Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This paper examines the thermal properties of cement composites reinforced with vegetable bagasse fibres (1.5% and 3% wrtc). Thermal properties have been correlated to macroscopic density and porosity in order to estimate thermal conductivity of fibres using a calculation inspired from the Maxwell-Eucken modelling. Experimental investigations reveal that adding retified bagasse fibres reduces composites thermal conductivity and yields a weaker specific heat in comparison with composites made with alkaline bagasse fibres. Moreover, the more the fibres, the lighter the specimen; lower its thermal conductivity and lower its specific heat. Thermal conductivity of alkaline fibres is lower than retified fibres one.
ISSN: 1359-835X

hal-00809831
https://hal.univ-antilles.fr/hal-00809831
DOI : 10.1016/j.compositesa.2010.01.002

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
Most kimberlites contain abundant dunitic nodules. These are centimetre-sized, rounded and multi-grained assemblages of xenocrystic olivine with a wide range of compositions (Fo83 to Fo94). The absence of orthopyroxene and other mantle minerals and the range of olivine compositions have been attributed to reaction between mantle peridotite and (proto)kimberlitic fluid or melt, but the timing of the reaction is a subject of debate. In a kimberlite from the Kangamiut region of Greenland, nodule cores are surrounded by fine-grained outer margins with near-constant Fo contents (∼Fo88) but highly variable minor element contents (e.g. 500–2500 ppm Ni). These margins crystallized from the kimberlite melt and we show that their compositions can be explained by crystallization of olivine alone, if a high partition coefficient for Ni between melt and olivine (DNi > 20) is assumed. Orthopyroxene assimilation is not required, removing the constraint that its dissolution occurred during ascent of the kimberlite magma. Within some nodules, in addition to the usual core-to-margin gradients, we observe asymmetric compositional changes (variable Fo but near-constant minor element contents) across mobile grain boundaries. These changes document fluid percolation at the grain scale that occurred during dynamic recrystallization in the deforming lithospheric mantle. We note that chemical gradients associated with mobile grain boundaries are observed in olivines that cover the entire compositional range of the nodules, and propose that fluid-assisted dynamic recrystallization took place in dunite that was already compositionally heterogeneous. Reaction between peridotite and protokimberlitic melt or fluid and dissolution of orthopyroxene thus occurred within the lithospheric mantle, immediately (a few days) prior to the ascent of the kimberlite melt and the entrainment of the dunite nodules. We propose that the grain boundary zones probably mimic, at a fine scale, the fluid–peridotite interaction that caused, at a larger scale, orthopyroxene dissolution and formation of compositionally diverse olivine in kimberlites.
ISSN: 0022-3530

hal-01277963
https://hal.archives-ouvertes.fr/hal-01277963
DOI : 10.1093/petrology/egv054

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Predicting the impact of underground engineering on the environment requires the knowledge of natural media at different scales. In particular, understanding basic phenomena controlling the properties of rocks in the presence of complex fluids necessitates a detailed atomic description of the solid/fluid/solid contacts, the subject of Part I of the present study. First, building the solid interspace between two different crystals in a non-periodic situation is achieved using the ab initio and molecular mechanics code GenMol (TM). A description of the fluid confined within the interspace is then derived from the original genetic iterative multi-species (GIMS) algorithm implemented in the same code. This approach consists of equilibrating chemical potentials, cycle after cycle and species after species, between the confined fluid and the free natural fluid. An elementary iteration for a species k consists of different steps incrementing the number N-k of particles k, with other numbers N-k remaining constant. At each step, an optimum fluid composition is obtained by a genetic process distributing the fluid particles on a grid by stochastic shots, followed in fine by a refining process. The effectiveness of the GIMS approach is demonstrated in the case study of a fluid confined between two (0 0 1) kaolinite faces, with apertures h varying between 4 and 10 A. connected to a 9-species external solution [H2O, Cl-, Na+ CO2(aq), NaCl(aq), Ca2+, Mg2+, HCO3-, H3O+] where concentrations are ranging from 55 to 10(-4) mol/L. The results show a drastic variation in the solute/solvent and cations/ions ratios in the confined fluid when aperture h is lowered to less than 1 nm. These results obtained with a very rapid convergence of the iterative algorithm combined with a very competitive genetic optimizer are validated with high precision on a free solution. This description of contacts between crystals is original and unattainable by standard crystal interface approaches. It opens the way to understanding and/or predicting phenomena between crystals in a complex natural environment, such as adhesion or repulsion investigated in the Part II of this study.
ISSN: 0022-0248

hal-00544569
https://hal.archives-ouvertes.fr/hal-00544569
DOI : 10.1016/j.jcrysgro.2010.08.009

