Éditeur(s) : Université des Antilles AREBio Groupe de recherche BIOSPHERES : BIOlogie, Sciences Physiques & Humaines pour les énergies Renouvelables, l
Extrait de : 1er colloque international BIOSPHERES, du 18 au 20 juin 2019. Université des Antilles
Description : The Chemical Purification, analysis and Screening core laboratories (CPAS) are located at the University of South Florida campus in Tampa. This core offers instrumentation and expertise in fractionation, purification, and various chemical analyses to support synthetic and natural products drug discovery research groups. Our main equipment are dedicated to chromatographic separation and purification (MPLC, HPLC) and mass-spectrometry for analytic detection, quantification and identification (LC-MS SQ, QqQ and QToF). The CPAS services also include Circular Dichroism spectrometry, general spectroscopic characterization (UV, FTIR), lyophilization (bench top and high capacity freeze-dryers), synthesis (microwave reactor), ADME screening (permeability and drug solubility testing), and high-throughput screening development capability (automated liquid handler and multimode plate reader). An example of three significant studies will be presented at the conference to illustrate the CPAS core facility services: 1) Identification of new bioactive compounds from mangrove endophytic fungi as potential alternatives to malaria drug resistance, 2) Myricanol isolated from Bayberry (Myrica Cerifera) and its synthetic derivatives targeting the microtubuleassociated protein tau accumulation in the Alzheimer's disease and 3) New ent-labdane diterpenes with solid tumor cell lines antiproliferative properties from the endemic plant Eupatorium obtusissmum from the island of Hispaniola. The core provides research lab training workshops in advanced technology and assistance so users can operate any instruments available in the laboratories to successfully accomplish their analyses and research projects.

Droits : CC-BY-NC-ND - Attribution - Pas d'utilisation commerciale - Pas de modification
Permalien : http://www.manioc.org/fichiers/V19063
V19063

Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : International audience
Separated olivine grains from a deeply subducted serpentinized wehrlite (Changawuzi in the western Tianshan ultrahigh-pressure belt, China) were analysed with unpolarized transmission FTIR and the Ti contents were determined using LA-ICP-MS. The major bands in the olivine spectra display striking similarities to Ti-clinohumite and are interpreted as OH in lamellae. The quantification of the water content in lamellae requires calibration of the IR-absorption for such bands. We have obtained a new absorption coefficient for Ti-clinohumite of 0.125+/−0.017 ppm cm2 based on polarized FTIR measurements on three orthogonal sections through a large single crystal of Ti-clinohumite from Val Malenco, which has a known water content of 1.53 wt%. The resulting water content in olivine using this calibration factor ranges from 440 to 2,600 ppm and correlates positively with the Ti content that ranges from 130 to 1,400 ppm. For the quantification of the water content in Ti-chondrodite and Ti-clinohumite that are associated with olivine, we developed a new method using attenuated total reflectance FTIR spectroscopy. Ti-chondrodite and Ti-clinohumite display similar IR bands at ~3,562, 3,525 and ~3,583–3,586 cm−1. As in olivine, the water content and Ti content correlate in both Ti-clinohumite and Ti-chondrodite, indicating an intergrowth of these minerals, which has been confirmed by TEM analyses. Our results confirm previous suggestions that there is a strong correlation between the Ti content of ultramafic rocks and their capacity to transport water to the deeper mantle in subduction zones beyond conditions where hydrous phases are stable.
ISSN: 0010-7999

hal-01172237
https://hal.archives-ouvertes.fr/hal-01172237
DOI : 10.1007/s00410-014-0992-8

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This paper presents the first remote measurements of La Soufrière gas emissions since the fumarolic and seismic reactivation in 1992. The chemical composition of the plumes has been measured from May 2003 to September 2004 using an Open Path Fourier Transform InfraRed (OP-FTIR) spectrometer, up to 15 m downwind the South Crater. HCl is clearly detected (concentration between 2.4 and 12 ppmv) whereas SO2 and H2S generally remain below the detection limit of the OP-FTIR. Direct measurements of SO2 and H2S near the South Crater with a Lancom III analyzer show a fast decrease of their concentrations with the distance. Calculated Cl / S mass ratios are high: from 9.4 ± 1.7 at 15 m from the vent to 2.8 ± 0.6 at 140 m. The enrichment in HCl of the gas emitted at La Soufrière, observed since 1998, corresponds to the degassing of a magma enriched in Cl and depleted in S. This result agrees with isotopic measurements which suggest a magmatic origin of the gases. Readjustments inside the volcanic system may have taken place during the seismic activity beginning in 1992 and enhance the transfer of magmatic gases to the summit.
ISSN: 0377-0273

hal-00144949
https://hal.archives-ouvertes.fr/hal-00144949
DOI : 10.1016/j.jvolgeores.2005.08.001

