High-pressure phase transformations in the system CaSiO3-Al2O3

Phase assemblages for five selected compositions in the system CaSiO₃-Al₂O₃ have been investigated in the pressure range 100–300 kbar and at about 1000°C in a diamond-anvil press coupled with laser heating. At pressures below about 250 kbar, the assemblage of grossularite plus corundum is stable for compositions containing more than 25 mole% Al₂O₃. Above about 250 kbar, phase assemblages for the latter compositions are truncated by those in the join CaAl₂O₄-SiO₂. Garnet solid solutions are stable between about 10 and 25 mole% Al₂O₃. Grossularite transforms to a new tetragonal form at pressures greater than about 250 kbar, but the stability field for the garnet solid solutions extends to pressures up to about 300 kbar. The perovskite modification appears to be stable at pressures above about 150 kbar, but is probably limited to nearly pure CaSiO₃ composition. Phase behaviour for calcium-bearing silicates or aluminosilicates in the lower mantle are apparently more complicated than was suggested earlier.     

Disproportionation of Ni2SiO4 to stishovite plus bunsenite at high pressures and temperatures

Samples of Ni₂SiO₄ in both olivine and spinel phases have been compressed to pressures above 140 kbar in a diamond-anvil cell and heated to temperatures of 1400–1800°C using a continuous YAG laser. After quenching and releasing pressure, X-ray diffraction examination indicates that the samples disproportionate to a mixture of stishovite (SiO₂) and bunsenite (NiO) at pressures between 140 and 190 kbar. The exact disproportionation pressure is not certain due to transient increases in pressure during the local and rapid heating. However, thermodynamic calculations suggest that the transition pressure is about 192 ± 4 kbar at 1545°C and that the equation of the spinel-mixed oxides phase boundary isP(kbar) = 121 + (0.046 ± 0.020) T (°C).     

Disproportionation of kyanite to corundum plus stishovite at high pressure and temperature

Natural kyanite (Al₂SiO₅) has been found to disproportionate into a mixture of its component oxides, corundum and stishovite, at a loading pressure of about 160 kbar and temperature between 1000–1400°C in a diamond-anvil press. The exact transition pressure is not certain due to transient increases in pressure during the local and rapid heating by a continuous YAG laser. The phase boundary, however, has been estimated to be P(kbar) = (138 ～ 174) + 0.011 T (°C) on the basis of the available thermodynamic data. The shock-wave Hugoniot data above 650 kbar for andalusite (Al₂SiO₅) and sillimanite (Al₂SiO₅) as starting materials are consistent with the present results.     

The system enstatite-wollastonite at high pressures and temperatures,with emphasis on diopside

High-pressure phase transformations for three intermediate compositions (including diopside) in the system enstatite (MgSiO₃)-wollastonite (CaSiO₃) were investigated in the pressure range 100–300 kbar at about 1000°C in a diamond-anvil press coupled with laser heating. The phase behaviour of the two end components (enstatite and wollastonite) at high pressure has been reported earlier. The results of this study reveal that there is very limited solid solution of diopside (CaMgSi₂O₆) in the various high-pressure phase assemblages of enstatite. At pressures greater than about 200 kbar, diopside and a composition between diopside and wollastonite were found to transform into non-quenchable phases, as does wollastonite. It is thought probable that diopside and wollastonite form solid solutions with the perovskite structure at high pressure, but that on release of pressure it is not possible to preserve the high-pressure modification.     

High-pressure decomposition of Ca2GeO4 and Ca2MnO4 with the K2NiF4-type structures

