Experimental study of the stability of cordierite and garnet in pelitic compositions at high pressures and temperatures

The stability of cordierite and garnet has been studied experimentally in complex, silica oversaturated compositions (in the systems MgO-FeO-Al₂O-CaO₃-Na₂O-K₂OSiO₂) in which the molecular ratio Al₂O₃/FeO+MgO<1. Compositions with 100 Mg/Mg+Fe²⁺ ratios (X) of 0, 30, 50, 70 and 100 have been used to investigate the role of this ratio in determining phase assemblages and P, T coordinates of reactions. The minimum pressure for appearance of garnet at a given temperature is strongly dependent on X _{total rock}.The X-values of co-existing phases (chiefly garnet, cordierite, hypersthene) in divariant equilibrium are a function of temperature and pressure and have been experimentally determined at 900° C, 1000° C and 1100° C. At high temperature (>1050° C) the phases sapphirine and spinel are stable with quartz in Mg-rich and Fe-rich compositions respectively. Experiments in the system MgO-FeO-Al₂O₃-SiO₂ show that for a given X-value and temperature the pressure required to produce Ca-free garnet from hypersthene-cordierite assemblages is 1–2 kb greater than that required to produce garnet containing 6±2 mol percent grossular solid solution in the more complex Ca-bearing system.     

Experimental study of the stability of cordierite and garnet in pelitic compositions at high pressures and temperatures

The stability of cordierite and garnet relative to their anhydrous breakdown products, i.e. hypersthene, sapphirine, olivine, spinel, sillimanite and quartz, has been studied experimentally in model pelitic compositions (system MgO-FeO-Al₂O₃-CaO-K₂O-SiO₂). Below 1000° C cordierite breaks down according to the divariant reaction cordierite garnet+sillimanite+quartz (1) for most values of the MgO/MgO + FeO ratio (X). At very high values of X (ca. X0.9) garnet in reaction (1) is replaced by hypersthene. The position and width of the divariant field (in terms of pressure and temperature) in which cordierite and garnet coexist, is a function of the MgO/MgO + FeO ratio. If this ratio is increased then the stability field of garnet is reduced and that of cordierite extended towards higher pressure. Compositions of coexisting cordierite and garnet in divariant equilibrium have been analysed by electron probe micro-analyser. These compositions are unique functions of pressure and temperature. Above ca. 1000° C the breakdown of cordierite involves the phases sapphirine and hercynite-rich spinel in Mg-rich and Fe-rich compositions respectively.     

On saturation of magnesian cordierite with alkanes at high temperatures and pressures

 Incorporation of hydrocarbons (CH₄, C₂H₆, C₃H₈, C₄H₁₀) in cordierite channels was experimentally studied at 700 °C and at pressures from 200 to 1000 MPa, (avoiding recrystallization). The maximum concentrations of hydrocarbons determined by gas chromatographic analysis are CH₄=78.3, C₂H₆=134, C₂H₄ + C₂H₆=26, C₃H₈=28, C₄H₁₀=32, C₅H₁₂=23, and C₆H₁₄=7 × 10⁻³ wt%). According to IR spectroscopy data, the channel forms of hydrocarbons differ from the forms on the surface. As a result of interactions with the framework oxygen, normal hydrocarbons are converted to saturated oligomers and their fragments. Small amounts of water molecules of the first and second types (up to 0.3 wt%) are formed in the same way. As pressure grows from 200 to 1000 MPa, the total content of structural hydrocarbons is nearly doubled. Special runs on cordierite saturation in mixtures of hydrocarbons with water showed that low contents of hydrocarbons in natural cordierites correspond to their large concentrations in fluid. Received: 7 May 2001 / Accepted: 17 July 2001     

The stability of hercynite at high pressures and temperatures

The stability of hercynite (FeAl₂O₄) has been investigated experimentally between 7 and 24 GPa and 900 and 1,700°C. Hercynite breaks down to its constituent oxides at 7–8.5 GPa and temperatures >1,000°C. The incorporation of a small magnetite component in the hercynite necessitated a small correction to fix the location of the endmember reaction: FeAl₂O₄  = Al₂O₃ + FeO in P–T space. After making this correction, the position of the phase boundary was used to evaluate thermodynamic data for hercynite. Our results support a relatively large S ₂₉₈^° for hercynite, on the order of 115 J mol⁻¹ K⁻¹. Experiments up to 24 GPa and 1,400°C failed to detect any high-pressure polymorph of FeAl₂O₄; only corundum + wüstite were detected. This behaviour contrasts with that observed for the analogous MgAl₂O₄ system where the constituent oxides recombine at high pressure to produce “post-spinel” phases with CaFe₂O₄-type and CaTi₂O₄-type structures.     