Éditeur(s) : HAL CCSD
Résumé : International audience
The aim of this study was to optimize the extraction and characterization of lycopene, a carotenoid, from a tropical fruit, Psidium guajava L. and to demonstrate its health benefits. Deionised water, mixed with organic solvents, was used for extraction, and the depletion stage was reached in order to define the number of extractions needed to extract most of the lycopene. Optimum extraction was achieved with petroleum ether combined with guava puree:deionised water ratio of 40% using 15 ml of water. Four extractions were a satisfactory compromise to maximize the amount of lycopene recovered and to minimize the use of organic solvent. Excellent purification of lycopene was obtained by HPLC-VIS detection (470 nm) with acetonitrile/methanol/tetrahydrofuran mobile phase. Characterization was confirmed by FTIR analysis. A modification of the DPPH test made it possible to assess the EC50, thereby ranking lycopene among good antioxidants. As Psidium guajava is already widely used in the food industry, these results support claims for health benefits for products derived from guava.
ISSN: 23192399

hal-01672063
https://hal.univ-antilles.fr/hal-01672063
DOI : 10.9790/2402-1104016773

Éditeur(s) : HAL CCSD Elsevier
Résumé : Siberian cratonic mantle
International audience
The processes that control water distribution in nominally anhydrous minerals from peridotites are twofold. Melt depletion will remove water while metasomatism can potentially add water to these minerals. These processes can lead to a wide range of outcomes in water contents, which in turn could play a role in mantle rheology and long-term cratonic root stability. To examine these complexities, water concentrations in minerals from well-characterized peridotites from the Udachnaya kimberlite in the central Siberian craton were analyzed by FTIR. The peridotites span a complete top to bottom cross-section of typical cratonic lithospheric mantle (2-7 GPa and 700-1400 °C). Diffusion modeling of water content profiles across olivine grains shows that water loss during decompression is limited to the 100 μm rims of olivines; the cores preserved their mantle water contents. Water contents range from 6 to 323 ppm wt H2O in olivine, 28-301 ppm H2O in orthopyroxene (opx), 100-272 ppm H2O in clinopyroxene (cpx) and 0-23 ppm H2O in garnet. Melting modeling cannot reproduce the high water contents of cratonic mantle peridotites and any potential partial melting trend must have been erased by later events. The water contents of minerals, however, are correlated with modal abundances of clinopyroxene and garnet, bulk rock FeO, TiO2 and SiO2 as well as with light and middle rare earth elements in clinopyroxene and garnet. These relationships are best interpreted as interaction of residual, melt-depleted peridotites with silicate melt, which produced modal and cryptic metasomatism. Importantly, the water enrichment in the Siberian cratonic mantle took place prior to kimberlite magmatism and eruption. Water addition by metasomatism occurred from pressures >4 GPa all the way to the base of the cratonic root below central Siberia, but was limited to shallower levels (<5 GPa) in the Kaapvaal cratonic lithosphere. The difference in olivine water contents at the deepest levels of the Kaapvaal (<5 ppm H2O) and Siberian (6-323 ppm H2O) cratonic roots may be linked to oxygen fugacity and resulting fluid speciation or, alternatively, to reaction with different metasomatic agents. Calculated viscosities for the deepest Udachnaya samples are similar to those inferred for the asthenosphere. If these xenoliths are representative of the deep cratonic lithosphere, water is not as important a parameter as previously thought in the strength of cratonic lithosphere, otherwise the cratonic root beneath Udachnaya would have been delaminated. Alternatively, the metasomatic xenoliths may not be representative of the Siberian cratonic root and kimberlites preferentially sample cratonic mantle lithosphere material located near, and metasomatized by, melt conduits, which served as channels for upward migration of water-rich melts and fluids including kimberlites. In that case, the cratonic root overall still may have relatively low water contents, which in addition to its less metasomatized (more refractory) and thereby buoyant nature, still play a role in making it strong enough to resist delamination by the surrounding asthenosphere.
ISSN: 0016-7037

hal-01053920
https://hal.archives-ouvertes.fr/hal-01053920
DOI : 10.1016/j.gca.2014.04.011

