Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study presents the geochemical composition of superficial sediment under oxic and suboxic bottom water conditions along the Chilean continental margin (SE Pacific), where evidence for benthic chemosynthetic activity associated with diffuse seeping of chemically reduced fluids has been reported. The exploration was carried out at: (1) the Chilean Triple Junction (CTJ), at a water depth of ∼2900 m, with the additional indication of hydrothermal activity near a methane-rich cold-seep area (46°S) (German et al., 2010); and (2) the El Quisco methane seep site (EQSS), at ∼340 m water depth (33°S) (Melo et al., 2007; Krylova et al., 2014). While the deeper CTJ is located within an oxic environment (dissolved oxygen in the bottom waters: 164 μM), the shallower EQSS lies within a suboxic environment (dissolved oxygen in bottom water: 23 μM), located within the lower limit of the SE Pacific oxygen minimum zone (OMZ).Pore water from short cores was analyzed for dissolved major, minor, and trace elements (Cl, Na, Mg, K, Ca, Sr, Si, B, P, Ba, Pb, Mn, Fe, Cd, U, and Mo), δ13DIC, sulfide, sulfate, and methane. The solid sediment fraction was likewise analyzed for total organic carbon (TOC), metals, and redox potential. Elevated sediment temperatures were found in superficial sediments (5–13 °C) at the CTJ site, which could be due to warm fluids associated with the proximity of the ridge, where hydrothermal vents may occur. Reduced fluids were also present here, indicated by higher Mn fluxes toward the water column even in oxidized sediments (RPD > 8 cm), which contrasted with the lower fluxes in reduced sediments of the EQSS site (RPD ∼ 2 cm). 13C-depleted DIC, anomalously low pore water Cl (∼15 ppb), and low concentrations of other major elements may be the result of dilution by fluid seeping and precipitation of major elements, producing authigenic enrichment (Ca, Mg, Sr). The fluid could also: (a) be diluted by pure water produced during methane hydrate dissociation, as observed in other cold-seep areas; and (b) correspond to clay mineral dehydration, as reported in plate subduction systems. The reducing conditions established at the CTJ conduct the Cd enrichment at a similar magnitude of that seen at the shallower suboxic site (EQSS). Evidence of chimney or vent fauna was not observed. At the EQSS, higher TOC and total sulfide contents were consistent with enhanced deposition of organic matter and reducing conditions developed in the OMZ, favoring the authigenic enrichment of Cd, U and Pb. The geochemical evidence, based only on methane concentrations and δ13DIC, is insufficient to establish the presence of methane seeps, as previously reported.
ISSN: 0079-6611

hal-01412700
https://hal.archives-ouvertes.fr/hal-01412700
DOI : 10.1016/j.pocean.2016.09.002

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Volumetrically minor microsyenites, alkali microgranite and related trachytic dykes intrude early Pliocene OIB-like alkali basaltic and basanitic flows of the Meseta del Lago Buenos Aires in Central Patagonia (47 degrees S-71 degrees 30'W), and occur together with scarce trachytic lava flows. Whole-rock K-Ar ages between 3.98 and 3.08 Ma indicate that the emplacement of these felsic rocks occurred more or less synchronously with that of the post-plateau basaltic sequence that they intrude, during a bimodal mafic-felsic magmatic episode devoid of intermediate compositions. Chemically, these rocks have A(1)-type granitoid affinities and are characterized by high silica and alkali contents (60-68 wt.% SiO2; 8.7-10.8 wt.% Na2O+K2O), major and trace elements patterns evidencing evolution by low-pressure fractional crystallization, and Sr and Nd isotopic signatures similar to those of coeval basalts ((Sr-87/Sr-86)o=0.70488-0.70571; (Nd-143/Nd-144)(o)=0.512603-0.512645). Nevertheless, some of them have the most radiogenic Sr values ever reported for a magmatic rock in the Meseta and even in the whole Neogene Patagonian Plateau Lavas province ((Sr-17/Sr-86)(o)= 0.70556-0.70571; (Nd-143/Nd-144)(o)=0.512603-0.512608). In addition, very high contents of strongly incompatible elements in the most evolved rocks, together with Sr isotopic ratios higher than those of coeval basalts, suggest the occurrence of open-system magmatic processes. Continuous fractional crystallization from a primitive basaltic source, similar to post-plateau coeval basalts, towards alkali granites combined with small rates of assimilation of host Jurassic tuffs (AFC) in a shallow magmatic reservoir, best explains the geochemical and petrographic features of the felsic rocks. Therefore, A(1)-type magmatic rocks can be generated by open-system crystallization of deep asthenospheric melts in back-are tectonic settings. In Central Patagonia, these similar to 3-4 Ma old alkaline intrusions occur aligned along a similar to N160-170 trending lineament, the Zeballos Fault Zone, stacking the morphotectonic front of one segment of the Patagonian Cordillera. Intrusion along this fault zone
ISSN: 0024-4937

hal-00412030
https://hal.archives-ouvertes.fr/hal-00412030
DOI : 10.1016/j.lithos.2007.07.002

