Growth of multilayered polycrystalline reaction rims in the MgO–SiO<Subscript>2</Subscript> system,part II: modelling

Part I of this contribution (Gardés et al. in Contrib Mineral Petrol, 2010) reported time- and temperature-dependent experimental growth of polycrystalline forsterite-enstatite double layers between single crystals of periclase and quartz, and enstatite single layers between forsterite and quartz. Both double and single layers displayed growth rates decreasing with time and pronounced grain coarsening. Here, a model is presented for the growth of the layers that couples grain boundary diffusion and grain coarsening to interpret the drop of the growth rates. It results that the growth of the layers is such that (Δx)² ∝ t ^1−1/n , where Δx is the layer thickness and n the grain coarsening exponent, as experimentally observed. It is shown that component transport occurs mainly by grain boundary diffusion and that the contribution of volume diffusion is negligible. Assuming a value of 1 nm for the effective grain boundary width, the following Arrhenius laws for MgO grain boundary diffusion are derived: log D _gb,0^Fo (m²/s) = −2.71 ± 1.03 and E _gb^Fo = 329 ± 30 kJ/mol in forsterite and log D _gb,0^En (m²/s) = 0.13 ± 1.31 and E _gb^En = 417 ± 38 kJ/mol in enstatite. The different activation energies are responsible for the changes in the enstatite/forsterite thickness ratio with varying temperature. We show that significant biases are introduced if grain boundary diffusion-controlled rim growth is modelled assuming constant bulk diffusivities so that differences in activation energies of more than 100 kJ/mol may arise. It is thus important to consider grain coarsening when modelling layered reaction zones because they are usually polycrystalline and controlled by grain boundary transport.     

Effect of grain growth on cation exchange between dunite and fluid: implications for chemical homogenization in the upper mantle

The effect of grain growth on the cation exchange between synthesized forsterite aggregates (i.e., dunite) and nickel-rich aqueous fluid was evaluated experimentally at 1.2 GPa and 1,200°C. The grain boundary (GB) migration caused nickel enrichment in the area swept by the GBs in a fashion similar to that reported for stable isotope exchange in the quartz aggregates. The progress of the grain growth resulted in an increase in the average nickel concentration in the dunites of up to ~80 times that was calculated for a system having stationary GBs. The overall diffusivity of the nickel along the wet GBs and interconnected fluid networks was found to be 6.5 × 10⁻¹⁹–6.7 × 10⁻¹⁸ m³/s, which is 4–5 orders of magnitude higher than the grain boundary diffusivity in the dry dunite. These results show that the grain growth rate is a fundamental factor in the evaluation of the time scale of chemical homogenization in the upper mantle.     

Synchrotron X-ray analysis of norbergite, Mg2.98Fe0.01Ti0.02Si0.99O4(OH0.31F1.69) structure at high pressure up to 8.2?GPa

The natural norbergite, Mg_2.98Fe_0.01Ti_0.02Si_0.99O₄(OH_0.31F_1.69) is examined by synchrotron X-ray diffraction analysis at pressures up to 8.2 GPa. The measured linear compressibilities of the crystallographic axes are β _a  = 2.18(4) × 10⁻³, β _b  = 2.93(7) × 10⁻³, and β _c  = 2.77(7) × 10⁻³ (GPa⁻¹), respectively and the calculated isothermal bulk modulus of the norbergite is K _T = 113(2) GPa based on the Birch–Murnaghan equation of state assuming a pressure derivative of K′ = 4. The crystal structures of norbergite are refined at room temperature and pressures of 4.7, 6.3, and 8.2 GPa, yielding R values for the structure refinements of 4.6, 5.3, and 5.3%, respectively. The bulk moduli of the polyhedral sites are 293(15) GPa for the tetrahedron, 106(5) GPa for the M2 octahedron, 113(2) GPa for the M3 octahedron, and 113(3) GPa for the total void space. The bulk modulus exhibits a good linear correlation with the filling factor for polyhedral sites in structures of the humite minerals and forsterite, reflecting the Si⁴⁺ + 4O²⁻ ⇔ □ + 4(OH, F)⁻ substitution in the humite minerals. Moreover, two simply linear trends were observed in the relationship between bulk modulus and packing index for natural minerals and dense hydrous magnesium silicate minerals. This relationship would reflect that the differences in compression mechanism were involved with hydrogen bonding in these minerals. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