Résumé : En 2003 des mesures au spectromètre IR à Transformée de Fourier (FTIR) ont permis d'identifier et de mesurer les COV émis par la décharge à ciel ouvert de la Gabarre, principale de l'île Guadeloupe, située entre une zone urbaine et une mangrove. Ces COV ont été retrouvés (2004) la nuit dans les cités, justifiant les plaintes des riverains. Dans le cadre de cette thèse, des mesures au spectromètre de masse portatif MS 200 ont validé ces résultats du FTIR. De nouvelles mesures au MS 200 ont été menées dans toute la zone de la décharge. Les cités concernées étant à l'opposé du flux synoptique d'Alizés-Est, les facteurs météorologiques permettant la dispersion et le transport des COV de la décharge vers la zone urbaine ont été recherchés. La diminution nocturne de l'intensité des Alizés au dessus de l'ile peut laisser place à des phénomènes locaux tels les brises. L'idée d'une brise terre-mer a été éliminée. Un maillage autou~ de la décharge (cités et mangrove) avec 8 thermomètres a révélé un îlot de chaleur urbain nocturnegénérant une brise thermique d'environ Ims- I (mesurée et calculée). Avec les radiosondages Météo France et un SODAR installé dans la décharge, une très forte stabilité dans les basses couches atmosphériques de la couche limite nocturne avec une inversion de surface d'environ 120mvv apparait. Ces facteurs expliquent la pollution des cités par les COV de la décharge, Un modèlevGaussien en tenant compte a été validé par les mesures de COV.vCette étude peut être étendue à d'autres décharges à ciel ouvert et à d'autres types de traitement de polluants de décharge.
In 2003, the VOC emissions coming from "La Gabarre", the main open landfill in Guadeloupe, located in-between an urban area and a mangrove, were identified and quantified with a portable FTIR spectrometer. In 2004, COVs found at nighttime in the urban area nearby confirmed why residents complain about. As part of this thesis, portable mass spectrometer MS 200 measurements validated these FTIR figures. New systematic SM measurements have been carried on around the landfill. Since the polluted urban area stands on the opposite way of the East Trade winds synoptic flux, aIl the weather factors likely to scatter and transport the dump COVs were scrutinized. At night, the strength of the Trade winds decreases over Guadeloupe, which may give way to local phenomena such as breezes. The occurrence of land/sea breeze was eliminated. A close surveying surrounding the landfill with 8 thermometers both in the projects and in the mangrove revealed an urban heat island causing thermal breezes of about lms-l (measured and calculated). Using soundings from Meteo France, and a SODAR inside the dump, we found a great stability of the night boundary layer with a surface inversion near 120m. Pollution of the nearby urban area with landfill COVs is elucidatcd by the above factors. A transport Gaussian model is in agreement with COV measurements. This study can be extended to different open landfills and different types of polluting matters processes in dumps

http://www.theses.fr/2013AGUY0700/document

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
Low-level water measurements of geological materials are fundamental in understanding the volatile inventories of the Earth from the mantle to crustal reservoirs. Here we describe the development of microanalytical techniques using the new SHRIMP SI ion microprobe to measure the abundances of OH− (as a proxy for water) in volcanic glass and nominally anhydrous minerals (NAMs). Samples were first analysed at the Carnegie Institute of Washington (CIW) on their Cameca ims-6f with calibrations based on previous FTIR and manometry analyses. SHRIMP SI is a large geometry ion microprobe and is currently mainly used for O and S isotope analyses. The analytical protocol used here incorporates multiple collection of 16O− and 16O1H− allowing rapid measurements. A single calibration line incorporating all glasses and NAMs for the SHRIMP SI allows calibration of 16O1H−/16O− to H2O over a wide range in concentration (50 to 15 000 ppm H2O). This calibration line has around a 10% uncertainty, which appears to be limited only by sample heterogeneity. The current background for SHRIMP analysis is between 20–40 ppm but this is expected to improve with improved pumping on the source chamber. A current limitation to water analysis of NAM samples, by any technique, is having a range of standard materials to enable OH− calibration to absolute H2O concentrations. Data are presented for 7 NAM samples (2 olivines, 2 orthopyroxenes and 3 clinopyroxenes) that appear to be promising as potential standards for international laboratory H2O measurements. These NAM samples have been analysed and characterised here by SHRIMP SI, FTIR, EMP and the Cameca ims-6f ion microprobe at CIW. Four of these samples have previously been measured by manometry to determine absolute H2O concentrations.
ISSN: 0267-9477

hal-01243514
https://hal.archives-ouvertes.fr/hal-01243514
DOI : 10.1039/c5ja00047e