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Serpentinites are one of the major components of the oceanic lithosphere and are stable in the slab and the mantle wedge up to 100-150 km depth in subduction zones. During oceanic mantle hydration and alteration, they trap trace and fluid mobile (FME: B, Li, As, Sb, Rb, Ba, Cs, Sr, U and Pb) elements that participate to elemental transfer occurring between the dehydrating slab and the mantle wedge in subduction context. The Lanzo massif is an eclogitized oceanic lithosphere that preserved its oceanic structure and recorded different steps of serpentinization/de-serpentinization from oceanic lizardite to prograde antigorite in subduction context, up to its dehydration and secondary olivine crystallization, and finally retrograde antigorite during massif exhumation. It constitutes a suitable place to study trace element behavior during serpentinization/de-serpentinization processes and associated chemical transfers between the different envelopes of the oceanic lithosphere and the mantle wedge. Geochemical analyses of serpentine and associated minerals show that the serpentinization/de-serpentinization of the Lanzo massif took place in a relatively closed system without significant trace element transfer between the different parts of the oceanic lithosphere. In the deeper part of the lithosphere, from the slightly serpentinized mantle peridotites (SSP, < 20% serpentinization) to the paleo-Moho, composed of massive serpentinites (MS, 80% serpentinization), the trace elements mobility is reduced. The chemical composition of lizardite and antigorite is homogenized with the local degree of serpentinization: in SSP, serpentine veins composition is inherited from the host mineral while, in MS, their composition is homogenous between destabilized phases at the scale of the outcrop (~ 5 m). In the shallowest part of the oceanic lithosphere, from the paleo-Moho to the oceanic paleo-seafloor, the serpentinites are foliated (FS, > 90% serpentinization). In that zone, the alpine deformation enhances the mobility of trace elements and permits their redistribution and the homogenization of antigorite composition at massif scale. Locally, in the SSP and MS, the crystallization of metamorphic veins of ~ 1-2 m corresponds to channelized fluid flows that allowed fluid transfers - and thereby trace elements - to longer distance. The successive crystallizations of antigorite and then olivine are accompanied by a diminution of some FME (B, Li, As, Sb, Ba, Rb) and Eu contents attesting that these elements are removed from slab to mantle wedge during subduction.
ISSN: 0009-2541

hal-00937661
https://hal.archives-ouvertes.fr/hal-00937661
DOI : 10.1016/j.chemgeo.2013.08.025

Éditeur(s) : HAL CCSD Public Library of Science
Résumé : International audience
Little information exists on the effects of ocean acidification (OA) on the digestive and post-digestive processes in marine fish. Here, we investigated OA impacts (Δ pH = 0.5) on the trophic transfer of select trace elements in the clownfish Amphiprion ocellaris using radiotracer techniques. Assimilation efficiencies of three essential elements (Co, Mn and Zn) as well as their other short-term and long-term kinetic parameters in juvenile clownfish were not affected by this experimental pH change. In complement, their stomach pH during digestion were not affected by the variation in seawater pH. Such observations suggest that OA impacts do not affect element assimilation in these fish. This apparent pCO2 tolerance may imply that clownfish have the ability to self-regulate pH shifts in their digestive tract, or that they can metabolically accommodate such shifts. Such results are important to accurately assess future OA impacts on diverse marine biota, as such impacts are highly species specific, complex, and may be modulated by species-specific metabolic processes.
ISSN: 1932-6203

hal-01564009
https://hal-univ-perp.archives-ouvertes.fr/hal-01564009
https://hal-univ-perp.archives-ouvertes.fr/hal-01564009/document
https://hal-univ-perp.archives-ouvertes.fr/hal-01564009/file/trophic%20transfer.pdf
DOI : 10.1371/journal.pone.0174344

Éditeur(s) : HAL CCSD Elsevier
Résumé : Handheld energy dispersive portable X-ray spectrometers (pXRF) are generally designed and used for qualitative survey applications. We developed shipboard quantitative analysis protocols for pXRF and employed the instrument to make over 2000 individual abundance measurements for a selection of major and trace elements on over 1200 m of recovered core during the eight weeks of the International Ocean Discovery Program (IODP) Expedition 352 to the Izu-Bonin forearc. pXRF analytical performance, accuracy and precision were found to be the same on powdered rock samples and on freshly cut rock surfaces, and sample results were similar within error to measurements made via shipboard ICP-OES analysis save at low abundance levels for a few elements. Instrument performance was optimal for elements between Z = 19 and Z = 40, and the system yielded reproducible data for K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, Rb, Sr, and Zr on both powdered samples and rock surfaces. Working curves developed via pXRF measurement of a suite of geologic standard reference materials and well-characterized lavas permitted accurate quantitative measurements for many of the examined elements on both sample powders and rock surfaces. Although pXRF has been sporadically employed on previous cruises, Expedition 352 is the first time a detailed, high-density chemostratigraphy of recovered core samples was collected using pXRF measurements of rock core surfaces. These high-resolution data allowed the recognition of chemically distinct eruptive units in near real-time. The rapid identification of geochemical trends vastly improved our selection of samples for shipboard and shore-based analysis, permitted a more comprehensive interpretation of our Expedition results, and provided key decision-making information for drilling operations.
ISSN: 0009-2541

hal-01553188
https://hal.archives-ouvertes.fr/hal-01553188
DOI : 10.1016/j.chemgeo.2017.01.007

