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 : 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 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 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 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
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 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
This study reports petrostructural observations in the pargasite and phlogopite-bearing Finero peridotite massif (Italian Western Alps), which suggest that the pervasive foliation in this massif was formed by deformation concomitant with percolation of hydrous Si-rich melts: (1) diffuse contacts, but systematic parallelism between the pyroxenitic layers and the foliation of the peridotite (2) strong shape and crystal preferred orientations (SPO and CPO), but subhedral or interstitial shapes and weak intracrystalline deformation of the hydrous phases, (3) CPO, but interstitial shapes of the pyroxenes, (4) very coarse olivine grain sizes, which are correlated to the olivine abundance, and (5) elongated shapes, but weak intracrystalline deformation, and extremely weak and highly variable CPO of olivine. The pervasive deformation of the Finero peridotite occurred therefore under conditions that allowed coexistence of H2O–CO2-bearing melts, pargasite, and spinel, that is, temperatures of 980–1080 °C and pressures <2 GPa. The petrostructural observations suggest that the presence of hydrous melts results in accommodation of large amounts of deformation by stress-controlled dissolution–precipitation and advective transport of matter by the melts and in fast grain boundary migration in olivine. By consequence, it produces significant rheological weakening. Water contents in olivine are <4 ppm wt., implying limited contribution of hydration of olivine to weakening. In addition, the analysis of protomylonites composing the external domains of the shear zones that overprint the pervasive foliation indicates that the transition to melt-free conditions results in enhanced contribution of dislocation creep to the deformation. The associated increase of the peridotites' strength leads to onset of strain localization. The latter is not correlated to the local abundance in pargasite or phlogopite, implying that crystallization of amphiboles or phlogopite, even at concentrations of 25 vol.%, does not produce rheological weakening in the upper mantle.
ISSN: 0012-821X

hal-01667879
https://hal.archives-ouvertes.fr/hal-01667879
DOI : 10.1016/j.epsl.2017.08.015

Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : International audience
The hydrogen content of nominally anhydrous minerals is of great interest, because it can influence many physical and mechanical properties of mantle rocks. Moreover, the hydrogen diffusion profiles can be used to constrain timescales related to magma eruptions. Here, we report models of ionic diffusion for trace elements in anisotropic crystals and apply them to hydrogen diffusing out of mantle-derived olivine. We first compare and discuss the characteristics of 1D and 3D models and show that only 3D anisotropic diffusion models can lead to diffusion profiles exhibiting non-equilibrium plateau at the center of the solid along the slowest axis, as measured in natural samples. In a second part, we discuss the differences between hydration and dehydration of olivine for diffusion that is linked to two different atomic sites involved in hydrogen mobility. Finally, we apply our 3D anisotropic model to previous results on mantle-derived olivine from Pali-aike to better characterize diffusion coefficients and their anisotropy that could be relevant for dehydration of olivine. Our results show that dehydration has to be strongly anisotropic, with a fast [100] axis and a significantly slower [001] axis.
ISSN: 0342-1791

hal-01115253
https://hal.archives-ouvertes.fr/hal-01115253
DOI : 10.1007/s00269-014-0685-x

