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     

High-pressure Raman spectroscopic study of Co- and Ni-olivines

 The Raman spectra of synthetic α-Co₂SiO₄ and α-Ni₂SiO₄ olivines have been studied at room temperature and various pressures. All the Raman frequencies of the two olivines increase with increasing pressure, and most of the frequency–pressure plots obtained under both quasi- and nonhydrostatic conditions are nonlinear. It has been found that the average pressure derivative of Raman frequencies of the lattice modes in both Co- and Ni-olivines is smaller than that of the internal modes of SiO₄, indicating that the distortion of SiO₄ tetrahedra under static compression may be more severe than that of MO₆ octahedra. In addition, four new Raman bands were observed in Ni-olivine under nonhydrostatic compression and above 30 GPa. This result suggests that a new phase of Ni-olivine should be formed at 30 GPa or amorphization may occur at still higher pressure. Received: 11 July 2000 / Accepted: 19 December 2000     

High-<Emphasis Type="Italic">P</Emphasis>, <Emphasis Type="Italic">T</Emphasis> phase relations in the NaAlSi<Subscript>2</Subscript>O<Subscript>6</Subscript> system from first principles computation

Vibrational density of states of the NaAlSi₂O₆ jadeite and NaAlSiO₄ calcium ferrite (CF)-type, and SiO₂ stishovite is calculated as a function of pressure up to 50 GPa using density functional perturbation theory. The calculated frequencies are used to determine the thermal contribution to the Helmholtz free energy within the quasi-harmonic approximation and to derive the equation of state and several thermodynamic properties of interest. A dissociation of jadeite into a mixture of a CF-type phase and stishovite is predicted to occur at 23.4 GPa and 1,800 K with a positive Clapeyron slope of 2.8 MPa/K. Elastic anisotropy for jadeite, the CF-type phase, and stishovite also computed clearly shows that stishovite and the CF-type phase are the most anisotropic and isotropic in these three phases, respectively.     

High-pressure phase transformations in the MgFe2O4 and Fe2O3–MgSiO3 systems

 The crystal structure of MgFe₂O₄ was investigated by in situ X-ray diffraction at high pressure, using YAG laser annealing in a diamond anvil cell. Magnesioferrite undergoes a phase transformation at about 25 GPa, which leads to a CaMn₂O₄-type polymorph about 8% denser, as determined using Rietveld analysis. The consequences of the occurrence of this dense MgFe₂O₄ form on the high-pressure phase transformations in the (MgSi)_0.75(Fe^III)_0.5O₃ system were investigated. After laser annealing at about 20 GPa, we observe decomposition to two phases: stishovite and a spinel-derived structure with orthorhombic symmetry and probably intermediate composition between MgFe₂O₄ and Mg₂SiO₄. At pressures above 35 GPa, we observe recombination of these products to a single phase with Pbnm perovskite structure. We thus conclude for the formation of Mg₃Fe₂Si₃O₁₂ perovskite. Received: 27 March 2000 / Accepted: 1 October 2000     

Mg-Fe partitioning between silicate spinel and magnesiowüstite at high pressure: experimental determination and calculation of phase relations in the system Mg2SiO4-Fe2SiO4

 Mg-Fe partitioning experiments between (Mg,Fe)₂SiO₄ spinel and (Mg,Fe)O magnesiowüstite were carried out at pressures of 17–21.3 GPa at temperatures of 1400 and 1600 °C, using a multi-anvil apparatus, in order to determine interaction parameters of spinel and magnesiowüstite solid solutions and also to constrain the equilibrium boundaries of the postspinel transition in the Fe-rich side in the system Mg₂SiO₄-Fe₂SiO₄. The obtained values of the interaction parameters were 3.4 ± 1.5 and 13.9 ± 1.4 kJ mol⁻¹, respectively, for spinel and magnesiowüstite solid solutions at 19 GPa and 1600 °C. The partitioning data in the system Mg₂SiO₄-Fe₂SiO₄ at 1400 and 1600 °C showed that the transition boundary between spinel and the mixture of magnesiowüstite and stishovite has a negative dP/dT slope. Using the above interaction parameters and available thermodynamic data of the Mg₂SiO₄ and Fe₂SiO₄ end members, the transition boundaries of spinel to the mixture of magnesiowüstite and stishovite were calculated. Within the uncertainties of the data used, the calculated boundaries are in good agreement with the boundaries at 1400 and 1600 °C experimentally determined in this study. The dissociation boundary of Fe₂SiO₄ spinel to wüstite and stishovite, calculated from the thermodynamic data, has a negative slope of −1.5 ± 0.6 MPa K⁻¹. Received: 18 February 1998 / Revised, accepted: 18 October 1999     