By using the diamond-anvil pressure cell coupled with laser heating, Ca₂GeO₄ in the K₂NiF₄-type structure has been found to decompose into the mixture Ca₃Ge₂O₇ plus CaO at pressures greater than 200 kbar and at about 1000°C, and the same type of structure for Ca₂MnO₄ has been found to decompose into the mixture CaMnO₃ (perovskite) plus CaO at pressures greater than 100 kbar and at about 1400°C. The decomposition product of Ca₃Ge₂O₇ is a new compound which is isostructural with Sr₃Ti₂O₇ and has the lattice parameters of a = 3.72 ± 0.01 and $\text{c = 19.32 ± 0.05}\text{A}\text{?}$ at room temperature and 1 bar pressure. The results of the study of Ca₂GeO₄ and Ca₂MnO₄ (both with the K₂NiF₄-type structure) strongly support the view that compounds possessing the K₂NiF₄-type structure are unstable relative to corresponding mixtures possessing the perovskite and rocksalt structures. It is concluded that, in the earth's mantle, the K₂NiF₄-type Ca₂SiO₄ would ultimately decompose into the mixture CaSiO₃ (perovskite) + CaO or would otherwise transform to other as-yet-unknown phase(s), and that the mixture of MgSiO₃ (perovskite) + MgO (the post-spinel phase of Mg₂SiO₄) would not adopt the K₂NiF₄-type structure.     

High-pressure phase transformations in baddeleyite and zircon,with geophysical implications

Phase transformations in baddeleyite (ZrO₂) and zircon (ZrSiO₄) have been investigated in the pressure range between 100 and 300 kbar at about 1000°C in a diamond-anvil press coupled with laser heating. Baddeleyite has been found to transform to an orthorhombic cotunnite-type structure at pressures greater than 100 kbar, and is the first oxide known to adopt this structure. The lattice parameters of the cotunnite-type ZrO₂ at room temperature and atmospheric pressure area = 3.328 ± 0.001 ,b = 5.565 ± 0.002 , andc = 6.503 ± 0.003A? withZ = 4 , and its volume is 14.3% smaller than baddeleyite and 7.6% smaller than the fluorite-type ZrO₂. It is suggested that all the polymorphic structures of ZrO₂ are possible high-pressure models for the post-rutile phase of SiO₂. The polyhedral coordination in these model structures varies from 7 to “9”, compared with 6 for stishovite. If SiO₂ were to adopt any of these structures in the deep mantle, Birch's hypothesis of a mixed-oxide lower mantle may still be viable, but the primary coordination of silicon would be greater than 6. Zircon has been found to transform to a scheelite-type structure at about 120 kbar as noted earlier. The scheelite-type ZrSiO₄ was found to decompose further into a mixture of ZrO₂ (cotunnite-type) plus SiO₂ (stishovite) in the pressure range 200–250 kbar. As implied by the transitions in zircon, the large cations of U and Th in the earth's deep mantle are most likely to occur in dioxides with structures such as the cotunnite-type, rather than to occur in silicates.     

Compression and phase behavior of solid CO2 to half a megabar

CO₂ has been investigated up to 514 kbar at23 ± 2°C by both optical and in situ X-ray diffraction studies using a diamond-anvil pressure cell. CO₂ solidifies in an unknown structure in the pressure range 5 to 23 kbar, and transforms to ordinary dry-ice structure above 23 kbar at room temperature. Isothermal compression data for dry ice have been obtained above about 24 kbar. These appear to be the first data at room temperature known in the literature. The data fitted to the Birch equation of state yieldK₀ = 29.3 ± 1.0kbar andK₀^′ = 7.8 assuming the volume of the hypothetical dry ice at zero-pressure and room temperature is 31.4 ± 0.2 cm³/mole. The isothermal bulk modulus(K₀) thus derived is consistent with the compression data and compressibilities for dry ice obtained at low temperatures using dilatometry and ultrasonic techniques, respectively, reported in the literature. By comparing shock-wave data for relevant materials, it is suggested that CO₂ is not likely to transform to one of the crystalline forms of SiO₂ which is otherwise expected from empirical grounds, but may instead decompose into C (diamond) + O₂, at high pressures.     