Éditeur(s) : HAL CCSD
Résumé : This study provides additional constraints on the relations between deformation, hydration and percolation of fluids and melts in the subcontinental lithospheric mantle beneath a craton and a rift, as well as their implication on its geodynamical behaviour. I have analysed the microstructures, the CPOs, and the hydrogen content of mantle xenoliths from the Kaapvaal craton, and two sets of xenoliths from different localities along the East African Rift (North Tanzanian Divergence and SE Ethiopia).The coarse-granular microstructures and the well-defined CPOs in Kaapvaal peridotites suggest a deformation followed by a long quiescence time. Orthorhombic olivine CPOs predominates, but axial-[100] and axial-[010] are also measured. Cratonic peridotites record multiple metasomatic episodes, leading to a significant compositional heterogeneity, which cannot be imaged by seismic studies. Olivine hydrogen contents are variable, but tend to increase until 150 km depth, reaching up to 50 ppm wt. H2O. The deeper samples are almost dry. Piston-cylinder experiments on hydrogen diffusion between a volatile-rich kimberlitic melt and forsterite suggest that the presence of CO2 in the system could significantly decrease water fugacity and thus forsterite hydration. These experimental results indicate that the hydrogen contents measured in olivine were acquired during a metasomatic event rather than during xenolith extraction by kimberlites. However, this metasomatism was not followed by remobilization of the cratonic root.In the North Tanzanian Divergence, localities within the rift axis and the volcanic transverse belt (Lashaine and Olmani) show significant differences in microstructures and olivine CPO patterns. In Lashaine, coarse-granular microstructures and orthorhombic to axial-[100] CPO patterns in olivine can be explained by transpressional deformation during the formation of the Mozambique belt, or by the occurrence of a remnant of a cratonic domain embedded within the Mozambique belt. Within the rift axis, porphyroclastic to mylonitic microstructures suggest a recent rift-related deformation accompanied by syn-kinematic melt-rock reactions, and followed by variable annealing. The strong heterogeneity in microstructures and olivine CPO suggests that this deformation was acquired during multiple tectonic events probably linked to episodic magma percolation, separated by quiescence episodes. The axial-[100] patterns in olivine and the oblique fast directions reported by SKS studies are coherent with transtensional deformation within the lithospheric mantle beneath the rift.The peridotites from SE Ethiopia are less recrystallized than the rift-axis Tanzanian peridotites, displaying coarse-porphyroclastic microstructures. Microstructures and orthorhombic CPOs in olivine suggest syn- to post-metasomatic deformation. S-waves polarization anisotropies calculated for these samples cannot explain alone the delay times reported by SKS studies in this part of the East-African Rift.
Les travaux réalisés durant cette thèse apportent de nouvelles contraintes sur les relations entre déformation, hydratation et percolation de fluides et/ou de magmas dans le manteau subcontinental sous un craton et sous un rift, et leurs implications sur son comportement rhéologique. Il repose sur l'analyse des microstructures, des OPRs et des teneurs en hydrogène de xénolites mantelliques du craton du Kaapvaal, et sur deux séries de xénolites provenant de différentes localités le long du rift Est-Africain (Divergence Nord Tanzanienne et SE de l'Ethiopie). Les microstructures granulaires à gros grains et les OPRs bien définies des péridotites du craton du Kaapvaal sont cohérentes avec un épisode de déformation suivi d'une longue période de quiescence. Les OPRs de l'olivine sont majoritairement à symétrie orthorhombique, mais des symétries axiale-[100] et axiale-[010] sont aussi mesurées. Les péridotites cratoniques enregistrent de multiples épisodes métasomatiques, ayant entraîné une hétérogénéité de compositions à petite échelle ne pouvant être détectée par les études sismiques. Les teneurs en hydrogène mesurées dans l'olivine sont variables, mais ont tendance à augmenter jusqu'à 150 km de profondeur, atteignant alors jusqu'à 50 ppm wt. H2O. En dessous de cette profondeur, les échantillons montrent des teneurs en hydrogène très faibles. Les expériences réalisées en piston-cylindre sur la diffusion de l'hydrogène issue d'un liquide kimberlitique vers de la forstérite suggèrent que la fugacité en eau pourrait fortement être diminuée par la présence de CO2, empêchant l'hydratation de l'olivine durant extraction des xénolites par les kimberlites. Ces résultats expérimentaux suggèrent que les teneurs en hydrogène dans l'olivine des péridotites du craton du Kaapvaal ont été acquises durant un épisode métasomatique en profondeur et non pendant leur extraction par les kimberlites. Ces teneurs n'ont toutefois pas à ce jour entraîné de remobilisation de la racine cratonique. Enfin, le calcul des propriétés sismiques des péridotites cratoniques révèle que les anisotropies générées par les OPRs de ces échantillons sont suffisantes pour expliquer les anisotropies mesurées par les ondes SKS et les ondes de surface.Les xénolites de la Divergence Nord-Tanzanienne, montrent des variations significatives de microstructures et d'OPR de l'olivine entre les péridotites des localités dans l'axe du rift et celles de la chaîne volcanique transverse (Lashaine et Olmani). A Lashaine, les microstructures granulaires à gros grains et les OPRs de type orthorhombique et axial-[010] peuvent être expliquée par une déformation en transpression liée à la formation de la chaîne Mozambique ou par la présence d'une relique d'un domaine cratonique à l'intérieur de la chaîne Mozambique. Dans l'axe du rift, les microstructures porphyroclastiques à mylonitiques suggèrent une déformation plus récente, accompagnée de réactions magma-roche sous des conditions proches du solidus, suivie d'un recuit variable. L'hétérogénéité des microstructures enregistrées par les échantillons du rift suggère de multiples épisodes de déformation localisée, probablement liés à l'injection percolation épisodique de magmas, espacés de périodes d'accalmie. Les OPRs de l'olivine de type axial-[100] et l'orientation des directions de polarisation des ondes SKS suggère que le rift s'est formé en régime de transtension Les péridotites du Sud-Est de l’Éthiopie présentent des microstructures porphyroclastiques à gros grains moins recristallisées qu'en Tanzanie. Les microstructures et les OPRs principalement de type orthorhombique suggèrent une déformation syn- à post-métasomatisme. Les anisotropies de polarisation des ondes S calculées pour ces échantillons sont insuffisantes pour expliquer à elles seules les déphasages des ondes SKS dans cette partie du rift.
https://tel.archives-ouvertes.fr/tel-01684759

Droits : info:eu-repo/semantics/OpenAccess
NNT : 2014MON20139
tel-01684759
https://tel.archives-ouvertes.fr/tel-01684759
https://tel.archives-ouvertes.fr/tel-01684759/document
https://tel.archives-ouvertes.fr/tel-01684759/file/43443_BAPTISTE_2014_archivage_cor.pdf