Hydrostatic compression and crystal structure of pyrope to 33 GPa

The equation of state and crystal structure of pyrope were determined by single crystal X-ray diffraction under hydrostatic conditions to 33 GPa, a pressure that corresponds to a depth of about 900 km in the lower mantle. The bulk modulus K _T0 and its pressure derivative K ^' _T0 were determined simultaneously from an unweighted fit of the volume data at different pressures to a third order Birch-Murnaghan equation of state. They are 171(2) GPa and 4.4(2), respectively. Over the whole pressure range, MgO₈ polyhedra showed the largest compression of 18.10(8)%, followed by AlO₆ and SiO₄ polyhedra, with compression of 11.7(1)% and 4.6(1)%, respectively. The polyhedral bulk moduli for MgO₈, AlO₆ and SiO₄ are 107(1), 211(11) and 580(24) GPa, respectively, with K ^' _T0 fixed to 4. Significant compression of up to 1.8(1)% in the very rigid Si−O bonding in pyrope could be detected to 33 GPa. Changes in the degree of polyhedral distortion for all three types of polyhedra could also be observed. These changes could be found for the first time for AlO₆ and SiO₄ in pyrope. It seems that the compression of pyrope crystal structure is governed by the kinking of the Al−O−Si angle between the octahedra and tetrahedra. No phase transition could be detected to 33 GPa. Received: 24 March 1997 / Revised, accepted: 29 July 1997     

Calculations of pressure-induced phase transitions in mantle minerals

The crystal structures and energies of SiO₂ stishovite, MgO periclase, Mg₂SiO₄ spinel, and MgSiO₃ perovskite were calculated as a function of pressure with the polarization-included electron gas (PEG) model. The calculated pressures of the spinel to perovskite phase transitions in the Mg₂SiO₄ and MgSiO₃ systems are 26.0 GPa and 27.0 GPa, respectively, compared to the experimental zero temperature extrapolations of 27.4 GPa and 27.7 GPa. The two oxide phases are found to be the most stable form in the pressure range 24.5 GPa to 31.5 GPa, compared to the experimental zero temperature extrapolation of 26.7 GPa to 28.0 GPa. The volume changes associated with the phase transitions are in good agreement with experiment. The transition pressures calculated with the PEG model, which allows the ions to distort from spherical symmetry, are in much better agreement with experiment than those calculated with the modified electron gas (MEG) model, which constrains the ions to be spherical.     

Dissociation of CAS phase in the uppermost lower mantle

The high-pressure stability limit of calcium aluminosilicate (CAS) phase has been examined in its end-member CaAl₄Si₂O₁₁ composition at 18–39 GPa and 1,670–2,300 K in a laser-heated diamond-anvil cell (LHDAC). The in-situ synchrotron X-ray diffraction measurements revealed that the CAS phase decomposes into three-phase assemblage of cubic Al-bearing CaSiO₃ perovskite, Al₂O₃ corundum, and SiO₂ stishovite above 30 GPa and 2,000 K with a positive pressure–temperature slope. Present results have important implications for the subsolidus mineral assemblage of subducted sediment and the melting phase relation of basalt in the lower mantle.     

High-pressure transformations of ilmenite to perovskite, and lithium niobate to perovskite in zinc germanate

In-situ X-ray powder diffraction measurements conducted under high pressure confirmed the existence of an unquenchable orthorhombic perovskite in ZnGeO₃. ZnGeO₃ ilmenite transformed into perovskite at 30.0 GPa and 1300±150 K in a laser-heated diamond anvil cell. After releasing the pressure, the lithium niobate phase was recovered as a quenched product. The perovskite was also obtained by recompression of the lithium niobate phase at room temperature under a lower pressure than the equilibrium phase boundary of the ilmenite–perovskite transition. Bulk moduli of ilmenite, lithium niobate, and perovskite phases were calculated on the basis of the refined X-ray diffraction data. The structural relations among these phases are considered in terms of the rotation of GeO₆ octahedra. A slight rotation of the octahedra plays an important role for the transition from lithium niobate to perovskite at ambient temperature. On the other hand, high temperature is needed to rearrange GeO₆ octahedra in the ilmenite–perovskite transition. The correlation of quenchability with rotation angle of GeO₆ octahedra for other germanate perovskites is also discussed.     