Éditeur(s) : HAL CCSD
Résumé : Volatile-rich, silica-undersaturated alkaline lavas record the important role of fluids during fluid-rock and magma-rock interactions in the mantle, which are key processes to understand the dynamics of the convective mantle and lithosphere-asthenosphere interactions in intracontinental settings. The aim of this thesis is to bring new constraints on the genesis of alkaline magmas by characterizing the crystallization conditions, the source and the partial melting processes taking part in the genesis of olivine nephelinites, pyroxene nephelinites and basanites from the Jbel Saghro volcanic field in the Moroccan Anti Atlas.The petrological and geochemical study of rocks and minerals coupled with the analysis of fluid inclusions constrains the pre-eruptive conditions of Saghro nephelinites to 1.7–2.2 GPa and ~1350 °C. Minerals show that nephelinitic magmas are rich in volatile elements (Cl, F, S), and fluid inclusions indicate that magmas were saturated with a CO2-rich fluid at pressures > 590 MPa. The various mineralogical assemblages and the presence of peridotite xenoliths suggest a rapid ascent for olivine nephelinites and more complex processes at depth for pyroxene nephelinites.Fractional crystallization and partial melting modelling of Saghro mafic lavas indicate that they are low-degree melts (0.6–2.5 %) of an amphibole-bearing carbonated peridotite enriched in incompatible elements, at the garnet-spinel transition (~80–85 km). Saghro nephelinites display a temporal evolution with a slight increase of the degree of melting and a decrease of the amount of residual amphibole from the oldest (olivine nephelinites, 9.6 Ma) to the most recent (pyroxene nephelinites, 2.9 Ma). Basanites form a system that is independent from nephelinites and are slightly higher-degree melts. Important variations in their chemical composition suggest variable amounts of fractional crystallization during ascent.The peculiar characteristics of Saghro nephelinites and basanites (enrichment in incompatible elements, negative anomalies in K, Zr, Hf and Ti, high Ca/Al and Zr/Hf ratios) indicate that their source was affected by carbonatitic metasomatism. The influence of this metasomatism is stronger for pyroxene nephelinites than for olivine nephelinites. These results suggest fluid-rock interactions beneath the Northwest African Craton, leading to the formation of a metasomatized mantle by CO2-rich carbonatitic components at the lithosphere-asthenosphere transition. The origin of the metasomatism inducing source enrichment and the formation of amphibole veins could be attributed to the melting of relict subducted oceanic lithosphere. The relatively low melting temperatures (< 1350 °C) suggest the absence of a thermal anomaly beneath the Jbel Saghro, and thus support a lithosphere delamination model as precursor of Saghro volca0,3nism. However, the increasing degree of partial melting over time, also observed in the Middle Atlas, together with the isotopic and geochemical similarities with Canary Islands alkaline lavas does not allow us to discard the influence of a deviation of the Canary mantle plume beneath northwest Africa.
Les laves alcalines sous-saturées riches en éléments volatils sont les marqueurs du rôle important des fluides dans le manteau et des interactions fluide-roche et magma-roche, processus clés pour comprendre la dynamique du manteau convectif et les interactions asthénosphère-lithosphère en domaine intracontinental. L’objectif de cette thèse est d’apporter de nouvelles contraintes sur la genèse des magmas alcalins en caractérisant les conditions de cristallisation, la source et les processus de fusion partielle à l’origine des néphélinites à olivine, des néphélinites à pyroxène et des basanites du champ volcanique du Jbel Saghro dans l’Anti-Atlas marocain.L’étude pétrologique et géochimique des roches et des minéraux, couplée à l’analyse des inclusions fluides a permis de contraindre les conditions pré-éruptives des néphélinites de Saghro à 1.7–2.2 GPa et ~1350 °C. Les minéraux montrent que les magmas néphélinitiques sont riches en éléments volatils (Cl, F, S), et les inclusions fluides indiquent que les magmas étaient saturés en fluide riche en CO2 à des pressions > 590 MPa. Les différents assemblages minéralogiques des néphélinites et la présence de xénolites péridotitiques suggèrent une ascension rapide des néphélinites à olivine et des processus plus complexes en profondeur pour les néphélinites à pyroxène.La modélisation des processus de cristallisation fractionnée et de fusion partielle des laves mafiques de Saghro a permis de déterminer qu’elles sont issues de faibles taux de fusion partielle (0.6–2.5 %) d’une péridotite carbonatée enrichie en éléments incompatibles, au niveau de la transition grenat–spinelle (~80–85 km) et en présence d’amphibole. Les néphélinites de Saghro montrent une évolution temporelle avec une légère augmentation du taux de fusion et une diminution de la quantité d’amphibole au résidu des plus anciennes (néphélinites à olivine, 9.6 Ma) aux plus récentes (néphélinites à pyroxène, 2.9 Ma). Les basanites forment un système indépendant des néphélinites et sont issues de taux de fusion plus élevés. Les fortes variations dans leur composition chimique suggèrent qu’elles ont subi de la cristallisation fractionnée lors de leur ascension.Les caractéristiques particulières des néphélinites et basanites de Saghro (enrichissement en éléments incompatibles, anomalies négatives en K, Zr, Hf et Ti, rapports Ca/Al et Zr/Hf élevés) indiquent que leur source a subi un métasomatisme principalement carbonatitique. L’influence de ce métasomatisme est plus forte pour les néphélinites à pyroxène que pour les néphélinites à olivine, impliquant une évolution temporelle de l’intensité du métasomatisme. Ces résultats suggèrent des interactions fluide-roche sous le craton Nord-Ouest Africain, entraînant la formation d'un manteau métasomatisé par des composants carbonatitiques riches en CO2 au niveau de la transition lithosphère-asthénosphère. L’origine du métasomatisme provoquant l’enrichissement de la source et la formation de veines d’amphibole pourrait être liée à la fusion de reliquats de croûte océanique subductée. Les températures de fusion relativement faibles (< 1350 °C) suggèrent l’absence d’anomalie thermique sous le Jbel Saghro, et favorisent donc un modèle de délamination de la lithosphère comme initiateur du volcanisme. Cependant, l’augmentation du taux de fusion partielle au cours du temps, également observée dans le Moyen Atlas, et les similitudes isotopiques et géochimiques avec les laves alcalines des îles Canaries ne permettent pas d’exclure une influence du panache des Canaries sur la source du volcanisme alcalin du Jbel Saghro.
https://tel.archives-ouvertes.fr/tel-01615888

