalondialdéhyde) et tissulaire (altérations histopathologiques), a permis de mettre enévidence une modulation des processus de défense contre les perturbations induites par lapollution et l’identification des altérations histopathologiques (structurales) au niveau desbranchies et de la glande digestive impliquant un impact sévère des contaminants sur l’état desanté de la palourde. L’étude des interactions spatio-temporelles entre les facteurs abiotiqueset biotiques a permis d’identifier la température et la reproduction comme paramètresprincipaux affectant la réponse biochimique de défense et d’effet. L’analyse en composanteprincipale (ACP), regroupant tous les paramètres analysés pendant le printemps, nous apermis d’identifié le site Z2 comme le site le plus affecté par la pollution. Dans un secondtemps, le benzo(a)pyrène (BaP), déjà identifié dans la lagune de Tunis, a été employé dansdes conditions contrôlées au laboratoire afin de caractériser les réponses moléculaires etbiochimiques chez les bivalves (Ruditapes philippinarum et Crassostrea gigas) face à desexpositions subaiguës et aiguës à ce contaminant. Cette étude nous a permis d’identifier unemodulation des biomarqueurs biochimiques de métabolisation, de stress oxydant et deneurotoxicité et de l’expression des gènes impliqués dans les processus de métabolisation, derespiration mitochondriale, de défense antioxydante, de reproduction et de défenseimmunitaire. L’analyse de l’altération de l’ADN a révélé un pouvoir génotoxique précoce etélevé du BaP chez les deux bivalves.
(06/10/2015)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
POPs in free-ranging pilot whales, sperm whales and fin whales from the Mediterranean Sea: Influence of biological and ecological factors
The pilot whale Globicephala melas, the sperm whale Physeter macrocephalus, and the fin whale Balaenoptera physalus are large cetaceans permanently inhabiting the Mediterranean Sea. These species are subjected to numerous anthropogenic threats such as exposure to high levels of contaminants. Therefore, selected persistent organic pollutants POPs (29 PCBs, 15 organochlorine compounds, 9 PBDEs and 17 PCDD/Fs) were analysed in blubber biopsies of 49 long-finned pilot whales, 61 sperm whales and 70 fin whales sampled in the North Western Mediterranean Sea (NWMS) from 2006 to 2013. Contamination profile and species feeding ecology were then combined through the use of stable isotopes. δ13C, δ15N values and POPs levels were assessed through IR-MS and GC–MS respectively. To assess the toxic potency of the dioxin-like compounds, the TEQ approach was applied. δ15N values were 12.2±1.3‰ for sperm whales, 10.5±0.7‰ for pilot whales and 7.7±0.8‰ in fin whales, positioning sperm whales at higher trophic levels. δ13C of the two odontocetes was similar and amounted to −17.3±0.4‰ for sperm whales and −17.8±0.3‰ for pilot whales; whilst fin whales were more depleted (−18.7±0.4‰). This indicates a partial overlap in toothed-whales feeding habitats, while confirms the differences in feeding behaviour of the mysticete. Pilot whales presented higher concentrations than sperm whales for ΣPCBs (38,666±25,731 ng g−1 lw and 22,849±15,566 ng g−1 lw respectively), ΣPBDEs (712±412 ng g−1 lw and 347±173 ng g−1 lw respectively) and ΣDDTs (46,081±37,506 ng g−1 lw and 37,647±38,518 ng g−1 lw respectively). Fin whales presented the lowest values, in accordance with its trophic position (ΣPCBs: 5721±5180 ng g−1 lw, ΣPBDEs: 177±208 ng g−1 lw and ΣDDTs: 6643±5549 ng g−1 lw). Each species was characterized by large inter-individual variations that are more related to sex than trophic level, with males presenting higher contaminant burden than females. The discriminant analysis (DA) confirmed how DDTs and highly chlorinated PCBs were influential in differentiating the three species. Pollutant concentrations of our species were significantly higher than both their Southern Hemisphere and North Atlantic counterparts, possibly due to the particular Mediterranean geomorphology, which influences pollutants distribution and recycle. Dioxin-like PCBs accounted for over 80% of the total TEQ. This study demonstrated (1) an important exposure to pollutants of Mediterranean cetaceans, often surpassing the estimated threshold toxicity value of 17,000 ng g−1 lw for blubber in marine mammals; and (2) how the final pollutant burden in these animals is strongly influenced not only by the trophic position but also by numerous other factors such as sex, age, body size and geographical distribution.
(Environmental Research. vol. 142, n° 0013-9351, pp. 185-196, 01/10/2015)
IMS, UB, CNRS, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, ULiège
Indian monsoon variations during three contrasting climatic periods: The Holocene, Heinrich Stadial 2 and the last interglacial–glacial transition
In contrast to the East Asian and African monsoons the Indian monsoon is still poorly documented throughout the last climatic cycle (last 135,000 years). Pollen analysis from two marine sediment cores (NGHP-01-16A and NGHP-01-19B) collected from the offshore Godavari and Mahanadi basins, both located in the Core Monsoon Zone (CMZ) reveals changes in Indian summer monsoon variability and intensity during three contrasting climatic periods: the Holocene, the Heinrich Stadial (HS) 2 and the Marine Isotopic Stage (MIS) 5/4 during the ice sheet growth transition. During the first part of the Holocene between 11,300 and 4200 cal years BP, characterized by high insolation (minimum precession, maximum obliquity), the maximum extension of the coastal forest and mangrove reflects high monsoon rainfall. This climatic regime contrasts with that of the second phase of the Holocene, from 4200 cal years BP to the present, marked by the development of drier vegetation in a context of low insolation (maximum precession, minimum obliquity). The historical period in India is characterized by an alternation of strong and weak monsoon centennial phases that may reflect the Medieval Climate Anomaly and the Little Ice Age, respectively. During the HS 2, a period of low insolation and extensive iceberg discharge in the North Atlantic Ocean, vegetation was dominated by grassland and dry flora indicating pronounced aridity as the result of a weak Indian summer monsoon. The MIS 5/4 glaciation, also associated with low insolation but moderate freshwater fluxes, was characterized by a weaker reduction of the Indian summer monsoon and a decrease of seasonal contrast as recorded by the expansion of dry vegetation and the development of Artemisia, respectively. Our results support model predictions suggesting that insolation changes control the long term trend of the Indian monsoon precipitation, but its millennial scale variability and intensity are instead modulated by atmospheric teleconnections to remote phenomena in the North Atlantic, Eurasia or the Indian Ocean.
(Quaternary Science Reviews. vol. 125, n° 0277-3791, pp. 50-60, 01/10/2015)
SCTA, UQAM, EPHE, PSL, IFP, MEAE, CNRS, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, UNH, WHOI