Textures in deforming forsterite aggregates up to 8 GPa and 1673 K

We report results from axisymmetric deformation experiments carried out on forsterite aggregates in the deformation-DIA apparatus, at upper mantle pressures and temperatures (3.1–8.1 GPa, 1373–1673 K). We quantified the resulting lattice preferred orientations (LPO) and compare experimental observations with results from micromechanical modeling (viscoplastic second-order self-consistent model—SO). Up to 6 GPa (~185-km depth in the Earth), we observe a marked LPO consistent with a dominant slip in the (010) plane with one observation of a dominant [100] direction, suggesting that [100](010) slip system was strongly activated. At higher pressures (deeper depth), the LPO becomes less marked and more complex with no evidence of a dominant slip system, which we attribute to the activation of several concurrent slip systems. These results are consistent with the pressure-induced transition in the dominant slip system previously reported for olivine and forsterite. They are also consistent with the decrease in the seismic anisotropy amplitude observed in the Earth’s mantle at depth greater than ~200 km.     

Static compression of α-MnS at 298 K to 21 GPa

To investigate the equation of state of -MnS at high pressure and the possibility of a phase transition, the compression curve was measured at 298 K from 0 to 21 GPa using powder x-ray diffraction with a diamond anvil cell. The compression data are fit to a thirdorder Birch-Murnaghan equation of state, with parameters K ₀ = 72(2) GPa and K ₀ = 4.2(13). To compare present results with previous work, the data sets from three previous investigations (Clendenen and Drickamer 1966; Wakabayashi et al. 1968; Kraft and Greuling 1988) are refit to a Birch-Murnaghan equation of state. In the low pressure region (P < 10=" gpa),=" the=" results=" of=" clendenen=" and=" drickamer=" (1966)=" agree=" with=" the=" present=" data;=" however=" the=" results=" of=" wakbayashi=" et=" al.=" (1968)=" differ=" by=" more=" than=" 10%.=" a=" greater=" discrepancy=" between=" the=" present=" and=" previous=" results=" occurs=" above=" 10=" gpa.=" kraft=" and=" greuling=" (1988)=" reported=" a=" structure=" transition=" at=" 7=" gpa,=" and=" clendenen=" and=" drickamer=" (1966)=" observed=" a=" structure=" distortion=" at=" approximately=" 10=" gpa;=" the=" present=" data=" show=" no=" evidence=" of=" either=" transition,=" and=" are=" well=" fit=" by=" a=" single=" equation=" of=" state=" from=" 0=" to=" 21=" gpa.=" nonhydrostatic=" stress=" is=" discussed=" as=" one=" possibility=" for=" the=">     

Thermo-elastic behaviour of Be2BO3OH (hambergite) up to 7 GPa and 1,100 K

The thermo-elastic behaviour of Be₂BO₃(OH)_0.96F_0.04 (i.e. natural hambergite, Z = 8, a = 9.7564(1), b = 12.1980(2), c = 4.4300(1) Å, V = 527.21(1) ų, space group Pbca) has been investigated up to 7 GPa (at 298 K) and up to 1,100 K (at 0.0001 GPa) by means of in situ single-crystal X-ray diffraction and synchrotron powder diffraction, respectively. No phase transition or anomalous elastic behaviour has been observed within the pressure range investigated. P?V data fitted to a third-order Birch–Murnaghan equation of state give: V ₀ = 528.89(4) ų, K _T0 = 67.0(4) GPa and K′ = 5.4(1). The evolution of the lattice parameters with pressure is significantly anisotropic, being: K _T0(a):K _T0(b):K _T0(c) = 1:1.13:3.67. The high-temperature experiment shows evidence of structure breakdown at T > 973 K, with a significant increase in the full-width-at-half-maximum of all the Bragg peaks and an anomalous increase in the background of the diffraction pattern. The diffraction pattern was indexable up to 1,098 K. No new crystalline phase was observed up to 1,270 K. The diffraction data collected at room-T after the high-temperature experiment showed that the crystallinity was irreversibly compromised. The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α ₀ + α ₁ T ^?1/2. The refined parameters for Be₂BO₃(OH)_0.96F_0.04 are: α ₀ = 7.1(1) × 10^?5 K^?1 and α ₁ = ?8.9(2) × 10^?4 K ^?1/2 for the unit-cell volume, α ₀(a) = 1.52(9) × 10^?5 K^?1 and α ₁(a) = ?1.4(2) × 10^?4 K ^?1/2 for the a-axis, α ₀(b) = 4.4(1) × 10^?5 K^?1 and α ₁(b) = ?5.9(3) × 10^?4 K ^?1/2 for the b-axis, α ₀(c) = 1.07(8) × 10^?5 K^?1 and α ₁(c) = ?1.5(2) × 10^?4 K ^?1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α ₀(a):α ₀(b):α ₀(c) = 1.42:4.11:1. The main deformation mechanisms in response to the applied temperature, based on Rietveld structure refinement, are discussed.     

