The high-pressure phases of MgSiO3

The high-pressure and temperature phase transformations of MgSiO₃ have been investigated in a diamond-anvil cell coupled with laser heating from 150 to 300 kbar at 1000–1400°C. X-ray diffraction study of the quenched samples reveals that the sequence of phase transformations for this compound is clinoenstatite → β-Mg₂SiO₄ plus stishovite → Mg₂SiO₄(spinel) plus stishovite → ilmenite phase → perovskite phase with increasing pressure. The hexagonal form of MgSiO₃ observed by Kawai et al. is demonstrated to have the ilmenite structure and the “hexagonal form” of MgSiO₃ observed by Ming and Bassett is shown to be predominantly the orthorhombic perovskite phase plus the ilmenite phase. The mixture of oxides, periclase plus stishovite, reported by Ming and Bassett was not observed in this study. The very wide stability field for the ilmenite phase of MgSiO₃ found in this study suggests that this phase is of importance in connection with the observed rapid increase of velocity in the transition zone of the earth's mantle. On the basis of the extremely dense-packed structure of the perovskite phase of MgSiO₃, this phase should be the most important component for the lower mantle.     

Pyroxene-garnet solid-solution equilibria in the systems Mg4Si4O12Mg3Al2Si3O12 and Fe4Si4O12Fe3Al2Si3O12 at high pressures and temperatures

Pyroxene-garnet solid-solution equilibria have been studied in the pressure range 41–200 kbar and over the temperature range 850–1,450°C for the system Mg₄Si₄O₁₂Mg₃Al₂Si₃O₁₂, and in the pressure range 30–105 kbar and over the temperature range 1,000–1,300°C for the system Fe₄Si₄O₁₂Fe₃Al₂Si₃O₁₂. At 1,000°C, the solid solubility of enstatite (MgSiO₃) in pyrope (Mg₃Al₂Si₃O₁₂) increases gradually to 140 kbar and then increases suddenly in the pressure range 140–175 kbar, resulting in the formation of a homogeneous garnet with composition Mg₃(Al_0.8Mg_0.6Si_0.6)Si₃O₁₂. In the MgSiO₃-rich field, the three-phase assemblage of β- or γ-Mg₂SiO₄, stishovite and a garnet solid solution is stable at pressures above 175 kbar at 1,000°C. The system Fe₄Si₄O₁₂Fe₃Al₂Si₃O₁₂ shows a similar trend of high-pressure transformations: the maximum solubility of ferrosilite (FeSiO₃) in almandine (Fe₃Al₂Si₃O₁₂) forming a homogeneous garnet solid solution is 40 mol% at 93 kbar and 1,000°C.If a pyrolite mantle is assumed, from the present results, the following transformation scheme is suggested for the pyroxene-garnet assemblage in the mantle. Pyroxenes begin to react with the already present pyrope-rich garnet at depths around 150 km. Although the pyroxene-garnet transformation is spread over more than 400 km in depth, the most effective transition to a complex garnet solid solution takes place at depths between 450 and 540 km. The complex garnet solid solution is expected to be stable at depths between 540 and 590 km. At greater depths, it will decompose to a mixture of modified spinel or spinel, stishovite and garnet solid solutions with smaller amounts of a pyroxene component in solution.     

High-pressure phase transformations in the system of MgSiO3-FeSiO3

Two synthetic pyroxenes (FeSiO₃, MgSiO₃) and five natural pyroxenes with compositions of about Fs₈₀En₂₀, Fs₆₀En₄₀, Fs₅₀En₅₀, Fs₄₀En₆₀, and Fs₂₀En₈₀ have been subjected to pressures up to250 ± 50kbars at a temperature of about1500 ± 200°C in a diamond anvil cell heated by an infrared laser beam. After quenching and unloading X-ray data analysis indicates that (1) those with Mg less than 50% undergo the following reactions: 2(Mg,Fe)SiO₃ (pyroxene) → (Mg,Fe)₂SiO₄ (spinel) + SiO₂ (stishovite) → 2(Mg,Fe)O (magnesiowu¨stite) + SiO₂ (stishovite) with increase of pressure, and (2) those with Mg higher than 60%, undergo the following reactions: 2(Mg,Fe)SiO₃ (pyroxene) → (Mg,Fe)₂SiO₄ (spinel) + SiO₂ (stishovite) → 2(Mg,Fe)SiO₃ (hexagonal phase) → 2(Mg,Fe)O (magnesiowu¨stite) + SiO₂ (stishovite) with increase of pressure.     