Simulation of thermodynamic mixing properties of garnet solid solutions at high temperatures and pressures

We present results of high temperature, high pressure atomistic simulations aimed at determining the thermodynamic mixing properties of key binary garnet solid solutions. Computations cover the pressure range 0–15 GPa and the temperature range 0–2000 K. Through a combination of Monte-Carlo and lattice-dynamics calculations, we derive thermodynamic mixing properties for garnets with compositions along the pyrope–almandine and pyrope–grossular joins, and compare these with existing experimental data. Across the pressure–temperature range considered, simulations show virtually ideal mixing behaviour in garnet on the pyrope–almandine join, while large excess volumes and enthalpies of mixing are predicted for garnet along the pyrope–grossular join. Excess heat capacities and entropies are also examined. These simulations shed additional light on the link between the behaviour at the atomic level and macroscopic thermodynamic properties: we illustrate the importance of certain atomistic Ca–Mg contacts in the pyrope–grossular solid solutions. For simulation techniques of this type to become sufficiently accurate for direct use in geological applications such as geothermobarometry, there is an urgent need for improved experimental determinations of several key quantities, such as the enthalpies of mixing along both joins.     

Raman spectroscopic study of PbCO3 at high pressures and temperatures

Cerussite (PbCO₃) has been investigated by high-pressure and high-temperature Raman spectroscopy up to pressures of 17.2 GPa and temperatures of 723 K. Two pressure induced phase transitions were observed at about 8.0(2) and 16.0(2) GPa, respectively. The post-aragonite transition (PbCO₃-II) at 8.0(2) GPa is accompanied by softening of the v ₂-out-of-plane mode of the CO ₃ ^2? group and disappearance of the B_1g (v ₄-in-plane band of the CO ₃ ^2? group) mode. Stronger shifts of the carbonate group modes after the phase transition suggest that the new structure is more compressible. The formation of a second high-pressure polymorph begins at about 10 GPa. It is accompanied by the occurrence of three new bands at different pressures and splitting of the v ₁-symmetric C–O stretching mode of the CO ₃ ^2? group. The transitions are reversible on pressure release. A semi-quantitative phase diagram for PbCO₃ as a function of pressure and temperature is proposed.     

Structures of micas synthesized at high pressures and temperatures

Thermal karst, exposed in mine shafts, has been significantly developed in the commercial stratum of oil shales. Geochemical investigations in this karst have for the first time established the secondary changes in the kerogen of the oil shales, namely, an anomalous content of bituminoid A + C, the presence of processes of aromatization, the significant amount of hydrocarbon compounds and humic acids, and changes in the elemental composition of the residual organic matter (in particular, an increase in the C/H ratio). The secondary changes suggest that a favorable geochemical and thermobaric environment existed in the thermal karst for intense bitumen formation. The results obtained are of interest in the study of the kerogen of oil shales as a possible parental source for oil and gas. —Authors.     

Phonon density of states in iron at high pressures and high temperatures

The phonon density of states (DOS) in iron has been measured in situ by nuclear resonance inelastic X-ray scattering (NRIXS) at high pressures and high temperatures in a resistively heated diamond anvil cell. The DOS data provide a variety of thermodynamic and elastic parameters essential for characterizing iron at depth in the Earth interior, such as average sound velocity, Debye temperature, atomic mean square displacement, average kinetic energy, vibrational entropy and specific heat. The NRIXS data were collected at 6, 20, and 29 GPa and at temperatures up to 920 K. Temperatures were directly determined from the measured spectra by the ratio of intensities of the phonon creation/annihilation side bands that are determined only by the Boltzmann factor. The change of the DOS caused by the structural transition from -Fe to -Fe is small and not resolvable within the experimental precision. However, the phonon energies in -Fe are clearly shifted to lower values with respect to - and -Fe. The temperature dependence of derived thermodynamic parameters is presented and compared with those obtained by Debyes model. The Debye temperatures that best describe the data decrease slightly with increasing temperature.     