Éditeur(s) : HAL CCSD Elsevier
Résumé : The uppermost mantle in back arc regions is the site of complex interactions between partial melting, melt percolation, and fluid migration. To constrain these interactions and evaluate their consequences on geochemical cycles, we carried out an in situ trace element and water study of a suite of spinel peridotite xenoliths from two regions of the Japan back arc system, Ichinomegata (NE Japan) and Oki-Dogo (SW Japan), using LA-ICPMS and FTIR spectrometry, respectively. This study provides the first full dataset of trace element and hydrogen compositions in peridotites including analyses of all their main constitutive silicate minerals: olivine, orthopyroxene and clinopyroxene. The Ichinomegata peridotites sample a LREE-depleted refractory mantle (Mg# olivine = 0.90; Cr# spinel = 0.07–0.23; Yb clinopyroxene = 7.8–13.3 × C1-chondrite, and La/Yb clinopyroxene = 0.003–0.086 × C1-chondrite), characterized by Th-U positive anomalies and constant values of Nb/Ta. The composition of the studied Ichinomegata samples is consistent with that of an oceanic mantle lithosphere affected by cryptic metasomatic interactions with hydrous/aqueous fluids (crypto-hydrous metasomatism). In contrast, the Oki-Dogo peridotites have low Mg# olivine (0.86–0.93) and a broad range of compositions with clinopyroxene showing “spoon-shaped” to flat, and LREE-enriched patterns. They are also characterized by their homogeneous compositions in the most incompatible LILE (e.g., Rb clinopyroxene = 0.01–0.05 × primitive mantle) and HFSE (e.g., Nb clinopyroxene = 0.01–2.16 × primitive mantle). This characteristic is interpreted as resulting from various degrees of melting and extensive melt-rock interactions. FTIR spectroscopy shows that olivine in both Ichinomegata and Oki-Dogo samples has low water contents ranging from 2 to 7 ppm wt. H2O. In contrast, the water contents of pyroxenes from Ichinomegata peridotites (113–271 ppm wt. H2O for orthopyroxene, and 292–347 ppm wt. H2O for clinopyroxene) are significantly higher than in Oki-Dogo peridotites (9–35 ppm wt. H2O for orthopyroxene, and 15–98 ppm wt. H2O for clinopyroxene). This indicates a relationship between melt-rock interaction and water concentrations in pyroxenes. Our study suggests that the water content of the Japan mantle wedge is controlled by the late melt/fluid/rock interactions evidenced by trace element geochemistry: a mechanism triggered by magma-rock interactions may have acted as an efficient dehydrating process in the Oki-Dogo region while the Ichinomegata mantle water content is controlled by slab-derived crypto-hydrous metasomatism.
ISSN: 0016-7037

hal-01553105
https://hal.archives-ouvertes.fr/hal-01553105
DOI : 10.1016/j.gca.2017.03.042

Éditeur(s) : HAL CCSD Elsevier
Résumé : We have studied the phase transformation of forsterite to wadsleyite under shear stress at the Earth's transition zone pressure and temperature conditions. Two-step experiments were performed using a multi-anvil press. First, we hot pressed iron-free forsterite at 6 or 11 GPa and 1100 degrees C. Then we deformed a slab of this starting material using a direct simple shear assembly at 16 GPa and 1400 degrees C for 1, 15, 35, 40, or 60 min. Both the starting material and the deformed samples were characterized using optical and scanning electron microscopy including measurements of crystal preferred orientations (CPO) by electron back scattered diffraction (EBSD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). The phase transformation occurs very rapidly, in less than 1 min, and metastable forsterite relics are not observed after deformation. The grain size of wadsleyite is slightly smaller than the forsterite starting material. The water contents obtained from FTIR analyses in forsterite and wadsleyite are 65-124 wt ppm H2O and 114-736 wt ppm H2O, respectively, which are well below water solubility at similar conditions in the presence of free water. Wadsleyite aggregates display weak CPO patterns with [1 0 0] axes concentrated at low angle to the shear direction, [0 1 0] axes perpendicular to the shear plane and nearly random [0 0 1] axes. Only a few dislocations were observed in wadsleyite with TEM. This observation is consistent with the assumption that most dislocations formed during the initial high-stress stages of these stress-relaxation experiments, were consumed in the phase transformation, probably enhancing the transformation rate. CPO patterns vary as a function of the water content: with increasing water content the density of [1 0 0] axes parallel to the shear direction decreases, and the density of [0 0 1] axes increases. Viscoplastic self-consistent modeling of CPO evolution using previously reported glide systems for wadsleyite, i.e., [1 0 0]{0 k 1} and 1/2 (1 1 1){1 0 1}, cannot reproduce the measured CPO, unless the [0 0 1](0 1 0) system, for which dislocations have not been observed by TEM, is also activated. In addition, wadsleyite grain growth suggests the participation of diffusion-assisted processes in deformation. Calculated anisotropies for P and S-waves using measured CPO are always below 1%. This very low anisotropy is due to both the low finite strain achieved in the experiments, which leads to weak wadsleyite CPO, and to the diluting effect of added majorite. The present experiments emphasize the importance of stress, grain size evolution and water content in the forsterite to wadsleyite phase transformation and subsequent deformation in the transition zone.
ISSN: 0031-9201

hal-00617430
https://hal.archives-ouvertes.fr/hal-00617430
DOI : 10.1016/j.pepi.2010.11.001