HgO at high pressures: the transition to the NaCl structure (HgO-III) and the equation of state of tetragonal HgO-II

The high-pressure behavior of HgO-montroydite was investigated up to 36.5 GPa using angle-dispersive X-ray diffraction. The tetragonal phase of this material (HgO-II), a distortion of the NaCl structure, transforms into the cubic NaCl structure (HgO-III) above ~31.5 GPa. The transformation of mercury oxide from the orthorhombic Pnma (HgO-I) structure to a tetragonal I4/mmm structure (HgO-II) is confirmed to occur at 13.5 ± 1.5 GPa. Neither of the high-pressure phases, HgO-II nor HgO-III, is quenchable in pressure. The derived isothermal bulk modulus of HgO-II and its pressure derivative strongly depend on the assumed zero-pressure volume of this phase, but our elasticity results on HgO-II nevertheless lie significantly closer to theoretical calculations than prior experimental results, and the measured pressure of the phase transformation to the NaCl structure is also in agreement with recent theoretical results. The general accord with theory supports the existence of significant relativistic effects on the high-pressure phase transitions of HgO.     

The pressure and temperature dependence of the elastic properties of single-crystal fayalite Fe2SiO4

The nine adiabatic elastic stiffness constants of synthetic single-crystal fayalite, Fe₂SiO₄, were measured as functions of pressure (range, 0 to 1.0 GPa) and temperature (range, 0 to 40° C) using the pulse superposition ultrasonic method. Summary calculated results for a dense fayalite polycrystalline aggregate, based on the HS average of our single-crystal data, are as follows: V_p = 6.67 km/s; V_s = 3.39km/s; K= 127.9 GPa; μ = 50.3 GPa; (?K/?P)_T = 5.2; (?μ/?P)_T=1.5;(?K/?T)_P= ?0.030 GPa/K;and,(?/?T)_P =-0.013 GPa/K (the pressure and temperature data are referred to 25° C and 1 atm, respectively). Accuracy of the single-crystal results was maintained by numerous cross and redundancy checks. Compared to the single-crystal elastic properties of forsterite, Mg₂SiO₄, the fayalite stiffness constants, as well as their pressure derivatives, are lower for each of the on-diagonal (C _ij for which i=j) values, and generally higher for the off-diagonal (C _ij for which i≠j) data. As a result, the bulk moduli (K) and dK/dP for forsterite and fayalite are very similar, but the rigidity modulus (μ) and dμ/dP for polycrystalline fayalite are much lower than their forsterite counterparts. The bulk compression properties derived from this study are very consistent with the static-compression x-ray results of Yagi et al. (1975). The temperature dependence of the bulk modulus of fayalite is somewhat greater (in a negative sense) than that of forsterite. The rigidity dependencies are almost equivalent. Over the temperature range relevant to this study, the elastic property results are generally consistent with the data of Sumino (1978), which were obtained using the RPR technique. However, some of the compressional modes are clearly discrepant. The elastic constants of fayalite appear to be less consistent with a theoretical HCP model (Leibfried 1955) than forsterite, reflecting the more covalent character of the Fe-O bonding in the former.     

Transition from fracturing to viscous flow in granulite facies perthitic feldspar (Lofoten,Norway)

Recrystallization of perthites in granulite facies (T = 700–730 °C, P = 0.65–0.8 GPa) shear zones in mangerite-charnockite rocks from Lofoten (Norway) is localized along intracrystalline bands parallel to fractures. Fracturing preferentially occurred along the cleavage planes (010) and (001). EBSD analysis of perthite porphyroclasts indicates a very low degree of internal misorientation (within 5°) and the lack of recovery features. Recrystallized grains show coarsening with increasing width of the bands, and chemical changes with respect to the host grains. Crystallographic orientation of the new grains does not show a host-control relation to the parent perthite grains. In summary, the microstructure and CPO data consistently indicate intragranular recrystallization by nucleation and growth from fractured grains. Perthite porphyroclasts are surrounded by a matrix of recrystallized plagioclase + K-feldspar ± amphibole ± biotite. There is extensive evidence of syndeformational nucleation of new phases and of phase boundary migration in the matrix, with plagioclase grains forming bulges and protrusions towards K-feldspar. The spatial distribution of K-feldspar and plagioclase in the recrystallized matrix is characterized by the predominance of phase boundaries over grain boundaries. All these observations are consistent with diffusion creep as the dominant deformation mechanism in the matrix, associated with grain boundary sliding. Accordingly, recrystallized plagioclase and K-feldspar show a very weak crystallographic preferred orientation, which is interpreted in terms of oriented growth during diffusion creep. Fracturing of perthites promoted extensive grain size reduction, recrystallization, fluid infiltration, and operation of grain-size sensitive creep, resulting in strain localization.     