Phase transformations in a harzburgite composition to 26 GPa: implications for dynamical behaviour of the subducting slab

The mineralogy adopted by a depleted harzburgite composition has been studied over the pressure interval 5–26 GPa at temperatures of 1300–1400°C. The pyroxene-garnet component of the harzburgite composition (harzburgite minus 82 wt.% olivine) transforms to majorite garnet by 18–19 GPa, and further disproportionates to the assemblage of garnet + stishovite + Mg₂SiO₄ spinel above 20 GPa. At still higher pressures, first ilmenite (22–24 GPa) and then perovskite MgSiO₃ (24–26 GPa) are found to coexist with garnet. Garnet disappears at 26 GPa and almost complete transition to perovskite is achieved at this pressure. The mineral proportions and density profiles in the subducting oceanic lithosphere, modelled by a combination of 80% harzburgite + 20% primitive MORB compositions are calculated as a function of depth under conditions isothermal with surrounding pyrolite mantle, and also for a temperature distribution in which the slab is substantially cooler than surrounding mantle to below 700 km. Under isothermal conditions, the slab has a density similar to surrounding mantle to a depth of 600 km. However, between 600 and 700 km, the slab is up to 0.08 g/cm³ denser than surrounding mantle. This is caused primarily by the higher alumina content in pyrolite as compared to harzburgite, which causes the transition to perovskite in pyrolite to occur at substantially higher pressures than in harzburgite. The presence of alumina also smears out the garnet-perovskite transition in pyrolite over a depth interval of 50 km, whereas this transformation is much sharper in the harzburgite composition. Calculations based on the observed phase equilibria also show that a subducted cool slab remains much denser (by 0.1–0.3 g/cm³) than surrounding mantle to a depth of 700 km but possesses a density similar to surrounding mantle below this depth. These results have important implications for the dynamical behaviour of slabs possessing different thermal regimes when they encounter the 670 km discontinuity and also for the nature of this discontinuity.     

Melting of enstatite from 13 to 18 GPa under hydrous conditions

Experiments on MgSiO₃ enstatite were conducted in the pressure range from 13 to 18 GPa under hydrous conditions in order to clarify the effect of water on the melting phase relations of enstatite at pressures corresponding to the Earth’s mantle transition zone. In some previous experiments [Geol. Soc. Am. Bull. 79 (1968) 1685; Phys. Earth Planet. Inter. 85 (1994) 237], incongruent melting behavior to form Mg₂SiO₄ forsterite and SiO₂ enriched liquid up to 5 GPa was observed, and congruent melting behavior at pressures up to 12 GPa was observed. Under hydrous conditions, we found that the melting reaction changes from congruent to incongruent at around 13.5 GPa. Liquid formed above 13.5 GPa is enriched in MgO component relative to MgSiO₃ because it coexists with stishovite (SiO₂). Moreover, the solidus temperature decreases drastically at around 13.5 GPa, in unison with the change in the melting reaction. The solidus temperature is about 1400 °C at 13 GPa, but approximately 900 °C at 15 GPa. Our results show that the liquidus phase changes from clinoenstatite to stishovite with increasing pressure and water content above 13.5 GPa. MgSiO₃ enstatite is one of the major constituent minerals in the Earth’s mantle, and it is expected that MgO-enriched liquid will be generated in the transition zone if water is present.     