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
Abstract View references (38)This work presents a facile, scalable method for the fabrication of graphene oxide-iron oxide (GO-Fe3O4) nanocomposites produced by co-precipitation of iron ions onto the GO surfaces in basic aqueous media. FTIR and XRD characterisation suggests that Fe3O4 was chemically anchored to the GO sheets, possibly via the carboxyl and hydroxyl groups. Small GO loadings of 0.5 and 1 wt% were not sufficient to alter the Fe3O4 structures. However, increasing the GO loading to 5 and 10 wt% resulted in significant loss in pore volume, thus suggesting the lamellar GO sheets decorated with Fe3O4 were assembling into GO-Fe3O4 nanocomposite stacks. It was found that the GO-Fe3O4 nanocomposites had an enhanced catalytic activity in the heterogeneous Fenton-like oxidation of Acid Orange 7 (AO7) compared to pure GO flat sheets and Fe3O4 nanoparticles. Interestingly, the GO-Fe3O4 nanocomposite with 5 wt% loading ratio exhibited the best catalytic activity with 76% degradation of AO7 dye observed within 90 min of reaction. This was attributed to the synergistic effect of GO by enriching the adsorbed AO7 molecules onto the nanocomposite to be further oxidised in the vicinities of active sites. This finding suggests the promising employment of GO-Fe3O4 nanocomposites in removing organic dyes from polluted water by heterogeneous Fenton-like reaction. © 2014 by American Scientific Publishers.
SCIENCE OF ADVANCED MATERIALS

hal-01683207
https://hal.univ-antilles.fr/hal-01683207
DOI : 10.1166/sam.2014.1812

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This work shows the preparation and separation performance assessment of carbon membranes derived from phenolic resin by a vacuum-assisted method and carbonisation in an inert atmosphere. The vacuum time played an important role in tailoring the structure of the membranes. For instance, pore volumes and surface areas increased from 0.81 and 834 to 2.2 cm3g−1and 1910 m2g−1, respectively, as the vacuum time exposure increased from 0 to 1200 s. The significant structural changes correlated very well with water permeation, as fluxes increased by 91% as the vacuum time increased from 0 to 1200 s reaching up to 169 L m−2h−1at 5 bar. Molecular weight cut-off tests showed no rejection for the smaller glucose and sucrose molecules, though this increased to ~ 80% and full rejection for 36 kDa and 400 kDa polyvinyl pyrrolidine. Interestingly, FTIR spectra showed that the peaks of C–H stretching vibration (2800–3200 cm−1) and C–O stretching (1030 cm−1) became more pronounced as a function of increasing vacuum time, strongly suggesting that the use of vacuum further assisted in the polycondensation of phenolic oligomers. Based on these outcomes, a cluster to cluster model is proposed, whereby vacuum application promoted crosslinking reactions of the phenolic resin, creating microporous regions within the clusters, and mesoporous regions between the clusters. © 2016 Elsevier B.V
ISSN: 0376-7388

hal-01683220
https://hal.univ-antilles.fr/hal-01683220
DOI : 10.1016/j.memsci.2016.11.002

Éditeur(s) : HAL CCSD ACS American Chemical Society - Publications
Résumé : International audience
ABSTRACT: In this paper, the structural, optical and thermal properties of n-type (100),p-type (100) and (111) mesoporous silicon (MePSi) are reported. The mesoporous silicon wasprepared by an electrochemical process from bulk silicon wafer. Depending on the etchingdepth, analyses show that the porosity of p-type (111) increased by 32 to 40% compared to p(100) which, in turn, increased by 22 to 48% compared to n-type (100). The structuremorphology and the abundance of Si-Ox and Si-Hy also depended heavily on the type andcrystal orientation of MePSi. The thermal properties of the MePSi layers such as thermalconductivity (κ), volumetric heat capacity (ρCp) and thermal contact resistance (Rth) weredetermined using the pulsed photothermal method. The thermal conductivity of bulk silicondropped sharply after etching, decreasing by more than twenty-fold in the case of n-type (100)and by over forty-five fold for p-type (100) and (111). According to the percolation modeldepending on both porosity and phonon confinement, the drop in thermal conductivity wasmainly due to the nanostructure formation after etching. Thermal investigations showed thatthe volumetric heat capacity (ρCp) followed the barycentric model which depends mainly onthe porosity. The thermal contact resistances of MePSi layers were estimated to be in therange of 1x10-8 to 1x10-7 K⋅m2⋅W-1.
The Journal of Physical Chemistry C

hal-01495490
https://hal.archives-ouvertes.fr/hal-01495490
DOI : 10.1021/acs.jpcc.6b13101