NNT : 2015MONTS070
tel-01615888
https://tel.archives-ouvertes.fr/tel-01615888
https://tel.archives-ouvertes.fr/tel-01615888/document
https://tel.archives-ouvertes.fr/tel-01615888/file/53752_CHAMBOREDON_2015_archivage_cor.pdf

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
A full equilibrium treatment of molecular aggregation is presented for prototypes of 1D and 3D aggregates, with and without nucleation. By skipping complex kinetic parameters like aggregate size-dependent diffusion, the equilibrium treatment allows to predict directly time-independent quantities such as critical concentrations. The relationships between the macroscopic equilibrium constants for the different paths are first established by statistical corrections and so as to comply with the detailed balance constraints imposed by nucleation, and the composition of the mixture resulting from homogeneous aggregation is then analyzed using the polylogarithm function. Several critical concentrations are distinguished: the residual monomer concentation in equilibrium (RMC) and the critical nucleation concentration (CNC), that is the threshold concentration of total subunits necessary for initiating aggregation. When increasing the concentration of total subunits, the RMC converges more strongly to its asymptotic value, the equilibrium constant of depolymerization, for 3D aggregates and in case of nucleation. The CNC moderately depends on the number of subunits in the nucleus, but sharply increases with the difference between the equilibrium constants of polymerization and nucleation. As the RMC and CNC can be numerically but not analytically determined, ansatz equations connecting them to thermodynamic parameters are proposed
PCCP : Physical chemistry chemical physics

Droits : info:eu-repo/semantics/OpenAccess
hal-01565995
https://hal.archives-ouvertes.fr/hal-01565995
https://hal.archives-ouvertes.fr/hal-01565995/document
https://hal.archives-ouvertes.fr/hal-01565995/file/Aggregates_in_equilibrium.pdf
DOI : 10.1039/c6cp08369b