The compressibility of Fe- and Al-bearing phase D to 30 GPa

High-pressure in situ X-ray diffraction experiment of Fe- and Al-bearing phase D (Mg_0.89Fe_0.14Al_0.25Si_1.56H_2.93O₆) has been carried out to 30.5 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields values of V ₀ = 86.10 ± 0.05 ų; K ₀ = 136.5 ± 3.3 GPa and K′ = 6.32 ± 0.30. If K′ is fixed at 4.0 K ₀ = 157.0 ± 0.7 GPa, which is 6% smaller than Fe–Al free phase D reported previously. Analysis of axial compressibilities reveals that the c-axis is almost twice as compressible (K _c  = 93.6 ± 1.1 GPa) as the a-axis (K _a  = 173.8 ± 2.2 GPa). Above 25 GPa the c/a ratio becomes pressure independent. No compressibility anomalies related to the structural transitions of H-atoms were observed in the pressure range to 30 GPa. The density reduction of hydrated subducting slab would be significant if the modal amount of phase D exceeds 10%.     

Behavior of epidote at high pressure and high temperature: a powder diffraction study up to 10 GPa and 1,200 K

The thermo-elastic behavior of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction. No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V ₀ = 458.8(1)ų, K _T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K _T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain” vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated with a linearized BM-EoS are: a ₀ = 8.8877(7) Å, K _T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b ₀ = 5.6271(7) Å, K _T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c ₀ = 10.1527(7) Å, K _T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K _T0(a):K _T0(b):K _T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, β_P(°) = β_P0 −0.0286(9)P +0.00134(9)P ² (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α₀ + α₁ T ^−1/2. The refined parameters for epidote are: α₀ = 5.1(2) × 10⁻⁵ K⁻¹ and α₁ = −5.1(6) × 10⁻⁴ K^1/2 for the unit-cell volume, α₀(a) = 1.21(7) × 10⁻⁵ K⁻¹ and α₁(a) = −1.2(2) × 10⁻⁴ K^1/2 for the a-axis, α₀(b) = 1.88(7) × 10⁻⁵ K⁻¹ and α₁(b) = −1.7(2) × 10⁻⁴ K^1/2 for the b-axis, and α₀(c) = 2.14(9) × 10⁻⁵ K⁻¹ and α₁(c) = −2.0(2) × 10⁻⁴ K^1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α₀(a): α₀(b): α₀(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with β_T(°) = β_T0 + 2.5(1) × 10⁻⁴ T + 1.3(7) × 10⁻⁸ T ². A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out.     

The effects of K2O on the compositions of near-solidus melts of garnet peridotite at 3 GPa and the origin of basalts from enriched mantle