Éditeur(s) : Université de Pau et des Pays de l'Adour
Résumé : In a context of decline of European eel (Anguilla anguilla L.) and search for biological markers of habitat use and quality, a multidisciplinary approach was engaged on the Adour estuary and its associated wetlands. Two axes were developed. The first axe aimed at highlighting the successive presence of the species in different ecosystems based on the otolith elemental composition. The second aimed at the evaluation of the chemical pressure underwent by eels based on the contaminant bioconcentration in soft tissues and the early molecular response to the chemical stress. With a view to the analyses of otolith elemental composition taking into account the 3D structure, the low elemental concentration in the matrix and keeping the finest spatial resolution, four micro sampling strategies and multi elemental analyses using femtosecond laser ablation ICP-MS were tested (crater, 1D scan, 2D scan, flash ablation). The strategy showing the best compromise according to the objectives (continuous recording, multi elemental approach) was applied on otolith of yellow eels from the Adour. The simultaneous use of Sr and Ba profiles, after validation, represents a new tool, easy, fast and reliable for the reconstruction of freshwater and brackish ecosystems use by eel avoiding misinterpretation due to vaterite inclusions. Three major behaviors were highlighted on the Adour: a residency in brackish water, a residency in freshwater and nomad behavior. The last one is illustrated by a shift to brackish water after three to four years spent in freshwater. Simultaneously, the study of inorganic and organic contamination of eel soft tissues showed that sampled wetlands are moderately contaminated. These results were confirmed by the first estimation, in wild conditions, of the early response to the chemical stress using the hepatic expression of CYP1A1 gene measured by real time RT-PCR. Conversely, in the downstream part of the Adour estuary, Hg loads in eels, especially methyl mercury, and PCBs analyses indicate values that need further investigations considering the European norms of consumption. The comparison of the different markers used (heavy metal and organochlorinated compounds contamination of soft tissues, condition index) support a lower quality of the estuary despite higher eel growth rate on this site. This study supports the use of numerous markers in integrated studies in order to understand and specify the relationships between eels and their continental growth zones.
Dans un contexte de déclin de l'anguille européenne (Anguilla anguilla L.) et de recherche de marqueurs biologiques retraçant la fréquentation des divers habitats et renseignant sur la qualité de ceux-ci, une approche pluridisciplinaire a été mise en place sur l'estuaire de l'Adour et ses zones humides. Deux axes ont été privilégiés. Le premier cherchait à visualiser la présence successive de l'espèce dans différents écosystèmes en se basant sur la composition élémentaire des otolithes. Le deuxième avait pour but d'évaluer la pression chimique inorganique et organique subie par l'anguille dans les zones d'études en s'appuyant sur la bioconcentration des contaminants dans les tissus mous et la réponse moléculaire précoce au stress chimique. En vue des analyses de la composition élémentaire des otolithes et pour répondre au mieux à la structure en trois dimensions, à la faible concentration des éléments dans la matrice tout en conservant une résolution spatiale la plus fine possible, quatre stratégies de micro-échantillonnage et d'analyses multiélémentaires par ablation laser femtoseconde ICP-MS ont été testées (cratère, scan 1D, scan 2D, ablation flash). La méthodologie présentant le meilleur compromis par rapport aux objectifs fixés (enregistrement continu, approche multiélémentaire) a ensuite été appliquée sur les otolithes d'anguilles jaunes du Bas-Adour. L'utilisation simultanée des profils continus de Sr et de Ba, après validation, constitue un outil facile d'utilisation, rapide et fiable pour reconstruire les historiques de fréquentation des différents écosystèmes estuariens et dulçaquicoles par l'anguille tout en s'affranchissant des problèmes potentiels liés aux inclusions de vatérite, un polymorphe du carbonate de calcium. Trois grands types de comportement ont pu être mis en évidence sur l'Adour : résidence en eau saumâtre, résidence en eau douce et nomadisme. Ce dernier est plus particulièrement illustré par un mouvement marqué vers l'eau saumâtre pour des individus ayant passé de trois à quatre ans dans l'eau douce. Parallèlement, l'étude de la contamination organique et inorganique des tissus mous de l'anguille a permis de déduire à la faible contamination des zones humides échantillonnées. La première estimation en condition naturelle de la réponse précoce au stress chimique par évaluation de l'expression hépatique du gène CYP1A1 par RT-PCR en temps réel confirme ces résultats. En revanche, dans la partie estuarienne aval de l'Adour, les niveaux en Hg, présent en majorité sous sa forme méthylée dans les anguilles, et l'analyse des PCBs indiquent des valeurs qui suscitent un examen plus approfondi au regard des normes européennes en vigueur. La confrontation des différents descripteurs (contamination des tissus mous par les métaux lourds et organochlorés, indice de condition) utilisés conforte la qualité moindre de la zone estuarienne malgré des performances de croissance de l'anguille favorisées sur ces sites. Ainsi, cette étude supporte l'intérêt de la mise en oeuvre de descripteurs multiples utilisés (niveaux de métaux lourds et organochlorés dans les tissus mous, réponse moléculaire au stress chimique, microchimie de l'otolithe, indice de condition, taux de croissance) dans des approches intégrées pour comprendre et préciser les relations existantes entre l'anguille et ses zones de croissance continentales.

