Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Diffusion parameters for HTO, 36Cl−, and 125I− were determined on Upper Toarcian argillite samples from the Tournemire Underground Research Laboratory (Aveyron, France) using the through diffusion technique. The direction of diffusion was parallel to the bedding plane. The purpose of the present study was 3-fold; it was intended (i) to confirm the I− interaction with Upper Toarcian argillite and to verify the effects of initial I− concentration on this affinity, as previously observed by means of radial diffusion experiments, (ii) to highlight any discrepancy between Cl− and I− diffusivity, and (iii) to investigate the effect of an increase of the ionic strength of the solution on the anionic tracers' diffusive behaviour. The results show that the effective diffusion coefficient (De) and diffusion accessible porosity (εa) values obtained with an ionic strength (I.S.) synthetic pore water of 0.01 eq L−1 are: De = 2.35-2.50 × 10−11 m2 s−1 and εa = 12.0-15.0% for HTO, and De = 14.5-15.5 × 10−13 m2 s−1 and εa = 2.5-2.9% for 36Cl−. Because of anionic exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than HTO, taken as a water tracer. The associated effective diffusion coefficient (De) and rock capacity factor (α) obtained for 125I are: De = 7.00-8.60 × 10−13 m2 s−1 and α = 4.3-7.2%. Such values make it possible to calculate low 125I distribution ratios (0.0057 < RD < 0.0192 mL g−1) which confirm the trend indicating that the 125I rock capacity factor increases with the decrease of the initial I− concentration. Additional through-diffusion experiments were carried out with a higher ionic strength synthetic pore water (I.S. = 0.11 eq L−1). No evolution of HTO diffusion parameters was observed. The anionic tracers' effective diffusion coefficient increased by a factor of two but no clear evolution of their accessible porosity was observed. Such a paradox could be related to the particularly small mean pore size of the Upper Toarcian argillite of Tournemire. The most significant finding of this study is the large discrepancy (factor of two) between the values of the effective diffusion coefficient for 125I and 36Cl. Whatever the ionic strength of the synthetic solution used, 125I exhibited De values two times lower than those of 36Cl. A detailed explanation for this difference cannot be given at present even if a hypothesis based on ion-pairing or on steric-exclusion cannot be excluded. This makes questionable the assumption usually made for quantifying 125I sorption and postulating that 36Cl and 125I would diffuse in the same porosity. In other terms, at Tournemire, 125I sorption could be more pronounced than previously indicated.
ISSN: 0883-2927

hal-00757749
https://hal.archives-ouvertes.fr/hal-00757749
DOI : 10.1016/j.apgeochem.2011.12.017

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 wiley
Résumé : International audience
The slow advance of a crack in sodo-silicate glasses was studied at nanometer scale by in-situ atomic force microscopy (AFM) in a well-controlled atmosphere (N2 and H2O). An enhanced diffusion of sodium ions in the stress-gradient field at the sub-micrometric vicinity of the crack tip was revealed through several effects: growth of nodules in height images, changes in the AFM tip–sample energy dissipation as detected in phase images. Ex-situ chemical micro-analyses completed the AFM measurements. The nodules patterns revealed a dewetting phenomenon evidenced by “breath figures”, i.e. analog to the fogging that occurs when a vapour condenses onto a 'cold' surface [D. Beysens et al., Phys. Rev. Let. 57, 1433 (1986)]. These experimental results were explained by a two-step process: i) a fast migration of sodium ions towards the fracture surfaces as proposed by Langford et al. [J. Mat. Res. 6, 1358 (1991)], ii) a slow backwards diffusion of the cations as evidenced in these AFM experiments (typical time: few minutes). Measurements of the diffusion coefficient of that relaxing process were done at room temperature. Our results strengthen the theoretical concept of a near-surface structural relaxation due to the stress-gradient at the vicinity of the crack tip. Raman and SIMS studies revealed that nodules – for samples studied after exposition to common air - are preferentially covered by an organic overlayer of a carboxylate salt with a long aliphatic chain. The catalytic role of sodium ions in that chemical process is suspected.
Fractography of glasses an ceramics V
Rochester, United States

