Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
TEM Study of Heavitree quartzite deformed at high temperatures and a pressure of 1.5 GPa with three different preparations: water-added, vacuum dried, and sodium doped show a wide range of dislocation microstructure. The vacuum dried sample has a very heterogeneous dislocation distribution varying from almost no dislocations to very high densities. Dislocation nucleation occurs by cross-slip mechanisms, such as Frank-Read sources and Orowan loops around hard inclusions. Shear bands develop in the basal plane composed of two closely spaced shear planes. Dislocations have straight segments and they are aligned along directions of dense packing, suggesting strong Peierls stress control due to the crystal structure. No voids, bubbles or dislocation walls where observed in the vacuum dried sample. The sodium-doped sample had a homogeneous high dislocation density. The water-added sample has a significantly lower, relatively uniform dislocation density. Bubbles associated with dislocations are seen in every grain. Dislocations were either present in loops around bubbles or as straight dislocations with small bubbles spaced along the dislocation line. Some of the long straight dislocations are aligned parallel to the c-axis. Sub-grains where very frequent, sometimes form cells of about 2 p,m in diameter with straight edges. Analysis of dislocations show 1/3 < a > and [c] dislocations in sub-grain walls and free 1/3 < a > dislocations on prism planes. There is clear evidence for dislocation climb with sub-grain walls, dislocation cells, dislocation junctions and dislocation debris of small loops. The major difference between vacuum dried and water-added samples are the homogeneity of the microstructure and evidence for climb in the water-added sample. Glide is clearly difficult, with a high Peierls stress in the vacuum dried sample as shown by areas of very low and very high dislocation density and the crystallographic control of dislocation line direction. The sodium-doped sample indicates that nucleation was easy by the high homogenous dislocation density, but no climb recovery has taken place. The density is high and the dislocations are strongly interacting causing tangles; no evidence for crystallographic control can be observed at these levels of strain. The activation energy for creep in Heavitree quartzite decreases with inferred water content of the specimens form 185 kJ mol(-1) for vacuum dried to 151 for 0.4 wt% water-added samples. Analysis of diffusion data for oxygen under hydrothermal conditions and inferred diffusion data for the hydrogarnet defect and dislocation velocity suggests activation energies for these processes are similar to the activation energy for the dislocation creep of Heavitree quartzite and other quartz aggregates. For data from the previously published experiments with the highest stress resolution there is a correlation between the A pre-factor in the power law creep equation and the activation energy for creep. It is speculated that the correlation may be due to variable hydrogarnet defect concentrations.
ISSN: 0031-9201

hal-00413112
https://hal.archives-ouvertes.fr/hal-00413112
DOI : 10.1016/j.pepi.2008.07.009

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
The brittle to ductile transition (BDT) in rocks may strongly influence their transport properties (i.e., permeability, porosity topology ...) and the maximum depth and temperature where hydrothermal fluids may circulate. To examine this transition in the context of Icelandic crust, we conducted deformation experiments on a glassy basalt (GB) and a glass-free basalt (GFB) under oceanic crust conditions. Mechanical and micro-structural observations at a constant strain rate of 10(-5) s(-1) and at confining pressure of 100-300 MPa indicate that the rocks are brittle and dilatant up to 700-800 degrees C. At higher temperatures and effective pressures the deformation mode becomes macroscopically ductile, i.e., deformation is distributed throughout the sample and no localized shear rupture plane develops. The presence of glass is a key component reducing the sample strength and lowering the pressure of the BDT. In the brittle field, strength is consistent with a Mohr-Coulomb failure criterion with an internal coefficient of friction of 0.42 for both samples. In the ductile field, strength is strain rate-and temperature-dependent and both samples were characterized by the same stress exponent in the range 3 < n < 4.2 but by very different activation energy Q(GB) = 59 +/- 15 KJ/mol and Q(GFB) = 456 +/- 4 KJ/mol. Extrapolation of these results to the Iceland oceanic crust conditions predicts a BDT at similar to 100 degrees C for a glassy basalt, whereas the BDT might occur in non-glassy basalts at deeper conditions, i.e., temperatures higher than 550 +/- 100 degrees C, in agreement with the Icelandic seismogenic zone.
ISSN: 0148-0227

hal-00760905
https://hal.archives-ouvertes.fr/hal-00760905
DOI : 10.1029/2011JB008884