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/2009/these-7381.pdf
http://archimer.ifremer.fr/doc/00000/7381/

Éditeur(s) : HAL CCSD Oxford University Press (OUP): Policy B - Oxford Open Option A Oxford University Press (OUP)
Résumé : International audience
Peridotites exhumed in the footwall of axial detachment faults at slow-spreading ridges are highly serpentinized. Most mid-ocean ridge detachment settings are magmatically active and hydrous fluid circulation in and near the fault has been shown to be influenced by the presence of melt or magmatic lithologies. Our working area along the Southwest Indian Ridge (62–65°E) is nearly amagmatic and represents an end-member to study the hydrous alteration of exhumed peridotites without these magmatic influences. We use an integrated petrological approach combining microstructural, mineralogical and chemical observations to unravel the sequence of serpentinization in 272 dredged samples of variably serpentinized peridotites and to document the circulation of serpentinizing fluids in and near the exhumation faults. We find that serpentine recrystallization and veins overprint the initial serpentinite mesh texture in ∼25% of the samples. Oxygen isotope data suggest that this sequence developed at relatively high temperatures (271–336°C) and under increasing fluid–rock ratios, from near stoichiometry for mesh texture formation to >10 during recrystallization. Increasing fluid supersaturation relative to serpentine favors the replacement of mesh texture lizardite by chrysotile and polygonal or polyhedral serpentine. We attribute local recrystallization into antigorite to moderate Si-metasomatism, possibly following pyroxene serpentinization. We do not observe the more pronounced Si-metasomatism leading to talc replacing serpentine that is reported for the more magmatically active Mid-Atlantic Ridge detachment settings and is attributed to prior leaching of magmatic rocks. Scales of preferential fluid pathways in our samples evolved from pervasive and close-spaced (<500 µm) microfractures during the formation of the initial serpentine mesh texture, to centimeter-thick planar domains of enhanced fluid flux, spaced at ∼10 cm intervals and probably grouped in corridors that may be up to ∼100 m across. Serpentine minerals are enriched in some fluid-mobile elements (Cl, B, U) relative to the peridotite protolith, and several elements (Al, Fe, Si, Cu, As, Sb, REE) are redistributed at the millimeter to decimeter scale. Serpentinizing fluids were seawater-derived, probably mildly alkaline (small to no europium anomalies), reducing and H2-enriched (formation of magnetite). These fluids may have been similar to, though warmer than, those venting at the ultramafic-hosted Lost City hydrothermal fluid (30°N, Mid-Atlantic Ridge).
ISSN: 0022-3530

hal-01174047
https://hal.archives-ouvertes.fr/hal-01174047
DOI : 10.1093/petrology/egv014

Éditeur(s) : HAL CCSD
Résumé : The ecological success of cnidarian-dinoflagellate symbiosis mainly relies on nutrient recycling. Environmental changes, such as global warming or pollution, often result to symbiosis breakdown, also called cnidarian bleaching. The understanding of mechanisms regulating the symbiosis establishment, maintenance and breakdown is essential to prevent massive bleaching phenomena. In this respect, my PhD project focused on the characterization of chemical mediators expressed in the sea anemone Anemonia viridis, their localization and their modulation by stress conditions. A comparative study was first conducted to characterize the chemical mediators and analyze their distribution within the symbiotic sea anemone. We described a great abundance and diversity of lipids in A. viridis tissues. From these results, we proposed possible transfers of FAs between the symbiotic partners. A thermal stress and a chemical stress have also been applied in laboratory-controlled conditions in order to induce symbiosis breakdown and bleaching of the sea anemones, in order to correlate A. viridis metabolome to its symbiotic status. A mapping of these metabolites has been performed by MALDI-MSI of tentacle cross-sections, as well as their evolution following stress. Some betaine lipids have thus been proposed as short-term indicators of stress. A. viridis stress response has also been evaluated with a lipidomic approach, and allowed to identify 3 lipid indicators of early stress response based on membrane fluidity markers. Overall, this study provides insight on key chemical mediators that may regulate the symbiosis maintenance, and may contribute to the symbiosis breakdown.
Le succès évolutif des Cnidaires symbiotiques réside en grande partie dans leurs échanges trophiques établis avec les Dinoflagellés du genre Symbiodinium. Cependant, le réchauffement climatique global ainsi que les pollutions ont un impact fort sur les écosystèmes coralliens, notamment en conduisant à la rupture de la symbiose, phénomène appelé blanchissement. La compréhension des mécanismes qui régissent l’établissement, le maintien et la rupture de la symbiose est essentielle à la prévention des épisodes de blanchissement massif. Dans ce contexte, les objectifs de mon projet de thèse sont de caractériser les médiateurs chimiques de l’anémone de mer Anemonia viridis, de les localiser, et d’analyser leur réponse face à un stress. Parmi les composés caractérisés, les lipides et les bétaïnes sont les plus abondants et présentent une grande diversité. Certains sont transférés des symbiotes vers l’hôte. Des anémones de mer ont ensuite été traitées en laboratoire afin de provoquer la rupture de la symbiose et le blanchissement des individus. Une étude cinétique a été menée par une approche globale comparative identique à celle réalisée sur l’anémone symbiotique. Par ailleurs, une cartographie de l’évolution de composés clé a été réalisée par MALDI-MSI. La réponse au stress a été évaluée et a permis d’identifier des lipides de bétaïne et trois indicateurs lipidiques comme marqueurs de réponse précoce au stress. L’ensemble de ces résultats apporte de nouveaux éléments de réponse concernant le rôle des médiateurs chimiques clés dans le maintien de la symbiose, ainsi que leur influence sur sa rupture.
https://tel.archives-ouvertes.fr/tel-01310668

NNT : 2015NICE4108
tel-01310668
https://tel.archives-ouvertes.fr/tel-01310668
https://tel.archives-ouvertes.fr/tel-01310668/document
https://tel.archives-ouvertes.fr/tel-01310668/file/2015NICE4108.pdf