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A suite of eclogite xenoliths from the Roberts Victor kimberlite (South Africa) is remarkable for its high abundances of base metal sulfides (BMS; up to 2 modal %). However, while sulfides are nearly ubiquitous in Type I eclogites (garnet > 0.07% Na2O), Type II eclogites (garnet < 0.07% Na2O) systematically lack sulfides. Two different sulfide assemblages are recognised within the Type I xenolith suite. Both populations are polyphase Cu-Ni-Fe sulfides, one characterised by the pyrrhotite (Po) + pentlandite (Pn) + chalcopyrite (Cp) assemblage and the other by the smythite/violarite (Smy/Vi) + (Ni)pyrite (Py) + Cp assemblage. The latter is the most abundant assemblage and reflects the supergene alteration of the "primary" Po + Pn + Cp assemblage. This process overprints the original composition of the sulfides by remobilising elements such as S, Fe, Ni, Se and Te. In the Type I eclogites, BMS occur as inclusions within silicates (garnet and clinopyroxene) and as interstitial grains. No chemical differences were observed between enclosed and interstitial sulfides. However, their relative abundances are correlated, indicating a similar origin. The Po + Pn + Cp assemblage is identical to eclogitic sulfides previously described in some Roberts Victor diamonds. Silicate-enclosed sulfides could appear to be early phases, but they are restricted to the outer parts of the silicate grains, suggesting a late incorporation during partial recrystallisation of silicate phases, induced by fluid-rock percolation-reaction during a metasomatic event. Positive whole-rock correlations between Se and (La/Sm)N⁎ and between Cu and ΣLREEN⁎ indicate a direct link between sulfide content and the enrichment of Mg + incompatible elements in the Type I eclogites, further supporting a metasomatic origin of the sulfide component. Similarly, a negative correlation between ΣLREEN⁎ and Cucpx implies that the metasomatic agent was at least partially composed of S-rich fluid (e.g. H2S, SO2) that reacted with the rock and leached Cu out of the silicates. The coupling between sulfides and LREE in the Type I eclogites, as well as the absence of sulfides and metasomatic features (e.g. unequilibrated grain boundaries, melt pockets, fluid inclusions, phlogopite) in the Type II eclogites, demonstrate that Type II eclogites did not undergo such a metasomatic event and therefore may represent the less-modified protoliths of Type I eclogites.
ISSN: 0009-2541

hal-00903856
https://hal.archives-ouvertes.fr/hal-00903856
DOI : 10.1016/j.chemgeo.2013.06.015

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
Silane coating of fibers is a promising process for improving durability and adhesion of vegetable fibers used as reinforcement material in a cementitious matrix. The work presented in this paper gives an insight into the effect of combining pyrolysis treatment with silane treatment. Indeed, this study focuses on silane treatment of unpyrolyzed and pyrolyzed sugar cane bagasse fibers with an alkyltrialkoxysilane (RSi(OR′)3), S1 or a dialkyldialkoxysilane (R2Si(OR″)2), S2. The silane solutions used vary from 0.5% to 8% by volume. This paper describes the effect of two silane compounds on parameters such as the porosity, dimension, morphology and hygroscopic character of silane-coated sugar cane bagasse fibers. Preliminary studies on natural fiber reinforced composite setting time show the importance of the silane chemistry/structure, for fiber treatments with silane solution containing up to 6% (volume percent) silane. In the case of composites reinforced with unpyrolyzed bagasse fibers, setting time increases with silane coating. Combining pyrolysis and silane treatment improve the water resistance of the fibers, which become more hydrophobic.
ISSN: 1359-835X

hal-00809830
https://hal.univ-antilles.fr/hal-00809830
DOI : 10.1016/j.compositesa.2008.05.013

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Low Density Polyethylene (LDPE) films were treated by direct fluorination at different conditions, i.e. static and dynamic ones. Modification of the treated films chemical composition was studied by spectroscopic methods (solid state NMR, XPS and infrared spectroscopy). Surface morphology was investigated by SEM and AFM. Also surface energy measurements and electron paramagnetic resonance (EPR) were carried out. Direct fluorination resulted in printability, barrier properties towards O2 and tribological properties enhancement. On the contrary, the barrier properties towards water, initially good, were not improved but maintained.
ISSN: 0257-8972

hal-01324133
https://hal.archives-ouvertes.fr/hal-01324133
DOI : 10.1016/j.surfcoat.2016.03.021