Enrichment in K₂O in oceanic island basalts (OIB) is correlated with high SiO₂, low CaO/Al₂O₃, and radiogenic isotopic signatures indicative of enriched mantle sources (EM1 and EM2). These are also chemical characteristics of the petit-spot lavas, which are highly enriched in K₂O (3–4 wt%) compared to other primitive oceanic basalts. We present experimentally derived liquids with varying concentrations of K₂O in equilibrium with a garnet lherzolite residue at 3 GPa to test the hypothesis that the major element characteristics of EM-type basalts are related to their enrichment in K₂O. SiO₂ is known to increase with K₂O at pressures less than 3 GPa, but it was previously unknown if this effect was significant at the high pressures associated with partial melting at the base of the lithosphere. We find that at 3 GPa for each 1 wt% increase in the K₂O content of a garnet lherzolite saturated melt, SiO₂ increases by ~0.5 wt% and CaO decreases by ~0.5 wt%. MgO and $K_{D}^{{{\text{Fe}} - {\text{Mg}}}}$ K D Fe - Mg each decrease slightly with K₂O concentration, as do Na₂O and Cr₂O₃. The effect of K₂O alone is not strong enough to account for the SiO₂ and CaO signatures associated with high-K₂O OIB. The SiO₂, CaO, and K₂O concentrations of experimentally derived partial melts presented here resemble those of petit-spot lavas, but the Al₂O₃ concentrations from the experimental melts are greater. Partitioning of K₂O between peridotite and melt suggests that petit spots, previously considered to sample ambient asthenosphere, require a source more enriched in K₂O than the MORB source.     

Electrical conductivity of NaCl-bearing aqueous fluids to 600 °C and 1 GPa

The electrical conductivity of aqueous fluids containing 0.01, 0.1, and 1 M NaCl was measured in an externally heated diamond cell to 600 °C and 1 GPa. These measurements therefore more than double the pressure range of previous data and extend it to higher NaCl concentrations relevant for crustal and mantle fluids. Electrical conductivity was generally found to increase with pressure and fluid salinity. The conductivity increase observed upon variation of NaCl concentration from 0.1 to 1 M was smaller than from 0.01 to 0.1 M, which reflects the reduced degree of dissociation at high NaCl concentration. Measured conductivities can be reproduced (R ² = 0.96) by a numerical model with log \(\sigma\) = ?1.7060– 93.78/T + 0.8075 log c + 3.0781 log \(\rho\) + log \(\varLambda\) ₀(T, \(\rho\)), where \(\sigma\) is the conductivity in S m^?1, T is temperature in K, c is NaCl concentration in wt%, \(\rho\) is the density of pure water (in g/cm³) at given pressure and temperature, and \(\varLambda\) ₀ (T, \(\rho\)) is the molar conductivity of NaCl in water at infinite dilution (in S cm² mol^?1), \(\varLambda\) ₀ = 1573–1212 \(\rho\) + 537 062/T–208 122 721/T ². This model allows accurate predictions of the conductivity of saline fluids throughout most of the crust and upper mantle; it should not be used at temperatures below 100 °C. In general, the data show that already a very small fraction of NaCl-bearing aqueous fluid in the deep crust is sufficient to enhance bulk conductivities to values that would be expected for a high degree of partial melting. Accordingly, aqueous fluids may be distinguished from hydrous melts by comparing magnetotelluric and seismic data. H₂O–NaCl fluids may enhance electrical conductivities in the deep crust with little disturbance of v _p or v _p/v _s ratios. However, at the high temperatures in the mantle wedge above subduction zones, the conductivity of hydrous basaltic melts and saline aqueous fluids is rather similar, so that distinguishing these two phases from conductivity data alone is difficult. Observed conductivities in forearc regions, where temperatures are too low to allow melting, may be accounted for by not more than 1 wt% of an aqueous fluid with 5 wt% NaCl, if this fluid forms a continuous film or fills interconnected tubes.     

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

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

Experimental study of quartz inclusions in garnet at pressures up to 3.0 GPa: evaluating validity of the quartz-in-garnet inclusion elastic thermobarometer