Late‐stage orogenic loading revealed by contact metamorphism in the northern Appalachians,New York

Pelitic schists from contact aureoles surrounding mafic–ultramafic plutons in Westchester County, NY record a high‐P (~0.8 GPa) high‐T (~790 °C) contact overprint on a Taconic regional metamorphic assemblage (~0.5 GPa). The contact metamorphic assemblage of a pelitic sample in the innermost aureole of the Croton Falls pluton, a small (<10 km²) gabbroic body, consists of quartz–plagioclase–biotite–garnet–sillimanite–ilmenite–graphite–Zn‐rich Al‐spinel. Both K‐feldspar and muscovite are absent, and abundant biotite, plagioclase, sillimanite, quartz and ilmenite inclusions are found within subhedral garnet crystals. Unusually low bulk‐rock Na and K contents imply depletion of alkalic components and silica through anatexis and melt extraction during contact heating relative to typical metapelites outside the aureole. Thermobarometry on nearby samples lacking a contact overprint yields 620–640 °C and 0.5–0.6 GPa. In the aureole sample, WDS X‐ray chemical maps show distinct Ca‐enriched rims on both garnet and matrix plagioclase. Furthermore, biotite inclusions within garnet have significantly higher Mg concentration than matrix biotite. Thermobarometry using GASP and garnet–biotite Mg–Fe exchange equilibria on inclusions and adjacent garnet host interior to the high‐Ca rim zone yield ~0.5 ± 0.1 GPa and ~620 ± 50 °C. Pairs in the modified garnet rim zone yield ~0.9 ± 0.1 GPa and ~790 ± 50 °C. Thermocalc average P–T calculations yield similar results for core (~0.5 ± ~0.1 GPa, ~640 ± ~80 °C) and rim (~0.9 ± ~0.1 GPa, ~800 ± ~90 °C) equilibria. The core assemblages are interpreted to record the P–T conditions of peak metamorphism during the Taconic regional event whereas the rim compositions and matrix assemblages are interpreted to record the P–T conditions during the contact event. The high pressures deduced for this later event are interpreted to reflect loading due to the emplacement of Taconic allochthons in the northern Appalachians during the waning stages of regional metamorphism (after c. 465 Ma) and before contact metamorphism (c. 435 Ma). In the absence of contact metamorphism‐induced recrystallization, it is likely that this regional‐scale loading would remain cryptic or unrecorded.     

Single-crystal elastic constants of fluorite (CaF2) to 9.3 GPa

 The second-order elastic constants of CaF₂ (fluorite) have been determined by Brillouin scattering to 9.3 GPa at 300 K. Acoustic velocities have been measured in the (111) plane and inverted to simultaneously obtain the elastic constants and the orientation of the crystal. A notable feature of the present inversion is that only the density at ambient condition was used in the inversion. We obtain high-pressure densities directly from Brillouin data by conversion to isothermal conditions and iterative integration of the compression curve. The pressure derivative of the isentropic bulk modulus and of the shear modulus determined in this study are 4.78 ± 0.13 and 1.08 ± 0.07, which differ from previous low-pressure ultrasonic elasticity measurements. The pressure derivative of the isothermal bulk modulus is 4.83 ± 0.13, 8% lower than the value from static compression, and its uncertainty is lower by a factor of 3. The elastic constants of fluorite increase almost linearly with pressure over the whole investigated pressure range. However, at P ≥ 9 GPa, C ₁₁ and C ₁₂ show a subtle structure in their pressure dependence while C ₄₄ does not. The behavior of the elastic constants of fluorite in the 9–9.3 GPa pressure range is probably affected by the onset of a high-pressure structural transition to a lower symmetry phase (α-PbCl₂ type). A single-crystal Raman scattering experiment performed in parallel to the Brillouin measurements shows the appearance of new features at 8.7 GPa. The new features are continuously observed to 49.2 GPa, confirming that the orthorhombic high-pressure phase is stable along the whole investigated pressure range, in agreement with a previous X-ray diffraction study of CaF₂ to 45 GPa. The high-pressure elasticity data in combination with room-pressure values from previous studies allowed us to determine an independent room-temperature compression curve of fluorite. The new compression curve yields a maximum discrepancy of 0.05 GPa at 9.5 GPa with respect to that derived from static compression by Angel (1993). This comparison suggests that the accuracy of the fluorite pressure scale is better than 1% over the 0–9 GPa pressure range. Received: 10 July 2001 / Accepted: 7 March 2002     