The equation of state of Al,H-bearing SiO2 stishovite to 58 GPa

We have determined the P-V equation of state of Al-rich H-bearing SiO₂ stishovite by X-ray powder diffraction at pressures up to 58 GPa using synchrotron radiation. The sample contained 1.8 wt% Al₂O₃ and up to 500 ppm H₂O, and had a composition that would coexist with Mg-silicate perovskite in a subducted slab. By fitting a third-order Birch-Murnaghan equation of state to our compression data, we obtained a bulk modulus K _T0=298(7) GPa with K′=4.3(5). With K′ fixed to a value of 4, the bulk modulus K _T0=304(3) GPa. Our results indicate that Al³⁺ and H⁺ have a small effect on the elastic properties of stishovite. Compared with data obtained up to 43.8 GPa, peak intensities changed and we observed a decreased quality of fit to a tetragonal unit cell at pressures of 49 GPa and higher. These changes may be an indication that the rutile↔CaCl₂ transition occurs between these pressures. After laser annealing of the sample at 58.3(10) GPa and subsequent decompression to room conditions, the cell volume is the same as before compression, giving strong evidence that the composition of the recovered sample is also unchanged. This suggests that Al and H are retained in the sample under extreme P-T conditions and that stishovite can be an agent for transporting water to the deepest lower mantle.     

Pseudopotential periodic Hartree-Fock study of Mg2SiO4 polymorphs: Olivine,modified spinel and spinel

Pseudopotential periodic Hartree-Fock calculations have been performed on the three polymorphs of Mg₂SiO₄ with a polarized split valence basis set. The energy differences between polymorphs at their experimental geometries are correctly predicted. The olivine to modified spinel and olivine to spinel phase transition pressures have been estimated and agree within a few GPa with their experimental values. The bonding in Mg₂SiO₄ is discussed from the point of view of the, band structures, projected density of states, electron density and electron localization function (ELF) curves. It is concluded that both Mg-O and Si-O bonds are highly ionic.     

Decarbonation reaction of magnesite in subducting slabs at the lower mantle

High-pressure and temperature experiments (28–62 GPa, and 1,490–2,000 K, corresponding to approximately 770–1,500 km depth in the mantle) have been conducted on a MgCO₃ + SiO₂ mixture using a laser-heated diamond anvil cell combined with analytical transmission electron microscope observation of the product phases to constrain the fate of carbonates carried on the subducting basalt into the lower mantle. At these conditions, the decarbonation reaction MgCO₃ (magnesite) + SiO₂ (stishovite) → MgSiO₃ (perovskite) + CO₂ (solid) has been recognized. This indicates that above reaction takes place as a candidate for decarbonation of the carbonated subducting mid ocean ridge basalts in the Earth’s lower mantle.     

Structural evolution of rutile-type and CaCl2-type germanium dioxide at high pressure

 Germanium dioxide was found to undergo a transition from the tetragonal rutile-type to the orthorhombic CaCl₂-type phase above 25 GPa. The detailed structural evolution of both phases at high pressure in a diamond anvil cell has been investigated by Rietveld refinement using angle-dispersive, X-ray powder-diffraction data. The square of the spontaneous strain (a−b)/(a+b) in the orthorhombic phase was found to be a linear function of pressure and no discontinuities in the cell constants and volume were observed, indicating that the transition is second-order and proper ferroelastic. Compression of the GeO₆ octahedra was found to be anisotropic, with the apical Ge-O distances decreasing to a greater extent than the equatorial distances and becoming shorter than the latter above 7 GPa. Above this pressure, the GeO₆ octahedron exhibits the common type of tetragonal distortion predicted by a simple ionic model and observed for most rutile-type structures such as those of the heavier group-14 dioxides and the metal difluorides. Above the phase transition, the columns of edge-sharing octahedra tilt about their two fold axes parallel to c and the rotation angle reaches 10.2(5)° by 36(1) GPa so as to yield a hexagonal close-packed oxygen sublattice. The compressibility increases at the phase change as is expected for a second-order transition at which an additional compression mechanism becomes available.     