Petrogenesis of basalts from the project FAMOUS area: experimental study from 0 to 15 kbars

Tholeiitic basalt glasses from the FAMOUS area of the Mid-Atlantic Ridge are among the most primitive basaltic liquids reported from the ocean basins. One of the more primitive of these[Mg/(Mg+Fe²⁺) = 0.68;Ni= 232ppm;TiO₂ = 0.61] glasses (572-1-1) was selected for an experimental investigation. This study found olivine to be the liquidus phase from 1 atm to 10.5 kbar where it is replaced by clinopyroxene. The sequence of appearance of phases at 1 atm pressure is olivine (1268°C), plagioclase (1235°C) and clinopyroxene (1135°C). The sample is multiply saturated at 10.5 kbar with olivine (Fo₈₈), clinopyroxene (Wo₃₂En₆₀Fs₉), and orthopyroxene (Wo₅En₈₃Fs₁₂). From the 1-atm data we have measured (FeO/MgO) olivine/(FeO*/MgO) liquid (K′_D) for olivine-melt pairs equilibrated at 12 temperatures in the range 1268–1205°C.K′_D varies from 0.30 at 1205°C to 0.27 at 1268°C. Analysis of high-pressure olivine melt pairs indicates a systematic increase inK′_D with pressure.Evaluation of the 1-atm experiments reveals that fractionation of olivine followed by olivine + plagioclase can generate much of the variation in major element chemistry observed in the FAMOUS basalt glasses. However, it cannot account for the entire spectrum of glass compositions — particularly with respect to TiO₂ and Na₂O. The variations in these components are such as to require different primary liquids.Comparison of clinopyroxene microphenocrysts/xenocrysts found in oceanic tholeiites with experimental clinopyroxenes reveal that the majority of those in the tholeiites may have crystallized from the magma at pressures greater than ～ 10 kbar and are not accidental xenocrysts. Clinopyroxene fractionation at high pressures may be a viable mechanism for fractionating basaltic magmas.The major and minor element mineral/meltK′_d's from our experiments have been used to model the source region residual mineralogy for given percentages of partial melting. These data suggest that ～20% partial melting of a lherzolite source containing 0–10% clinopyroxene can generate the major and minor element concentrations in the parental magmas of the Project FAMOUS basalt glasses.     

Viscosity and structural changes of albite (NaAlSi3O8) melt at high pressures

Viscosity of anhydrous albite melt, determined by the falling-sphere method in the solid-media, piston-cylinder apparatus, decreases with increasing pressure from 1.13 × 10⁵ P at 1 atm to 1.8 × 10⁴ P at 20 kbar at 1400°C. The rate of decrease in viscosity is larger between 12 and 15 kbar than in other pressure ranges examined. The density of the quenched albite melt increases with increasing pressure of quenching from 2.38 g/cm³ at 1 atm to 2.53 g/cm³ at 20 kbar. The rate of increase in density is largest at pressures between 15 and 20 kbar. The melting curve of albite shows an inflexion at about 16 kbar. These observations strongly suggest that structural changes of albite melt would take place effectively at pressures near 15 kbar. Melt of jadeite (NaAlSi₂O₆) composition shows very similar changes in viscosity and density and a melting curve inflexion at pressures near 10 kbar. Difference in pressure for the suggested effective structural changes of albite and jadeite melts is 5–6 kbar, which is nearly the same as that between the subsolidus reaction curves nepheline + albite= 2jadeite and albite=jadeite + quartz. The structural changes of the melts are, however, continuous and begin to take place at pressures lower than those of the crystalline phases.     

Volume relaxation of compacted SiO2 glass: a model for the conservation of natural diaplectic glasses

Relaxation experiments on vitreous SiO₂, densified at 900°C, 20 kbar to a permanent density of 2.36 g cm^?3 yield an activation energy of69 ± 5kcal mol^?1 in the temperature range 700–800°C. The data can be used to estimate minimum cooling rates, maximum depositional temperatures or maximum thicknesses of shock-metamorphosed rocks containing diaplectic glasses, if relaxation of a glass densified under dynamic conditions is assumed to be similar to that of statically densified glass.     

