Equation of state of silicate melts with densified intermediate-range order at the pressure condition of the Earth’s deep upper mantle

The knowledge from the compression behavior of densified SiO₂ glass suggests that SiO₂ melt may behave as a single phase having a densified network structure (intermediate-range order) at the pressure condition of the Earth’s deep upper mantle, including the transition zone. A simple and easy-to-use equation of state of silicate melts which is applicable to a wide range of chemical composition at the pressure condition of the deep upper mantle is proposed based on the assumption that SiO₂ component is in its densified state (or phase). The equation of state proposed in this study is consistent with all the available density data of silicate melts with an SiO₂ content of about 35–55 mol% measured with large-volume presses at pressures between 8 and 22 GPa. The equations of state in previous studies differ considerably from each other. The main reason for the discrepancies seems to be that the compression behavior of multiple states (or phases) of silicate melts has been described in most cases with a single equation of state. It is necessary to consider that silicate melts are in their densified states (or phases) in the deep upper mantle.     

Mössbauer studies of iron silicate spinel at high pressure

We have measured in situ Mössbauer transmission spectra of iron silicate spinel (γ-Fe₂SiO₄) in a diamond anvil cell at room temperature and pressures up to 16 GPa. The observed spectra show a doublet characteristic of the paramagnetic state. The isomer shift and quadrupole splitting at atmospheric pressure are 1.10 and 2.63 mm/s, respectively, which are smaller than those of fayalite (α-Fe₂SiO₄). Both the isomer shift and quadrupole splitting decrease linearly with pressure with slope of ?0.003(1) and ?0.020(1) mm/sec · GPa, respectively. This simple linear trend suggests that no electronic or polymorphic transitions occur under 16 GPa except for those due to the small and continuous changes of volume and local symmetry under pressure. On the basis of a crystalline field calculation, the negative pressure derivative of the quadrupole splitting is associated with a trend towards an ideal cubic symmetry of the oxygen sublattice.     

An infrared spectroscopic study of lawsonite to 20 GPa

The infrared spectrum of CaAl₂Si₂O₇ · H₂O-lawsonite, has been characterized to pressures of 20 GPa at 300 K. Our results constrain the response to compression of the silicate tetrahedra, hydroxyl units, and water molecules in this material. The asymmetric and symmetric stretching and bending vibrations of the Si₂O₇ groups (at zero pressure frequencies between 600 and 1000 cm⁻¹) increase in frequency with pressure at rates between 3.6 and 5.9 cm⁻¹/GPa. All silicate modes appear to shift continuously with pressure to 20 GPa, although the lowest frequency stretching vibration becomes unresolvable above 18 GPa, and a splitting of the main bending vibration is observed near this pressure. The O-H stretches of the hydroxyl units exhibit a discontinuity in their mode shifts at ∼8–9 GPa, which we interpret to be produced by a pressure-induced change in hydrogen bonding. The stretching and bending vibrations of the water molecule are relatively unaffected by compression to 20 GPa, thus demonstrating that the structural cavities in which water molecules reside are relatively rigid. Significant changes in the amplitude of the O-H stretches of the hydroxyl and water units are observed at this pressure as well; nevertheless, our results demonstrate that the dominant structural units in lawsonite persist metastably at 300 K with only modest structural modifications well beyond the known stability field of this phase. Received: 10 July 1998 / Revised, accepted: 23 October 1998     

Tetrahedral compression in (Mg,Fe)SiO3 orthopyroxenes

Single-crystal structure determinations at pressure have shown that the structural response of synthetic (Mg_0.6Fe_0.4)SiO₃ orthopyroxene to compression is the same as that previously observed in MgSiO₃ orthoenstatite. At pressure below ～4?GPa there is no significant compression of the SiO₄ tetrahedra, while above ～4?GPa the tetrahedra decrease in volume as a result of Si?O bond shortening. A study of the compressional behaviour of synthetic FeSiO₃ orthoferrosilite also shows the same behaviour below 4?GPa, but studies at higher pressures are precluded due to the transformation of the sample to the higher density C2/c high-clinoferrosilite polymorph. A further single-crystal study to 6?GPa of a Ca²⁺-containing natural orthopyroxene shows that chemical substitution of, primarily, Al³⁺ and Ca²⁺ into the structure of orthopyroxene inhibits the initial rapid compression of the M2?O3 bonds observed in the synthetic samples, and no significant tetrahedral compression is observed in this sample. Raman data collected from synthetic MgSiO₃ orthoenstatite show that there is a change in the rate of change of frequency with pressure, δν/δP, between 3.5 and 6.0?GPa, but no changes in the number of observed bands. These observations indicate a non-symmetry-breaking change in the properties of the orthoenstatite, which is associated with the change in compression mechanism observed using X-ray diffraction techniques at this pressure.     