hal-00408605
https://hal.archives-ouvertes.fr/hal-00408605

Éditeur(s) : HAL CCSD Elsevier
Résumé : The slow advance of a crack in soda-silicate glasses was studied at nanometer scale by in-situ and real-time atomic force microscopy (AFM) in a well-controlled atmosphere. An enhanced diffusion of sodium ions in the stress-gradient field at the sub-micrometric vicinity of the crack tip was revealed through several effects: growth of nodules in AFM height images, changes in the AFM tip–sample energy dissipation. The nodules patterns revealed a dewetting phenomenon evidenced by ‘breath figures'. Complementary chemical micro-analyses were done. These experimental results were explained by a two-step process: (i) a fast migration (typical time: few milliseconds) of sodium ions towards the fracture surfaces as proposed by Langford et al. [J. Mat. Res. 6 (1991) 1358], (ii) a slow backwards diffusion of the cations as evidenced in these AFM experiments (typical time: few minutes). Measurements of the diffusion coefficient of that relaxing process were done at room temperature. Our results strengthen the theoretical concept of a near-surface structural relaxation due to the stress-gradient at the vicinity of the crack tip. The inhomogeneous migration of sodium ions might be a direct experimental evidence of the presence of sodium-rich channels in the silicate structure [A. Meyer et al., Phys. Rev. Let. 93 (2004) 027801].
ISSN: 0022-3093

hal-00407634
https://hal.archives-ouvertes.fr/hal-00407634
DOI : 10.1016/j.jnoncrysol.2006.09.034

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 American Chemical Society
Résumé : The distribution of water and ions in nanoporous membranes, in particular close to their surfaces with external reservoirs, is investigated by means of molecular dynamics (MD) simulations using classical polarizable force fields. A sodium iodide (NaI) aqueous solution is considered in uncharged weakly hydrophilic (WH) and highly hydrophilic (HH) nanoporous materials modeled by a single truncated nanopore in contact with two reservoirs. In the inner part of the nanopore, the spatial distribution of water and ions is obtained by coupling semi-infinitesimal longitudinal and semi-infinitesimal radial descriptions. In the HH material, in contrast with the WH material, species are no longer uniformly distributed in the inner nanopore and water molecules are distributed in a nearly frozen axially periodic corona-like structure which leads to the formation of ionic tunnels. In the reservoirs, water molecules and ions attracted by the membrane surface create a necking of the confined solution which acts as a barrier at the entrance of the nanopore. In the WH nanopore subsurface, close to the surface of the membrane, the species distribution is analogous to the interface distribution between an aqueous electrolyte solution and air. In the HH nanopore subsurface, this distribution is modulated by the water corona-like structure. These results provide useful information for predicting properties of nanoporous membranes, in particular the drastic reduction of diffusion coefficients in HH materials, and give a guide to designing synthetic membranes for applications in nanofiltration, etc.
ISSN: 1932-7447

hal-00682155
https://hal.archives-ouvertes.fr/hal-00682155
DOI : 10.1021/jp2078924

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 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 high proportion of crystallized apatite forming the bones and teeth should theoretically allow the use of fission track analysis to date vertebrate fossils when burying of the fossiliferous series did not subject them to temperatures exceeding 60 degrees C. However several major obstacles arise such as the complexity of fossils' internal structures, diagenetic modifications and substitutions of the hydroxyapatite by other minerals, and massive U uptake or loss during diagenesis. In this work, those various problems are addressed combining optical microscope observation of the fossils, a systematic fission track analysis of the best samples, alpha and gamma spectrometry and Secondary Ion Mass Spectrometry. Even if the problems caused by internal structures and mineral substitutions can be solved, U movements in and out of the fossils are generally too complex to allow fission track analysis dating of the fossils.
ISSN: 0009-2541

hal-00411880
https://hal.archives-ouvertes.fr/hal-00411880
DOI : 10.1016/j.chemgeo.2007.10.009

Éditeur(s) : HAL CCSD Taylor & Francis: STM, Behavioural Science and Public Health Titles
Résumé : International audience
The dislocation microstructures in a single crystal of olivine deformed experimentally in uniaxial compression at 1090 °C and under a confining pressure of 300 MPa, have been investigated by transmission electron tomography in order to better understand deformation mechanisms at the microscale relevant for lithospheric mantle deformations. Investigation by electron tomography reveals microstructures, which are more complex than previously described, composed of and dislocations commonly exhibiting 3D configurations. Numerous mechanisms such as climb, cross-slip, double cross-slip as well as interactions like junction formations and collinear annihilations are the source of this complexity. The diversity observed advocates for microscale deformation of olivine significantly less simple than classic dislocation creep reported in metals or ice close to melting temperature. Deciphering mechanism of hardening in olivine at temperatures where ionic diffusion is slow and is then expected to play very little role is crucial to better understand and thus model deformation at larger scale and at temperatures (900–1100 °C) highly relevant for the lithospheric mantle.
ISSN: 1478-6443

hal-01667146
https://hal.archives-ouvertes.fr/hal-01667146
DOI : 10.1080/14786435.2017.1367858