Éditeur(s) : Copernicus Gesellschaft Mbh
Résumé : Boundary Exchange (BE - exchange of elements between continental margins and the open ocean) has been emphasized as a key process in the oceanic cycle of neodymium (Nd) (Lacan and Jeandel, 2005a). Here, we use a regional eddy-permitting resolution Ocean General Circulation Model (1/4A degrees) of the North Atlantic basin to simulate the distribution of the Nd isotopic composition, considering BE as the only source. Results show good agreement with the data, confirming previous results obtained using the same parameterization of the source in a coarse resolution global model (Arsouze et al., 2007), and therefore the major control played by the BE processes in the Nd cycle on the regional scale. We quantified the exchange rate of the BE, and found that the time needed for the continental margins to significantly imprint the chemical composition of the surrounding seawater (further referred as characteristic exchange time) is of the order of 0.2 years. However, the timescale of the BE may be subject to large variations as a very short exchange time (a few days) is needed to reproduce the highly negative values of surface waters in the Labrador Sea, whereas a longer one (up to 0.5 years) is required to simulate the radiogenic influence of basaltic margins and distinguish the negative isotopic signatures of North Atlantic Deep Water from the more radiogenic southern origin water masses. This likely represents geographical variations in erosion fluxes and the subsequent particle load onto the continental margins. Although the parameterization of the BE is the same in both configurations of the model, the characteristic exchange time in the eddy-permitting configuration is significantly lower than the previous evaluations using a low resolution configuration (6 months to 10 years), but however in agreement with the available seawater Nd isotope data. This results highlights the importance of the model dynamics in simulating the BE process.
Ocean Science (1812-0784) (Copernicus Gesellschaft Mbh), 2010 , Vol. 6 , N. 3 , P. 789-797

Droits : Author(s) 2010. This work is distributed, EGU
http://archimer.ifremer.fr/doc/00013/12412/9201.pdf
DOI:10.5194/os-6-789-2010
http://archimer.ifremer.fr/doc/00013/12412/

Éditeur(s) : HAL CCSD GeoScienceWorld
Résumé : International audience
Due to their "iron-loving" properties, platinum-group elements (PGE) are expected to be stored in the Earth's core. Although very low, at a few parts per billion, PGE concentrations measured in mantle-derived rocks are too high to be in chemical equilibrium with the core. The "late veneer" model offers the best explanation for this paradox-it postulates that a flux of primitive meteorites hit the early Earth after core formation had ceased. However, the inferred PGE composition of the hypothetical primitive mantle exhibits slight positive excesses of Ru, Rh, and Pd compared to the canonical chondritic signature. Such deviations have trigger debate about the composition of the late veneer and the extent of reworking of PGE signatures by igneous processes within the Earth's mantle.
ISSN: 1811-5209

hal-00411483
https://hal.archives-ouvertes.fr/hal-00411483
DOI : 10.2113/GSELEMENTS.4.4.247

Éditeur(s) : HAL CCSD Elsevier Masson
Résumé : Ten international laboratories participated in an inter-laboratory comparison of a fossil bone composite with the objective of producing a matrix and structure-matched reference material for studies of the bio-mineralization of ancient fossil bone. We report the major and trace element compositions of the fossil bone composite, using in-situ method as well as various wet chemical digestion techniques. For major element concentrations, the intra-laboratory analytical precision (%RSDr) ranges from 7 to 18%, with higher percentages for Ti and K. The %RSDr are smaller than the inter-laboratory analytical precision (%RSDR; <15-30%). Trace element concentrations vary by similar to 5 orders of magnitude (0.1 mg kg(-1) for Th to 10,000 mg kg(-1) for Ba). The intra-laboratory analytical precision %RSDr varies between 8 and 45%. The reproducibility values (%RSDR) range from 13 to <50%, although extreme value >100% was found for the high field strength elements (Hf, Th, Zr, Nb). The rare earth element (REE) concentrations, which vary over 3 orders of magnitude, have %RSDr and %RSDR values at 8-15% and 20-32%, respectively. However, the REE patterns (which are very important for paleo-environmental, taphonomic and paleo-oceanographic analyses) are much more consistent. These data suggest that the complex and unpredictable nature of the mineralogical and chemical composition of fossil bone makes it difficult to set-up and calibrate analytical instruments using conventional standards, and may result in non-spectral matrix effects. We propose an analytical protocol that can be employed in future inter-laboratory studies to produce a certified fossil bone geochemical standard. (C) 2007 Elsevier B.V. All rights reserved.
ISSN: 0003-2670

hal-00407629
https://hal.archives-ouvertes.fr/hal-00407629
DOI : 10.1016/j.aca.2007.08.015

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Whole-rock concentrations of Se and Te were determined in 53 peridotite samples collected in orogenic bodies from the Eastern Pyrenees, including the Lherz massif (33 samples), the type-locality of Iherzolite. Orogenic Iherzolites tectonically emplaced into the continental crust escaped devolatilisation that may strongly alter concentrations of those volatile trace elements in basalt-hosted peridotite xenoliths. The Se and Te concentration ranges (<3.5-100.7 ppb; <1-11 ppb) are consistent with the few analyses of mantle samples yet available, yet extending to higher Se concentrations. In-situ analyses performed by LAM-ICPMS on base metal sulfides indicate that the Se budget is controlled by sulfides whereas a large fraction of Te (50 +/- 30%) does not reside in sulfides. The missing fraction is accounted for by fractional crystallization of Pt-Pd tellurides from Cu-Ni sulfide melts. A maximum of one third of the S budget of Eastern Pyrenean peridotites was added by assimilation of crustal sulfides, which crystallized as pyrite. Disregarding those contaminated samples, some features of the Se and Te systematics (e.g. bivariate plots vs. fertility index) cannot be explained by partial melting processes. The best fit for 33 peridotites (mostly from Lherz) yields higher than chondritic S/Se (3.1213 +/- 500; r(2) = 0.96) for near chondritic Se/Te (8.6 +/- 2; r(2) = 0.9). Our study suggest that such superchondritic S/Se ratios are better explained by petrogenetic processes involving refertilization of harzburgitic lithosphere by metal (Cu,Ni)-rich sulfide melts precipitated along with clinopyroxene and Al-spinel from silicate melts en-route to the surface.
ISSN: 0009-2541