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
The effect of trace concentrations of Ti on the rate and mechanism of hydrogen diffusion in pure forsterite was investigated experimentally. Forsterite doped with 350–400 ppm Ti (predominantly octahedral Ti3+, minor tetrahedral Ti4+) was prepared by diffusing Ti into pure synthetic forsterite at high temperature (1500 °C), very low oxygen fugacity (~QFM-5) at atmospheric pressure. The Ti-doped forsterite was then diffusively hydroxylated in a piston-cylinder apparatus at much lower temperatures (650–1000 °C) and higher oxygen fugacities, at 1.5–2.5 GPa, with chemical activities buffered by forsterite-enstatite or forsterite-periclase and partial pressure of H2O equal to total pressure. This produced hydrogen concentration-distance profiles of several hundred micrometers in length. Diffusion of hydrogen through the Ti-doped forsterite, even at very high Embedded Image , does not lead to redox re-equilibration of the high Ti3+/ΣTi ratio set during the synthesis of the starting material at extremely reducing conditions—the metastable point defects are partially preserved.Three main hydroxylated point defects are observed; hydroxyl is associated with Ti4+ (titano-clinohumite point defects), Ti3+ (and possibly other trivalent cations), and M-site vacancies. Concentration-distance profiles represent an interplay between diffusion and reaction (i.e., site rearrangement) to form the observed point defects. In all experiments, the concentration-distance profiles of the hydroxylated Ti defects coincide with the concentration-distance profiles of the M-site vacancy substitution, with the same crystallographic anisotropy. This suggests that the macroscopic movement of hydrogen through the crystal is due to one diffusion mechanism (the diffusion of hydroxylated M-site vacancies). The net H diffusion coefficient [logD(ΣH)], between 650–1000 °C, is Embedded Image where the values of logD0(ΣH) parallel to [100] and [001] directions are −3.0 ± 0.4 and −2.2 ± 0.4, respectively; diffusion is therefore around one order of magnitude faster along the c axis than along the a axis. The diffusion of hydrogen is slightly faster in Ti-doped forsterite than in pure forsterite. There is no effect of chemical activity or oxygen fugacity on the rate of diffusion. Hydrogen diffusion profiles represent a complex interplay between the movement of H through the crystal lattice and point-defect reactions to maintain charge balance.
ISSN: 0003-004X

hal-01467402
https://hal.archives-ouvertes.fr/hal-01467402
DOI : 10.2138/am-2016-55681571

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Four fibers from banana-trees (leaf, trunk) and coconut-tree (husk, fabric) were examined before their incorporation in cementitious matrices, in order to prepare insulating material for construction. Their botanical compositions have been determined following a method described previously. Thermal degradation of these fibers were studied between 200 and 700 °C under nitrogen gas flow. Temperature of pyrolysis was the experimental parameter investigated. The solid residues obtained were analyzed by classical elemental analysis, Fourier Transform Infra Red (FTIR) spectroscopy and were observed by Scanning Electron Microscopy (SEM). This study has shown (1) the relation between botanical, chemical composition with both localization of fibers in the tree and type of tree; (2) the rapid and preferential decomposition of banana fibers with increasing temperature of pyrolysis and (3) the rough samples are made of hollow fibers.
ISSN: 0960-8524

hal-00809780
https://hal.univ-antilles.fr/hal-00809780
DOI : 10.1016/j.biortech.2005.11.030

