A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.     

A mapping of the electron localization function for earth materials

The electron localization function, ELF, generated for a number of geometry-optimized earth materials, provides a graphical representation of the spatial localization of the probability electron density distribution as embodied in domains ascribed to localized bond and lone pair electrons. The lone pair domains, displayed by the silica polymorphs quartz, coesite and cristobalite, are typically banana-shaped and oriented perpendicular to the plane of the SiOSi angle at ~0.60 Å from the O atom on the reflex side of the angle. With decreasing angle, the domains increase in magnitude, indicating an increase in the nucleophilic character of the O atom, rendering it more susceptible to potential electrophilic attack. The Laplacian isosurface maps of the experimental and theoretical electron density distribution for coesite substantiates the increase in the size of the domain with decreasing angle. Bond pair domains are displayed along each of the SiO bond vectors as discrete concave hemispherically-shaped domains at ~0.70 Å from the O atom. For more closed-shell ionic bonded interactions, the bond and lone pair domains are often coalesced, resulting in concave hemispherical toroidal-shaped domains with local maxima centered along the bond vectors. As the shared covalent character of the bonded interactions increases, the bond and lone pair domains are better developed as discrete domains. ELF isosurface maps generated for the earth materials tremolite, diopside, talc and dickite display banana-shaped lone pair domains associated with the bridging O atoms of SiOSi angles and concave hemispherical toroidal bond pair domains associated with the nonbridging ones. The lone pair domains in dickite and talc provide a basis for understanding the bonded interactions between the adjacent neutral layers. Maps were also generated for beryl, cordierite, quartz, low albite, forsterite, wadeite, åkermanite, pectolite, periclase, hurlbutite, thortveitite and vanthoffite. Strategies are reviewed for finding potential H docking sites in the silica polymorphs and related materials. As observed in an earlier study, the ELF is capable of generating bond and lone pair domains that are similar in number and arrangement to those provided by Laplacian and deformation electron density distributions. The formation of the bond and lone pair domains in the silica polymorphs and the progressive decrease in the SiO length as the value of the electron density at the bond critical point increases indicates that the SiO bonded interaction has a substantial component of covalent character.     

A modeling of the structure and compressibility of quartz with a molecular potential and its transferability to cristobalite and coesite

Several computer models of quartz were developed and tested. A simple model based on a potential energy function, derived in large part from quantum mechanical calculations on the molecule H₆Si₂O₇, was found to reproduce the compressibility curve for quartz up to pressures of 8 GPa. The potential includes quadratic expressions for the SiO bond lengths, the OSiO angles and a parameter spanning the SiOSi angle together with an exponential OO repulsion term for non co-dimer O atoms. The variations in the cell edges and in the SiOSi angle, as a function of pressure, parallel observed trends when the bond lengths and angles calculated for the molecule are used as rgressor values. Poisson ratios calculated using the model match those observed. Two configurations for quartz related by the Dauphiné twin law are generated as minimum energy structures of the model with about equal frequencies as observed in nature. It is shown that the model, devised for quartz, can also be applied to the silica polymorph cristobalite, giving reasonable estimates of its compressibility curve, structural parameters and its negative Poisson ratio. When the observed bond lengths and angles are used as regressor values, the model generates the absolute coordinates of the atoms and the cell dimensions for quartz to within 0.005 Å and those of cristobalite to within 0.001 Å, on average, both at zero pressure. When applied to coesite, the model yields a zero pressure structure that is close to that observed but which is significantly softer than observed. The resulting SiO bond lengths are linearly correlated with f _s (O), as observed for coesite, despite the use of a single bond length and a single SiOSi angle as regressor values in the calculation. When the structures are optimized assuming P1 space group symmetry and triclinic cell dimensions, the resulting frameworks of silicate tetrahedra exhibit the translational, rotational and reflection symmetries observed for quartz, cristobalite and coesite. The fact that the resulting frameworks exhibit observed space group symmetries is evidence that the symmetry adopted by the silica polymorphs can be explained by short ranged forces.     