Éditeur(s) : HAL CCSD European Geosciences Union
Résumé : The properties of the subduction interplate domain are likely to affect not only the seismogenic potential of the subduction area but also the overall subduction process, as it influences its viability. Numerical simulations are performed to model the long-term equilibrium state of the subduction interplate when the diving lithosphere interacts with both the overriding plate and the surrounding convective mantle. The thermomechanical model combines a non-Newtonian viscous rheology and a pseudo-brittle rheology. Rock strength here depends on depth, temperature and stress, for both oceanic crust and mantle rocks. I study the evolution through time of, on one hand, the brittle-ductile transition (BDT) depth, zBDT, and, on the other hand, of the kinematic decoupling depth, zdec, simulated along the subduction interplate. The results show that both a high friction and a low ductile strength at the asthenospheric wedge tip shallow zBDT. The influence of the weak material activation energy is of second order but not negligible. zBDT becomes dependent on the ductile strength increase with depth (activation volume) if the BDT occurs at the interplate decoupling depth. Regarding the interplate decoupling depth, it is shallowed (1) significantly if mantle viscosity at asthenospheric wedge tip is low, (2) if the difference in mantle and interplate activation energy is weak, and (3) if the activation volume is increased. Very low friction coefficients and/or low asthenospheric viscosities promote zBDT = zdec. I then present how the subducting lithosphere age affects the brittle-ductile transition depth and the kinematic decoupling depth in this model. Simulations show that a rheological model in which the respective activation energies of mantle and interplate material are too close hinders the mechanical decoupling at the down-dip extent of the interplate, and eventually jams the subduction process during incipient subduction of a young (20-Myr-old) and soft lithosphere under a thick upper plate. Finally, both the BDT depth and the decoupling depth are a function of the subducting plate age, but are not influenced in the same fashion: cool and old subducting plates deepen the BDT but shallow the interplate decoupling depth. Even if BDT and kinematic decoupling are intrinsically related to different mechanisms of deformation, this work shows that they are able to interact closely. Comparison between modelling results and observations suggests a minimum friction coefficient of 0.045 for the interplate plane, even 0.069 in some cases, to model realistic BDT depths. The modelled zdec is a bit deeper than suggested by geophysical observations. Eventually, the better way to improve the adjustment to observations may rely on a moderate to strong asthenosphere viscosity reduction in the metasomatised mantle wedge.
ISSN: 1869-9510

hal-00795559
https://hal.archives-ouvertes.fr/hal-00795559
DOI : 10.5194/se-3-467-2012, 2012

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The origin of plate tectonics is one of the most fundamental issues in earth and planetary sciences. Laboratory experiments indicate that the viscosity of silicate rocks is so strongly temperature-dependent that the entire surface of the Earth should be one immobile rigid plate. The rheology of oceanic lithosphere is, however, still poorly understood, and there exist few constraints on the temperature dependency of viscosity on the field scale. Here we report a new kind of observational constraint based on the geoid along oceanic fracture zones. We identify a large number of conspicuous small-scale geoid anomalies, which cannot be explained by the standard evolution model of oceanic lithosphere, and estimate their source density perturbations using a new Bayesian inversion method. Our results suggest that they are caused most likely by small-scale convection involving temperature perturbations of ∼300 K±100 K∼300 K±100 K. Such thermal contrast requires the activation energy of mantle viscosity to be as low as View the MathML source100±50 kJmol−1 in case of diffusion creep, and View the MathML source225±112 kJmol−1 in case of dislocation creep, substantially reducing the thickness of the stiffest part of oceanic lithosphere. Oceanic lithosphere may thus be broken and bent much more easily than previously thought, facilitating the operation of plate tectonics.
ISSN: 0012-821X

hal-01467827
https://hal.archives-ouvertes.fr/hal-01467827
DOI : 10.1016/j.epsl.2016.05.027

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Synthetic hydroxylated titanium-bearing and undoped MgO-buffered forsterite crystals were heated at atmospheric pressure in air at temperatures from 800 to 1200 °C to determine hydrogen diffusion as a function of the type of point-defect mechanism by which the hydroxyl is incorporated. OH-stretching bands, measured by infrared spectroscopy, were assigned to the four substitution mechanisms: Ti-clinohumite point defects, silicon and magnesium vacancies, and point defects associated with trivalent cations. In the experiments at 800 to 1000 °C, hydrous defects related to trivalent cations and Mg-vacancies disappear first in the Ti-doped forsterite, followed by the hydrous defects related to Ti and a fraction of the hydrated Si-vacancies. Measured bulk diffusion coefficients for hydrogen exchange related to the latter process are one order of magnitude slower than previously reported and with higher activation energy (View the MathML source296±14 kJmol−1). After the elimination of the defects related to Ti, the hydroxyl concentration related to Si-vacancies remained constant for the duration of the experiments. This observation is in agreement with the very slow diffusivity of hydrogen in Si-vacancies measured in the undoped MgO-buffered dehydroxylation experiments at higher temperatures (from 1000 to 1200 °C), which were ∼3 orders of magnitude slower than previously reported at 1000 °C, and with an activation energy of View the MathML source461±11 kJmol−1. Hydrogen diffusion in forsterite is far more complex than previously assumed. This complexity can be used to gain more information on the timescales of the processes causing olivine to lose its structural “water”, but quantitative modeling will require not only the knowledge of the intrinsic diffusivities of the different hydrous defects but also their relative proportions and the possible reactions between them.
ISSN: 0012-821X