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Hydrogen distribution between nominally anhydrous minerals (NAMs) of a garnet-lherzolite under subsolidus conditions has been investigated. Separated NAMs from a garnet-peridotite from Patagonia (Chile) are annealed together (olivine, orthopyroxene, clinopyroxene, and garnet) using a piston-cylinder at 3 GPa and 1100 °C using talc-pyrex cell assembly for 10, 25, and 100 h. The talc-pyrex assembly provides enough hydrogen in the system to re-equilibrate the hydrogen concentrations at high pressure. The three coexisting nominally anhydrous minerals (NAMs, i.e., olivine, orthopyroxene, and clinopyroxene) were successfully analyzed using FTIR. The resulting hydrogen concentrations exceed significantly the initial hydrogen concentration by a factor of 13 for olivine and a factor of 3 for both pyroxenes. Once mineral-specific infrared calibrations are applied, the average concentrations in NAMs are 115 ± 12 ppm wt H2O for olivine, 635 ± 75 ppm wt H2O for orthopyroxene, and 1214 ± 137 ppm wt H2O for clinopyroxene, garnet grains are dry. Since local equilibrium seems achieved over time (for 100 h), the calculated concentration ratios are interpreted as mineral-to-mineral hydrogen partition coefficients (i.e., Nernst’s law) for a garnet-peridotite assemblage. It yields, based on mineral-specific infrared calibrations, DOpx/Ol = 5 ± 1, DCpx/Ol = 10 ± 2, and DCpx/Opx = 1.9 ± 0.4. While DCpx/Opx is in agreement (within error) with previous results from experimental studies and concentration ratios observed in mantle-derived peridotites, the DPx/Ol from this study are significantly lower than the values reported from mantle-derived xenoliths and also at odd with several previous experimental studies where melt and/or hydrous minerals co-exists with NAMs. The results confirm the sensitivity of hydrogen incorporation in olivine regarding the amount of water-derived species (H) in the system and/or the amount of water in the coexisting silicate melt. The results are in agreement with an important but incomplete dehydration of mantle-derived olivine occurring at depth, during transport by the host magma or during slow lava flow cooling at the surface. The rapid concentration modification in mantle pyroxenes also points out that pyroxenes might not be a hydrogen recorder as reliable as previously thought.
ISSN: 0003-004X

hal-01622132
https://hal.archives-ouvertes.fr/hal-01622132
DOI : 10.2138/am-2017-6089

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We report concentrations of hydrogen (H) in upper mantle minerals of peridotites (olivine and pyroxenes) transported by alnöitic lavas, which erupted on the southwestern border of the Ontong Java Plateau (Malaita, Solomon Islands, West Pacific). Unpolarized FTIR analyses show that olivine, orthopyroxene, and diopside contain 2–32 ppm, 162–362 ppm and 159–459 ppm wt H2O, respectively. In the studied lherzolites, garnets are anhydrous. The concentration of hydrogen within individual olivine and pyroxene grains is almost homogeneous, indicating no evidence of dehydration or hydration by ionic diffusion. In the lherzolite, the concentration of hydrogen in olivine tends to increase weakly with depth (based on geothermobarometry), consistent with the increase of water solubility with increasing water fugacity as a function of pressure, but concentrations remain well below water-saturation values determined experimentally. The highest concentration of H in olivine (32 ppm wt H2O) is, however, found in refractory spinel harzburgites, which equilibrated at depths of 85 km., while deeper specimens as the high-temperature spinel harzburgites, and some of the garnet lherzolites, contain less hydrogen in olivine. Olivines from pyroxene- or pargasite-rich peridotites have also lower hydrogen concentrations. We interpret the high hydrogen concentrations in olivine from the refractory spinel harzburgites as due to (1) simultaneous hydration and metasomatism of the lithospheric mantle by a water-rich silicate melt/fluid, during which hydrogen follows MREE and where spinel harzburgite have experienced ‘stealth’ metasomatism, and/or (2) to a late ‘fleeting’ hydrogen metasomatism, which would hydrate the rock after this first ‘stealth’ metasomatism event. In the second case, the composition of the ‘fleeting’ percolating fluid (small volume fraction of very evolved fluids, with high volatiles concentration and transient properties) is likely to be linked to the decrease of the plume activity and resulting in the downwelling of the lithosphere asthenosphere boundary. The difference in hydrogen concentration between harzburgites and lherzolites could be linked to variation in trace elements in olivine induced by the first ‘stealth’ metasomatism alone or associated to the late ‘fleeting’ hydrogen metasomatism, triggered by the lack of secondary crystallization of clinopyroxenes in the harzburgite. To conclude, H concentrations in upper mantle minerals may thus be correlated to metasomatic events, with the later yielding variation of the mineral assemblage and trace element composition that constitute the peridotites.
ISSN: 0024-4937

hal-01143385
https://hal.archives-ouvertes.fr/hal-01143385
DOI : 10.1016/j.lithos.2014.11.005