An X-ray diffraction study of shock-wave-densified SiO<Subscript>2</Subscript> glasses

 The densification and structural changes in SiO₂ glass compressed up to 43.4 GPa by shock experiments are investigated quantitatively by the X-ray diffraction technique. Direct structural data (average Si–O and Si–Si distances and Si–O–Si angles, coordination number of the Si atom) of these shock-densified SiO₂ glasses have been obtained by analyzing the radial distribution function curves, RDF(r), calculated with X-ray diffraction data. The coordination number of all densified glasses is about 4 and shows almost no pressure variation. The SiO₂ glass has shown density increase of 11% at a shock compression of 26.3 GPa. This density evolution could not be explained by the coordination change. The reduction of the average Si–O–Si angle (144° at 0 GPa to 136° at 26.3 GPa) obtained from RDF(r) data may account for this density increase. This Si–O–Si angle change may be caused by shrinkage of the network structure and the increase of small rings of SiO₄ tetrahedra. For higher shock pressure, a decrease in the Si–O–Si angle to 140° was observed. This is consistent with the decrease in density at 32.0 and 43.2 GPa. This decrease in the Si–O–Si angle and density could be attributed to an annealing effect due to high after-shock residual temperature. This pressure dependence of average Si–O–Si angles in shock-densified SiO₂ glass agrees with the results of our previous Raman spectroscopic study. On the other hand, the pressure variation for the first sharp diffraction peak (FSDP) was analyzed to estimate the evolution of intermediate range structures. It is suggested that the mean d value (d _m ) obtained from the position of FSDP strongly depends on the shock and residual temperature, as well as shock pressure. Received: 29 June 2001 / Accepted: 14 November 2001     

Do carbonate liquids become denser than silicate liquids at pressure? Constraints from the fusion curve of K<Subscript>2</Subscript>CO<Subscript>3</Subscript> to 3.2 GPa

Brackets on the melting temperature of K₂CO₃ were experimentally determined at 1.86 ± 0.02 GPa (1,163–1,167°C), 2.79 ± 0.03 GPa (1,187–1,195°C), and 3.16 ± 0.04 GPa (1,183–1,189°C) in a piston-cylinder apparatus. These new data, in combination with published experiments at low pressure (<0.5 GPa), establish the K₂CO₃ fusion curve to 3.2 GPa. On the basis of these experiments and published thermodynamic data for crystalline and liquid K₂CO₃, the high-pressure density and compressibility of K₂CO₃ liquid were derived from the fusion curve. The pressure dependence of the liquid compressibility (K′₀ = dK ₀/dP, where K ₀ = 1/β₀) is between 16.2 and 11.6, with a best estimate of 13.7, in a third-order Birch–Murnaghan equation of state (EOS). This liquid K′₀ leads to a density of 2,175 ± 36 kg/m³ at 4 GPa and 1,500°C, which is ∼30% lower than that reported in the literature on the basis of the falling-sphere method at the same conditions. The uncertainty in the liquid K′₀ leads to an error in melt density of ± 2% at 4 GPa; the error decreases with decreasing pressure. With a K′₀ of 13.7, the compressibility of K₂CO₃ at 1,500°C and 1 bar (K ₀ = 3.8 GPa) drops rapidly with increasing pressure ( ), which prevents a density crossover with silicate melts, such as CaAlSi₂O₈ and CaMgSi₂O₆, at upper mantle depths.     