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

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
The mantle above a subducting slab is the site of complex interactions between deformation, partial melting, fluid migration and magma transport. To constrain these interactions and their effects on olivine deformation, we analyze microstructures, crystal preferred orientations, and water contents of peridotite xenoliths entrained by andesites of the Avacha volcano, southern Kamchatka arc. These xenoliths are refractory spinel harzburgites that have coarse-grained microstructures with widely spaced subgrain boundaries and sinuous grain boundaries in olivine, consistent with deformation by dislocation creep under low deviatoric stress (< 13 MPa) and with a significant contribution from diffusional processes. Analysis of crystal preferred orientations (CPO) indicates dominant activation of high-temperature, low-stress {0kl}[100] slip systems in olivine and of(100)[001] in orthopyroxene. In most samples, coarse opx crystals, elongated parallel to the lineation, enclose small olivine grains in crystallographic continuity with neighbouring crystals, indicating crystallization of orthopyroxene at the expense of olivine as a result of reactive percolation of Si-rich fluids coeval with the high-temperature deformation. Secondary crystallization of interstitial orthopyroxene led locally to development of opx-rich lenses parallel to the foliation, characterized by a decrease in olivine grain size and dispersion of the olivine CPO without changing the dominant slip systems. Half of the samples also show acicular orthopyroxene aggregates with which is associated a fine-grained matrix composed of rounded strain-free olivine, orthopyroxene, spinel, and rare amphibole crystals. This matrix occurs pervasively along grain boundaries or forms millimeter-scale irregular lenses and anastomosing veinlets that crosscut the coarse crystals and their ductile deformation structures. Both acicular orthopyroxene and the fine-grained matrix are interpreted as resulting from reactive transport of H2O-rich fluids under static conditions, probably in the lithospheric mantle. Infrared analyses show that olivine contains 1-8 center dot 6 ppm by weight of water. These low water contents are similar to those observed in spinel peridotites from other subduction zones and probably record both the low solubility of water in olivine at low pressure and dehydration during exhumation of the xenoliths. Water contents in orthopyroxene are highly variable (25-506 ppm H2O), probably recording spatially heterogeneous interaction with fluids or melts and compositional disequilibrium in the studied samples. Change in the dominant percolation mechanism from porous flow to fracturing suggests cooling, consistent with the low temperatures estimated from pyroxene thermometry (< 800-900 degrees C). The Avacha xenoliths therefore record pervasive deformation of a region of the mantle under asthenospheric conditions, followed by its accretion to the base of the lithosphere, probably as a result of cooling of the mantle wedge. Percolation of Si-rich fluids or hydrous melts is recorded at all stages; this probably enhanced diffusion and lowered deviatoric stresses during ductile deformation, but did not change the dominant slip direction in olivine from [100] to [001].
ISSN: 0022-3530

hal-00456053
https://hal.archives-ouvertes.fr/hal-00456053
DOI : 10.1093/petrology/egp085

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The Middle Atlas is a region where xenolith-bearing volcanism roughly coincides with the maximum of lithospheric thinning beneath continental Morocco. It is therefore a key area to study the mechanisms of lithospheric thinning and constrain the component of mantle buoyancy that is required to explain the Moroccan topography. Samples from the two main xenolith localities, the Bou Ibalghatene and Tafraoute maars, have been investigated for their mineralogy, microstructures, crystallographic preferred orientation, and whole-rock and mineral compositions. While Bou Ibalghatene belongs to the main Middle Atlas volcanic field, in the ‘tabular’ Middle Atlas, Tafraoute is situated about 45 km away, on the North Middle Atlas Fault that separates the ‘folded’ Middle Atlas, to the South-East, from the ‘tabular’ Middle Atlas, to the North-West. Both xenolith suites record infiltration of sub-lithospheric melts that are akin to the Middle Atlas volcanism but were differentiated to variable degrees as a result of interactions with lithospheric mantle. However, while the Bou Ibalghatene mantle was densely traversed by high melt fractions, mostly focused in melt conduits, the Tafraoute suite records heterogeneous infiltration of smaller melt fractions that migrated diffusively, by intergranular porous flow. As a consequence the lithospheric mantle beneath Bou Ibalghaten was strongly modified by melt–rock interactions in the Cenozoic whereas the Tafraoute mantle preserves the record of extensional lithospheric thinning, most likely related to Mesozoic rifting. The two xenolith suites illustrate distinct mechanisms of lithospheric thinning: extensional thinning in Tafraoute, where hydrous incongruent melting triggered by decompression probably played a key role in favouring strain localisation, vs. thermal erosion in Bou Ibalghatene, favoured and guided by a dense network of melt conduits. Our results lend support to the suggestion that lithospheric thinning beneath the Atlas mountains results from the combination of different mechanisms and occurred in a piecewise fashion at a short wavelength scale.
ISSN: 0040-1951

hal-01171756
https://hal.archives-ouvertes.fr/hal-01171756
DOI : 10.1016/j.tecto.2014.11.020

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

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