Garnet-ilmenite-perovskite transitions in the system Mg4Si4O12-Mg3Al2Si3O12 at high pressures and high temperatures: phase equilibria, calorimetry and implications for mantle structure

Phase relations in the system Mg₄Si₄O₁₂-Mg₃Al₂Si₃O₁₂ were examined at pressures of 19-27 GPa and relatively low temperatures of 800-1000 °C using a multianvil apparatus to clarify phase transitions of pyroxene-garnet assemblages in the mantle. Both of glass and crystalline starting materials were used for the experiments. At 1000 °C, garnet solid solution (s.s.) transforms to aluminous ilmenite s.s. at 20-26 GPa which is stable in the whole compositional range in the system. In Mg₄Si₄O₁₂-rich composition, ilmenite s.s. transforms to a single-phase aluminous perovskite s.s., while Mg₃Al₂Si₃O₁₂-rich ilmenite s.s. dissociates into perovskite s.s. and corundum s.s. These newly determined phase relations at 1000 °C supersede preliminary phase relations determined at about 900 °C in the previous study. The phase relations at 1000 °C are quite different from those reported previously at 1600 °C where garnet s.s. transforms directly to perovskite s.s. and ilmenite is stable only very close to Mg₄Si₄O₁₂. The stability field of Mg₃Al₂Si₃O₁₂ ilmenite was determined at 800-1000 °C and 25-27 GPa by reversed phase boundaries. In ilmenite s.s., the a-axis slightly increases but the c-axis and molar volume decrease substantially with increasing Al₂O₃ content. Enthalpies of ilmenite s.s. were measured by differential drop-solution calorimetry method using a high-temperature calorimeter. The excess enthalpy of mixing of ilmenite s.s. was almost zero within the errors. The measured enthalpies of garnet-ilmenite and ilmenite-perovskite transitions at 298 K were 105.2±10.4 and 168.6±8.2 kJ/mol, respectively, for Mg₄Si₄O₁₂, and 150.2±15.9 and 98.7±27.3 kJ/mol, respectively, for Mg₃Al₂Si₃O₁₂. Thermodynamic calculations using these data give rise to phase relations in the system Mg₄Si₄O₁₂-Mg₃Al₂Si₃O₁₂ at 1000 and 1600 °C that are generally consistent with those determined experimentally, and confirm that the single-phase field of ilmenite expands from Mg₄Si₄O₁₂ to Mg₃Al₂Si₃O₁₂ with decreasing temperature. The earlier mentioned phase relations in the simplified system as well as those in the Mg₂SiO₄-Fe₂SiO₄ system are applied to estimate mineral proportions in pyrolite as a function of depth along two different geotherms: one is a horizontally-averaged temperature distribution in a normal mantle, and the other being 600 °C lower than the former as a possible representative geotherm in subducting slabs. Based on the previously described estimated mineral proportions versus depth along the two geotherms, density and compressional and shear wave velocities are calculated as functions of depth, using available mineral physics data. Along a normal mantle geotherm, jumps of density and velocities at about 660 km corresponding to the post-spinel transition are followed by steep gradients due to the garnet-perovskite transition between 660 and 710 km. In contrast, along a low-temperature geotherm, the first steep gradients of density and velocities are due to the garnet-ilmenite transition between 610 and 690 km. This is followed by abrupt jumps at about 690 km for the post-spinel transition, and steep gradients between 700 and 740 km that correspond to the ilmenite-perovskite transition. In the latter profile along the low-temperature geotherm, density and velocity increases for garnet-ilmenite and ilmenite-perovskite transitions are similar in magnitude to those for the post-spinel transition. The likely presence of ilmenite in cooler regions of subducting slabs is suggested by the fact that the calculated velocity profiles along the low-temperature geotherm are compatible with recent seismic observations indicating three discontinuities or steep velocity gradients at around 600-750 km depth in the regions of subducting slabs.     

