Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study analyses the interactions between deformation and reactive fluid and melt percolation, and their effects on sub-arc mantle seismic properties based on microstructural observations on mantle xenoliths extracted by the Tubaf and Edison seamounts close to the Lihir Island, in the Papua New Guinea archipelago. These xenoliths sample an oceanic lithosphere, which has experienced high-temperature deformation in the presence of fluids or melts. This was followed by metasomatism under static conditions. Syn-kinematic percolation of reactive Si-rich melts or fluids in peridotites has produced pyroxene-enrichment, grain size reduction, and dispersion of olivine crystal preferred orientation (CPO). Fourier transform infrared spectroscopy analyses show that olivine has very low water contents (1-4 wt. ppm H2O), similar to spinel peridotites from other subduction zones. These low values may record both low water solubility in olivine at low pressure and dehydration during transport and exhumation. Water contents in pyroxenes are highly variable and likely result from spatially heterogeneous melt or fluid percolation. Analysis of olivine CPO indicates dominant activation of both (010)[100] and (001)[100] slip systems, which are characteristic of deformation under high temperature, low stress, low pressure and low to moderate hydrous conditions. Fast S-wave polarization and P- and Rayleigh propagation directions are thus parallel to the mantle flow direction. The pyroxene enrichment by melt-rock reactions is accompanied by dispersion of olivine CPO and induces a significant decrease of the maximum S-wave and P-wave anisotropy in the peridotites. The calculated seismic properties also show that the lowest Vp/Vs ratios (< 1.7) mapped in fore-arc mantle may only be explained by taking in consideration the CPO-induced elastic anisotropy of the peridotites.
ISSN: 0040-1951

hal-00950058
https://hal.archives-ouvertes.fr/hal-00950058
DOI : 10.1016/j.tecto.2013.09.024

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 Springer Verlag
Résumé : International audience
Hydrogen can be stored in the structure of nominally anhydrous minerals as point defects, and these impurities substantially modify many physical properties of Earth's mantle minerals. However, mantle rocks are composed of mineral grains separated by grain boundaries and interphase grains boundaries. Therefore, as a potential hydrogen reservoir, grain boundaries should be given proper attention. Here, I report an experimental investigation into hydrogen diffusion through grain boundaries in polycrystalline aggregates Sintering and diffusion experiments were performed using a gas-medium high-pressure vessel at under pressure of 300 MPa and over a temperature range of 900-1,250 degrees C. The diffusion assembly consisted of a polycrystalline cylinder of aluminous spinel + olivine crystals with a talc cylinder as the main hydrogen source. A Ni capsule was used to buffer the oxygen fugacity at Ni-NiO Experimental durations varied from 5 min to 5 h. The presence of hydrogen in the crystals was measured by Fourier-transform infrared spectroscopy. The calculation of the diffusion coefficients was based on the estimation of the characteristic distance. The absence or presence of hydrogen recorded by the 'hydrogen sensor' olivines embedded in the aggregate allows the estimation of bounds on this characteristic distance. Results presented here suggest that hydrogen effective diffusion coefficients are only one order of magnitude faster (similar to 10(-9) m(2)s(-1) at 1,000 degrees C) than in an olivine single crystal along the [100] axis. Resulting diffusion coefficients for hydrogen in grain boundary are four orders of magnitude faster than in a single crystal, but this diffusivity is not fast enough to affect hydrogen mobility in mantle rocks with grain sizes greater than similar to 1 mm. Thus, very limited chemical homogenization would occur using grain boundaries diffusion in mantle hydrous peridotite for incompatible and volatile element, such as hydrogen.
ISSN: 0010-7999

hal-00564353
https://hal.archives-ouvertes.fr/hal-00564353
DOI : 10.1007/s00410-010-0512-4

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 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 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) : Wiley-blackwell
Résumé : Aims Exopolysaccharides (EPS) are industrially valuable molecules with numerous useful properties. This study describes the techniques used for the identification of a novel Vibrio bacterium and preliminary characterization of its EPS. Methods and Results Bioprospection in marine intertidal areas of New Caledonia followed by screening for EPS producing brought to selection of the isolate NC470. Phylogenetic analysis (biochemical tests, gene sequencing and DNADNA relatedness) permitted to identify NC470 as a new member of the Vibrio genus. The EPS was produced in batch fermentation, purified using the ultrafiltration process and analysed by colorimetry, Fourier Transform Infrared spectroscopy, gas chromatography, Nuclear Magnetic Resonance and HPLC-size exclusion chromatography. This EPS exhibits a high N-acetyl-hexosamines and uronic acid content with a low amount of neutral sugar. The molecular mass was 672x103Da. These data are relevant for possible technological exploitation. Conclusions We propose the name Vibrio neocaledonicus sp. nov for this isolate NC470, producing an EPS with an unusual sugar composition. Comparison with other known polymers permitted to select applications for this polymer. Significance and Impact of the Study This study contributes to evaluate the marine biodiversity of New Caledonia. It also highlights the biotechnological potential of New Caledonia marine bacteria.
Journal Of Applied Microbiology (1364-5072) (Wiley-blackwell), 2013-06 , Vol. 114 , N. 6 , P. 1702-1712