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     

The effect of sulfur content on density of the liquid Fe–S at high pressure

The density of liquid Fe–S was measured at 4 GPa and 1,923 K using a sink/float method with a composite density marker. The density marker consisted of a Pt rod core and an Al₂O₃ tube surrounding. The uncertainty in the density of the composite marker is much smaller than that of the composite sphere, which had been used in previous density measurements. The density of liquid Fe–S decreases nonlinearly with increasing sulfur content at 4 GPa and 1,923 K. This tendency is consistent with the results measured at ambient pressure. The molar volume of FeS calculated from the measured density gradually increases with sulfur content. The excess molar volume from ideal mixing of Fe and S at 4 GPa was negative value. The new method proposed here is applicable to the density measurement of other Fe alloys at high pressure. The tendency of the molar volume and the excess molar volume with sulfur content at ambient pressure is consistent with these at high pressure at least up to 4 GPa. The excess molar volume at high pressure is essential for estimating the amount of light elements in the outer core.     

Pressure-induced phase transition in synthetic trioctahedral Rb-mica

 The crystal structure of a synthetic Rb analog of tetra-ferri-annite (Rb–TFA) 1M with the composition Rb_0.99Fe²⁺ _3.03(Fe³⁺ _1.04 Si_2.96)O_10.0(OH)_2.0 was determined by the single-crystal X-ray diffraction method. The structure is homooctahedral (space group C2/m) with M1 and M2 occupied by divalent iron. Its unit cell is larger than that of the common potassium trioctahedral mica, and similar lateral dimensions of the tetrahedral and octahedral sheets allow a small tetrahedral rotation angle α=2.23(6)°. Structure refinements at 0.0001, 1.76, 2.81, 4.75, and 7.2 GPa indicate that in some respects the Rb–TFA behaves like all other micas when pressure increases: the octahedra are more compressible than the tetrahedra and the interlayer is four times more compressible than the 2:1 layer. However, there is a peculiar behavior of the tetrahedral rotation angle α: at lower pressures (0.0001, 1.76, 2.81 GPa), it has positive values that increase with pressure [from 2.23(6)° to 6.3(4)°] as in other micas, but negative values −7.5(5)° and −8.5(9)° appear at higher pressures, 4.75 and 7.2 GPa, respectively. This structural evidence, together with electrostatic energy calculations, shows that Rb–TFA has a Franzini A-type 2:1 layer up to at least 2.81 GPa that at higher pressure yields to a Franzini B-type layer, as shown by the refinements at 4.75 and 7.2 GPa. The inversion of the α angle is interpreted as a consequence of an isosymmetric displacive phase transition from A-type to B-type structure between 2.81 and 4.75 GPa. The compressibility of the Rb–TFA was also investigated by single-crystal X-ray diffraction up to a maximum pressure of 10 GPa. The lattice parameters reveal a sharp discontinuity between 3.36 and 3.84 GPa, which was associated with the phase transition from Franzini-A to Franzini-B structure. Received: 21 October 2002 / Accepted: 25 February 2003     

High-pressure phases in the Al2SiO5 system and the problem of aluminous phase in the Earth's lower mantle: ab initio calculations

 One of the main uncertainties in mineralogical models of the Earth's lower mantle is the nature of the aluminous mineral: it is not clear whether Al forms its own minerals or is mainly contained in (Mg,Fe)SiO₃-perovskite. This question is very important, since it is known that if Al were mainly hosted by perovskite, it would radically change Fe/Mg-partitioning and phase equilibria between mantle minerals, and also alter many physical and chemical properties of perovskite, which is currently believed to comprise ca. 70% of the volume of the lower mantle. This, in turn, would require us to reconsider many of our geochemical and geophysical models for the lower mantle. This work considers the possibility of a V₃O₅-type structured modification of Al₂SiO₅ to be the main host of Al in the lower mantle, as proposed by previous workers. We report ab initio calculations, based on density functional theory within the generalised gradient approximation (GGA) with plane wave basis set and nonlocal pseudopotentials. We consider polymorphs of Al₂SiO₅ (kyanite, andalusite, sillimanite, and hypothetical V₃O₅-like and pseudobrookite-like phases), SiO₂ (stishovite, quartz) and Al₂O₃ (corundum). Computational conditions (e.g., plane-wave energy cutoff, Brillouin zone sampling) were carefully chosen in order to reproduce small energy changes associated with phase transitions between the Al₂SiO₅ polymorphs. Good agreement of crystal structures, bulk moduli, atomisation energies and the phase diagram of Al₂SiO₅ with experimental data was found. Strong disagreement between the calculated lattice parameters and density of V₃O₅-like phase of Al₂SiO₅ and experimental values, assigned to it by previous workers, suggests that a V₃O₅-structured phase of Al₂SiO₅ was never observed experimentally. In addition, we found that the most stable high-pressure assembly in Al₂SiO₅ system is corundum+stishovite, and the value of the transition pressure at T = O K (113 kbar) is in excellent agreement with experimental estimates (95–150 kbar). We explain the instability of octahedrally coordinated silicates of Al to decomposition on the basis of Pauling's second rule. Received: 18 May 1999 / Accepted: 5 November 1999     