A modeling of the structure and favorable H-docking sites and defects for the high-pressure silica polymorph stishovite

Employing first-principles methods, the docking sites for H were determined and H, Al, and vacancy defects were modeled with an infinite periodic array of super unit cells each consisting of 27 contiguous symmetry nonequivalent unit cells of the crystal structure of stishovite. A geometry optimization of the super-cell structure reproduces the observed bulk structure within the experimental error when P1 translational symmetry was assumed and an array of infinite extent was generated. A mapping of the valence electrons for the structure displays mushroom-shaped isosurfaces on the O atom, one on each side of the plane of the OSi₃ triangle in the nonbonded region. An H atom, placed in a cell near the center of the super cell, was found to dock upon geometry optimization at a distance of 1.69 Å from the O atom with the OH vector oriented nearly perpendicular to the plane of the triangle such that the OH vector makes a angle of 91° with respect to [001]. However, an optimization of a super cell with an Al atom replacing Si and an H atom placed nearby in a centrally located cell resulted in an OH distance of 1.02 Å with the OH vector oriented perpendicular to [001] as observed in infrared studies. The geometry-optimized position of the H atom was found to be in close agreement with that (0.44, 0.12, 0.0) determined in an earlier study of the theoretical electron density distribution. The docking of the H atom at this site was found to be 330 kJ mol^–1 more stable than a docking of the atom just off the shared OO edge of the octahedra as determined for rutile. A geometry optimization of a super cell with a missing Si generated a vacant octahedra that is 20% larger than that of the SiO₆ octahedra. The valence electron density distribution displayed by the two-coordinate O atoms that coordinate the vacant octahedral site is very similar to those displayed by the bent SiOSi angles in coesite. The internal distortions induced by the defect were found to diminish rather rapidly with distance, with the structure annealing to that observed in the bulk crystal to within about three coordination spheres.     

SiO and GeO bonded interactions as inferred from the bond critical point properties of electron density distributions

The topological properties of the electron density distributions for more than 20 hydroxyacid, geometry optimized molecules with SiO and GeO bonds with 3-, 4-, 6- and 8-coordinate Si and Ge cations were calculated. Electronegativities calculated with the bond critical point (bcp) properties of the distributions indicate, for a given coordination number, that the electronegativity of Ge (∼1.85) is slightly larger than that of Si (∼1.80) with the electronegativities of both atoms increasing with decreasing bond length. With an increase in the electron density, the curvatures and the Laplacian of the electron density at the critical point of each bond increase with decreasing bond length. The covalent character of the bonds are assessed, using bond critical point properties and electronegativity values calculated from the electron density distributions. A mapping of the (3, −3) critical points of the valence shell concentrations of the oxide anions for bridging SiOSi and GeOGe dimers reveals a location and disposition of localized nonbonding electron pairs that is consistent with the bridging angles observed for silicates and germanates. The bcp properties of electron density distributions of the SiO bonds calculated for representative molecular models of the coesite structure agree with average values obtained in X-ray diffraction studies of coesite and danburite to within ∼5%. Received: 18 August 1997 / Revised, accepted: 19 February 1998     

蛇绿岩地幔岩中自由SiO2的发现及其地质意义

自由SiO_2系指石英及其同质多型物(polymorphs)柯石英、斯石英等。石英广泛分布于地壳中的各种岩石中,柯石英和斯石英只存在于超高压岩石和陨石坑中。由于石英和非饱和SiO_2的橄榄石不能共生,因此在地幔橄榄岩和超镁铁岩中不存在原生石英。最近笔者在西藏罗布莎蛇绿岩的地幔岩(方辉橄榄岩)的豆荚状铬铁矿中发现了自由SiO_2和柯石英相。根据高温高压相平衡实验资料,橄榄石、辉石这样的硅酸盐矿物在地幔深部的压力条件下可以分解成简单氧化物,如FeO(方铁矿)、MgO(方镁石)以及SiO_2(斯石英)等。由此推测,西藏蛇绿岩地幔岩中自由SiO_2可能是来自于下地幔的矿物,是地幔柱作用将其搬运到上地幔浅部。     

29Si MAS NMR relaxation study of shocked Coconino Sandstone from Meteor Crater, Arizona