Orthorhombic perovskite phases observed in olivine,pyroxene and garnet at high pressures and temperatures

Ferromagnesian silicate olivines, pyroxenes and garnets with Mg/(Mg + Fe)?0.3 (molar) have been found to transform to high-pressure phases characterized by the orthorhombic perovskite structure when compressed to pressures above 250 kbar in a diamond-anvil press and heated to temperatures above 1,000°C with a YAG laser. The zero-pressure density of the perovskite phase of (Mg,Fe)SiO₃ is about 3–4% greater than that of the close-packed oxides, rocksalt plus stishovite. For (Mg,Fe)₂SiO₄ compounds, the perovskite plus rocksalt phase assemblage is 2–3% denser than the mixed oxides. The experimental synthesis of such high-density perovskite phases in olivine, pyroxene and garnet compounds suggests that (Mg,Fe)SiO₃-perovskite is the dominant mineral phase in the earth's lower mantle.     

Calculations of high-pressure phase transitions in the system MgOSiO2 and implications for mantle discontinuities

By incorporating the knowledge of the observed high-pressure phase transformations, the measured equilibrium phase boundaries for certain transitions, and the measured thermochemical data for certain phases in the system MgOSiO₂, the equilibrium phase boundaries for all the phase transitions in this system at 1000°C have been calculated on the basis of an assumption that volume change across a phase boundary is independent of temperature. Three major seismic velocity discontinuities in the mantle (420, 570, and 650 km) have been chosen for comparison with the measured and calculated equilibrium phase boundaries for the high-pressure phases observed in the system MgOSiO₂. Complications of phase changes due to the addition of FeO and Al₂O₃ to the system have also been accounted for. It is suggested by the results of this study that the 420- and 570-km discontinuities are probably related to phase transitions observed in the system MgOSiO₂, but that the 650-km discontinuity is not likely to be associated with any of the equilibrium phase boundaries observed in olivine, pyroxene, and garnet, but may instead be a chemical change.     

High-pressure phase equilibria in a garnet lherzolite,with special reference to Mg2+Fe2+ partitioning among constituent minerals

Phase equilibria in a natural garnet lherzolite nodule (PHN 1611) from Lesotho kimberlite and its chemical analogue have been studied in the pressure range 45–205 kbar and in the temperature range 1050–1200°C. Partition of elements, particularly Mg²⁺Fe²⁺, among coexisting minerals at varying pressures has also been examined. High-pressure transformations of olivine(α) to spinel(γ) through modified spinel(β) were confirmed in the garnet lherzolite. The transformation behavior is quite consistent with the information previously accumulated for the simple system Mg₂SiO₄Fe₂SiO₄. At pressures of 50–150 kbar, a continuous increase in the solid solubility of the pyroxene component in garnet was demonstrated in the lherzolite system by means of microprobe analyses. At 45–75 kbar and 1200°C, the Fe²⁺/(Mg + Fe²⁺) value becomes greater in the ascending order orthopyroxene, Ca-rich clinopyroxene, olivine and garnet. At 144–146 kbar and 1200°C, garnet exhibits the highest Fe²⁺/(Mg + Fe²⁺) value; modified spinel(β) and Ca-poor clinopyroxene follow it. When the modified spinel(β)-spinel(γ) transformation occurred, a higher concentration of Fe²⁺ was found in spinel(γ) rather than in garnet. As a result of the change in the Mg²⁺Fe²⁺ partition relation among coexisting minerals, an increase of about 1% in the Fe₂SiO₄ component in (Mg,Fe)₂SiO₄ modified spinel and spinel was observed compared with olivine.These experimental results strongly suggest that the olivine(α)-modified spinel(β) transformation is responsible for the seismic discontinuity at depths of 380–410 km in the mantle. They also support the idea that the minor seismic discontinuity around 520 km is due to the superposition effect of two types of phase transformation, i.e. the modified spinel(β)-spinel(γ) transformation and the pyroxene-garnet transformation. Mineral assemblages in the upper mantle and the upper half of the transition zone are given as a function of depth for the following regions: 100–150, 150–380, 380–410, 410–500, 500–600 and 600–650 km.     