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
The chemical and isotopic compositions of clay minerals such as illite and chlorite are commonly used to quantify diagenetic and low-grade metamorphic conditions, an approach that is also used in the present study of the Monte Perdido thrust fault from the South Pyrenean fold-and-thrust belt. The Monte Perdido thrust fault is a shallow thrust juxtaposing upper Cretaceous-Paleocene platform carbonates and Lower Eocene marls and turbidites from the Jaca basin. The core zone of the fault, about 6 m thick, consists of intensely deformed clay-bearing rocks bounded by major shear surfaces. Illite and chlorite are the main hydrous minerals in the fault zone. Illite is oriented along cleavage planes while chlorite formed along shear veins (<50 μm in thickness). Authigenic chlorite provides essential information about the origin of fluids and their temperature. δ18O and δD values of newly formed chlorite support equilibration with sedimentary interstitial water, directly derived from the local hanging wall and footwall during deformation. Given the absence of large-scale fluid flow, the mineralization observed in the thrust faults records the P-T conditions of thrust activity. Temperatures of chlorite formation of about 240°C are obtained via two independent methods: chlorite compositional thermometers and oxygen isotope fractionation between cogenetic chlorite and quartz. Burial depth conditions of 7 km are determined for the Monte Perdido thrust reactivation, coupling calculated temperature and fluid inclusion isochores. The present study demonstrates that both isotopic and thermodynamic methods applied to clay minerals formed in thrust fault are useful to help constrain diagenetic and low-grade metamorphic conditions.
ISSN: 0010-7999

hal-00757736
https://hal.archives-ouvertes.fr/hal-00757736
DOI : 10.1007/s00410-011-0718-0

Résumé : The MEDECO Leg 2 cruise followed the MEDECO Leg 1 cruise that had crossed the Mediterranean Sea from the west to the east to study benthic communities of the Var canyon, deep corals found on the Calabrian Margin and cold seep ecosystems of the Mediterranean Ridge. The main objective of the MEDECO Leg 2 cruise was to study and compare, using a multidisciplinary approach, the structure and dynamics of deep-sea ecosystems at various active cold seep sites from the Nile deep sea fan and the Calabrian Arc, in the Eastern Mediterranean sea. During MEDECO Legs 1 & 2, a multiscale strategy was promoted to integrate (1) a high resolution cartography of geological structures (km2 scale), (2) a detailed mapping, including video imagery, of smaller-scale areas (scale 100 to 300 m2), (3) the physical, chemical and sedimentary characteristics of the habitat (multiscale), (4) the structure and functioning of faunal communities, including microbes, in terms of composition, diversity and biomass (multiscale), (5) small scale studies of interactions between organisms and their environment (scale < m2), (6) detailed ecophysiological studies at the organism scale on invertebrates. The use of the ROV “Victor 6000” and of various equipments for in situ and ex situ observations and measurements has helped reaching our objectives. The MEDECO cruise represented the key-Mediterranean cruise of the HERMES project “Hotspot Ecosystem Research on the Margins of European Seas” (P.I. P. Weaver, NOC-Southampton). The cruise was organized to follow the objectives of the HERMES program to better understand the functioning of deep ecosystems of the continental margins aiming at obtaining: (1) the description and quantification of the natural drivers (geological, hydrological, chemical factors) that control the distribution of ecosystems on margins; (2) the characterization and quantification of biodiversity, from bacteria to megafauna, as well as the knowledge of ecosystem functioning; (3) the study of ecosystems dynamics including the biology/physiology of key-species. Specific objectives. Colonization experiments conducted in the frame of two European programs, Diwoo and Chemeco, have given the opportunity to recover the fauna installed in the devices deployed during the Bionil cruise (2006) and to deploy new ones at the same site located in the pockmark area of the central province of Nile deep sea fan.

Droits : 2008 Insu, Cnrs, Locean
http://archimer.ifremer.fr/doc/00134/24550/22583.pdf
http://archimer.ifremer.fr/doc/00134/24550/

Éditeur(s) : HAL CCSD E Schweizerbart Science Publishers
Résumé : Mafic microgranular enclaves produced by co-mingling between minette and syenite magmas are found in the Piquiri Syenite, southern Brazil. These enclaves were crystallized under upper mantle conditions. K-clinopyroxene and pyrope are among the early-crystallized phases, suggesting an initial pressure around 5GPa. The mineralogy of minettes comprises phenocrysts of magnesium biotite and diopside, occasionally apatite, in a groundmass formed by these minerals plus alkali feldspar. Two types of apatites are observed: (i) euhedral grains, as inclusions or groundmass constituents, and (ii) aciculate crystals formed during undercooling of mafic magma. Substitutional schemes suggested for these apatites are Si ⇆ P in the tetrahedral site, and Sr and LREE replacing Ca. La, Ce, Nd, and Sr concentrations reveal that these elements are extremely enriched in apatite. Partition coefficients between early-crystallized apatites and estimated melt compositions are DLa (11.8 - 30.6), DCe (16.1-33), DNd (12-31) and DSr (5.1-8.2). Apatite concentrates the LREE up to 200 times compared to clinopyroxene, even higher values were determined for ap/mica partitioning. The ap/cpx and ap/mica partition coefficients for undercooled minerals are close to the values determined for the near-liquidus phases, which indicates constant behavior of LREE and Sr between apatite-clinopyroxene-mica parageneses and minette liquids. Furthermore, these partitioning data preclude any chemical diffusion of these elements between minette and syenite magmas during co-mingling.
ISSN: 0935-1221

hal-00407602
https://hal.archives-ouvertes.fr/hal-00407602
DOI : 10.1127/0935-1221/2007/0019-0039