hal-01172253
https://hal.archives-ouvertes.fr/hal-01172253
DOI : 10.1016/j.epsl.2014.01.055

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
Abstract View references (60)Here we show the long term performance at high temperatures of a multi-tube module containing 8 membranes in 4 parallel lines with a total of 545 cm 2 area. The membranes were prepared via thin film dip coating of cobalt oxide silica (CoO xSi) sol-gel on tubular alumina supports. A preliminary study found that the sol-gel containing 20 mol% cobalt oxide formed the best microporous structure with the highest surface area and pore volume. All resulting membranes delivered permeances of ∼1 × 10 -7 mol m -2 s -1 Pa -1 at 500 °C, indicating a high repeatability for the membrane fabrication process. The permselectivities of helium (He) and hydrogen (H 2) over carbon dioxide (CO 2) and nitrogen (N 2) increased from 10-20 at 100 °C to values close to 1000 at 500 °C. Additionally, the apparent energies of activation (E act) for the smaller kinetic diameter gases He and H 2 at 12.2 and 19.5 kJ mol -1 were high and contrary to the negative values for larger gases N 2 and CO 2 at -1.8 and -7.4 kJ mol -1. These remarkable results were attributed to the molecular sieving mechanism of the microporous silica which was enhanced by the embedding of cobalt oxide into the matrix, delivering structural control with an average pore size of 3 Å. The E act for H 2 permeance was higher than that of He, indicating that the cobalt oxide played an important role in H 2 transport. Two membrane lines performed exceptionally well for binary gas mixture processing with H 2 purity reaching values close to 100% in the permeate stream for argon (Ar) concentrations of up to 80% in the retentate stream. A major finding here is that the binary gas selectivity was independent of temperature, contrary to the permselectivity observed for single gas permeance. Further, the H 2 flow rate was greatly affected by the concentration of Ar in the mixture, while the temperature dependency played only a marginal role. In particular, competitive adsorption in the percolative pathways containing pore constrictions or bottlenecks of the anisotropic CoO xSi matrix allowed Ar to impede H 2 diffusion. Finally, the CoO xSi membranes proved thermally stable and robust for 2000 h of testing for various thermal cycles up to 500 °C. © The Royal Society of Chemistry 2012.
Energy & Environmental Science

hal-01683199
https://hal.univ-antilles.fr/hal-01683199
DOI : 10.1039/c2ee03247c

Éditeur(s) : HAL CCSD
Résumé : International audience
The corrosion rates in the presence of some indole derivates, namely, 9H-pyrido[3,4-b]indole (norharmane) and 1-methyl-9H-pyrido[3,4-b]indole (harmane), as inhibitors of C38 steel corrosion inhibitor in 1 M HCl solution, were measured by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques, in the range of temperatures from 25 to 55∘C. Results obtained revealed that the organic compounds investigated have inhibiting properties for all temperatures. The inhibition was assumed to occur via adsorption of the indole molecules on the metal surface. Adsorption of indole derivates was found to follow the Langmuir isotherm. The apparent activation energies, enthalpies, and entropies of the dissolution process and the free energies and enthalpies for the adsorption process were determined by potentiodynamic polarization and electrochemical impedance. The fundamental thermodynamic functions were used to collect important information about indole inhibitory behaviour.
international Journal of Corrosion