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The minerals constituting the Earth's upper mantle are nominally anhydrous silicates (NAMs). However they do contain hydrogen as a trace element, decorating point defects in their crystalline structure. Experimental petrology and mineralogy have quantified the maximum concentration under several compositional and thermodynamic conditions, but systematic studies on the hydrogen concentration in minerals from mantle-derived rocks have only recently been carried out. Here, we have compiled the distribution of hydrogen in upper mantle peridotite xenoliths, from which several conclusions can be drawn. NAMs from peridotite xenoliths contain a few ppm wt. H2O in their structure. From the current database, the hydrogen concentrations in olivine regularly increase with increasing depth. The amount of hydrogen in NAMs from peridotite xenoliths from subduction contexts is not higher than in other geological context for similar temperature and pressure conditions. The highest hydrogen concentrations is found in peridotitic olivines from cratonic mantle, and are likely due to the depth of origin. The increasing hydrogen concentration in olivine with increasing depth is likely controlled by the increase of H partitioning into olivine at the expense of orthopyroxene as imposed by a decrease in Al content in opx with depth. However, the sparse data could also indicate that the bulk hydrogen concentration slightly increases with depth > 150 km. In this case, it would suggest, locally (Udachnaya for example), a possible increase in water fugacity due to fluid saturation. Even if the most abundant mineral in mantle rocks is olivine, the bulk hydrogen concentration in peridotites is controlled by the amount of hydrogen stored in pyroxenes. However, hydrogen concentration in olivine remains crucial for consequences on physical properties such as rheology and electrical conductivity. Kinetics of hydrogen transport is reviewed and hydrous melt/fluid percolation appears necessary to homogenize the hydrogen distribution at km-scale. Sampling of natural rock specimens is currently biased (e.g., in favor of optically attractive samples) and needs improvement, which will be achieved by increasing sample diversity (all type of grain sizes, lithologies, geological settings) and size of rock samples, as well as advances in analytical techniques. Acquisition of high quality data will be achieved by studying the co-existing minerals in mantle specimens, exploring each sample by linear and mapping measurements, and using appropriate FTIR calibrations for polarized and unpolarized radiation.
ISSN: 0024-4937

hal-01306676
https://hal.archives-ouvertes.fr/hal-01306676
DOI : 10.1016/j.lithos.2015.11.012

Éditeur(s) : HAL CCSD Springer/Terra Scientific Publishing Company
Résumé : International audience
Titanian clinohumite is an accessory phase found in peridotites, and it can be a key repository of volatile and other trace elements in sub-arc mantle. To characterize spectroscopic variations due to volatile elements in the phase, we have investigated the infrared spectroscopic characteristics of a suite of naturally occurring Ti clinohumite minerals with varying F and Ti concentrations. Samples were ultramafic rocks from Cerro del Almirez, Spain and Cima di Gagnone, Switzerland. The infrared spectra corresponding to OH vibrations showed systematic variation in regard to the abundance of F in Ti clinohumite. In particular, the intensity ratios of infrared absorption spectra at 3,565 and 3,390 cm-1 correlated linearly with the abundance of F independently of the crystal orientation. Raman spectra did not corroborate the Fourier transform infrared (FTIR) results. This intensity ratio provides an alternative analytical criterion for the characterization of Ti clinohumite.
ISSN: 1343-8832

hal-01133685
https://hal.archives-ouvertes.fr/hal-01133685
DOI : 10.1186/1880-5981-66-60

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We carried out detailed petrographic, major and trace element geochemical, microstructural and FTIR analyses on eight characteristic ultramafic xenoliths from Nyos and Barombi Mbo Lakes in the continental sector of the Cameroon Volcanic Line (CVL). The studied xenoliths are spinel lherzolites showing lithologies similar to the other xenoliths reported previously along the CVL. They have protogranular and porphyroclastic textures. One of the Barombi xenolith contains amphibole, which had not been previously reported in this locality. Amphibole is common in the Nyos xenoliths suite. Peridotite xenoliths from both localities show some chemical heterogeneity, but Barombi xenoliths generally are less depleted in basaltic elements with respect to Nyos xenoliths. Trace element compositions of Nyos spinel lherzolites show a moderately depleted initial (premetasomatic) composition and variable enrichment in REE. Evidence for both modal and cryptic metasomatism is present in Nyos xenoliths. Rare earth element patterns of clinopyroxene suggest that interaction between mafic melts and the upper mantle occurred beneath the Nyos locality. Barombi Mbo xenoliths, on the other hand, record a small degree of partial melting. The Barombi Mbo xenoliths have weak, dominantly orthorhombic olivine crystal preferred orientations, whereas Nyos ones have strong axial-[010] patterns, which may have formed in response to transpression. Nominally anhydrous mantle minerals (NAMs) of the Barombi Mbo xenoliths show generally higher bulk concentrations of ‘water’ (70–127 ppm) than Nyos xenoliths (32–81 ppm). The Barombi Mbo xenoliths could originate from a juvenile segment of the lithospheric mantle, which had been originally part of the asthenosphere. It became a part of the lithosphere in response to thermal relaxation following the extension, forming a weakly deformed lower lithospheric mantle region along the CVL. The Nyos xenoliths, however, represent a shallow lithospheric mantle bearing imprints of several depletion and enrichment events probably prior or following the extension (at ∼30 Ma).
ISSN: 0899-5362

hal-01236039
https://hal.archives-ouvertes.fr/hal-01236039
DOI : 10.1016/j.jafrearsci.2015.07.006