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     

High-pressure Raman spectroscopic study of Mn2GeO4, Ca2GeO4, Ca2SiO4, and CaMgGeO4 olivines

We present a Raman spectroscopic study of the structural modifications of several olivines at high pressures and ambient temperature. At high pressures, the following modifications in the Raman spectra are observed: 1)?in Mn₂GeO₄, between 6.7 and 8.6?GPa the appearance of weak bands at 560 and 860?cm^?1; between 10.6 and 23?GPa, the progressive replacement of the olivine spectrum by the spectrum of a crystalline high pressure phase; upon decompression, the inverse sequence of transformations is observed with some hysteresis in the transformation pressures; this sequence may be interpreted as the progressive transformation of the olivine to a spinelloid where Ge tetrahedra are polymerized, and then to a partially inverse spinel; 2)?in Ca₂SiO₄, the olivine transforms to larnite between 1.9 and 2.1?GPa; larnite is observed up to the maximum pressure of 24?GPa and it can partially back-transform to olivine during decompression; 3)?in Ca₂GeO₄, the olivine transforms to a new structure between 6.8 and 8?GPa; the vibrational frequencies of the new phase suggest that the phase transition involves an increase of the Ca coordination number and that Ge tetrahedra are isolated; this high pressure phase is observed up to the maximum pressure of 11?GPa; during decompression, it transforms to a disordered phase below 5?GPa; 4)?in CaMgGeO₄, no significant modification of the olivine spectrum is observed up to 15?GPa; between 16 and 26?GPa, broadening of some peaks and the appearance of a weak broad feature at 700–900?cm^?1 suggests a progressive amorphization of the structure; near 27?GPa, amorphization is complete and an amorphous phase is quenched down to ambient pressure; this unique behaviour is interpreted as the result of the incompatibilities in the high pressure behaviour of the Ca and Mg sublattices in the olivine structure.     

Molecular dynamics studies of CaAl2Si2O8 liquid. Part II: Equation of state and a thermodynamic model

A thermodynamic model and equation of state (EOS) is developed from the molecular dynamics simulation experiments of Spera et al. (2009) for CaAl₂Si₂O₈ liquid over the temperature range 3500-6000 K and pressure interval 0-125 GPa. The model is constructed utilizing the isothermal Universal EOS of Vinet et al. (1986) combined with an expression for the temperature-dependence of the internal energy derived from density functional theory (Rosenfeld and Tarazona, 1998). It is demonstrated that this model is more successful at reproducing the data than the temperature-dependent Universal EOS (Vinet et al., 1987) or the volume-explicit EOS of Ghiorso (2004a). Distinct parameterizations are required to model low (<20 GPa) and high (>20 GPa) pressure regimes. This result is ascribed to the affect of liquid structure on macroscopic thermodynamic properties, specifically the interdependence of average cation-oxygen coordination number on the bulk modulus. The thermodynamic transition between the high- and low-pressure parameterizations is modeled as second order, although the nature of the transition is open to question and may well be first order or lambda-like in character.Analysis of the thermodynamic model reveals a predicted region of liquid-liquid un-mixing at low-temperatures (<1624 K) and pressures (<1.257 GPa). These pressure-temperature conditions are above the glass transition temperature but within the metastable liquid region. They represent the highest temperatures yet suggested for liquid-liquid un-mixing in a silicate bulk composition. A shock wave Hugoniot curve is calculated for comparison with the experimental data of Rigden et al. (1989) and of Asimow and Ahrens (2008). The comparison suggests that the model developed in this paper underestimates the density of the liquid by roughly 10% at pressures greater than ∼20 GPa.     

High-pressure single-crystal X-ray diffraction and synchrotron Mössbauer study of monoclinic ferrosilite

The phase and spin transitions in single-crystal monoclinic ferrosilite, FeSiO₃, were investigated using X-ray diffraction and Mössbauer spectroscopy up to lower-mantle pressures and room temperature in a helium pressure medium. Using single-crystal X-ray diffraction, we measured the equation of state of ferrosilite up to about 43 GPa. We observed a P2₁/c-to-C2/c phase transition between 1.5 and 1.7 GPa and a phase transition from C2/c to a distinct P2₁/c structure between 30 and 34 GPa. With time-domain Mössbauer spectroscopy, we determined the hyperfine parameters of ferrous iron up to 95 GPa. The phase transitions were correlated with discontinuities in Mössbauer spectral features. We observed the onset of high-spin-to-low-spin transitions in the M1 and M2 sites at ～37 GPa and ～74 GPa, respectively. Understanding the electronic structure of iron in a well-characterized single crystal of ferrosilite may help interpret the behavior of iron in complex dense silicate phases.     