hal-01683120
https://hal.univ-antilles.fr/hal-01683120
DOI : 10.1155/2013/139798

Éditeur(s) : HAL CCSD
Résumé : International audience
The influence of Mn solute atoms on sub-grain boundary mobilities in Al has been determined by accurate electron backscatter diffraction analysis of the sub-grain sizes and misorientations during recovery annealing. High purity Al-0.1 and 0.3 wt.% Mn alloys were deformed by plane strain compression at room temperature to equivalent strains of 1.8 and annealed in the temperature range 150-300 °C. An original method of image analysis on sub-boundaries from electron backscatter diffraction maps was applied to quantify the sub-grain size distributions. The change in average sub-grain size with time at several temperatures was then used to estimate sub-grain boundary mobilities in both Al-Mn alloys. The activation energies for sub-grain mobility were found to be 48 and 52 and kJ.mol^-1 for the 0.1 and 0.3 % Mn alloys respectively, with the higher Mn alloy exhibiting lower rates. The sub-boundary mobilities are higher than expected from previous similar work on deformed Al-Si crystals. The orientation dependence of sub-grain growth is also examined.
International Journal of Materials Research

emse-00463551
https://hal-emse.ccsd.cnrs.fr/emse-00463551
DOI : 10.3139/146.110057

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The kinetics of hydrogenation of dry iron-bearing olivine single crystals was determined by performing hydration experiments under hydrothermal conditions at high pressure. The experiments were performed in a multi-anvil press at 3 GPa, for a temperature range between 900 and 1200 °C and for various durations. The oxygen fugacity was buffered along Ni-NiO joint. Polarized Fourier transform infrared spectroscopy and recent empirical calibration were used to quantify the hydroxyl distributions in the samples along crystallographic axes after the experiments. The chemical diffusion coefficients are similar (barely slower) than in olivine hydrated at lower pressure (0.2 and 0.3 GPa) for the same diffusion mechanism. Under the given experimental conditions, the anisotropy of diffusion is the same as for proton-vacancy mechanism, with diffusion along the [0 0 1] axis faster than along the [1 0 0]. However, the anisotropy at 3 GPa is weaker compared to measurements at lower pressures and the analysis of concentration profiles using 3D models shows that an isotropic solution could also be relevant. Fits of the diffusion data to an Arrhenius law yield activation energies for the slightly faster [0 0 1] axis of the crystallographic axes around 198 ± 5 kJ mol−1, a value only slightly lower than the results from previous experimental studies for natural iron-bearing olivine hydrogenated at lower confining pressure. At 3 GPa, hydrogenation can be well approximated by a single mechanism controlled by coupled diffusion of protons and octahedral vacancies (di- and tri-valent ions). The diffusion rates are fast enough to alter hydrogen concentration within olivine in xenoliths ascending from the mantle or experiencing hydrogen-rich metasomatism events, but too slow to permit complete homogenization of hydrogen in olivine-rich rocks at kilometer scale in less than one My.
ISSN: 0031-9201

hal-01412663
https://hal.archives-ouvertes.fr/hal-01412663
DOI : 10.1016/j.pepi.2016.08.005

Éditeur(s) : HAL CCSD
Résumé : International audience
In this work, an alkaloids extract from Annona squamosa plant have been studied as possible corrosion inhibitor for C38 steel in molar hydrochloric acid (1 M HCl). Potentiodynamic polarization and AC impedance methods have been used. The corrosion inhibition efficiency increases on increasing plant extract concentration. Polarisation studies showed that Annona squamosa extract was mixed-type inhibitor in 1 M HCl. The inhibition efficiency of Annona squamosa extract was temperaturedependent and its addition led to an increase of the activation corrosion energy revealing a physical adsorption between the extract and the metal surface. The adsorption of the Annona squamosa extractfollowed Langmuir’s adsorption isotherm. The inhibitive effect of Annona squamosa is ascribed to the presence of organic compounds in the extract. The examined extract is considered as non-cytotoxic substance.
International journal of electrochemical science

hal-01094042
https://hal-agroparistech.archives-ouvertes.fr/hal-01094042

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Metalloproteases involved in extracellular matrix remodeling play a pivotal role in cell response by regulating the bioavailability of cytokines and growth factors. Recently, the disintegrin and metalloprotease, ADAMTS1 has been demonstrated to be able to activate the transforming growth factor TGF-β, a major factor in fibrosis and cancer. The KTFR sequence from ADAMTS1 is responsible for the interaction with the LSKL peptide from the latent form of TGF-β, leading to its activation. While the atomic details of the interaction site can be the basis of the rational design of efficient inhibitory molecules, the binding mode of interaction is totally unknown. In this study, we show that recombinant fragments of human ADAMTS1 containing KTFR sequence keep the ability to bind the latent form of TGF-β. The recombinant fragment with the best affinity is modeled to investigate the binding mode of LSKL peptide with ADAMTS1 at the atomic level. Using a combined approach with molecular docking and multiple independent molecular dynamics (MD) simulations, we provide the binding mode of LSKL peptide with ADAMTS1. The MD simulations starting with the two lowest energy model predicted by molecular docking shows stable interactions characterized by 3 salt bridges (K3-NH3+ with E626-COO−; L4-COO− with K619-NH3+; L1-NH3+ with E624-COO−) and 2 hydrogen bonds (S2-OH with E623-COO−; L4-NH with E623-COO−). The knowledge of this interaction mechanism paves the way to the design of more potent and more specific inhibitors against the inappropriate activation of TGF-β by ADAMTS1 in liver diseases
ISSN: 1476-9271

hal-01269916
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01269916
DOI : 10.1016/j.compbiolchem.2016.01.012
PUBMED : 26878129