Static compression of the hydrous magnesium silicate phase D to 30 GPa at room temperature

Phase D is a dense hydrous magnesium silicate (ideal formula MgSi₂H₂O₆) which contains silicon cations exclusively in octahedral coordination. Measurements of the unit cell parameters of phase D were made to pressures of 30 GPa using a diamond anvil cell and employing synchrotron X-ray diffraction. A neon pressure medium was used. Using a third order Birch-Murnaghan equation of state the isothermal bulk modulus of phase D was determined as 166(±3) GPa with K′ equal to 4.1(±0.3). The compression of phase D is anisotropic with the c-axis twice as compressible as the a-axis. Above 20 GPa, however, the c/a ratio becomes pressure independent. Received: 29 July 1998/ Revised, accepted: 5 August 1998     

Thermal and redox state of the subcontinental lithospheric mantle of NE Spain from thermobarometric data on mantle xenoliths

Mantle xenoliths in within-plate Cenozoic alkaline mafic lavas from NE Spain are used to assess the local subcontinental lithospheric mantle geotherm and the influence of melting and metasomatism on its oxidation state. The xenoliths are mainly anhydrous spinel lherzolites and harzburgites and gradations between, with minor pyroxenites. Most types show protogranular textures, but transitional protogranular–porphyroclastic and equigranular lherzolites also exist. Different thermometers used in the estimates provide higher subsolidus equilibrium temperatures for harzburgites (1,062 ± 29°C) than for lherzolites (972 ± 89°C), although there is overlap; the lowest temperatures correspond to porphyroclastic lherzolites, whereas pyroxenites give the highest temperatures (up to 1,257°C). Maximum pressures for subsolidus equilibrium of peridotites are at 2.0–1.8 GPa. Later they followed adiabatic decompression and harzburgites registered lower pressures (1.02 ± 0.19 GPa) than lherzolites (1.41 ± 0.27 GPa). One pyroxenite gives values consistent with the spinel lherzolite field (1.08 GPa). The shallowest barometric data are in agreement with the highest local conductive geotherms, which implies that the lithosphere–asthenosphere boundary is at 70–60 km minimum depth. Higher equilibrium temperatures for the harzburgites could be explained by the existence of mafic magma bodies or dykes at the lower crust–mantle boundary. Paleo-fO₂ conditions during partial melting as inferred from the covariation between V and MgO concentrations are mainly between QFM−1 and QFM−2 in log units. However, most thermobarometric fO₂ estimates are between QFM−1 and QFM+1, suggesting oxidation caused by later metasomatism during uplift and cooling.     

Growth of multilayered polycrystalline reaction rims in the MgO–SiO<Subscript>2</Subscript> system,part I: experiments

Growth of transport-controlled reaction layers between single crystals of periclase and quartz, and forsterite and quartz was investigated experimentally at 1.5 GPa, 1100°C to 1400°C, 5 min to 72 h under dry and melt-free conditions using a piston-cylinder apparatus. Starting assemblies consisting of Per | Qtz | Fo sandwiches produced polycrystalline double layers of forsterite and enstatite between periclase and quartz, and enstatite single layers between forsterite and quartz. The position of inert Pt-markers initially deposited at the interface of the reactants and inspection of mass balance confirmed that both layer-producing reactions are controlled by MgO diffusion, while SiO₂ is relatively immobile. BSE and TEM imaging revealed thicknesses from 0.6 μm to 14 μm for double layers and from 0 to 6.8 μm for single layers. Both single and double layers displayed non-parabolic growth together with pronounced grain coarsening. Textural evolution and growth rates for each reaction are directly comparable. Forsterite–enstatite double layers are always wider than enstatite single layers, and the growth of enstatite in the double layer is slower than that in the single layer. In double layers, the enstatite/forsterite layer thickness ratio significantly increases with temperature, reflecting different MgO mobilities as temperature varies. Thus, thickness ratios in multilayered reaction zones may contain a record of temperature, but also that of any physico-chemical parameter that modifies the mobilities of the chemical components between the various layers. This potential is largely unexplored in geologically relevant systems, which calls for further experimental studies of multilayered reaction zones.     