Elasticity of polycrystalline stishovite

Ultrasonic data for the velocities of SiO₂-stishovite have been determined as a function of pressure to 10 kbar at room temperature for polycrystalline specimens hot-pressed at pressures P = 120kbar and temperatures T = 900°C. These cylindrical specimens are 2 mm in diameter and 0.9–1.4 mm long and have a grain size less than 10 μm. Compressional and shear wave velocities were measured both parallel and perpendicular to the axis of pressing and were found to be isotropic at 10 kbar with ν_p = 11.0 ± 0.2km/sec andν_s = 6.9 ± 0.3km/sec; this shear velocit is substantially higher than that of Mizutani et al. (1972) perhaps due to the presence of crack orientations in their specimen which affected ν_s but not ν_p. The Murnaghan P-V trajectories calculated from the ultrasonic data [bulk modulus K_s = 2.5 ± 0.3Mbar and assuming (?K_s/?P)_T = 6 ± 2] are consistent with recent hydrostatic compression data and with the shock wave compression data above 600 kbar. The combined evidence from the data of the ultrasonic and hydrostatic compression techniques suggests that the most probable value of the bulk modulus of stishovite at zero pressure is close to the upper limit of the uncertainty of our ultrasonically determined value, K₀ = 2.7?2.8Mbar. Elasticity data for rutile-type oxides are not compatible with normal K_s-V₀ systematics perhaps due to the neglect of non-central forces in the lattice model. These new stishovite data would make it impossible to satisfy the elasticity-density data of the lower mantle using an oxide mixture with either olivine or pyroxene stoichiometry.     

A new high-pressure phase of spinel

A new phase which is much denser than the component oxides of spinel (MgAl₂O₄) was synthesised at loading pressures greater than 250 kbar and at about 1000°C in a diamond-anvil press coupled with laser heating. The new phase (ε-MgAl₂O₄) was indexed on the basis of an orthorhombic cell with a = 8.507 ± 0.004, b = 2.740 ± 0.003, c = 9.407 ± 0.005Å, and Z = 4 at room temperature and 1 bar pressure. Thus the molar volume for ε-MgAl₂O₄ at the above conditions was calculated to be 33.01 ± 0.07 cm³, which is 10.3% less than that of the mixture corundum plus periclase. The dense phase of spinel found in shock-wave experiments can be reasonably interpreted as ε-MgAl₂O₄, and this may be a potentially important mineral component of the earth's lower mantle. The new structure may also provide a possible candidate for the dense phases of Fe₃O₄ and Mg₂SiO₄ which were found by shock experiments.     

Forecasting the duration of volcanic eruptions: an empirical probabilistic model

Various xenoliths have been found in lavas of the 1763 (“La Montagnola”), 2001, and 2002–03 eruptions at Mt. Etna whose petrographic evidence and mineral chemistry exclude a mantle origin and clearly point to a cognate nature. Consequently, cognate xenoliths might represent a proxy to infer the nature of the high-velocity body (HVB) imaged beneath the volcano by seismic tomography. Petrography allows us to group the cognate xenoliths as follows: i) gabbros with amphibole and amphibole-bearing mela-gabbros, ii) olivine-bearing leuco-gabbros, iii) leuco-gabbros with amphibole, and iv) Plg-rich leuco gabbros. Geobarometry estimates the crystallization pressure of the cognate xenoliths between 1.9 and 4.1 kbar. The bulk density of the cognate xenoliths varies from 2.6 to 3.0 g/cm³. P wave velocities (V _P ), calculated in relation to xenolith density, range from 4.9 to 6.1 km/s. The integration of mineralogical, compositional, geobarometric data, and density-dependent V _P with recent literature data on 3D V _P seismic tomography enabled us to formulate the first hypothesis about the nature of the HVB which, in the depth range of 3–13 km b.s.l., is likely made of intrusive gabbroic rocks. These are believed to have formed at the “solidification front”, a marginal zone that encompasses a deep region (>5 km b.s.l.) of Mt. Etna’s plumbing system, within which magma crystallization takes place. The intrusive rocks were afterwards fragmented and transported as cognate xenoliths by the volatile-rich and fast-ascending magmas of the 1763 “La Montagnola”, 2001 and 2002–03 eruptions.     