 ²⁹Si nuclear magnetic resonance (NMR) spectroscopy was used to characterize the silica phases in a moderately-shocked Coconino sandstone from Meteor Crater, Arizona. The spectra were recorded using direct polarization, magic-angle spinning, and variable delay times in a saturation recovery pulse sequence. Resonances observed at -97.3, -107.1, -113.9 and -191.2 ppm were assigned to a densified hydrous form of amorphous silica (D phase), quartz, coesite and stishovite phases, respectively. The relative percentages were estimated as 1.7, 80.6, 16.4 and 1.3% for the D, quartz, coesite, and stishovite phases. The power-law recoveries of the magnetization for the quartz and coesite phases can be interpreted in terms of their phase geometries. Received: January 3 1997 / Revised, accepted: August 4 1997     

Quartz paramorphs after former stishovite in UHP eclogite from the South Altyn Tagh,Western China and its Significance

The long prism/needle‐shaped polycrystalline quartz aggregates and square/parallelogram‐shaped singlephase quartz inclusions in omphacite and garnet of ultrahigh pressure eclogite were first discovered from the Jiangalesayi area, South Altyn UHP belt. Based on their morphology, these quartz inclusions are quartz paramorphs after stishovite. The minimum peak pressure of the eclogite is estimated to be >8–9 GPa at 800– 1000 °C based on the stability field of stishovite. This new evidence, together with previous stishovite exsolution microstructure in the gneiss from the same region, suggests an ultra‐deep subduction and exhumation of the South Altyn continental rocks to/from mantle depths in stishovite stability field. Evidence of ultra‐deep subduction of continental materials might be more common and diverse than previous thought. Exhumation of subducted continental rocks from≥300 km has been considered impossible because they are denser than mantle at these depths. How did the stishovite bearing continental rocks of the South Altyn exhumated? As we all know, the densities of stishovite (4.3 g/cm³) are much higher than coesite (2.9 g/cm³), and stishovite transforms into coesite with temperature increases. Density calculations were performed for subducted continental rocks along phase transition of stishovite to coesite, using the third‐order Birch‐Murnaghan equation of state based on mineral fractions obtained from experiments and Perple_X. The results show that the density of Siliceous rocks decrease remarkably, lower than the surrounding mantle in coesite stability field, whereas the density of Oligosiliceous and Silicon unsaturated rocks is higher than surrounding mantle. Thus, we propose that the thermal induced transformation could provide an initial driven force for the exhumation of ultra‐deep subducted silica‐enriched felsic continental rocks. Temperature increase could be derived from an increased geothermal gradient from convective mantle or mantle plume. Mafic to ultra‐mafic rocks and silica‐deficient rocks may be captured by the upwelling subducted continental rocks and exhumated together.     

Shock-induced growth and metastability of stishovite and coesite in lithic clasts from suevite of the Ries impact crater (Germany)

The microtextures of stishovite and coesite in shocked non-porous lithic clasts from suevite of the Ries impact structure were studied in transmitted light and under the scanning electron microscope. Both high-pressure silica phases were identified in situ by laser-Raman spectroscopy. They formed from silica melt as well as by solid-state transformation. In weakly shocked rocks (stage I), fine-grained stishovite (≤1.8 μm) occurs in thin pseudotachylite veins of quartz-rich rocks, where it obviously nucleated from high-pressure frictional melts. Generally no stishovite was found in planar deformation features (PDFs) within grains of rock-forming quartz. The single exception is a highly shocked quartz grain, trapped between a pseudotachylite vein and a large ilmenite grain, in which stishovite occurs within two sets of lamellae. It is assumed that in this case the small stishovite grains formed by the interplay of conductive heating and shock reverberation. In strongly shocked rocks (stages Ib–III, above ∼30 GPa), grains of former quartz typically contain abundant and variably sized stishovite (<6 μm) embedded within a dense amorphous silica phase in the interstices between PDFs. The formation of transparent diaplectic glass in adjacent domains results from the breakdown of stishovite and the transformation of the dense amorphous phase and PDFs to diaplectic glass in the solid state. Coesite formed during unloading occurs in two textural varieties. Granular micrometre-sized coesite occurs embedded in silica melt glass along former fractures and grain boundaries. These former high-pressure melt pockets are surrounded by diaplectic glass or by domains consisting of microcrystalline coesite and earlier formed stishovite. The latter is mostly replaced by amorphous silica.     