Droits : 2013 The Society for Applied Microbiology
http://archimer.ifremer.fr/doc/00144/25501/24036.pdf
DOI:10.1111/jam.12184
http://archimer.ifremer.fr/doc/00144/25501/

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Wadsleyites with various iron contents were synthesized at ~12-14 GPa and 1400 °C under oxidizing and hydrous conditions in coexistence with enstatite. The samples were studied using micro-X-ray absorption near edge structure (XANES) and micro-Mössbauer spectroscopy to determine the ferric iron contents in polyphasic samples and secondary ion mass spectrometry (SIMS) to determine the water concentrations. XANES and Mössbauer analyses show that ferric iron content increases with increasing total iron content, and reaches a maximum of ~30% Fe3+/Fetotal. Two XANES results were cross-checked by Mössbauer analysis and both methods are in reasonable agreement. The use of Fourier transform infrared spectroscopy reveals a new protonation scheme in wadsleyite, with a significant proportion of protons associated with the high-frequency band at 3611 cm−1 and a new band located at 3500 cm−1. The intensity of these two bands is higher for Fe3+-rich wadsleyite. SIMS analyses show that water contents in wadsleyite vary from 4500 to 9400 ppm H2O by weight. Pyroxene water contents range from 790 to 1600 ppm wt H2O. The concentration of water in both phases decreases with increasing iron content. The partition coefficient of water between wadsleyite and pyroxene varies between 5 and 9 and increases with increasing Fe-number of wadsleyite [i.e., XFe/(XFe + XMg) × 100 ratio]. The divalent cation concentrations (i.e., Mg2+ + Fe2+), the Si as well as the H content in wadsleyite decrease with increasing Fe3+ content, indicating an incorporation mechanism via substitution into the metal (Me = Mg2+ and Fe2+) and Si sites with a ratio of 5/3 for (Fe3++H+):Me and of 5/1 for (Fe3++H+):Si, similarly as in the dry system. Thus, coupled substitution of Fe3+ and H+ does not affect the incorporation mechanism of Fe3+, but does affect the location of H+, which is partly incorporated at tetrahedral edges forming [FeSi′-(OH)o*]X neutral defects substituting for Si. In this model 25% of the ferric iron occupies the tetrahedral sites.
ISSN: 0003-004X

hal-00758071
https://hal.archives-ouvertes.fr/hal-00758071
DOI : 10.2138/am.2012.3869

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
To test if hydrogen incorporation by ionic diffusion can occur between a volatile-rich kimberlitic liquid and forsterite, results of high-pressure and high-temperature experiments using a piston-cylinder apparatus at 1200–1300 °C and 1 GPa for durations of 1 min, 5 h, and 23 h, are reported here. Kimberlitic liquid in the system CaO-MgO-Al2O3-SiO2-CO2-H2O and synthetic forsterite single crystals were chosen as a first simplification of the complex natural kimberlite composition. Unpolarized Fourier transform infrared spectroscopy was used to quantify the concentrations of OH in the crystallographically oriented forsterite. Scanning electron microscopy, electron backscattered diffraction, electron microprobe analyses, and transmission electron microscopy were performed to identify the run products. After 5 and 23 h, a forsterite overgrowth crystallized with the same orientation as the initial forsterite single crystal. The kimberlitic liquid has crystallized as micrometer-scale euhedral forsterite neocrystals with random crystallographic orientations, as well as a nanoscale aluminous phase and a calcic phase. Despite theoretical water-saturation of the system and long duration, none of the initial forsterite single crystals display signs of hydration such as hydrogen diffusion profile from the border toward the center of the crystal. Most likely, the presence of CO2 in the system has lowered the H2O fugacity to such an extent that there is no significant hydration of the starting forsterite single crystal or its overgrowth. Also, the presence of CO2 enhances rapid forsterite crystal growth. Forsterite growth rate is around 2 × 108 μm3/h at 1250 °C. These experimental results suggest a deep mantle origin of the high OH content found in natural mantle-derived xenoliths transported in kimberlites, as reported from the Kaapvaal craton. In agreement with previous studies, it also points out to the fact that significant hydration must take place in a CO2-poor environment.
ISSN: 0003-004X

hal-01217157
https://hal.archives-ouvertes.fr/hal-01217157
DOI : 10.2138/am-2015-5200