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     

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.     

Mineral/melt partitioning of trace elements during hydrous peridotite partial melting

This experimental study examines the mineral/melt partitioning of incompatible trace elements among high-Ca clinopyroxene, garnet, and hydrous silicate melt at upper mantle pressure and temperature conditions. Experiments were performed at pressures of 1.2 and 1.6 GPa and temperatures of 1,185 to 1,370 °C. Experimentally produced silicate melts contain up to 6.3 wt% dissolved H ₂O, and are saturated with an upper mantle peridotite mineral assemblage of olivine+orthopyroxene+clinopyroxene+spinel or garnet. Clinopyroxene/melt and garnet/melt partition coefficients were measured for Li, B, K, Sr, Y, Zr, Nb, and select rare earth elements by secondary ion mass spectrometry. A comparison of our experimental results for trivalent cations (REEs and Y) with the results from calculations carried out using the Wood-Blundy partitioning model indicates that H ₂O dissolved in the silicate melt has a discernible effect on trace element partitioning. Experiments carried out at 1.2 GPa, 1,315 °C and 1.6 GPa, 1,370 °C produced clinopyroxene containing 15.0 and 13.9 wt% CaO, respectively, coexisting with silicate melts containing ~1–2 wt% H ₂O. Partition coefficients measured in these experiments are consistent with the Wood-Blundy model. However, partition coefficients determined in an experiment carried out at 1.2 GPa and 1,185 °C, which produced clinopyroxene containing 19.3 wt% CaO coexisting with a high-H ₂O (6.26±0.10 wt%) silicate melt, are significantly smaller than predicted by the Wood-Blundy model. Accounting for the depolymerized structure of the H ₂O-rich melt eliminates the mismatch between experimental result and model prediction. Therefore, the increased Ca ²⁺ content of clinopyroxene at low-temperature, hydrous conditions does not enhance compatibility to the extent indicated by results from anhydrous experiments, and models used to predict mineral/melt partition coefficients during hydrous peridotite partial melting in the sub-arc mantle must take into account the effects of H ₂O on the structure of silicate melts.     

Phase relation of CaSO<Subscript>4</Subscript> at high pressure and temperature up to 90 GPa and 2300 K

Calcium sulfate (CaSO₄), one of the major sulfate minerals in the Earth’s crust, is expected to play a major role in sulfur recycling into the deep mantle. Here, we investigated the crystal structure and phase relation of CaSO₄ up to ~90 GPa and 2300 K through a series of high-pressure experiments combined with in situ X-ray diffraction. CaSO₄ forms three thermodynamically stable polymorphs: anhydrite (stable below 3 GPa), monazite-type phase (stable between 3 and ~13 GPa) and barite-type phase (stable up to at least 93 GPa). Anhydrite to monazite-type phase transition is induced by pressure even at room temperature, while monazite- to barite-type transition requires heating at least to 1500 K at ~20 GPa. The barite-type phase cannot always be quenched from high temperature and is distorted to metastable AgMnO₄-type structure or another modified barite structure depending on pressure. We obtained the pressure–volume data and density of anhydrite, monazite- and barite-type phases and found that their densities are lower than those calculated from the PREM model in the studied P–T conditions. This suggests that CaSO₄ is gravitationally unstable in the mantle and fluid/melt phase into which sulfur dissolves and/or sulfate–sulfide speciation may play a major role in the sulfur recycling into the deep Earth.     