High-pressure X-ray diffraction studies on β- and γ-Mg2SiO4

Pressure effects on the lattice parameters of β- and γ-Mg₂SiO₄ have been measured at room temperature and at pressures up to 100 kbar using a multi-anvil high-pressure X-ray diffraction apparatus. The volume changes (ΔV/V₀) at 90 kbar are 5.4 · 10^?2 and 4.2 · 10^?2 for β- and γ-Mg₂SiO₄, respectively. Isothermal bulk moduli at zero pressure have been calculated from least-square fits of the data to straight lines. They turn out to be 1.66 ± 0.4 and 2.13 ± 0.1 Mbar for β- and γ-Mg₂SiO₄, respectively. The α → γ transition obeys Wang's linear V_φ?ρ relation but the α → β transition does not.     

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

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

Stability of forsterite + CO2 and its bearing on the role of CO2 in the mantle

An experimental determination of the reaction MgCO₃ + MgSiO₃ = Mg₂SiO₄ + CO₂ between 20 and 40 kbars and in the range 1000–1500°C yields an average pressure effect on the equilibrium of 44 bars/°C. This result shows that the assemblage forsterite and carbon dioxide is not stable under most pressure and temperature conditions expected in the upper mantle. Hypotheses requiring the presence of free CO₂ in the low-velocity zone, CO₂ as a drive mechanism for kimberlite emplacement, or action of a free CO₂ phase in ultramafic rocks may need considerable revision.     

Stability relation of (Mg,Fe)SiO3 garnets, major constituents in the Earth's interior

High-pressure and high temperature experiments at 20 GPa on (Mg,Fe)SiO₃ have revealed stability fields of two types of aluminium-free ferromagnesian garnets; non-cubic garnet and cubic garnet (majorite). Majorite garnet is stable only within a limited compositional variation, 0.2 < Fe/(Mg + Fe)< 0.4, and in the narrow temperature interval of 200°C around 2000°C, while the stability of non-cubic garnet with more iron-deficient compositions persists up to higher temperatures. These two garnets show fractional melting into iron-deficient garnet and iron-rich liquid, and the crystallization field of cubic garnet extends over Fe/(Mg + Fe)= 0.5. The assemblage silicate spinel and stishovite is a low-temperature phase, which also occurs in the iron-rich portion of the MgSiO₃—FeSiO₃ system. The sequence as given by the Fe/(Mg + Fe) value for the coexisting phases with the two garnets at 2000°C and 20 GPa is: silicate modified spinel aluminium-free garnets silicate spinel.Natural majorite in shock-metamorphosed chondrites is clarified to be produced at pressures above 20 GPa and temperatures around 2000°C. Similar shock events may cause the occurrence of non-cubic garnet in iron-deficient meteorites. Non-cubic garnet could be a stable phase in the Earth's mantle if a sufficiently low concentration of aluminium is present in the layer corresponding to the stable pressure range of non-cubic garnet. The chemical differentiation by melting in the deep mantle is also discussed on the basis of the present experimental results and the observed coexistence of majorite garnet with magnesiowüstite in chondrites.     

Post-ilmenite phases of silicates and germanates

MgSiO₃, ZnSiO₃, MgGeO₃, MnGeO₃, and ZnGeO₃ are the only silicates and germanates known to crystallize in the ilmenite-like structure at high pressures and high temperatures. With the exception of the zinc compounds, the above-mentioned ilmenites have all been found to transform to the orthorhombic modification of the perovskite structure at higher pressures. The ilmenite phase of ZnSiO₃, on the other hand, transforms to its component oxide mixture with the rocksalt and rutile structures, whereas ZnGeO₃ (ilmenite) transforms first to an as yet undetermined orthorhombic phase and then to its component oxide mixture. The direct transformation from the ilmenite to perovskite structures observed in the metasilicates and metagermanates is consistent with all other reported high-pressure post-ilmenite phases (CdTiO₃, CdSnO₃, MnVO₃, and (Fe,Mg)TiO₃). The observation of the ilmenite-perovskite transformation in MgSiO₃ and its solid solutions towards Al₂O₃ suggests that MgO (rocksalt) + SiO₂ (rutile) + Al₂O₃ (corundum) is not a stable mineral assemblage for the earth's lower mantle.     