hal-00544577
https://hal.archives-ouvertes.fr/hal-00544577
DOI : 10.1016/j.chemgeo.2010.09.007

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
LA-ICP-MS analysis of the chemical composition of biogenic carbonate has many applications in the environmental sciences but the characteristics of the material produced by the ablation process are largely unknown. To fill this gap, we have undertaken a study of the chemical and physical nature of particles produced by laser ablation of biogenic carbonates. SEM imaging suggests that laser ablation produces two distinct particle populations, one consisting of microsize particles and the other of nanosize particles. A 213 nm laser gives rise to a higher proportion of microsize particles than a 193 nm laser, probably because the 213 nm laser couples less completely with carbonate material. The microsize particles appear to form by photomechanical fracturing along lines of cleavage or weakness, rather than by hydrodynamic sputtering (as is generally observed for silicates). Chemical analysis of the carbonate particles suggests that little chemical fractionation of biogenic carbonates occurs during the ablation process or during transport to the plasma. This is supported by the constancy of the fractionation factor ([X/Ca](measured)/[X/Ca] true) during the course of an ablation of a carbonate standard. In contrast, changes in the fractionation factor during the first few seconds of ablation of the NIST 612 are observed for some elements. This difference in fractionation is likely to result from the different formation mechanisms of the microsize particles.
ISSN: 0267-9477

hal-00411933
https://hal.archives-ouvertes.fr/hal-00411933
DOI : 10.1039/b706727e

Éditeur(s) : HAL CCSD
Résumé : International audience
Many different proteins self-aggregate into insoluble fibrils growing apically by reversible addition of elementary building blocks. But beyond this common principle, the modalities of fibril formation are very disparate, with various intermediate forms which can be reshuffled by minor modifications of physico-chemical conditions or amino-acid sequences. To bypass this complexity, the multifaceted phenomenon of fibril formation is reduced here to its most elementary principles defined for a linear prototype of fibril. Selected generic features, including nucleation, elongation, and conformational recruitment, are modeled using minimalist hypotheses and tools, by separating equilibrium from kinetic aspects and in vitro from in vivo conditions. These reductionist approaches allow to bring out known and new rudiments, including the kinetic and equilibrium effects of nucleation, the dual influence of elongation on nucleation, the kinetic limitations on nucleation and fibril numbers, and the accumulation of complexes in vivo by rescue from degradation. Overlooked aspects of these processes are also pointed: the exponential distribution of fibril lengths can be recovered using various models because it is attributable to randomness only. It is also suggested that the same term "critical concentration" is used for different things, involved in either nucleation or elongation
Journal of Chemical Physics

hal-01263103
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01263103
DOI : 10.1063/1.4940149
PUBMED : 26801045

Éditeur(s) : Oxford Univ Press
Résumé : In subduction zones, melting and dehydration of the subducted slab introduce material into the mantle wedge and modify its chemical and isotopic composition. As a consequence, island arc lavas differ significantly from mid-ocean ridge basalts and ocean island basalts. In some arcs, the composition of lavas is strongly influenced by the sedimentary material introduced with the slab; in others, magma composition is mainly affected by aqueous fluids released by the slab. The Lesser Antilles arc is known for its extreme continental-crust-like signature but for some Lesser Antilles lavas subducted sediments are barely involved and enrichment in fluid-mobile elements (Ba, U, Sr, Pb, etc.) is the dominant feature. Here we evaluate whether La/Sm is a quantitative proxy of sediment involvement in volcanic arcs, and we relate dehydration and melting processes to the temperature and pressure conditions of the slab. We use Martinique as a case study because in this island both dehydration and sediment melting fingerprints coexist. We measured major and trace elements for about 130 age-constrained samples, carefully chosen to cover all volcanic phases of Martinique (25 Ma to present). Using these results we demonstrate that: (1) weathering does not modify the La/Sm ratio; (2) fractional crystallization of amphibole and/or garnet does not increase La/Sm by more than 20%; (3) rare earth element transfer from wall-rock to magma during fractionation is not significant; (4) melting of the mantle source increases La/Sm by only about 20%. As a consequence, we show that the proportion of slab sediment incorporated in the mantle wedge controls the La/Sm ratio of the source. The observed correlations between La/Sm and Nd and Hf isotopic compositions indicate that the effect of sediment addition is the overwhelming factor: La/Sm is a good proxy for slab sediment proportion in Martinique. We observe a geographical gradient between slab dehydration and sediment melting on the island. Whereas lavas located on the western side of the island display a clear sedimentary input in their source, lavas located on the eastern side of the island, closer to the trench, are clearly influenced by dehydration of the subducted slab. In addition, the aqueous fluids clearly come from the subducted basalt and they did not interact with the overlying sediments. The influence of sediment added to the source of the magmas increases from the eastern part to the western part of the island. We relate this geographical change to the pressure and temperature conditions at the slab surface. Sediments probably cross their solidus under Martinique and hydrous melting is triggered. Finally, we show that under all volcanic arcs where the signature of sediments overwhelms the signature of fluids, the slab surface reaches P-T conditions that allow the subducted sediments to melt. Inversely, under most volcanic arcs where the signal of aqueous fluids dominates over sediment melts, the subducted slab is not hot enough for the sedimentary pile to melt.
Journal Of Petrology (0022-3530) (Oxford Univ Press), 2012-12 , Vol. 53 , N. 12 , P. 2441-2464