Synthesis of a new high-pressure phase of manganese dioxide

Both amorphous and crystalline (rutile) forms of MnO₂ have been subjected to loading pressures of 220 and 250 kbar and heated by a laser to approximately 1000°C in a diamond-anvil press. In all runs, X-ray diffraction study of the quenched sample reveals a mixture of pyrolusite (the rutile form of MnO₂) plus an unknown phase. This phase has been tentatively indexed on the basis of a large cubic cell with lattice parameter a₀ = 9.868 ± 0.011Å. Shock-wave data for MnO₂ up to 1300 kbar indicate that any phase transformation must involve only a small volume change. If the high-pressure phase is the cubic phase of this paper, then the latter has 36 formula units per unit cell, implying a zero-pressure volume change of 3.2% from the rutile to cubic phase. The cubic phase may provide an alternative model for the high-pressure phase of oxides having the rutile structure.     

Phase relations in the system LiFMgF2 at elevated pressures: Implications for the proposed mixed-oxide zone of the earth's mantle

Solvi and liquidi for various LiFMgF₂ mixtures have been determined at pressures up to 40 kbar by differential-thermal-analysis in a piston-cylinder high-pressure device. The melting curves of pure LiF and MgF₂ were also studied and the initial slopes (dT_m/dP)_{P = 0} were found to be 11.2 and 8.3°C/kbar, respectively. The eutectic composition (LiF)_0.64(MgF₂)_0.36 is independent of pressure to 35 kbar and the eutectic temperature rises approximately 6.3°C per kbar. Initial slopes of 11°C/kbar and 35°C/kbar are inferred for the melting curves of MgO and SiO₂ (stishovite) respectively, on the basis of data for their structural analogue compounds. The observed solid solution of LiF in MgF₂ and other evidence suggest the possibility of solid solution in the system (Mg,Fe)OSiO₂ (stishovite) under mantle conditions which may have important consequences for the elastic properties of a “mixed-oxide” zone of the earth's mantle.     

Pressure dependence of nickel partitioning between forsterite and aluminous silicate melts

Nickel partitioning between forsterite and aluminosilicate melt of fixed bulk composition has been determined at 1300°C to 20 kbar pressure. The value of the forsterite-liquid nickel partition coefficient is lowered from >20 at pressures equal to or less than 15 kbar to <10 at pressures above 15 kbar.Published data indicate that melts on the join Na₂O-Al₂O₃-SiO₂ become depolymerized in the pressure range 10–20 kbar as a result of Al shifting from four-coordination at low pressure to higher coordination as the pressure is increased. This coordination shift results in a decreasing number of bridging oxygens in the melt. It is suggested that the activity coefficient of nickel decreases with this decrease in the number of bridging oxygens. As a result, the nickel partition coefficient for olivine and liquid is lowered.Magma genesis in the upper mantle occurs in the pressure range where the suggested change in aluminum coordination occurs in silicate melts. It is suggested, therefore, that data on nickel partitioning obtained at low pressure are not applicable to calculation of the nickel distribution between crystals and melts during partial melting in the upper mantle. Application of high-pressure experimental data determined here for Al-rich melts to the partial melting process indicates that the melts would contain about twice as much nickel as indicated by the data for the low-pressure experiments. If, as suggested here, the polymerization with pressure is related to the Al content of the melt, the difference in the crystal-liquid partition coefficient for nickel at low and high pressure is reduced with decreasing Al content of the melt. Consequently, the change ofD_Ni^{ol-andesite melt} is greater than that ofD_Ni^{ol-basalt melt}, for example.     

Elastic properties of polycrystalline diopside (CaMgSi2O6)

A polycrystalline specimen of clinopyroxene diopside has been hot-pressed at P = 15 kbar and T = 850°C in a piston-cylinder apparatus. Compressional (ν_P) and shear (ν_S) velocities are determined as a function of pressure to 7.5 kbar at room temperature by an ultrasonic pulse transmission technique. The velocities at 7.5 kbar are ν_P = 8.06 km/sec and ν_S = 4.77 km/sec. These data are consistent with velocity-density trends for orthopyroxenes due to the compensating effects of the monoclinic structure (positive) and Ca content (negative). With the addition of the new data for diopside, it is possible to calculate directly the velocities of various upper-mantle mineral assemblages.     