A high pressure infrared spectroscopic study of PbCO3-cerussite: constraints on the structure of the post-aragonite phase

We have measured the infrared spectrum of aragonite-structured PbCO₃-cerussite to 41 GPa at 300 K in the diamond anvil cell. We observed a phase transition from an orthorhombic to a trigonal structure beginning at ~15 GPa, manifested by a splitting of the ν₂-out-of-plane bending vibration and a broadening and dramatic decrease in amplitude of the ν₁-symmetric stretching vibration of the carbonate group. While the locations of the ν₁-symmetric stretching and ν₄-in-plane bending bands are similar between the low- and high-pressure phases, their mode shifts and peak shapes change markedly near the transition. In particular, the ν₁ symmetric stretch has an essentially zero pressure shift in the high pressure phase, and its dramatically enhanced peak width indicates that it may be symmetry forbidden. The decreased mode shifts of the carbonate vibrations after the phase transition suggest that the carbonate group is less compressible in the new structure. The spectral changes observed are consistent with a small, trigonal unit cell, with space group ${P\bar{3}{1c}}$ and two formula units, instead of a previously proposed orthorhombic cell with sixteen formula units. This structure is identical to that of the high-pressure phase of BaCO₃, and likely CaCO₃ as well. Our results thus indicate that the post-aragonite, high-pressure phase of divalent-cation carbonates may be a comparatively high-symmetry trigonal structure.     

Structure and properties of rare earth silicates with the apatite structure at high pressure

The pressure-induced structural transformation of rare earth, non-stoichiometric silicates, (REE_9.33(SiO₄)₆O₂, RE = La, Ce, Nd, Eu, and Gd) with the apatite structure type, were investigated by X-ray diffraction, photoluminescence, far-infrared spectroscopy, and DFT calculations. A pressure-induced degradation of symmetry from P6 ₃ /m to P6 ₃ occurs with increasing pressure. The transition is due to the tilting of SiO₄ tetrahedra and reduced symmetry constraints on one of the O atoms in the tetrahedron. The critical transition pressure increased from ~13 GPa in La_9.33(SiO₄)₆O₂ to ~25 GPa in Gd_9.33(SiO₄)₆O₂ with the decrease in lanthanide cation size. The high-pressure phase shows an unexpectedly low value for the bulk modulus over a narrow pressure range (below ~30 GPa), as compared with the low-pressure phase, especially for the structure with larger rare earth elements. High-pressure studies of alkaline earth-doped samples (Nd₈ A ₂(SiO₄)₆O₂ where A = Ca, Sr) showed that the pressure for the phase transition is mainly related to the size of lanthanides that occupy the large channels along the c axis of the apatite structure type.     

High pressure behaviour of lead feldspar (PbAl2Si2O8)

An in situ high pressure powder diffraction study, using high-brilliance synchrotron radiation, on lead feldspar (PbAl₂Si₂O₈) was performed. Two samples, with Q _od=0.68 and 0.76, were loaded in a diamond anvil cell and were compressed up to 11 GPa. Up to P=7.1 GPa the only phase present is lead feldspar. In the range 7.1–9.4 GPa sudden changes in the position of the reflections suggest the transformation of lead feldspar to a new phase (probably feldspar-like). The absence of split that would be compatible with triclinic symmetry rules out the monoclinic-triclinic transition, that was reported for the structurally similar strontium feldspar. At P>9.4 GPa some new extra reflections not indexable in the feldspar cell are present as well. During decompression the lead feldspar was the only phase present at P<6 GPa. Peak enlargement was observed with pressure, probably preliminary to amorphization. However almost complete amorphization was observed only after fortuitous shock compression at ∼18 GPa; the crystallinity was recovered at room pressure after decompression. The bulk modulus for lead feldspar was K=71.0(9) and 67.6(1.2) GPa for the two samples, in the range reported for feldspars. The cell parameters show a compression pattern which is similar to that observed in anorthite, with Δa/a ₀>Δc/c ₀>Δb/b ₀; comparison with the high temperature behaviour shows that for lead feldspar the strain tensor with pressure is more isotropic and the deformation along a is less prominent. A turnover in the behaviour of the β angle with pressure suggests a change in the compression behaviour at P∼2 GPa. Rietveld refinement of the Pb coordinates was performed in a series of spectra with pressure ranging from 0.6 to 6.5 GPa. The combined analysis of cell parameters and Pb coordinates with pressure showed that the compression of the structure is mainly achieved by an approach of Pb atoms along a *. Received: 21 July 1998 / Revised, accepted: 13 October 1998     