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study investigates if acclimatization to residual pesticide contamination in agricultural soils is reflected in detoxification, antioxidant enzyme activities and energy budget of earthworms. Five fields within a joint agricultural area exhibited different chemical and farming histories from conventional cultivation to organic pasture. Soil multiresidual pesticide analysis revealed up to 9 molecules including atrazine up to 2.4 ng g(-1) dry soil. Exposure history of endogeic Aporrectodea caliginosa and Allolobophora chlorotica modified their responses to pesticides. In the field, activities of soluble glutathione-S-transferases (sGST) and catalase increased with soil pesticide contamination in A. caliginosa. Pesticide stress was reflected in depletion of energy reserves in A. chlorotica. Acute exposure of pre-adapted and naïve A. caliginosa to pesticides (fungicide Opus(®), 0.1 μg active ingredient epoxiconazole g(-1) dry soil, RoundUp Flash(®), 2.5 μg active ingredient glyphosate g(-1) dry soil, and their mixture), revealed that environmental pre-exposure accelerated activation of the detoxification enzyme sGST towards epoxiconazole.
ISSN: 0269-7491

hal-01063923
https://hal.archives-ouvertes.fr/hal-01063923
DOI : 10.1016/j.envpol.2014.05.001
PUBMED : 24874794

Résumé : Le fluide chaud produit par les forages de la centrale géothermique de Bouillante (Guadeloupe) est enrichi en espèces dissoutes telles que la silice qui peuvent précipiter sous forme de dépôts solides lors de son refroidissement et gêner fortement la production électrique. L’un des principaux objectifs de ce travail de thèse a donc été d’améliorer l’état des connaissances sur les conditions physiques, chimiques et cinétiques de la précipitation de la silice amorphe à Bouillante. Après une étude des caractéristiques physico-chimiques des fluides et des dépôts associés au champ de Bouillante, des expériences sur la cinétique de précipitation de la silice, sur site, pour une large gamme de température (25 - 90°C) et de pH (4 - 12) ont été menées et analysées en détail.Pour l’ensemble de ces expériences, seule la polymérisation (réversible) de la silice dissoute, sous forme de suspensions colloïdales très stables en solution, a été observée. La modélisation des données expérimentales de cinétique montre que la vitesse de polymérisation de la silice suit une loi d’ordre 2 vis-à-vis de la silice dissoute jusqu’à l’équilibre en accord avec une dimérisation de la silice. Par contre, durant l’étape initiale de la réaction, une loi d’ordre 4 semble mieux adaptée, suggérant des réactions de polymérisation plus complexes avec formation de tétramères. La température a un effet limité sur la cinétique de polymérisation de la silice comparé à l’effet du pH qui est beaucoup plus important. L’énergie d’activation de la réaction globale est de 41 - 54 kJ pour des pH compris entre 5 et 8.La caractérisation de la silice précipitée a mis en évidence des différences notables entre la structure poreuse de la silice solide prélevée sur les installations de surface et celle de la silice colloïdale obtenue par polymérisation lors des expériences de cinétique, ce qui semble indiquer que des mécanismes différents interviennent dans ces deux contextes de précipitation de la silice dissoute.Le deuxième objectif de cette thèse était d’évaluer la possibilité de valoriser la silice extraite de l’eau géothermale de Bouillante dans un procédé de traitement des eaux naturelles par adsorption. Pour cela, les propriétés d’adsorption de la silice géothermale brute et fonctionnalisée par le poly(ethylèneimine) (ou PEI) ont été étudiées pour deux polluants : un colorant, le bleu de méthylène et un métal lourd, le plomb. Les résultats obtenus montrent que la silice brute possède une grande capacité d’adsorption vis-à-vis du bleu de méthylène. En outre, la fonctionnalisation de la silice par le PEI permet d’améliorer sa capacité d’adsorption vis-à-vis du plomb en solution, en accord avec un modèle cinétique du pseudo-second ordre suggérant une chimisorption. Le modèle d’isotherme de Redlich-Peterson est également en très bon accord avec les données expérimentales.
The hot geothermal fluid produced by the geothermal power plant of Bouillante (Guadeloupe) contains various dissolved components such as silica that can precipitate as solid deposits during their cooling and cause serious problems on the electricity generation. One of the aim of this study is to improve the understanding on the physical, chemical and kinetics conditions of the amorphous silica precipitation in the Bouillante geothermal field. After a study on the physical and chemical characteristics of the Bouillante fluids and deposits which can form during their exploitation, experiments on the kinetics of silica precipitation, on site, under a large range of temperature (25 – 90°C) and pH (4 – 12) have been carried out and analyzed in detail.During on site kinetics experimentations only dissolved silica polymerization (reversible) as colloidal gel, very stable in solution, was observed. Modeling of the experimental data showed that the kinetics polymerization is characterized by a 2-order kinetic law relative to dissolved silica until the equilibrium that is consistent with silica dimerization. On the other side, the initial stage of the reaction is better characterized by a 4-order kinetic law that suggested more complex polymerization reactions with tetramers formation.Temperature has a little effect on the polymerization kinetics compared with the pH which has an effect more important. The activation energy of silica precipitation calculated between 25 and 90°C, is about 41 - 54 kJ for pH ranging to 5 - 8.The characterization of the silica precipitate reveals significant differences in the porous structure of the silica collected on the surface installations and the one obtained from kinetic experiments that suggests different precipitation mechanisms. The second objective of this thesis was to evaluate the possibility to promote geothermal silica for the treatment of natural waters containing contaminants by adsorption. Adsorption properties of the untreated and functionalized by poly(ethylèneimine) (ou PEI) geothermal silica have been investigated for two pollutants: a colorant, the methylene blue and a heavy metal, the lead.Results showed that untreated silica has a great adsorption capacity concerning the methylene blue. Besides, silica functionalization by the PEI allows improving the adsorption capacity for lead in solution. The adsorption kinetics curves followed a pseudo-second order model consistent with a chimisorption. The isotherm model of Redlich-Peterson fitted well the experimental data.