Raman spectra of high-pressure polymorphs of SiO2 at various temperatures

Raman spectra of the two high-pressure polymorphs of SiO₂ (coesite and stishovite) were investigated in the temperature range 105–875 K at atmospheric pressure. Coesite remained intact after the highest temperature run, but stishovite became amorphous at temperatures above about 842～872 K. Most Raman modes exhibit a negative frequency shift with temperature for these polymorphs, but positive trends were also observed for some modes. Except for some weak modes, nonlinear temperature variation were established for these polymorphs within the experimental uncertainty and temperature range spanned. The slopes of the variation (δv_i/δT)_P for these polymorphs were compared with the published values. When compared with quartz and stishovite, the four-membered rings of SiO₄-tetrahedra in coesite exhibit very little change with both temperature and pressure. It is also suggested that temperature and pressure should have opposite effects on the Raman shift of each vibrational mode.     

A TEM investigation of shock metamorphism in quartz from the Vredefort dome, South Africa

The origin of the Vredefort structure in South Africa is still debated. Several causes have been discussed, namely asteroid impact, internal gas explosion or tectonic processes. Evidence of dynamic rock deformation is pervasive in the form of planar features in quartz grains, shatter cones, veins of pseudotachylite and occurrence of coesite and stishovite (high-pressure quartz polymorphs). A number of these characteristics is widely believed to support an impact origin. However, the planar features in quartz, which are generally considered as one of the strongest indicators of impact, are in the Vredefort case considered as anomalous when compared with those from accepted impact structures.

We have investigated by optical and transmission electron microscopy (TEM) the defect microstructures in quartz grains from different lithologies sampled at various places at the Vredefort structure. Whatever the locality, only thin mechanical Brazil twin lamellae in the basal plane are observed by TEM. So far, such defects have only been found in quartz from impact sites, but always associated with sets of thin glass lamellae in rhombohedral planes 10−1n with n = 1, 2, 3, and 4. At the scale of the optical microscope, Brazil twins in (0001) are easily detected in Vredefort quartz grains because of the numerous tiny fluid inclusions which decorate them. Similar alignments of tiny fluid inclusions parallel to other planes are also detected optically, but at the TEM scale no specific shock defects are detected along their traces. If these inclusion alignments initially were shock features, they are now so severely weathered that they can no longer be recognized as unambiguous shock lamellae. Fine-grained coesite was detected in the vicinity of narrow pseudotachylite veinlets in a quartzite specimen, but stishovite was not found, even in areas where its occurrence was previously reported. Finally, definite evidence of high-temperature annealing was observed in all the samples. These observations lead us to the conclusion that our findings regarding microdeformation in quartz are consistent with an impact origin for the Vredefort structure. Most of the original shock defects are now overprinted by an intense post-shock annealing episode. Only the thin mechanical twin lamellae in the basal plane have survived.     

A CNDO/2 molecular orbital study of the silica polymorphs quartz,cristobalite, and coesite

CNDO/2 MO calculations on H₁₂Si₅O₁₆ clusters modeling silicate tetrahedral linkage in the silica polymorphs show total energy minima at bent SiOSi angles and a correlation between the Si-O bond lengths, d(Si-O), used in the calculation and the minimum energy value of the SiOSi angle. Calculations on hydrogen saturated Si₅O₁₆ clusters isolated from the structures of low quartz, low cristobalite and coesite which were adjusted by DLS methods so that all d(Si-O) equal 1.61 Å and all _L OSiO equal 109.47° yield Mulliken bond overlap populations, n(Si-O), and Si-O two-center energies, E(Si-O), which correlate with observed bond lengths; shorter bonds involve larger n(Si-O) values and more negative E(Si-O) values.