Determination of the phase boundary between ilmenite and perovskite in MgSiO3 by in situ X-ray diffraction and quench experiments

Determination of the phase boundary between ilmenite and perovskite structures in MgSiO₃ has been made at pressures between 18 and 24 GPa and temperatures up to 2000 °C by in situ X-ray diffraction measurements using synchrotron radiation and quench experiments. It was difficult to precisely define the phase boundary by the present in situ X-ray observations, because the grain growth of ilmenite hindered the estimation of relative abundances of these phases. Moreover, the slow reaction kinetics between these two phases made it difficult to determine the phase boundary by changing pressure and temperature conditions during in situ X-ray diffraction measurements. Nevertheless, the phase boundary was well constrained by quench method with a pressure calibration based on the spinel-postspinel boundary of Mg₂SiO₄ determined by in situ X-ray experiments. This yielded the ilmenite-perovskite phase boundary of P (GPa) = 25.0 (±0.2) – 0.003 T (°C) for a temperature range of 1200–1800 °C, which is generally consistent with the results of the present in situ X-ray diffraction measurements within the uncertainty of ∼±0.5 GPa. The phase boundary thus determined between ilmenite and perovskite phases in MgSiO₃ is slightly (∼0.5 GPa) lower than that of the spinel-postspinel transformation in Mg₂SiO₄. Received: 19 May 1999 / Accepted: 21 March 2000     

The extrapolation of elastic moduli to high pressure and temperature

The elastic constants of a crystal under stress, defined as the second derivative of the crystal free energy with respect to strain, require a correction related to the static pressure at non-zero pressures. The corrections required for the elastic constants calculated by the free energy minimisation code PARAPOCS are described and tested by comparison with the elastic constants calculated numerically by applying small stresses in the appropriate orientations to simulated crystals of fluorite, forsterite, α-quartz and albite. The corrected elastic constants are then used to investigate the extrapolation of the bulk and shear moduli (and hence also the seismic wave velocities V _p and V _s) of β-spinel and forsterite to upper mantle pressures. A Murnaghan equation, thirdorder Eulerian finite strain equation, second order polynomial equation and a logistic equation were all fitted to the simulated bulk and shear moduli between 0 and 3 GPa pressure. The parameters derived for these equations are used to extrapolate the bulk and shear moduli to 14 GPa and the results are compared to the simulated high pressure moduli. Over this pressure range, the second order polynomial provides the best extrapolation of the bulk modulus, but the use of the logistic equation results in the best extrapolation of the shear modulus.     

Synchrotron X-ray powder diffraction study of natural P2 /n-omphacites at high-pressure conditions

 Synchrotron X-ray powder diffraction experiments at high pressure conditions (0.0001–13 GPa) were performed at ESRF (Grenoble-F), on the beamline ID9, to investigate the bulk elastic properties of natural P2/n-omphacites, with quasi-ideal composition. The monoclinic cell parameters a, b, c and β were determined as a function of pressure, and their compressibility coefficients are 0.00277(7), 0.00313(8), 0.00292(5) and 0.00116(4) GPa⁻¹, respectively. The third-order Birch-Murnaghan equation of state was used to interpolate the experimental P−V data, obtaining K ₀=116.6(±2.5) GPa and K′₀=6.03(±0.60). K ₀ was also determined by means of the axial and angular compressibilities [122.5(±1.7) GPa], and of the finite Lagrangian strain theory [121.5(±1.0) GPa]. The discrepancies on K ₀ are discussed in the light of a comparison between techniques to determine the bulk modulus of crystalline materials from static compression diffraction data. Received: 22 February 2000 / Accepted: 10 July 2000     

The system CaO-MgO-SiO2-CO2 at 1 GPa, metasomatic wehrlites, and primary carbonatite magmas