http://www.theses.fr/2014AGUY0698/document

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Despite many studies, our understanding of silica precipitation from natural waters remains limited, in particular for geothermal waters. Here we present a detailed study on the kinetics of silica polymerization as a function of fluid temperature and pH using high-temperature (250-260 °C) seawater-derived geothermal fluids as those discharged from the Bouillante geothermal site.We monitored the on-site decrease in monomeric silica concentration(initial SiO2 concentration of about 600 mg/l)with time using the molybdenum blue spectrophotometric method on samples of separated water collected from the high-pressure separator at 167 °C and cooled to 25, 50, 75, and 90 °C and for pH values ranging from 5 to 8. During all these experiments, only silica polymerization was observed, with the formation of colloidal particles in suspension in the solutions. No scaling of amorphous silica was formed. The collected data were after modeled in order to determine the useful kinetic parameters for predicting and preventing amorphous silica precipitation in the production wells during fluid exploitation in the specific context of Bouillante. Results under the investigated experimental conditions show that the kinetics of silica precipitation is affected more strongly by pH than by temperature change. The reaction in the acidic Bouillante solution begins with a transition period that significantly decreases the kinetics of silica polymerization. Modeling the experimental data indicates that the silica polymerization up to the state of equilibrium is characterized by a 2nd-order kinetic law relative to dissolved silica; this could indicate that the polymerization is controlled mainly by the formation of dimers. However, the first hour of the experiments is better characterized by a 4th-order kinetic law, suggesting more complex polymerization reactions in the initial stage with the formation of nanocolloidal particles containing 3 to 4 monomers. In both cases, the corresponding kinetics rate constant k is linearly dependent on pH for pH between 5 and 7. The activation energy Ea for the overall reaction, calculated using the Arrhenius equation under the considered pH and temperature conditions, ranges between 41±9.8 and 54±9.6 kJ/mol. To complete this work, the colloid particles formed at the end of the kinetics experiments were extracted and analyzed by SEM and TEM microscopy, X-ray Diffraction and the BET method. Results show that the size of the colloids increase and their specific surface decrease with increasing pH and are thus dependent on pH. Globally, our work provides a reliable database for understanding silica polymerization kinetics in natural geothermal brines or geologic waters characterized by a near neutral pH and moderate dissolved silica concentrations.
ISSN: 0009-2541

hal-01403092
https://hal-brgm.archives-ouvertes.fr/hal-01403092
DOI : 10.1016/j.chemgeo.2016.08.031