Immiscibility in sulfate-bearing fluid systems at high temperatures and pressures

Fluid equilibria in the H₂O-Na₂SO₄-SiO₂ system were experimentally studied at 700 and 800°C and pressures of 1, 2, and 3 kbar using synthetic fluid inclusions in quartz. The obtained results indicated a heterogeneous state of fluid within the whole range of experimental parameters of this study. Sodium sulfate underwent high-temperature hydrolysis, whose products chemically reacted with quartz. As a result, a noncrystalline phase containing substantial amounts of silica was formed at a temperature of 800°C and a pressure of 3 kbar. This phase was observed in the inclusions as glass. The thermometric investigation of inclusions that trapped fluid phases immiscible under experimental conditions showed that they can, in turn, become heterogeneous at temperatures of approximately 200–400°C. Under such conditions, three or four noncrystalline phases can be in equilibrium.     

Natural fluid phases at high temperatures and low pressures

Gas phases at low pressures and high (magmatic) temperatures have certain peculiar properties. The fluid is mainly water vapour, which is usually observed during discharging of crystal magmatic melts. At >700°C and <100 bar these peculiar properties include: formation of near ‘dry' salt melts as second fluid phase, very strong fractionation of hydrolysis products between vapour and melts, subvalence state of metals during transport processes, and high sensitivity of the gas to conditions of sublimate precipitation. Phase diagram analysis as well as results of field and laboratory experiments are presented in this article. The processes could be a model for industrial technologies to clean wastes from toxic, rare and heavy metals. Transport forms of some elements in volcanic gases are very similar to the species which were formed first in the protosolar nebula.     

Hydroxyl stretching in phyllosilicates at high pressures and temperatures: an infrared spectroscopic study

The hydroxyl stretching frequencies of four phyllosilicates have been measured at high pressures and temperatures using an externally heated diamond-anvil cell and synchrotron infrared spectroscopy. Spectra were measured up to 26, 31, 21 and 8 GPa at room temperature for samples of talc, pyrophyllite, muscovite and 10-Å phase, respectively. Spectra were also measured in the range 273–500 K at ambient pressure for all samples and at 8–9 GPa for talc and pyrophyllite. The frequency of the Mg₃OH band in talc increases with pressure due to the absence of hydrogen bonding. The different orientation of the hydroxyl group in pyrophyllite and muscovite leads to hydrogen bonding and a decrease in the frequency of the Al₂OH band with pressure. 10-Å phase is approximately equivalent to talc with the addition of interlayer H₂O. In a spectrum of a sample synthesised for 143 h, two hydroxyl stretching bands are clearly resolved on compression. One is the same as the Mg₃OH band in talc, indicating the presence of intra-layer hydroxyl in a talc-like environment with no hydrogen bonding. The other, which separates from the talc-like band at 1 GPa, is associated with intra-layer hydroxyl that is hydrogen bonded to interlayer H₂O. There are equivalent bands in high-pressure spectra of a sample of deuterated 10-Å phase, synthesised for 400 h. This sample shows a greater extent of hydrogen bonding at ambient pressure than the 143 h sample. For all of the phases studied, increasing temperature leads to a decrease in frequency for every hydroxyl stretching vibration, both at low and high pressures. The shifts in frequency with temperature are an order of magnitude greater than the shifts with pressure when normalised to previously measured structural parameters.     

Transformations of biotite and lepidomelane at high pressures and temperatures

Experimentally, at 66 kbar, biotite and lepidomelane are converted into associations of several minerals, at 1300–15000 and 900–1450°C, respectively, with the accompanying increase in the density; garnet is the densest product of both minerals; all of their original potassium passes into the low-density minerals during the conversion. The biotite and lepidomelane associations with garnet and other minerals are converted into biotite and lepidomelane above 1500° and 1450°C, respectively. Thus the range of instability of the micas, with its high pressures and relatively low temperatures, appears to be conducive to migration of potassium into upper horizons of the earth, e.g. by the gravitational differentation or by a fractionation in melting of the mantle substance. – V. P. Sokoloff.     