Garnet crystals with quartz inclusions were hydrothermally crystallized from oxide starting materials in piston–cylinder apparatuses at pressures from 0.5 to 3 GPa and temperatures ranging from 700 to 800 °C to study how entrapment conditions affect remnant pressures of quartz inclusions used for quartz-in-garnet (QuiG) elastic thermobarometry. Systematic changes of the 128, 206 and 464 cm^?1 Raman band frequencies of quartz were used to determine pressures of quartz inclusions in garnet using Raman spectroscopy calibrations that describe the P–T dependencies of Raman band shifts for quartz under hydrostatic pressure. Within analytical uncertainties, inclusion pressures calculated for each of the three Raman band frequencies are equivalent, which suggests that non-hydrostatic stress effects caused by elastic anisotropy in quartz are smaller than measurement errors. The experimental quartz inclusions have pressures ranging from ??0.351 to 1.247 GPa that span the range of values observed for quartz inclusions in garnets from natural rocks. Quartz inclusion pressures were used to model P–T conditions at which the inclusions could have been trapped. The accuracy of QuiG thermobarometry was evaluated by considering the differences between pressures measured during experiments and pressures calculated using published equation of state parameters for quartz and garnet. Our experimental results demonstrate that Raman measurements performed at room temperature can be used without corrections to estimate garnet crystallization pressures. Calculated entrapment pressures for quartz inclusions in garnet are less than ~?10% different from pressures measured during the experiments. Because the method is simple to apply with reasonable accuracy, we expect widespread usage of QuiG thermobarometry to estimate crystallization conditions for garnet-bearing silicic rocks.     

Synthetic lead bromapatite: X-ray structure at ambient pressure and compressibility up to about 20 GPa

Lead bromapatite [Pb₁₀(PO₄)₆Br₂] has been synthesized via solid-state reaction at pressures up to 1.0 GPa, and its structure determined by single-crystal X-ray diffraction at ambient temperature and pressure. The large bromide anion is accommodated in the c-axis channel by lateral displacements of structural elements, particularly of Pb2 cations and PO₄ tetrahedra. The compressibility of bromapatite was also investigated up to about 20.7 GPa at ambient temperature, using a diamond-anvil cell and synchrotron X-ray radiation. The compressibility of lead bromapatite is significantly different from that of lead fluorapatite. The pressure–volume data of lead bromapatite (P < 10 GPa) fitted to the third-order Birch-Murnaghan equation yield an isothermal bulk modulus (K _T ) of 49.8(16) GPa and first pressure derivative (K_T^￠ K_{T}^{\prime } ) of 10.1(10). If K_T^￠ K_{T}^{\prime } is fixed at 4, the derived K _T is 60.8(11) GPa. The relative difference of the bulk moduli of these two lead apatites is thus about 12%, which is about two times the relative difference of the bulk moduli (~5%) of the calcium apatites fluorapatite [Ca₁₀(PO₄)₆F₂]_, chlorapatite [Ca₁₀(PO₄)₆Cl₂] and hydroxylapatite [Ca₁₀(PO₄)₆(OH)₂]. Another interesting feature apparently related to the replacement of F by Br in lead apatite is the switch in the principle axes of the strain ellipsoid: the c-axis is less compressible than the a-axis in lead bromapatite but more compressible in lead fluorapatite.     

The stability and equation of state for the cotunnite phase of TiO2 up to 70 GPa

The stability and equation of state for the cotunnite phase in TiO₂ were investigated up to a pressure of about 70 GPa by high-pressure in situ X-ray diffraction measurements using a laser-heated diamond anvil cell. The transition sequence under high pressure was rutile → α-PbO₂ phase → baddeleyite phase → OI phase → cotunnite phase with increasing pressure. The cotunnite phase was the most stable phase at pressures from 40 GPa to at least 70 GPa. The equation of state parameters for the cotunnite phase were established on the platinum scale using the volume data at pressures of 37–68 GPa after laser annealing, in which the St value, an indicator of the magnitude of the uniaxial stress component in the samples, indicates that these measurements were performed under quasi-hydrostatic conditions. The third-order Birch-Murnaghan equation of state at K ₀′ = 4.25 yields V ₀ = 15.14(5) cm³/mol and K ₀ = 294(9), and the second-order Birch-Murnaghan equation of state yields V ₀ = 15.11(5) cm³/mol and K ₀ = 306(9). Therefore, we conclude that the bulk modulus for the cotunnite phase is not comparable to that of diamond.     