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/00113/22392/20234.pdf
DOI:10.1093/petrology/egs055
http://archimer.ifremer.fr/doc/00113/22392/

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
Island arc picrites and boninites are magnesian magmatic rocks believed to be generated by high degrees of melting of depleted mantle sources fluxed by subduction-derived, volatile-rich components. These magmas can be probes of both the mantle wedge protoliths and subduction components, but are rare among other, usually more evolved, types of arc lavas. Furthermore, many arc picrites and boninites show evidence for late-stage differentiation prior to or during eruption, masking their primary, mantle-derived geochemical signatures. We report textural and chemical data on spinel-hosted melt inclusions of mantle origin in amphibole-bearing websterite veins cross-cutting spinel harzburgite xenoliths from the active andesitic Avacha volcano (south Kamchatka, Russia). The data are used to constrain the composition and origin of melts that formed the websterite veins in the sub-arc lithospheric mantle. The melt inclusions typically contain euhedral orthopyroxene and clinopyroxene and occasionally minor amphibole in silicate glass. The melt inclusions were homogenized using heating stages and gas-mixing furnaces. The homogenized glasses range from subalkaline primitive silica-rich picrite and high-Ca boninite (>15 wt % MgO, 48–54 wt % SiO2) to rhyolite. High-Ca boninite glasses have moderate volatile and low heavy rare earth element contents and elevated Cs, Rb, Ba, U, Sr, and Li abundances, with extremely high U/Th. In turn, the glasses display no negative spikes in the high field strength elements Nb, Ta, Zr, Hf, and Ti. We show that the silica-rich picrite and high-Ca boninite liquids in this study formed by high degrees of melting (>25%), at volatile under-saturation, of hybrid melt-depleted but silica-rich mantle sources at ≥1·5 GPa. The hybrid sources formed in two stages: first, by extraction of ∼15% melt from the convecting mantle to form a refractory protolith, which was subsequently enriched in silica via interaction with subduction-derived components prior to or during remelting in the mantle wedge. The subduction-derived components were enriched in fluid-mobile elements and probably oxidized. Overall, our results suggest that silica-rich picrites and high-Ca boninites can be primary melts in mature subduction zones and differentiate within the mantle wedge and the deep arc crust to form more evolved andesite magmas.
ISSN: 0022-3530

hal-01553676
https://hal.archives-ouvertes.fr/hal-01553676
DOI : 10.1093/petrology/egw066

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : Absolute Mα and Mβ X-ray intensities were measured for the elements Pt, Au, Pb, U, and Th by electron impact for energies ranging from 6 to 38 keV. Experimental data were obtained by measuring the X-ray intensity emitted from bulk samples with an electron microprobe using high-resolution wavelength-dispersive spectrometers. Recorded X-ray intensities were converted into absolute X-ray yields by evaluation of the detector efficiency and then compared with X-ray intensities calculated by means of Monte Carlo simulations. Simulated Mα and Mβ X-ray intensities were found to be in good agreement with the measurements, allowing their use in standardless quantification methods. A procedure and a software program were developed to accurately obtain virtual standard values. Standardless quantifications of Pb and U were tested on standards of PbS, PbTe, PbCl2, vanadinite, and UO2.
ISSN: 0003-2700

hal-01217495
https://hal.archives-ouvertes.fr/hal-01217495
DOI : 10.1021/acs.analchem.5b01443

Résumé : The conservation of crawfish requires the use of chemical substances making it possible to limit blackening. This phenomenon this blackening (melanine) is due to the coordinated action of three elements: - oxygen, - an enzyme (cupro-protein), - a suitable substrate, tyrosin or the dihydroxyphénylalanine. The absence of the one of them allows a notorious reduction in the phenomenon. Several antioxydant products, were used to prevent the formation of the mélanine. The métabisutfite of soda or potassium as well as soda bisulfite in acid solution, are currently used to treat crawfish and shrimps. Several methods of use of these pesticides exist, we propose in this report to present the principal ones, as well as the control methods making it possible to check the quality of the treatment.
La conservation des langoustines nécessite l'utilisation de substances chimiques permettant de limiter le noircissement. Ce phénomène ce noircissement (mélanine) est due à l'action coordonnée de trois éléments : - l'oxygène, - une enzyme (cupro-protéine), - un substrat convenable, la tyrosine ou la dihydroxyphénylalanine. L'absence de l'une d'entre elles permet une diminution notoire du phénomène. Plusieurs produits anti-oxydants, ont été utilisés pour prévenir la formation de la mélanine. Le métabisutfite de soude ou de potassium ainsi que le bisulfite de soude en solution acide, sont actuellement utilisés pour traiter les langoustines et les crevettes. Plusieurs méthodes d'utilisation de ces produits de traitement existent, nous nous proposons dans ce rapport de présenter les principales, ainsi que les méthodes de contrôle permettant de vérifier la qualité du traitement.