Impact of Poroelastic Response of Sandstones on Geothermal Power Production

During geothermal power production using a borehole doublet consisting of a production and injection well, the reservoir conditions such as permeability k, porosity φ and Skempton coefficient B at the geothermal research site Gross Schoenebeck/Germany will change. Besides a temperature decrease at the injection well and a change of the chemical equilibrium, also the pore pressure p _p will vary in a range of approximately 44 MPa ± 10 MPa in our reservoir at ?3850 to ?4258 m depth. This leads to a poroelastic response of the reservoir rocks depending on effective pressure p _eff (difference between mean stress and pore pressure), resulting in a change in permeability k, porosity φ and the poroelastic parameter Skempton coefficient B. Hence, we investigated the effective pressure dependency of Flechtinger sandstone, an outcropping equivalent of the reservoir rock via laboratory experiments. The permeability decreased by 21% at an effective pressure range from 3 to 30 MPa, the porosity decreased by 11% (p _eff = 6 to 65 MPa) and the Skempton coefficient decreased by 24% (p _eff = 4 to 25 MPa). We will show which mechanisms lead to the change of the mentioned hydraulic and poroelastic parameters and the influence of these changes on the productivity of the reservoir. The most significant changes occur at low effective pressures until 15 to 20 MPa. For our in situ reservoir conditions p _eff = 43 MPa a change of 10 MPa effective pressure will result in a change in matrix permeability of less than 4% and in matrix porosity of less than 2%. Besides natural fracture systems, fault zones and induced hydraulic fractures, the rock matrix its only one part of geothermal systems. All components can be influenced by pressure, temperature and chemical reactions. Therefore, the determined small poroelastic response of rock matrix does not significantly influence the sustainability of the geothermal reservoir.     

Elasticity of the ilmenite - perovskite phase transformation in CdTiO3

Ultrasonic data for the velocities of the ilmenite and perovskite polymorphs of CdTiO₃ have been determined as a function of pressure to 7.5 kbar at room temperature for polycrystalline specimens hot-pressed at pressures up to 25 kbar. This transition is characterized by the following velocity (ν)-density (?) relationships: (1) the changes in compressional (ν_p) and bulk sound (ν_?) velocities are comparable in percentage magnitude to the density jump, while the shear (ν_s) velocity jump is three times greater than that for ?; (2) (ν_p/ν_s) decreases across the transition from the low- to high-pressure phase; and (3) low slopes (linear or logarithmic) on ν-? diagrams. The (ν_p/ν_s) behaviour for the ilmenite-perovskite transformation is unusual for the transitions studied in our laboratory. The observed relationships (1) and (2) are typical of the elasticity behaviour across phase transformations which involve increases in cation-anion co-ordination and in nearest-neighbour interatomic distances, such as those exhibited by CdTiO₃ in transforming from the ilmenite to the perovskite phase. Elasticity systematics for isostructural sequences are used to estimate the bulk moduli of the perovskite polymorphs of CaSiO₃ (2.7 Mbar) and MgSiO₃ (2.8 Mbar).     

High-pressure decompositions in cobalt and nickel silicates

High-pressure stability relations in cobalt and nickel silicates have been studied over the pressure range 130–330 kbar employing a double-staged split-sphere-type high-pressure apparatus.γ-Co₂SiO₄ and γ-Ni₂SiO₄ decompose directly into their constituent oxide mixtures (rocksalt plus stishovite) 175 kbar and 280 kbar, respectively. The result that γ-Ni₂SiO₄ has a wider stability field in pressure than γ-Co₂SiO₄, is consistent with simple crystal-field theory.The experimental precision is high enough to show that the decomposition boundary of γ-Co₂SiO₄ has a positive slope (dP/dT > 0) and a preliminary determination of the boundary curve is P(kbar) = 0.065 T (°C) + 110.No positive evidence for the existence of high-pressure forms of CoSiO₃ and NiSiO₃ has been obtained in these quenching experiments, and they finally decompose into constituent oxide mixtures as in the cases of orthosilicates.