Éditeur(s) : Amer Geophysical Union
Résumé : In this study, we undertook a reconnaissance study of sediments provenance in the Gulf of Lions focusing over the last 16 ka. We used geochemical and isotopic tracers to determine the source of sediments and give insight into the weathering conditions prevailing. Sediments samples were selected both onshore and offshore from the western, eastern, and central part of the Gulf of Lions. We analyzed bulk sediments, coarse and fine silt, and clay fractions. Elemental and Nd isotope compositions appeared to differ from one grain size fraction to another one. These are interpreted in terms of zircon addition in the coarse silt fraction for the elemental concentrations and variable sources influences for the Nd isotope compositions. Our results indicate that sediments in the Gulf of Lions mainly originated from the Rhone River watershed although a contribution of Saharan dust is seen in one sample. Influence of Pyrenean small rivers is minor in these samples. Some Sr isotope compositions shifts are interpreted as reflecting variable amounts of chemical weathering that are consistent with published paleoclimatic reconstructions.
Geochemistry Geophysics Geosystems (1525-2027) (Amer Geophysical Union), 2011-08 , Vol. 12 , N. Q08006 , P. 20 p.

Droits : 2011 by the American Geophysical Union
http://archimer.ifremer.fr/doc/00043/15376/12734.pdf
DOI:10.1029/2011GC003523
http://archimer.ifremer.fr/doc/00043/15376/

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
Despite a relatively 'uniform' fertile composition (Al2O3 = 2 center dot 19-4 center dot 47 wt %; Fo% = 89 center dot 2 +/- 0 center dot 3%; Cr#(Spl) = 8 center dot 9 +/- 1 center dot 5%), the Montferrier peridotite xenoliths show a wide range of S contents (22-590 ppm). Most sulphides are interstitial and show peculiar pyrrhotite-pentlandite intergrowths and low abundances of Cu-rich phases. Sulphide-rich samples are characterized by strong enrichment in the light rare earth elements and large ion lithophile elements without concomitant enrichment of the high field strength elements. Such trace-element fractionation is commonly ascribed to metasomatism by volatile-rich melts and/or carbonatitic melts. S and Se (11-67 ppb), as well as S/Se (up to approximate to 12 000), are correlated with La/Sm. Cu, however, remains broadly constant (30 +/- 5 ppm). These features strongly suggest that the percolation-reaction of such volatile-rich fluids has led to sulphide enrichment with an atypical signature marked by strong fractionation of the chalcophile elements (i.e. S vs Se and Cu). S-rich xenoliths are also characterized by high (Pd/Ir)(N) (1 center dot 2-1 center dot 9; where subscript N indicates normalized to chondrite), (Pd/Pt)(N) between 1 center dot 5 and 2 center dot 2, and (Os/Ir)(N) up to 1 center dot 85. Despite the relative uniform fertile composition of the xenoliths, Re/Os ranges between 0 center dot 02 and 0 center dot 18. Os-187/Os-188 is extremely variable even within a single sample and can be as high as 0 center dot 1756 for the most S-rich samples. Sulphides show highly fractionated and variable abundances of the highly siderophile elements (HSE) [0 center dot 03 (Pd/Ir)(N) < 1283] and Re-Os isotopic composition (0 center dot 115 < Os-187/Os-188 < 0 center dot 172). Such variation can be observed at the thin-section scale. Whole-rock and in situ sulphide data demonstrate that chalcophile and HSE systematics and the Os isotopic composition of the upper mantle could be significantly modified through metasomatism, even with volatile-rich fluids. These features highlight the complex behaviour of the HSE in fluid-rock percolation-reaction models and suggest a complex interplay between sulphide addition (crystallization or sulphidation) and partial equilibration of pre-existing sulphide. The specific fractionations observed in chemical proxies such as S and Se, Os and Ir, and Pd and Pt, as well as the low abundance of Cu-rich sulphides, suggest that sulphide addition may not have occurred via sulphide melts. Rather, we infer that S was present as a dissolved species in a (supercritical) oxidizing, volatile-rich fluid (C-O-H-S +/- Cl) along with other chalcophile and siderophile elements such as Os, Pd, Re and Au. The highly radiogenic Os composition of this fluid ( Os-187/ Os-188 > 0 center dot 17) would imply that such fluids are derived from an uncommon type of mantle source possibly related to carbonatite melts.
ISSN: 0022-3530

hal-00644524
https://hal.archives-ouvertes.fr/hal-00644524
DOI : 10.1093/petrology/egr038