The join grossularite-calcite through the system CaO—Al2O3—SiO2—CO2 at 30 kilobars: Crystallization range of silicates and carbonates on the liquidus

At 30 kbar, calcite melts congruently at 1615°C, and grossularite melts incongruently to liquid + gehlenite (tentative identification) at 1535°C. The assemblage calcite + grossularite melts at 1450°C to produce liquid + vapor, with piercing point at about 49 wt.% CaCO₃. Vapor phase is present in all hypersolidus phase fields except for those with less than about 7% CaCO₃ or 8% Ca₃Al₂Si₃O₁₂. These results, together with known liquidus data for CaO—SiO₂—CO₂ and inferred results for CaO—Al₂O₃—CO₂ and Al₂O₃—SiO₂—CO₂, permit construction of the position of the CO₂- saturated liquidus surface in the quaternary system, and estimation of the positions of liquidus field boundaries separating some of the primary crystallization fields on this surface. The field of calcite is separated from those for grossularite and quartz by a field boundary with about 50% dissolved CaCO₃. Crystallization paths of silicate liquids in the range Ca₂SiO₄—Ca₃Al₂Si₃O₁₂—SiO₂, with some dissolved CO₂, will terminate at a quaternary eutectic on this field boundary, with the precipitation of calcite together with grossularite and quartz, at a temperature below 1450°C. Addition of Al₂O₃ to CaO—SiO₂—CO₂ in amounts sufficient to stabilize garnet thus causes little change in the general liquidus pattern as far as carbonates and silicates are concerned. With addition of MgO, we anticipate that silicate liquids with dissolved CO₂ will also follow liquidus paths to fields for the precipitation of carbonates; we conclude that similar paths link kimberlite and some carnbonatite magmas.     

Synthesis of pyrope-knorringite solid solution series

The garnet solid solution series between pyrope Mg₃Al₂Si₃O₁₂ and knorringite Mg₃Cr₂Si₃O₁₂ has been synthesized from oxide mixtures at pressures of 60–80 kbars and 1400–1500°C. Lattice parameters and refractive indices of solid solutions vary linearly with (molecular) composition within the limits of measurement. The lattice parameter of pure knorringite is 11.600Åand its refractive index is 1.83. The genetic significance of mineral inclusions in natural diamonds is discussed, particularly in the light of the very high knorringite contents often found in garnet inclusions. It is suggested that the most common mineral assemblage occurring as inclusions in diamonds (olivine + knorringite-rich garnet + enstatite) might be explained in terms of subduction into the mantle of olivine + chrome-spinel + enstatite cumulates originally formed by crystallization of mafic magmas within the oceanic crust. The cumulate assemblage experienced alteration by circulating hydrothermal solutions, resulting in the introduction of some carbonate and serpentine minerals. During subduction, this assemblage was partially melted at depth below 150 km, accompanied by reduction of carbonate, to form a reconstituted assemblage consisting of olivine + knorringite-rich garnet + enstatite ± diamond.     

Oxygen isotope fractionation in mantle minerals

The increment method is adopted to calculate oxygen isotope fractionation factors for mantle minerals, particularly for the polymorphic phases of MgSiO₃ and Mg₂SiO₄. The results predict the following sequence of¹⁸O-enrichment:pyroxene (Mg, Fe, Ca)₂Si₂O₆>olivine (Mg, Fe)₂SiO₄ > spinel (Mg, Fe)₂SiO₄> ilmenite (Mg, Fe, Ca) SiO₃>perovskite (Mg, Fe, Ca) SiO₃. The calculated fractionations for the calcite-perovskite (CaTiO₃) System are in excellent agreement with the experimental calibrations. If there would be complete isotopic equilibration in the mantle, the spinel-structured silicates in the transition zone are predicted to be enriched in¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle might result from differences in the chemical composition and crystal structure of mineral phases at different mantle depths. Assuming isotopic equilibrium on a whole earth scale, the chemical structure of the Earth’s interior can be described by the following sequence of¹⁸O-enrichment:upper crust>lower crust>upper mantle>transition zone>lower mantle>core. Project supported by the National Natural Science Foundation of China and the Chinese Academy of Sciences.     