     

Ab initio calculated geometries and charge distributions for H4SiO4 and H6Si2O7 compared with experimental values for silicates and siloxanes

Ab initio STO-3G molecular orbital theory has been used to calculate energy-optimized Si-O bond lengths and angles for molecular orthosilicic and pyrosilicic acids. The resulting bond length for orthosilicic acid and the nonbridging bonds for pyrosilicic acid compare well with Si-OH bonds observed for a number of hydrated silicate minerals. Minimum energy Si-O bond lengths to the bridging oxygen of the pyrosilicic molecule show a close correspondence with bridging bond length data observed for the silica polymorphs and for gas phase and molecular crystal siloxanes when plotted against the SiOSi angle. In addition, the calculations show that the mean Si-O bond length of a silicate tetrahedron increases slightly as the SiOSi angle narrows. The close correspondence between the Si-O bond length and angle variations calculated for pyrosilicic acid and those observed for the silica polymorphs and siloxanes substantiates the suggestion that local bonding forces in solids are not very different from those in molecules and clusters consisting of the same atoms with the same coordination numbers. An extended basis calculation for H₄SiO₄ implies that there are about 0.6 electrons in the 3d-orbitals on Si. An analysis of bond overlap populations obtained from STO-3G* calculations for H₆Si₂O₇ indicates that Si-O bond length and SiOSi angle correlations may be ascribed to changes in the hybridization state of the bridging oxygen and (d – p) π-bonding involving all five of the 3d AO's of Si and the lone-pair AO's of the oxygen. Theoretical density difference maps calculated for H₆Si₂O₇ show a build-up of charge density between Si and O, with the peak-height charge densities of the nonbridging bonds exceeding those of the bridging bonds by about 0.05 e Å^?3. In addition, atomic charges (+1.3 and ?0.65) calculated for Si and O in a SiO₂ moiety of the low quartz structure conform reasonably well with the electroneutrality postulate and with experimental charges obtained from monopole and radial refinements of diffraction data recorded for low quartz and coesite.     

Calculated trends of oh infrared stretching vibrations with composition and structure in aluminosilicate molecules

Ab initio, molecular orbital calculations have been performed on a variety of hypothetical aluminosilicate molecules to investigate relationships among composition, structure, and infrared spectra of OH. Vibrational analyses of the full-optimized molecular geometries at the 3–21G^** level were performed with Gaussian 92 to determine theoretical infrared spectra. Theoretical infrared OH frequencies, ν(OH), shift 10 to 100 cm^?1 with ionic substitutions. The inverse correlation of theoretical infrared OH intensities with OH stretching frequencies in these aluminosilicate molecules is similar to that observed for aluminosilicate glasses (Paterson 1982). O-H bond lengths, H-bond distances, and H?nd angles correlate with frequency. The dominant factor affecting ν(OH) is the H-bond distance, if this distance is less than 2 Å. Beyond H-bond distances of 2 Å, structural and compositional effects exert competitive influences on ν(OH).     

High temperature X-ray study of single crystal stishovite synthesized with Li2WO4 as flux

Single crystal stishovite with a square prismatic habit and maximum length 0.8 mm was grown from α-quartz at 120 kbar and ～1,300° C. Li₂WO₄, chosen as a result of a previous experiment in growing coesite, was also successful as flux for stishovite. Single crystal X-ray structure analysis of the crystals thus obtained has been carried out at high temperatures under ambient pressure. Lattice constant measurements give a larger thermal expansion coefficient along the a-axis than along the c-axis. The bond distances and bond angles show a decreasing distortion of the SiO₆ octahedron with increasing temperature. The increasing amplitude of thermal vibrations of oxygen atoms with increasing temperature results in increasing O-O repulsion in the basal plane, which explains the observed crystallographic changes.     

Calculated thermodynamic properties of silica polymorphs

Accurate interatomic potentials have been employed to compute the phonon density of states of αquartz, stishovite and coesite polymorphs of silica. The temperature variation of several thermodynamic properties is calculated by using the phonon density of states to describe the vibrational entropy contribution to the free energy. Results for these polymorphs are in surprisingly good agreement with available experimental data. Moreover, the microscopic origin of quantitative differences in the heat capacity behavior of low and high density polymorphs is established.     

Fe2N-type SiO2 from shocked quartz

The modified niccolite structure (Fe₂N-type) of SiO₂, previously found in diamond anvil experiments at 35 to 40 GPa, was formed in a porous mixture of crystalline α-quartz and copper powder at shock pressures estimated at 12 to 27 GPa. It is suggested that quartz can invert during shock compression not only to coesite, stishovite and an amorphous or glass phase of silica, but also to Fe₂N-type SiO₂, depending upon the shock history.     