The effect of chemical composition and oxygen fugacity on the electrical conductivity of dry and hydrous garnet at high temperatures and pressures

The in situ electrical conductivity of hydrous garnet samples (Py₂₀Alm₇₆Grs₄–Py₇₃Alm₁₄Grs₁₃) was determined at pressures of 1.0–4.0 GPa and temperatures of 873–1273 K in the YJ-3000t apparatus using a Solartron-1260 impedance/gain-phase analyzer for various chemical compositions and oxygen fugacities. The oxygen fugacity was controlled by five solid-state oxygen buffers (Fe₂O₃ + Fe₃O₄, Ni + NiO, Fe + Fe₃O₄, Fe + FeO, and Mo + MoO₂). Experimental results indicate that within a frequency range from 10⁻² to 10⁶ Hz, electrical conductivity is strongly dependent on signal frequency. Electrical conductivity shows an Arrhenius increase with temperature. At 2.0 GPa, the electrical conductivity of anhydrous garnet single crystals with various chemical compositions (Py₂₀Alm₇₆Grs₄, Py₃₀Alm₆₇Grs₃, Py₅₆Alm₄₃Grs₁, and Py₇₃Alm₁₄Grs₁₃) decreases with increasing pyrope component (Py). With increasing oxygen fugacity, the electrical conductivity of dry Py₇₃Alm₁₄Grs₁₃ garnet single crystal shows an increase, whereas that of a hydrous sample with 465 ppm water shows a decrease, both following a power law (exponents of 0.061 and −0.071, respectively). With increasing pressure, the electrical conductivity of this hydrous garnet increases, along with the pre-exponential factors, and the activation energy and activation volume of hydrous samples are 0.7731 ± 0.0041 eV and −1.4 ± 0.15 cm³/mol, respectively. The results show that small hopping polarons ( \textFe_\textMg ^· ) \left( {{\text{Fe}}_{\text{Mg}}^{ \cdot } } \right) and protons ( \textH ^· {\text{H}}^{ \cdot } ) are the dominant conduction mechanisms for dry and wet garnet single crystals, respectively. Based on these results and the effective medium theory, we established the electrical conductivity of an eclogite model with different mineral contents at high temperatures and high pressures, thereby providing constraints on the inversion of field magnetotelluric sounding results in future studies.     

Stability relations of chromium kyanite at high pressures and temperatures

The pseudobinary section Al₂SiO₅-Cr₂SiO₅ of the system Al₂O₃-Cr₂O₃-SiO₂ has been investigated at 20 and 30 kb pressure in the temperature range 1,000–1,600° C. The solubility of Cr₂SiO₅ in kyanite (Al₂SiO₅) extends up to 24 mole % Cr₂SiO₅ at 20 kb and 31 mole % at 30 kb. The extent of this solid solution is not notably dependent on temperature in the range studied. The stability of kyanite is increased by the substitution Cr Al by about 80° C at 20 kb as compared to Cr-free kyanite. Cr-poor sillimanite and Cr-rich kyanite can stably coexist in a temperature interval of up to 80° C at 20 kb and about 150° C at 25 kb.     

An experimental study of the stability of copper chloride complexes in water vapor at elevated temperatures and pressures

The solubility of copper chloride in liquid-undersaturated HCl-bearing water vapor was investigated experimentally at temperatures of 280 to 320°C and pressures up to 103 bars. Results of these experiments show that the solubility of copper in the vapor phase is significant and increases with increasing f_H2O, but is retrograde with respect to temperature. This solubility is attributed to the formation of hydrated copper-chloride gas species, interpreted to have a copper-chlorine ratio of 1:1 (e.g., CuCl, Cu₃Cl₃, etc.) and a hydration number varying from 7.6 at 320°C, to 6.0 at 300°C, and 6.1 at 280°C. Complex formation is proposed to have occurred through the reaction:

A1     

In situ Raman spectroscopy on kerogen at high temperatures and high pressures

Kerogen samples were treated at temperatures and pressures up to 25–600°C and ~9 GPa, respectively. In situ micro-Raman spectroscopy was used to measure the systematic changes in the first-order Raman spectral features during the process of temperature or pressure increment. Three Raman bands, D1, D2, and G bands, were examined to characterize the structural and chemical changes of kerogen at high temperatures and pressures. We found that the wavenumbers of D1, D2 and G bands showed a linear variation with both temperature and pressure. Therefore, a correlation between R1 and R2 and the peak temperature in regionally metamorphosed rocks cannot be applied to this work. This result implies that the G band may serve as a temperature or pressure indicator during the promotion of maturation of kerogen. Kerogen possesses reversible properties in contrast with the natural samples recovered from the field suffered from prolonged thermal history during regional metamorphism.