Gas- and Particle-Phase Products from the Chlorine-Initiated Oxidation of Polycyclic Aromatic Hydrocarbons
The chlorine atom (Cl)-initiated oxidation of three polycyclic aromatic hydrocarbons (PAHs; namely, naphthalene, acenaphthylene, and acenaphthene) was investigated. Experiments were performed in an atmospheric simulation chamber using a proton transfer reaction time-of-flight mass spectrometer (TOF-MS) and an aerosol TOF-MS to characterize the oxidation products in the gas and particle phases, respectively. The major products identified from the reaction of Cl atoms with naphthalene were phthalic anhydride and chloronaphthalene, indicating that H atom abstraction and Cl addition reaction pathways are both important. Acenaphthenone was the principal product arising from reaction of Cl with acenaphthene, while 1,8-naphthalic anhydride, acenaphthenone, acenaphthenequinone, and chloroacenaphthenone were all identified as products of acenaphthylene oxidation, confirming that the cylcopenta-fused ring controls the reactivity of these PAHs toward Cl atoms. Possible reaction mechanisms are proposed for the formation of these products, and favored pathways have been suggested. Large yields of secondary organic aerosol (SOA) were also observed in all experiments, and the major products were found to undergo significant partitioning to the particle-phase. This work suggests that Cl-initiated oxidation could play an important role in SOA formation from PAHs under specific atmospheric conditions where the Cl atom concentration is high, such as the marine boundary layer.
(Journal of Physical Chemistry A. vol. 119, n° 1089-5639, pp. 11170-11181, 02/11/2015)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
Combined effects of pollutants and salinity on embryo-larval development of the Pacific oyster, Crassostrea gigas
For several years, low larval recruitment has been observed in Arcachon Bay, in southwest France. Exposure to pollutants could partly account for the reduction of early life stages of the Pacific oyster. This study evaluated the effects of copper and S-metolachlor in combination with salinity on the early life stages of Crassostrea gigas. Embryos were exposed to concentrations of copper (1, 10 and 50 μg L(-1)) or S-metolachlor (10, 100 and 1000 ng L(-1)) and six salinities (18, 21, 24, 27, 30 and 33 u.s.i). Embryotoxicity was measured by considering both the percentage of abnormalities and arrested development in D-shaped larvae. Embryo-larval development was only affected at salinities ≤24 u.s.i, which have never been observed during C. gigas reproduction period in Arcachon Bay. Both contaminants had an effect at environmental concentrations. Our results suggest that copper and metolachlor toxicity was enhanced with decreasing salinity.
(Marine Environmental Research. vol. 113, n° 0141-1136, pp. 31-38, 01/11/2015)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
Organic matter characterization and distribution in sediments of the terminal lobes of the Congo deep-sea fan: Evidence for the direct influence of the Congo River
The terminal lobe complex of the Congo River submarine fan sits on the abyssal Atlantic plain, at 5000 m water depth, 760 km offshore from the river mouth estuarine area. While most rivers deliver particulate material to the continental shelf, particulate matter from the Congo River largely bypasses the shelf and is transported by turbidity currents through the Congo submarine canyon system. We determined the quantity and quality of the organic matter reaching the terminal lobe complex at five sites with marked morphological differences that may influence the distribution of organic matter. A suite of bulk geochemical (% OC, δ13Corg, δ15N, C: N), 137Cs and palynofacies analyses were done on cores collected from the terminal lobe area. These results were also compared to the composition of sediments collected upstream at the Malebo Pool (Congo River). Distal lobe complex sediments contain high amounts of terrestrial organic carbon (3–5 wt.%) that is homogeneously distributed in surficial (22 cm) and deeper sediments (580 cm) silty–clay facies. Strongly altered soil-derived organic matter with well-preserved land plant detritus from the Congo River predominates. A terrestrial soil origin for the particulate load was confirmed by the elevated 137Cs activity in lobe sediments. The vertical distribution of the 137Cs signal suggests that there has been a massive arrival of terrestrial sediments since 1963, consistent with a turbiditic origin. From the locations surveyed, we estimate a maximum accumulation of terrestrial organic carbon of ca. 1 kg OC m− 2 y− 1 for the distal lobe. However, transport modifies the organic matter both in terms of quantity and quality. Observed differences were attributed to preferential degradation of nitrogenous matter during diagenesis and to the addition of highly remineralized marine organic matter. Results from our temporal reference site (E) suggest that organic matter may be preserved in turbidite facies for thousands of years. The good preservation state of the accumulated organic matter shows that turbiditic lobe complexes should be considered as a sink for terrestrial organic carbon in the deep ocean.
(Marine Geology. vol. 369, n° 0025-3227, pp. 182-195, 01/11/2015)
iSTeP, INSU - CNRS, SU, CNRS, LECOB, SU, CNRS, OOB, SU, CNRS, LSCE, UVSQ, INSU - CNRS, CNRS, DRF (CEA), CEA, OCEANIS, LSCE, UVSQ, INSU - CNRS, CNRS, DRF (CEA), CEA, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, GM, IFREMER, IFREMER, LEMAR, IRD, IFREMER, UBO EPE, CNRS
Accumulation trends of metal contamination in sediments of the former Pb–Zn mining district of Touiref (NW Tunisia)
Wastes of the former Pb–Zn mining district of Touiref (Pb/Zn) can be eroded during strong rainfall. The presence of a downstream lake offers the opportunity to perform geochemical characterisation of lacustrine sediments and analyze the temporal evolution of metal contamination. For this reason, a sedimentary core (C1) has been collected at the outlet of the Oued Sidi Bou Said which runs along the North side of the dike flotation tailings and a second core (C2) was sampled in front of the river flowing outside the mine site and reaching the plain on the East side of the endoreic study area. The scope of the present paper is characterize the temporal variability of major and minor elements in both sedimentary cores. The study of the historical contamination in both Touiref cores shows a clear impact of mining on the total endorheic basin, especially for the period going from 1914 until 1955 as well as the influence of urban development.
(Journal of African Earth Sciences. vol. 111, n° 1464-343X, pp. 231-243, 01/11/2015)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
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