Crystal structures of Zn2SiO4 III and IV synthesized at 6.5–8 GPa and 1,273 K

We report the crystal structures determined under ambient condition for two Zn₂SiO₄ polymorphs synthesized at 6.5 GPa and 1,273 K (phase III) and 8 GPa and 1,273 K (phase IV) and also compare their ²⁹Si MAS NMR spectroscopic characteristics with those of other Zn₂SiO₄ polymorphs (phases I, II and V). Electron microprobe analysis revealed that both of phases III and IV are stoichiometric like the lower-pressure polymorphs (phases I and II), contrary to previous report. The crystal structures were solved using an ab initio structure determination technique from synchrotron powder X-ray diffraction data utilizing local structural information from ²⁹Si MAS NMR as constraints and were further refined with the Rietveld technique. Phase III is orthorhombic (Pnma) with a = 10.2897(5), b = 6.6711(3), c = 5.0691(2) Å. It is isostructural with the high-temperature (Zn_1.1Li_0.6Si_0.3)SiO₄ phase and may be regarded as a ‘tetrahedral olivine’ type that resembles the ‘octahedral olivine’ structure in the (approximately hexagonally close packed) oxygen arrangement and tetrahedral Si positions, but has Zn in tetrahedral, rather than octahedral coordination. Phase IV is orthorhombic (Pbca) with a = 10.9179(4), b = 9.6728(4), c = 6.1184(2) Å. It also consists of tetrahedrally coordinated Zn and Si and features unique edge-shared Zn₂O₆ dimers. The volumes per formula under ambient condition for phases III and IV are both somewhat larger than that of the lower-pressure polymorph, phase II, suggesting that the two phases may have undergone structural changes during temperature quench and/or pressure release.     

Thermoelastic properties of the high-pressure phase of SnO2 determined by in situ X-ray observations up to 30 GPa and 1400 K

 In situ synchrotron X-ray experiments in the system SnO₂ were made at pressures of 4–29 GPa and temperatures of 300–1400 K using sintered diamond anvils in a 6–8 type high-pressure apparatus. Orthorhombic phase (α-PbO₂ structure) underwent a transition to a cubic phase (Pa3ˉ structure) at 18 GPa. This transition was observed at significantly lower pressures in DAC experiments. We obtained the isothermal bulk modulus of cubic phase K ₀= 252(28) GPa and its pressure derivative K ^′=3.5(2.2). The thermal expansion coefficient of cubic phase at 25 GPa up to 1300 K was determined from interpolation of the P-V-T data obtained, and is 1.7(±0.7) × 10⁻⁵ K⁻¹ at 25 GPa. Received: 7 December 1999 / Accepted: 27 April 2000     

Experimental study of reaction between perovskite and molten iron to 146 GPa and implications for chemically distinct buoyant layer at the top of the core

Partitioning of oxygen and silicon between molten iron and (Mg,Fe)SiO₃ perovskite was investigated by a combination of laser-heated diamond-anvil cell (LHDAC) and analytical transmission electron microscope (TEM) to 146 GPa and 3,500 K. The chemical compositions of co-existing quenched molten iron and perovskite were determined quantitatively with energy-dispersive X-ray spectrometry (EDS) and electron energy loss spectroscopy (EELS). The results demonstrate that the quenched liquid iron in contact with perovskite contained substantial amounts of oxygen and silicon at such high pressure and temperature (P–T). The chemical equilibrium between perovskite, ferropericlase, and molten iron at the P–T conditions of the core–mantle boundary (CMB) was calculated in Mg–Fe–Si–O system from these experimental results and previous data on partitioning of oxygen between molten iron and ferropericlase. We found that molten iron should include oxygen and silicon more than required to account for the core density deficit (<10%) when co-existing with both perovskite and ferropericlase at the CMB. This suggests that the very bottom of the mantle may consist of either one of perovskite or ferropericlase. Alternatively, it is also possible that the bulk outer core liquid is not in direct contact with the mantle. Seismological observations of a small P-wave velocity reduction in the topmost core suggest the presence of chemically-distinct buoyant liquid layer. Such layer physically separates the mantle from the bulk outer core liquid, hindering the chemical reaction between them.     