New experimental data in CaO-MgO-SiO₂-CO₂ at 1 GPa define the vapor-saturated silicate-carbonate liquidus field boundary involving primary minerals calcite, forsterite and diopside. The eutectic reaction for melting of model calcite (1% MC)-wehrlite at 1 GPa is at 1100 °C, with liquid composition (by weight) 72% CaCO₃ (CC), 9% MgCO₃ (MC), and 18% CaMgSi₂O₆ (Di). These data combined with previous results permit construction of the isotherm-contoured vapor-saturated liquidus surface for the calcite/dolomite field, and part of the adjacent forsterite and diopside fields. Nearly pure calcite crystals in mantle xenoliths cannot represent equilibrium liquids. We recently determined the complete vapor-saturated liquidus surface between carbonates and model peridotites at 2.7 GPa; the peritectic reaction for dolomite (25% MC)-wehrlite at 2.7 GPa occurs at 1300 °C, with liquid composition 60% CC, 29% MC, and 11% Di. The liquidus field boundaries on these two surfaces provide the road-map for interpretation of magmatic processes in various peridotite-CO₂ systems at depths between the Moho and about 100 km. Relationships among kimberlites, melilitites, carbonatites and the liquidus phase boundaries are discussed. Experimental data for carbonatite liquid protected by metasomatic wehrlite have been reported. The liquid trends directly from dolomitic towards CaCO₃ with decreasing pressure. The 1.5 GPa liquid contains 87% CC and 4% Di, much lower in silicate components than our phase boundary. However, the liquids contain approximately the same CaCO₃ (90 ± 1 wt%) in terms of only carbonate components. For CO₂-bearing mantle, all magmas at depth must pass through initial dolomitic compositions. Rising dolomitic carbonatite melt will vesiculate and may erupt as primary magmas through cracks from about ˜70 km. If it percolates through metasomatic wehrlite from 70 km toward the Moho at 35–40 km, primary calcic siliceous carbonatite magma can be generated with silicate content at least 11–18% (70–40 km) on the silicate-carbonate boundary. Received: 22 June 1998 / Accepted: 7 July 1999     

Melting of iron–silicon alloy up to the core–mantle boundary pressure: implications to the thermal structure of the Earth’s core

The melting temperature of Fe–18 wt% Si alloy was determined up to 119 GPa based on a change of laser heating efficiency and the texture of the recovered samples in the laser-heated diamond anvil cell experiments. We have also investigated the subsolidus phase relations of Fe–18 wt% Si alloy by the in-situ X-ray diffraction method and confirmed that the bcc phase is stable at least up to 57 GPa and high temperature. The melting curve of the alloy was fitted by the Simon’s equation, P(GPa)/a = (T _m(K)/T ₀) ^c , with parameters, T ₀ = 1,473 K, a = 3.5 ± 1.1 GPa, and c = 4.5 ± 0.4. The melting temperature of bcc Fe–18 wt% Si alloy is comparable with that of pure iron in the pressure range of this work. The melting temperature of Fe–18 wt% Si alloy is estimated to be 3,300–3,500 K at 135 GPa, and 4,000–4,200 K at around 330 GPa, which may provide the lower bound of the temperatures at the core–mantle boundary and the inner core–outer core boundary if the light element in the core is silicon.     

Equation of state, elasticity, and shear strength of pyrite under high pressure

 Physical properties including the equation of state, elasticity, and shear strength of pyrite have been measured by a series of X-ray diffraction in diamond-anvil cells at pressures up to 50 GPa. A Birch–Murnaghan equation of state fit to the quasihydrostatic pressure–volume data obtained from laboratory X-ray source/film techniques yields a quasihydrostatic bulk modulus K _0T =133.5 (±5.2) GPa and bulk modulus first pressure derivative K ^′ _0T =5.73 (±0.58). The apparent equation of state is found to be strongly dependent on the stress conditions in the sample. The stress dependency of the high-pressure properties is examined with anisotropic elasticity theory from subsequent measurements of energy-dispersive radial diffraction experiments in the diamond-anvil cell. The calculated values of K _0T depend largely upon the angle ψ between the diffracting plane normal and the maximum stress axis. The uniaxial stress component in the sample, t=σ₃−σ₁, varies with pressure as t=−3.11+0.43P between 10 and 30 GPa. The pressure derivatives of the elastic moduli dC ₁₁/dP=5.76 (±0.15), dC ₁₂/dP=1.41 (±0.11) and dC ₄₄/dP=1.92 (±0.06) are obtained from the diffraction data assuming previously reported zero-pressure ultrasonic data (C ₁₁=382 GPa, C ₁₂=31 GPa, and C ₄₄=109 GPa). Received: 21 December 2000 / Accepted: 11 July 2001     