Coesite inclusions and prograde compositional zonation of garnet in whiteschist of the HP-UHPM Kokchetav massif, Kazakhstan: a record of progressive UHP metamorphism

Coarse-grained whiteschist, containing the assemblage: garnet+kyanite+phengite+talc+quartz/coesite, is an abundant constituent of the ultrahigh-pressure metamorphic (UHPM) belt in the Kulet region of the Kokchetav massif of Kazakhstan.

Garnet displays prograde compositional zonation, with decreasing spessartine and increasing pyrope components, from core to rim. Cores were recrystallized at T=380°C (inner) to 580°C (outer) at P<10 kbar (garnet–ilmenite geothermometry, margarite+quartz stability), and mantles at T=720–760°C and P_H20=34–36 kbar (coesite+graphite stability, phengite geobarometer, KFMASH system reaction equilibria). Textural evidence indicates that rims grew during decompression and cooling, within the Qtz-stability field.

Silica inclusions (quartz and/or coesite) of various textural types within garnets display a systematic zonal distribution. Cores contain abundant inclusions of euhedral quartz (type 1 inclusions). Inner mantle regions contain inclusions of polycrystalline quartz pseudomorphs after coesite (type 2), with minute dusty micro-inclusions of chlorite, and more rarely, talc and kyanite in their cores; intense radial and concentric fractures are well developed in the garnet. Intermediate mantle regions contain bimineralic inclusions with coesite cores and palisade quartz rims (type 3), which are also surrounded by radial fractures. Subhedral inclusions of pure coesite without quartz overgrowths or radial fractures (type 4) occur in the outer part of the mantle. Garnet rims are silica-inclusion-free.

Type 1 inclusions in garnet cores represent the low-P, low-T precursor stage to UHPM recrystallization, and attest to the persistence of low-P assemblages in the coesite-stability field. Coesites in inclusion types 2, 3, and 4 are interpreted to have sequentially crystallized by net transfer reaction (kyanite+talc=garnet+coesite+H₂O), and were sequestered within the garnet with progressively decreasing amounts of intragranular aqueous fluid.

During the retrograde evolution of the rock, all three inclusion types diverged from the host garnet P–T path at the coesite–quartz equilibrium, and followed a trajectory parallel to the equilibrium boundary resulting in inclusion overpressure. Coesite in type 2 inclusions suffered rapid intragranular H₂O-catalysed transformation to quartz, and ruptured the host garnet at about 600°C (when inclusion P27 kbar, garnet host P9 kbar). Instantaneous decompression to the host garnet P–T path, passed through the kyanite+talc=chlorite+quartz reaction equilibrium, resulting in the dusty micro-assemblage in inclusion cores. Type 3 inclusions suffered a lower volumetric proportion transformation to quartz at the coesite–quartz equilibrium, and finally underwent rupture and decompression when T<400°C, facilitating coesite preservation. Type 4 coesite inclusions are interpreted to have suffered minimal transformation to quartz and proceeded to surface temperature conditions along or near the coesite–quartz equilibrium boundary.     

Calorimetric study of the coesite-stishovite transformation and calculation of the phase boundary

High temperature drop-solution calorimetry in molten 2 PbO · B₂O₃ at 1044 K for coesite and stishovite polymorphs of silica was carried out to determine the enthalpy of the coesite-stishovite transition. These experiments were performed on high-purity, single-phase samples of coesite and stishovite. Our new value for the enthalpy of the coesitestishovite transition (ΔH ₂₉₈ ⁰ ) is 29.85 ± 0.78 kJ/mol, which is about 35% lower than previously reported by Akaogi and Navrotsky (1984) and Holm et al. (1967), but which compares well with new measurements by Akaogi et al. (1994b). Using these new data, we have calculated the equilibrium phase boundary between coesite and stishovite and obtained a slope, dP/dT=0.0031 (2) GPa/K. This calculated slope is in good agreement with that determined [0.0026 (2) GPa/K] from the in-situ X-ray diffraction study of Zhang et al. (1996).