Electronic state of Fe2+ in (Mg,Fe)(Si,Al)O3 perovskite and (Mg,Fe)SiO3 majorite at pressures up to 81 GPa and temperatures up to 800 K

Despite a large number of studies of iron spin state in silicate perovskite at high pressure and high temperature, there is still disagreement regarding the type and P–T conditions of the transition, and whether Fe²⁺ or Fe³⁺ or both iron cations are involved. Recently, our group published results of a Mössbauer spectroscopy study of the iron behaviour in (Mg,Fe)(Si,Al)O₃ perovskite at pressures up to 110 GPa (McCammon et al. 2008), where we suggested stabilization of the intermediate spin state for 8- to 12-fold coordinated ferrous iron (^[8–12]Fe²⁺) in silicate perovskite above 30 GPa. In order to explore the behaviour in related systems, we performed a comparative Mössbauer spectroscopic study of silicate perovskite (Fe_0.12Mg_0.88SiO₃) and majorite (with two compositions—Fe_0.18Mg_0.82SiO₃ and Fe_0.11Mg_0.88SiO₃) at pressures up to 81 GPa in the temperature range 296–800 K, which was mainly motivated by the fact that the oxygen environment of ferrous iron in majorite is quite similar to that in silicate perovskite. The ^[8–12]Fe²⁺ component, dominating the Mössbauer spectra of majorites, shows high quadrupole splitting (QS) values, about 3.6 mm s^?1, in the entire studied P–T region (pressures to 58 GPa and 296–800 K). Decrease of the QS of this component with temperature at constant pressure can be described by the Huggins model with the energy splitting between low-energy e _g levels of ^[8–12]Fe²⁺ equal to 1,500 (50) cm^?1 for Fe_0.18Mg_0.82SiO₃ and to 1,680 (70) cm^?1 for Fe_0.11Mg_0.88SiO₃. In contrast, for the silicate perovskite dominating Mössbauer component associated with ^[8–12]Fe²⁺ suggests the gradual change of the electronic properties. Namely, an additional spectral component with central shift close to that for high-spin ^[8–12]Fe²⁺ and QS about 3.7 mm s^?1 appeared at ~35 (2) GPa, and the amount of the component increases with both pressure and temperature. The temperature dependence of QS of the component cannot be described in the framework of the Huggins model. Observed differences in the high-pressure high-temperature behaviour of ^[8–12]Fe²⁺ in the silicate perovskite and majorite phases provide additional arguments in favour of the gradual high-spin—intermediate-spin crossover in lower mantle perovskite, previously reported by McCammon et al. (2008) and Lin et al. (2008).     

Phase relations and formation of sodium-rich majoritic garnet in the system Mg3Al2Si3O12–Na2MgSi5O12 at 7.0 and 8.5 GPa

The pseudo-binary system Mg₃Al₂Si₃O₁₂–Na₂MgSi₅O₁₂ modelling the sodium-bearing garnet solid solutions has been studied at 7 and 8.5 GPa and 1,500–1,950°C. The Na-bearing garnet is a liquidus phase of the system up to 60 mol% Na₂MgSi₅O₁₂ (NaGrt). At higher content of NaGrt in the system, enstatite (up to ∼80 mol%) and then coesite are observed as liquidus phases. Our experiments provided evidence for a stable sodium incorporation in garnet (0.3–0.6 wt% Na₂O) and its control by temperature and pressure. The highest sodium contents were obtained in experiments at P = 8.5 GPa. Near the liquidus (T = 1,840°C), the equilibrium concentration of Na₂O in garnet is 0.7–0.8 wt% (∼6 mol% Na₂MgSi₅O₁₂). With the temperature decrease, Na concentration in Grt increases, and the maximal Na₂MgSi₅O₁₂ content of ∼12 mol% (1.52 wt% Na₂O) is gained at the solidus of the system (T = 1,760°С). The data obtained show that most of natural diamonds, with inclusions of Na-bearing garnets usually containing <0.4 wt% Na₂O, could be formed from sodium-rich melts at pressures lower than 7 GPa. Majoritic garnets with higher sodium concentrations (>1 wt% Na₂O) may crystallize at a pressure range of 7.0–8.5 GPa. However the upper pressure limit for the formation of naturally occurring Na-bearing garnets is restricted by the eclogite/garnetite bulk composition.