Mechanisms and kinetics of the post-spinel transformation in Mg2SiO4

Mechanisms and kinetics of the post-spinel transformation in Mg₂SiO₄ were examined at 22.7–28.2 GPa and 860–1200 °C by in situ X-ray diffraction experiments using synchrotron radiation combined with microstructural observations of the recovered samples. The post-spinel phases nucleated on spinel grain boundaries and grew with a lamellar texture. Under large overpressure conditions, reaction rims were formed along spinel grain boundaries at the initial stage of the transformation, whereas under small overpressure conditions, the transformation proceeded without formation of reaction rims. Mg₂SiO₄ spinel metastably dissociated into MgSiO₃ ilmenite and periclase, and stishovite and periclase as intermediate steps in the transformation into the stable assemblage of MgSiO₃ perovskite and periclase. Topotactic relationships were found in the transformation from spinel into ilmenite and periclase. Kinetic parameters in the Avrami rate equation, time taken to 10% completion, and the growth rate were estimated by analysis of the kinetic data obtained by in situ X-ray observations. The empirical activation energy for 10% transformation decreases with increasing pressure because the activation energy for nucleation becomes smaller at larger overpressure conditions. Extrapolations of the 10% transformation to ∼700 °C, which is the lowest temperature expected for the cold slabs at ∼700 km depth, suggest that overpressure of more than ∼1 GPa is needed for the transformation. Because the growth rate is estimated to be large even at low-temperatures of ∼700 °C and overpressures of 1 GPa, the depth of the post-spinel transformation in the cold slabs is possibly controlled by nucleation kinetics.     

Petrology of the Green Knobs diatreme and implications for the upper mantle below the Colorado Plateau

Peridotite inclusions, crystal fragments, and kimberlite breccia at Green Knobs, New Mexico, have been studied to evaluate compositions and processes in the upper mantle below the Colorado Plateau. Most peridotite inclusions are spinel lherzolites and harzburgites, or their partly hydrated equivalents, in the Cr-diopside group. Orthopyroxene-rich websterites and olivine websterites comprise 3% of the peridotites and formed as cumulates. Typical anhydrous or slightly hydrated peridotites contain aluminous, calcic diopside (5–7% Al₂O₃), aluminous orthopyroxene (3–6% Al₂O₃), spinel, and olivine (near Fa₉). Geothermometers based on different mineral pairs yield temperatures from above 1100°C to below 700°C in single rocks. High values, derived from pyroxenes with included exsolution lamellae, may approximate temperatures of primary crystallization. Low values, based on olivine-spinel and olivine-clinopyroxene pairs, approach upper mantle temperatures before eruption. In rare samples, some spinel grains are rimmed by garnet while others are not rimmed; garnet formation was controlled by nucleation kinetics. About one-third of the peridotites were deformed shortly before eruption, with effects ranging from mild cataclasis to the production of ultramylonites.Discrete crystals of garnet, olivine (near Fa₈), and Cr-diopside represent garnet peridotite. Eclogites were not found. The garnet peridotite is more depleted than overlying spinel peridotite, and it is not a likely source for the minettes associated with the kimberlites.The mantle below Green Knobs consists of spinel peridotite from 45 to perhaps 60 km depth immediately underlain by more-depleted garnet peridotite. The position of the spinel-garnet transition may be fixed by kinetics. The kimberlite may have been produced when heat from ascending minette magma released volatiles from otherwise depleted garnet peridotite. Resulting gas-solid mixtures erupted along zones of deformation associated with Colorado Plateau monoclines. Sheared lherzolites formed during renewed movement along these zones.