Éditeur(s) : HAL CCSD Endocrine Society
Résumé : International audience
Sertoli cells (SCs), the only somatic cells within seminiferous tubules, associate intimately with developing germ cells. They not only provide physical and nutritional support but also secrete factors essential to the complex developmental processes of germ cell proliferation and differentiation. The SC transcriptome must therefore adapt rapidly during the different stages of spermatogenesis. We report comprehensive genome-wide expression profiles of pure populations of SCs isolated at 5 distinct stages of the first wave of mouse spermatogenesis, using RNA sequencing technology. We were able to reconstruct about 13 901 high-confidence, nonredundant coding and noncoding transcripts, characterized by complex alternative splicing patterns with more than 45% comprising novel isoforms of known genes. Interestingly, roughly one-fifth (2939) of these genes exhibited a dynamic expression profile reflecting the evolving role of SCs during the progression of spermatogenesis, with stage-specific expression of genes involved in biological processes such as cell cycle regulation, metabolism and energy production, retinoic acid synthesis, and blood-testis barrier biogenesis. Finally, regulatory network analysis identified the transcription factors endothelial PAS domain-containing protein 1 (EPAS1/Hif2α), aryl hydrocarbon receptor nuclear translocator (ARNT/Hif1β), and signal transducer and activator of transcription 1 (STAT1) as potential master regulators driving the SC transcriptional program. Our results highlight the plastic transcriptional landscape of SCs during the progression of spermatogenesis and provide valuable resources to better understand SC function and spermatogenesis and its related disorders, such as male infertility.
ISSN: 0888-8809

hal-01146846
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01146846
DOI : 10.1210/me.2014-1356
PUBMED : 25710594

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
An empirical relation is proposed to analyze the broad band observed in the photoluminescence spectra of CuInSe2 (CIS) due to donor-acceptor pair recombinations. This permits, together with the knowledge of the majority carrier concentration and the compensation ratio, the determination of the activation energy ED of the donor and EA of the acceptor levels and the mean distance R between D-A pairs. Values of the dielectric constant ϵ, ED and EA for CIS obtained with this model agree with reported data.
ISSN: 0167-577X

hal-00808657
https://hal.univ-antilles.fr/hal-00808657
DOI : 10.1016/S0167-577X(96)00133-4

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Mantle noble gases record important and ancient isotopic heterogeneities, which fundamentally influence our understanding of mantle geodynamics, yet these heterogeneities are difficult to fully interpret without understanding the basic mechanisms of noble gas storage and transport in mantle minerals. A series of annealing experiments that mimic mantle conditions (i.e. sub-solidus with natural, polycrystalline, texturally equilibrated olivines at low noble gas partial pressures) show that intergranular interfaces (grain boundaries) are major hosts for noble gases in the mantle, and that interfaces can dramatically fractionate noble gases from their radio-parents (U + Th and K). Therefore, noble gas isotopic heterogeneities in the mantle could result from grain size variations. Fine-grained lithologies (mylonites and ultramylonites, for example) with more grain boundaries will have lower U/3He ratios (compared to a coarse grained equivalent), which, over time, will preserve higher 3He/4He ratios. As predicted by theory of points defect diffusivity, these results show that noble gas diffusion along interfaces is different from those in the grain lattice itself at low temperatures. However, for grain size relevant of the Earth's mantle, the resulting effective correlated activation energies (Ea)(Ea) and pre-exponential factors (Do/a2)(Do/a2) produce similar diffusivities at mantle temperatures for interface- and lattice-hosted helium. Therefore, grain boundaries do not significantly affect helium transport at mantle conditions and length scales.
ISSN: 0012-821X

hal-01236013
https://hal.archives-ouvertes.fr/hal-01236013
DOI : 10.1016/j.epsl.2015.08.024

Éditeur(s) : HAL CCSD
Résumé : International audience
The effect of alkaloids extracted from Isertia coccinea plant (AEIC) on the corrosion of C38 steel in 1 M hydrochloric acid was investigated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. Potentiodynamic polarization curves indicated that the extract behave as mixed-type inhibitor. The experimental data obtained from EIS method show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The inhibition efficiencies of the extract calculated by three methods show the same tendency. Inhibition was found to increase with increasing concentration of the plant extract. The results obtained show that the extract solution of the plant could serve as an effective inhibitor for the corrosion of C38 steel in hydrochloric acid solution. The apparent activation energy of the process taking place in inhibitor presence was determined on the ground of four temperature values in the range from 25 °C to 55 °C using the data obtained by two independent methods. Theoretical fitting of different isotherms, Langmuir, Temkin and Frunkin, were tested to clarify the nature of adsorption.
International journal of electrochemical science