Raman spectroscopic study of hydrous <Emphasis Type="Italic">γ</Emphasis>-Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> to 56.5 GPa

 Raman spectra of a single-crystal fragment of hydrous γ-Mg₂SiO₄, synthesized in a multianvil press, have been measured in a diamond-anvil cell with helium as pressure-transmitting medium to 56.5 GPa at room temperature. All five characteristic spinel Raman modes shift continuously up to the highest pressure, showing no evidence for a major change in the crystal structure despite compression well beyond the stability field of ringwoodite in terms of pressure. At pressures above ∼30 GPa a new mode on the low-frequency site of the two silicate-stretching modes is clearly identifiable, indicating a modification in the spinel structure which is reversible on pressure release. The frequency of the new mode (802 cm⁻¹ extrapolated to 1 bar) suggests the presence of Si–O–Si linkages and/or a partial increase in the coordination of Si. Direct determination of the subtle structural change causing the new Raman mode would require high-pressure, single-crystal synchrotron X-ray diffraction experiments. The Raman modes of hydrous and anhydrous Mg-end-member ringwoodite are nearly identical up to 20 GPa, suggesting that protonation has only minor effect on the lattice dynamics over the entire pressure stability range for ringwoodite in the mantle. Received: 7 December 2001 / Accepted: 16 April 2002     

H<Subscript>2</Subscript>O storage capacity of MgSiO<Subscript>3</Subscript> clinoenstatite at 8–13 GPa, 1,100–1,400°C

We present H₂O analyses of MgSiO₃ pyroxene crystals quenched from hydrous conditions in the presence of olivine or wadsleyite at 8–13.4 GPa and 1,100–1,400°C. Raman spectroscopy shows that all pyroxenes have low clinoenstatite structure, which we infer to indicate that the crystals were high clinoenstatite (C2/c) during conditions of synthesis. H₂O analyses were performed by secondary ion mass spectrometry and confirmed by unpolarized Fourier transform infrared spectroscopy on randomly oriented crystals. Measured H₂O concentrations increase with pressure and range from 0.08 wt.% H₂O at 8 GPa and 1,300°C up to 0.67 wt.% at 13.4 GPa and 1,300°C. At fixed pressure, H₂O storage capacity diminishes with increasing temperature and the magnitude of this effect increases with pressure. This trend, which we attribute to diminishing activity of H₂O in coexisting fluids as the proportion of dissolved silicate increases, is opposite to that observed previously at low pressure. We observe clinoenstatite 1.4 GPa below the pressure stability of clinoenstatite under nominally dry conditions. This stabilization of clinoenstatite relative to orthoenstatite under hydrous conditions is likely owing to preferential substitution of H₂O into the high clinoenstatite polymorph. At 8–11 GPa and 1,200–1,400°C, observed H₂O partitioning between olivine and clinoenstatite gives values of D ^ol/CEn between 0.65 and 0.87. At 13 GPa and 1,300°C, partitioning between wadsleyite and clinoenstatite, D ^wd/CEn, gives a value of 2.8 ± 0.4.     

Molecular dynamics investigation of viscosity, chemical diffusivities and partial molar volumes of liquids along the MgO-SiO2 join as functions of pressure

Molecular dynamics simulations are carried out to systematically address the effects of composition and pressure on melts along the MgO-SiO₂ join and elucidate the role of structural modifier content on silicate melt properties. The MgO-SiO₂ system shows non-ideal mixing with a negative excess volume of mixing at low pressures, but the mixing becomes closer to ideal at higher pressures. At atmospheric pressure, the viscosities and diffusivities vary by more than 3 orders of magnitude as the composition is varied along this join, with the low SiO₂ melts characterized by lower viscosities and higher diffusivities; these results are in quantitative agreement with experimental results for the dependence of viscosity and diffusivity on structural modifier content in a wide range of silicate systems. The transport properties of melts in this system converge at higher pressures; at pressures greater than ∼15 GPa the viscosity and diffusivities vary by less than an order of magnitude across the entire range of compositions. The relevance of equations that relate the viscosity and diffusivity is also addressed.