Éditeur(s) : Gauthier-Villars
Résumé : We report here our findings on the chemistry of methane, manganese and chloride dissolved in the interstitial water of the Barbados accretionary complex. The decollement separating the subduction plate from the accretionary wedge is geochemically characterized by high methane and manganese and low chloride concentrations relative to buried seawater. Sandstone layers occurring below the decollement and the compressive structures recording some of the earliest effects of offscraping are also characterized by similar anomalies. A fluid with the same characteristics is also found six kilometres to the east of the deformation front within the oceanic plate. High manganese concentration and low chlorinity also occur in the pore water of the offscraped sediment packages, but without associated anomalous methane concentrations. These results suggest that: Dewatering processes occur below the decollement in association with thermogenic methane production; Fluid with low chlorinity and high methane concentrations circulates mainly along the decollement, its propagation in the oceanic domain and along the main fracture zones being associated with these detachment surfaces; Diagenetic processes essentially control the dissolved manganese concentration and probably affect the methane content of the interstitial waters; The observations made in this paper illustrate advective processes in the front of an accretionary prism.
Oceanologica Acta (0399-1784) (Gauthier-Villars), 1991 , Vol. 14 , N. 1 , P. 33-49

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/00101/21262/18873.pdf
http://archimer.ifremer.fr/doc/00101/21262/

Éditeur(s) : HAL CCSD
Résumé : International audience
Given the clinical success of commercial amphotericin B lipid products, investigators have begun making generic formulations of liposomal amphotericin B. Generic medicines are an attractive approach to help decrease the cost and accessibility to healthcare, provided that appropriate studies are performed to ensure bioequivalence with the parent product. This is of particular concern for liposomal drugs such as amphotericin B where liposomes are used as a carrier system to reduce the toxicity of the active agent. A favorable therapeutic profile for this form of the drug has to include the proper chemical composition along with strictly controlled manufacturing processes. Studies have shown that a comparison of liposomal amphotericin B products with different or the same chemical compositions, using different methods of production, will vary in size, and have significantly dissimilar in vitro and in vivo toxicities along with reduced efficacy. These results underscore the importance of establishing appropriate bioequivalence testing for liposome products to ensure uniformity of their therapeutic index
Medical Mycology

hal-01259233
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01259233
DOI : 10.1093/mmy/myv111
PUBMED : 26768369

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
Despite the impact of soil millipedes on litter fragmentation in tropical forests, there have been few studies dealing with factors determining their habitat preference in these ecosystems. In a natural secondary dry forest of Guadeloupe on Leptosol, two complementary studies were carried out in order to test the hypothesis that litter N-content strongly influences millipede distribution. Millipede abundance and species richness were described in the field under two tree species, Bursera simaruba and Pisonia subcordata, and were related to the chemical characteristics of their foliage. In addition, a laboratory experiment was done in order to assess millipede feeding preferences regarding the chemical characteristics of leaves from various species. Millipede abundance and species richness were significantly higher under P. subcordata than under B. simaruba, probably due to the higher N content of P. subcordata leaves. Moreover, millipedes fed preferentially on N-rich leaves. The present study confirms that there was a close correlation between the preferred food, its chemical composition and the local distribution of millipede populations.
ISSN: 0178-2762

hal-00495211
https://hal.archives-ouvertes.fr/hal-00495211
https://hal.archives-ouvertes.fr/hal-00495211/document
https://hal.archives-ouvertes.fr/hal-00495211/file/BFSO-D-08-00133-1.pdf
DOI : 10.1007/s00374-008-0321-3