hal-01097030
https://hal-agroparistech.archives-ouvertes.fr/hal-01097030

Éditeur(s) : HAL CCSD Elsevier
Résumé : Nominally anhydrous minerals (NAMs) of Earth's mantle can contain hydrogen as atomic impurity in their crystal structures. This hydrogen substantially modifies many physical properties of Earth's mantle rocks. Also, the Earth's deep interior is made of rocks where minerals are separated by nanometer-scale interfaces call grain boundaries and interphase boundaries. These grain boundaries should carefully be considered as a potential hydrogen reservoir as well. I report here an experimental investigation of hydrogen diffusion through grain boundaries in olivine polycrystalline aggregates. Hot-press and diffusion experiments were performed using a gas-medium high-pressure vessel at a confining pressure of 300 MPa, over a temperature range of 1000-1200 degrees C. The diffusion assembly consisted of a dense polycrystalline cylinder of natural olivine from San Carlos (Arizona) mixed with olivine singles crystals of millimeter size. This mixture was couple with a talc cylinder. Ni capsule were used to buffer the oxygen fugacity at Ni-NiO level. Experiment durations varied from 3 min to 4 h. The presence of hydrogen in the sample was quantified using Fourier transform infrared spectroscopy. The calculation of the diffusion coefficients was based on the estimation of the length of polycrystalline solid affected by the diffusion of hydrogen. The absence or presence of hydrogen was recorded by the large olivines behaving here as "hydrogen sensor", which are implanted in the aggregate. The results indicate that effective hydrogen diffusivity which includes grain boundaries effect in olivine aggregate is barely one order of magnitude faster than hydrogen diffusion in an olivine single crystal with a diffusivity similar to 8.5x 10(-10) m(2) s(-1) 1000 degrees C and only twice faster similar to 2.1 x10(-9) m(2) s(-1) 1200 degrees C. Calculations of the diffusion data in relation to the Arrhenius Law, yield an activation energy of similar to 70 +/- 10 kJ mol(-l) . From these effective diffusivities and combined with published diffusion data for olivine single crystals, hydrogen diffusion in grain boundaries is extracted and yield diffusivities almost three order of magnitude faster (similar to 5 x 10(-6) m(2) s(-1) at 1200 degrees C) than in an olivine single crystal at the equivalent high temperature. On geological scales and for coarse-grain rocks, hydrogen diffusivity in grain boundaries is not fast enough to compete with lattice diffusion. The relative large grain size of mantle rocks will ensure a very limited hydrogen transport by effective diffusion, and a good conservation of water-rich zones in the Earth's mantle.
ISSN: 0012-821X

hal-00512821
https://hal.archives-ouvertes.fr/hal-00512821
DOI : 10.1016/j.epsl.2010.04.019

Éditeur(s) : HAL CCSD Nature Publishing Group
Résumé : International audience
Cancer cells display alterations in many cellular processes. One core hallmark of cancer is the Warburg effect which is a glycolytic reprogramming that allows cells to survive and proliferate. Although the contributions of environmental contaminants to cancer development are widely accepted, the underlying mechanisms have to be clarified. Benzo[a]pyrene (B[a]P), the prototype of polycyclic aromatic hydrocarbons, exhibits genotoxic and carcinogenic effects, and it is a human carcinogen according to the International Agency for Research on Cancer. In addition to triggering apoptotic signals, B[a]P may induce survival signals, both of which are likely to be involved in cancer promotion. We previously suggested that B[a]P-induced mitochondrial dysfunctions, especially membrane hyperpolarization, might trigger cell survival signaling in rat hepatic epithelial F258 cells. Here, we further characterized these dysfunctions by focusing on energy metabolism. We found that B[a]P promoted a metabolic reprogramming. Cell respiration decreased and lactate production increased. These changes were associated with alterations in the tricarboxylic acid cycle which likely involve a dysfunction of the mitochondrial complex II. The glycolytic shift relied on activation of the Na+/H+ exchanger 1 (NHE1) and appeared to be a key feature in B[a]P-induced cell survival related to changes in cell phenotype (epithelial-to-mesenchymal transition and cell migration).
ISSN: 2045-2322

Droits : http://creativecommons.org/licenses/by/
hal-01359569
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01359569
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01359569/document
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01359569/file/The%20environmental%20carcinogen-CCBY%20%281%29.pdf
DOI : 10.1038/srep30776