Electron density distribution of FeTiO<Subscript>3</Subscript> ilmenite under high pressure analyzed by MEM using single crystal diffraction intensities

Many of ilmenites ABO₃ compounds bearing transition elements have semiconductive, ferroelectric and antiferromagnetic properties. The high-pressure diffraction studies of FeTiO₃ have been conducted up to 8.2 GPa using synchrotron radiation in KEK at Tsukuba with diamond anvil cell. The compression mechanism of FeTiO₃ ilmenite has been investigated by the structure refinements converged to the reliable factors R = 0.05. The deformations of the FeO₆ and TiO₆ octahedra were reduced with increasing pressure. In order to elucidate the electric conductivity change with pressure, electron density distribution of ilmenite have been executed by maximum entropy method (MEM) using single-crystal diffraction intensity data. MEM based on F _obs(hkl) of FeTiO₃ clearly shows electron density in comparison with the difference Fourier synthesis based on F _obs(hkl) − F _calc(hkl). The radial distribution of the electron density indicates electron localization around the cation positions. The bonding electron density found in bond Fe–O and Ti–O is lowered with pressure. The isotropic temperature factors B _iso become smaller with increasing pressure. Nevertheless the thermal vibration is considerably restrained by the compression, the electric conductivity is enhanced with pressure. Neither charge transfer nor electron hopping between Fe and Ti along the c axis in FeTiO₃ is plausible under high pressure. But the electric conductivity due to electron super-exchange in Fe–Fe and Ti–Ti has been clarified by the MEM electron density distribution. The anisotropy in the electric conductivity has been clarified.     

Heat capacity,entropy and phase equilibria of stishovite

The low-temperature heat capacity (C _P) of stishovite (SiO₂) synthesized with a multi-anvil device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system (PPMS) and around ambient temperature using a differential scanning calorimeter (DSC). The entropy of stishovite at standard temperature and pressure calculated from DSC-corrected PPMS data is 24.94 J mol⁻¹ K⁻¹, which is considerably smaller (by 2.86 J mol⁻¹ K⁻¹) than that determined from adiabatic calorimetry (Holm et al. in Geochimica et Cosmochimica Acta 31:2289–2307, 1967) and about 4% larger than the recently reported value (Akaogi et al. in Am Mineral 96:1325–1330, 2011). The coesite–stishovite phase transition boundary calculated using the newly determined entropy value of stishovite agrees reasonably well with the previous experimental results by Zhang et al. (Phys Chem Miner 23:1–10, 1996). The calculated phase boundary of kyanite decomposition reaction is most comparable with the experimental study by Irifune et al. (Earth Planet Sci Lett 77:245–256, 1995) at low temperatures around 1,400 K, and the calculated slope in this temperature range is mostly consistent with that determined by in situ X-ray diffraction experiments (Ono et al. in Am Mineral 92:1624–1629, 2007).     

A study of phase transformation in hedenbergite to 40 GPa at ∼1200° C

Phase transformations in a natural sample of hedenbergite ((Ca_0.93Fe_0.61Mn_0.34Mg_0.08Na_0.01Zn_0.02Al_0.003)Si₂O₆) have been studied by X-ray diffraction up to 40 GPa at ∼ 1200°C in a diamond anvil cell interfaced with a laser heating system. The starting hedenbergite phase decomposed into a garnet plus γ-spinel and stishovite at ∼ 14 GPa; then into garnet plus stishovite and wüstite at ∼ 18 GPa; and finally into perovskite plus stishovite and wüstite at pressures higher than ∼ 24 GPa. On decompression to 0.1 MPa, all the high pressure phases are retained except for the cubic perovskite, which reverts back into the ɛ-CaSiO₃ phase, in accordance with previous reports. Energy-dispersive SEM analyses show that the garnet is present as a calcium-rich ABO ₃-type phase. As no garnet phase has been previously observed either in pure CaSiO₃ or in pure CaMgSi₂O₆, it appears that the observed calcium-rich garnet phase has been stabilized by the presence of other cations such as the Na⁺, Zn²⁺, Mn²⁺, Fe²⁺, Mn³⁺, Fe³⁺ and Al³⁺.