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 AGU and the Geochemical Society
Résumé : International audience
The 1415 m deep IODP Hole U1309D (Mid-Atlantic Ridge, 30 degrees N) is the second deepest hole drilled into slow spreading oceanic lithosphere. The recovered section comprises essentially gabbroic rocks, with a large range of compositions. The most primitive end-members of the gabbroic sequence, herein referred to as olivine-rich troctolites (ol > similar to 70%), have textures and geochemical compositions intermediate between that of mantle peridotites and primitive cumulates, indicative of melt impregnation processes. We carried out a detailed microstructural study to further characterize the petrogenetic processes leading to their formation, as well as discuss their mode of emplacement and relationship with neighboring mantle lithosphere. In olivine-rich troctolites, olivines range from coarse-grained subhedral crystals, commonly containing well-developed subgrains, to medium-grained rounded crystals with fewer or no substructures. They are embedded in large, undeformed pyroxene and plagioclase poikiloblasts. Olivine substructures reveal dislocation creep that is consistent with activation of the main high-temperature slip systems, dominantly (010)[100]. Olivine crystallographic preferred orientation is very weak but generally shows a relatively stronger, uncommon [001] concentration. These unusual olivine fabrics are interpreted as resulting from melt impregnation of a previously deformed olivine matrix: the solid olivine framework is disrupted by olivine corrosion along grain and subgrain boundaries, and the high-temperature plastic fabric is modified in a liquid-dominated regime. Based on mineral composition and fabrics and in comparison with what is observed in impregnated mantle rocks elsewhere, we posit that olivine represents relicts of mantle peridotites disaggregated by large melt influx, although the mantle origin of olivine is not unequivocally demonstrated yet. Whatever the initial lithology, impregnation by large volumes of melt has strongly modified the original composition and microstructure. If the mantle origin hypothesis is correct, the original olivine fabric could have been efficiently weakened by dunitization prior to disruption of the olivine framework by melt impregnation. Incorporation, at the base of the lithosphere, of small slivers of impregnated dunite into gabbroic sections, trapped between successive igneous units, may be a common mechanism of lower crustal accretion at slow spreading ridges. Extensive melt-rock interaction processes are expected to contribute significantly to the final chemical composition of erupted lavas.
ISSN: 1525-2027

hal-00496391
https://hal.archives-ouvertes.fr/hal-00496391
DOI : 10.1029/2009GC002995

Éditeur(s) : HAL CCSD
Résumé : In order to minimize CO2 atmospheric concentration, a solution consists in sequestrating CO2 in geological reservoirs. To estimate long term risks, it is necessary to quantify the couplings between reaction processes as well as structural and hydrodynamical modifications. We realised two experimental benches enabling injecting CO2-enriched-brine in conditions corresponding to in situ storage (T < 200 oC and P < 200 bar) and developed
an experimental protocol using X-Ray microtomography and fluid and rock analyses in order to measure the variations of physical and chemical parameters.
The study of carbonated reservoirs near the injection well, allows quantifying different k-phi relationships depending on the dissolution processes and triggered by the local fluid chemical composition and initials conditions. Away from the injection well, we observe carbonate precipitation decreasing the permeability. The study of fracturated caprock samples shows that alternative percolation of CO2-enriched-brine and CO2 gas increases the fracture permeability.
The study of silicated rocks indicates carbonate precipitation in zeolite sandstone and sintered dunite grains. Nevertheless, in zeolite sandstone we also observe the precipitation of clay particles located in the uid pathways which decrease strongly the permeability.
Afin de minimiser la concentration en CO2 dans l'atmosphère une solution consiste à le séquestrer dans les réservoirs géologiques. Pour évaluer les risques à long terme, il est nécessaire de quantifier les couplages entre les processus réactionnels et les modifications structurales et hydrodynamiques. Dans cette optique, nous avons construit deux dispositifs expérimentaux permettant d'injecter des saumures chargées en CO2 dans les conditions de stockage (T < 200 °C et P < 200 bar) et mis en oeuvre un protocole expérimental utilisant la microtomographie RX et l'analyse des roches et des fuides pour quantifier les variations des paramètres physiques et chimiques. Dans le cas des réservoirs carbonatés, on observe, près du puits d'injection, une forte variabilité des relations k-phi en fonction du régime de dissolution contrôlé par la chimie locale du fluide, ainsi que par les conditions initiales. A plus grande distance, on observe des processus de précipitation diminuant fortement la perméabilité. L'étude des roches de couverture fracturées (argilite) a montré qu'une percolation alternée d'une saumure chargée en CO2 et de CO2 gaz augmentait la perméabilité de fracture. Dans le cas des roches silicatées, la précipitation de carbonates est mise en évidence aussi bien dans les grès à zéolites que dans les frittés de dunite de San Carlos. Cependant, dans les grès à zéolites, la précipitation d'une phase argileuse est observée dans les chemins d'écoulement et engendre une forte diminution de la perméabilité.
https://tel.archives-ouvertes.fr/tel-00416408

tel-00416408
https://tel.archives-ouvertes.fr/tel-00416408
https://tel.archives-ouvertes.fr/tel-00416408/document
https://tel.archives-ouvertes.fr/tel-00416408/file/These_Luquot.pdf