Grain boundary and volume diffusion experiments in yttrium aluminium garnet bicrystals at 1,723 K: a miniaturized study

Yb-Y inter-diffusion along a single grain boundary of a synthetic yttrium aluminium garnet (YAG) bicrystal has been studied using analytical transmission electron microscopy (ATEM). To investigate the diffusion, a thin-film containing Yb as the diffusant was deposited perpendicular to the bicrystal grain boundary by pulsed laser deposition (PLD). Structural properties and their change with time in both the diffusant source and the grain boundary are reported. The diffusion profiles are incorporated in a numerical diffusion model, which is applied to determine the grain boundary diffusion coefficient, D _gb , at 1.723 K it is equal to 3 × 10⁻¹⁵ m²/s. We find that grain boundary diffusion is 4.85 orders of magnitude faster than volume diffusion, which was determined from the same diffusion experiment. This result is discussed in the context of special versus general grain boundaries. Finally, we successfully tested the capability of synchrotron-based nano-X-ray fluorescence analysis to map micro-chemical patterns in two dimensions with sub-micrometre resolution.     

Composition of aqueous fluid coexisting with mantle minerals at high pressure and its bearing on the differentiation of the Earth’s mantle

In order to understand the role of aqueous fluid on the differentiation of the mantle, the compositions of aqueous fluids coexisting with mantle minerals were investigated in the system MgO-SiO₂-H₂O at pressures of 3 to 10 GPa and temperatures of 1000 to 1500°C with an MA8-type multianvil apparatus. Phase boundaries between the stability fields of forsterite + aqueous fluid, forsterite + enstatite + aqueous fluid, and enstatite + aqueous fluid were determined by varying the bulk composition at constant temperature and pressure. The composition of aqueous fluid coexisting with forsterite and enstatite can be defined by the intersection of these two phase boundaries. The solubility of silicate components in aqueous fluid coexisting with forsterite and enstatite increases with increasing pressure up to 8 GPa, from about 30 wt% at 3 GPa to about 70 wt% at 8 GPa. It becomes almost constant above 8 GPa. The Mg/Si weight ratio of these aqueous fluids is much higher than at low pressure (0.2 at 1.5 GPa) and almost constant (1.2) at pressures between 3 and 8 GPa. At 10 GPa, it becomes about 1.4. Aqueous fluid migrating upward through the mantle can therefore dissolve large amounts of silicates, leaving modified Mg/Si ratios of residual materials. It is suggested that the chemical stratification of Mg/Si in the Earth may have been formed as a result of aqueous fluid migration.     

Grain boundary dissolution porosity in quartzofeldspathic ultramylonites: Implications for permeability enhancement and weakening of mid-crustal shear zones

Quartzofeldspathic ultramylonites from the Alpine Fault Zone, one of the world's major, active plate boundary-scale fault zones have quartz crystallographic preferred orientations (CPO) and abundant low-angle (<10° misorientation) boundaries, typical microstructures for dislocation creep-dominated deformation. Geometrically necessary dislocation density estimates indicate mean dislocation densities of ∼10⁹ cm⁻². A significant proportion (∼30%) of grain boundaries (>10° misorientation) are decorated by faceted pores, commonly with uniformly-oriented pyramidal shapes. Only grain boundaries with >10° misorientation angles in polymineralic aggregates are decorated by pores. Mean grain boundary pore densities are ∼5 × 10⁸ cm⁻². Grain boundary pores are dissolution pits generated during syn-deformational transient grain boundary permeability, nucleating on dislocation traces at dilatant grain boundary interfaces. They have not been removed by subsequent grain boundary closure or annealing. Pore decoration could have led to grain boundary pinning, triggering a switch in the dominant deformation mechanism to grain boundary sliding, which is supported by evidence of CPO destruction in matrix quartz. Pore-decorated grain boundaries have significantly reduced surface area available for adhesion and cohesion, which would reduce the tensile and shear strength of grain boundaries, and hence, the bulk rock. Grain boundary decoration also significantly decreased the mean distance between pores, potentially facilitating dynamic permeability. Consequently, these microstructures provide a new explanation for strain weakening and evidence of fluid flow along grain boundaries in mylonites at mid-crustal conditions.