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 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 Oxford University Press (OUP)
Résumé : International audience
The diffusion of titanium along with Ni, Co and Mn in pure synthetic forsterite has been studied as a function of temperature, oxygen fugacity, crystallographic orientation and chemical potentials in the four-component system MgO–SiO2–TiO2–TiO1·5. In over 100 different experimental conditions, no Ti diffusion profiles with the classical shape of the error function were observed. Instead, the profiles vary between ‘stepped’ at high fO2 (probably owing to diffusion on octahedral sites and trapping in tetrahedral sites), to hockey-stick shapes at low fO2 owing to concentration-dependent diffusion. The profile shapes vary systematically between these end-members according to oxygen fugacity. These profile shapes are also reproduced in experiments using natural San Carlos olivine. The change in profile shape is interpreted to be a function of valence-state change from Ti4+ to Ti3+, shown by a sigmoidal log fO2–diffusivity relationship. To distinguish between Ti4+ and Ti3+ in forsterite, a diffusion profile was also investigated using ‘hydroxylation spectroscopy’ whereby a crystal from a diffusion experiment was hydroxylated by annealing in an H2O-rich fluid at moderate pressure and temperature. The point defects associated with the added structural OH were then determined by infrared spectroscopy, providing evidence for the presence of Ti4+ and Ti3+ at intermediate oxygen fugacity. The transition from Ti4+ to Ti3+ occurs at considerably higher fO2 in these diffusion experiments than in equilibrium experiments in similar systems. Titanium diffusion, qualified using a mobility parameter (M), is fastest along the c-axis, at high activity of silica, low oxygen fugacity and high temperature. The rate of Ti diffusion is broadly similar to those of Mn, Ni and Co, and closer to published rates of Mg self-diffusion in olivine than Si self-diffusion. The observed Ti3+ and Ti4+ diffusion occurs on the M-sites. From statistical examination of the large Mn, Ni and Co diffusivity dataset, we determine that there is a 102/3 dependence of diffusion on aSiO2; the cations diffuse more rapidly at high aSiO2. In addition, diffusivity has a 10–1/8 dependence on fO2, suggested to be the result of increased concentration of loosely bound Ti3+–vacancy pairs, which enhance the mobility of other cations. This behaviour is likely to be present in natural systems where trivalent (e.g. Fe3+, Al3+, Cr3+) and divalent cations diffuse together. Consideration should be given to diffusive interference by highly charged, fast-moving cations when extracting time scales from frozen diffusion profiles.
ISSN: 0022-3530

hal-01531344
https://hal.archives-ouvertes.fr/hal-01531344
DOI : 10.1093/petrology/egw067

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
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