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/1991/rapport-1586.pdf
http://archimer.ifremer.fr/doc/00000/1586/

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Tsavorite, the vanadian variety of green grossular, is a high value economic gemstone. It is hosted exclusively in the metasedimentary formations from the Neoproterozoic Metamorphic Mozambique Belt. The deposits are mined in Kenya, Tanzania and Madagascar and other occurrences are located in Pakistan and East Antarctica. They are located within metasomatized graphitic rocks such as graphitic gneiss and calc-silicates, intercalated with meta-evaporites. Tsavorite is found as primary deposits either in nodule (type I) or in quartz vein (type II), and in placers (type III). The primary mineralizations (types I and II) are controlled by lithostratigraphy and/or structure. For the African occurrences, the protoliths of the host-rocks were deposited at the beginning of the Neoproterozoic within a marine coastal sabkha environment, located at the margin of the Congo-Kalahari cratons in the Mozambique Ocean. During the East African-Antarctican Orogeny, the rocks underwent high amphibolite to granulite facies metamorphism and the formation of tsavorite deposits occurred between 650 and 550 Ma. The nodules of tsavorite were formed during prograde metamorphism, calcium coming from sulphates and carbonates, whereas alumina, silicates, vanadium and chromium probably came from clays and chlorite. The veins were formed during the deformation of the metasedimentary platform units which experienced shearing, leading to the formation of fault-filled veins. Metasomatism developed during retrograde metamorphism. The metasedimentary sequences are characterized by the presence of evaporitic minerals such as gypsum and anhydrite, and scapolite. Evaporites are essential as they provide calcium and permit the mobilization of all the chemical elements for tsavorite formation. The H2S-S8 metamorphic fluids characterized in primary fluid inclusions of tsavorites and the δ11B values of coeval dravite confirm the evaporitic origin of the fluids. The V2O3 and Cr2O3 contents of tsavorite range respectively from 0.05 to 7.5 wt.%, while their δ18O values are in the range of 9.5-21.1‰. The genetic model proposed for tsavorite is metamorphic, based on chemical reactions developed between an initial assemblage composed of gypsum and anhydrite, carbonates and organic matter deposited in a sabkha-like sedimentary basin.
ISSN: 0169-1368

hal-00853279
https://hal.archives-ouvertes.fr/hal-00853279
DOI : 10.1016/j.oregeorev.2013.01.016

Résumé : Spiny lobsters are an important component of the coastal fisheries around the Martinique island. This study aimed to assess the contamination by kepone of the two main species Panulirus argus and P. guttatus in the main fishery area laying along the eastern coast of Martinique. The objectives of the study were to describe the distribution of the spiny lobster contamination in the area, to explore possible relationships with some biological parameters such as individual size, sex and colour of tegument, as well as characterize difference of kepone concentration between the muscle and soft flesh of the head, in view of helping the definition of further fishery management measures. The analyses were done from chemical analyses of 125 samples of spiny lobsters gathered from 2008 to 2010 all around the island, and from a specific set of 200 new observations from a specific survey carried out in 2011 in the study area. For both species, the results show a diffusion of the contamination all over the coral shoals, close to contaminated catchment basins, with a strong decrease just outside these areas. For the Caribbean spiny lobster, a strong relationship between kepone concentration and individual size was identified, and less for the Spotted spiny lobster. For the two species, the concentration of kepone found in soft flesh of the head was more than twice as in the muscle. Finally, the difference of contamination between the two species appeared strongly linked with their biology.
La langouste blanche Panulirus argus et la langouste brésilienne P. guttatus représentent environ 25 % du chiffre d’affaires des pêcheurs professionnels de Martinique. Une part très importante des captures de ces espèces proviennent du platier continental de la zone centre-atlantique de l’île. L’étude réalisée en 2011 visait à approfondir les connaissances sur la distribution de la contamination par la chlordécone des langoustes dans la zone centre- atlantique de la Martinique, d’explorer d’éventuelles relations entre cette contamination et des paramètres biologiques des individus comme la taille, le sexe et leur pigmentation tégumentaire, et d’analyser la différence de contamination entre la queue et les chairs molles du céphalothorax, en vue d’aider à la définition de mesures de réglementation de la pêche dans ce secteur. L’étude s’appuie sur un ensemble de 125 échantillons rassemblés de 2008 à 2010 pour les deux espèces autour de la Martinique, complétés par 200 échantillons constitués pour la présente étude dans la zone centre-atlantique en 2011. Le rapport est précédé d’un rappel d’éléments sur la biologie et sur l’état de la pêche des langoustes en Martinique. Pour les deux espèces, l’étude met en évidence une extension de la contamination à l’ensemble du platier corallien au pied des bassins versants contaminés, puis une nette diminution au-delà. Pour la langouste blanche, cette contamination est en relation avec la taille des individus, en liaison avec leur plongée progressive vers le large. Cette relation avec la taille est moins marquée pour la langouste brésilienne, espèce beaucoup plus inféodée aux eaux littorales. Pour les deux espèces, les chairs molles du céphalothorax apparaissent plus de deux fois plus contaminées que le muscle caudal. Les différences de contamination observées entre langouste blanche et la langouste brésilienne sont cohérentes avec les connaissances sur la biologie de chaque espèce.

Droits : Délégation Antilles
http://archimer.ifremer.fr/doc/00088/19971/17638.pdf
http://archimer.ifremer.fr/doc/00088/19971/