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.     

In situ measurements of sound velocities and densities across the orthopyroxene → high-pressure clinopyroxene transition in MgSiO3 at high pressure

Using acoustic measurement interfaced with a large volume multi-anvil apparatus in conjunction with in situ X-radiation techniques, we are able to measure the density and elastic wave velocities (V_P and V_S) for both ortho- and high-pressure clino-MgSiO₃ polymorphs in the same experimental run. The elastic bulk and shear moduli of the unquenchable high-pressure clinoenstatite phase were measured within its stability field for the first time. The measured density contrast associated with the phase transition OEN → HP-CEN is 2.6-2.9% in the pressure of 7-9 GPa, and the corresponding velocity jumps are 3-4% for P waves and 5-6% for S waves. The elastic moduli of the HP-CEN phase are K_S=156.7(8) GPa, G = 98.5(4) GPa and their pressure derivatives are K_S′=5.5(3) and G′ = 1.5(1) at a pressure of 6.5 GPa, room temperature. In addition, we observed anomalous elastic behavior in orthoenstatite at pressure above 9 GPa at room temperature. Both elastic wave velocities exhibited softening between 9 and 13-14 GPa, which we suggest is associated with a transition to a metastable phase intermediate between OEN and HP-CEN.     

High-pressure partial melting of garnet pyroxenite: possible mafic lithologies in the source of ocean island basalts

Many ocean island basalts (OIB) that have isotopic ratios indicative of recycled crustal components in their source are silica-undersaturated and unlike silicic liquids produced from partial melting of recycled mid-ocean ridge basalt (MORB). However, experiments on a silica-deficient garnet pyroxenite, MIX1G, at 2.0-2.5 GPa show that some pyroxenite partial melts are strongly silica-undersaturated [M.M. Hirschmann et al., Geology 31 (2003) 481-484]. These low-pressure liquids are plausible parents of alkalic OIB, except that they are too aluminous. We present new partial melting experiments on MIX1G between 3.0 and 7.5 GPa. Partial melts at 5.0 GPa have low SiO₂ (<48 wt%), low Al₂O₃ (<12 wt%) and high CaO (>12 wt%) at moderate MgO (12-16 wt%), and are more similar to primitive OIB compositions than lower-pressure liquids of MIX1G or experimental partial melts of anhydrous or carbonated peridotite. Solidus temperatures at 5.0 and 7.5 GPa are 1625 and 1825°C, respectively, which are less than 50°C cooler than the anhydrous peridotite solidus. The liquidus temperature at 5.0 GPa is 1725°C, indicating a narrow melting interval (∼100°C). These melting relations suggest that OIB magmas can be produced by partial melting of a silica-deficient pyroxenite similar to MIX1G if its melting residue contains significant garnet and lacks olivine. Such silica-deficient pyroxenites could be produced by interaction between recycled subducted oceanic crust and mantle peridotite or could be remnants of ancient oceanic lower crust or delaminated lower continental crust. If such compositions are present in plumes ascending with potential temperatures of 1550°C, they will begin to melt at about 5.0 GPa and produce appropriate partial melts. However, such hot plumes may also generate partial melts of peridotite, which could dilute the pyroxenite-derived partial melts.     

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.     

Titanium solubility in coexisting garnet and clinopyroxene at very high pressure: the significance of exsolved rutile in garnet

Exsolution microstructures including ilmenite±garnet in clinopyroxene and rutile in garnet are common in clinopyroxenite and eclogite from the Sulu ultrahigh-pressure (UHP) terrane. In order to understand the phase relations and Ti solubility in both garnet and clinopyroxene in a natural TiO₂-bearing system, several experiments at 5-15 GPa, 1000-1400°C were carried out using the multianvil high-pressure apparatus. The Hujianlin ilmenite-rich garnet clinopyroxenite showing exsolution microstructure was selected as starting material, because it closely approaches a composition lying in the TiO₂-CaO-MgO-FeO-Al₂O₃-SiO₂ system. Except for minor melt in one experiment at 1400°C and 5 GPa, other run products contain majoritic garnet+clinopyroxene±ilmenite (or rutile) and exhibit neoblastic texture. With increasing pressure, Ti and Ca, Mg and Si contents of neoblastic garnet increase with decreasing Al. The principal coupled substitutions are Ca²⁺Ti⁴⁺→2Al³⁺ and Si⁴⁺Mg²⁺→2Al³⁺ responding to majorite component increase. Titanium solubility (0.8-4.5 wt% as TiO₂) in garnet and Grt_Ti/Cpx_Ti ratio have a pronounced positive correlation with pressure between 5 and 15 GPa. On the other hand, the coexisting clinopyroxene contains low Ti (0.17-0.53 wt% as TiO₂), and shows no significant pressure effect. Rutile exsolution in garnet is coupled to that of pyroxene exsolution; both are exsolved from majoritic garnet on decompression. Therefore, the amount of such exsolved lamellae is a potential indicator of high-pressure metamorphism in exhumed rocks, whereas the TiO₂ content of clinopyroxene coexisting with garnet is not sensitive to pressure change.     

A fracture mechanics study of subcritical tensile cracking of quartz in wet environments

Load relaxation and cross-head displacement rate-change experiments have been used to establish log₁₀ stress intensity factor (K) versus log₁₀ crack velocity (v) diagrams for double torsion specimens, of synthetic quartz cracked on thea plane in liquid water and moist air.For crack propagation normal toz and normal tor at 20°C,K _Ic (the critical stress intensity factor) was found to be 0.852±0.045 MN·m^–3/2 and 1.002±0.048 MN·m^–3/2, respectively.Subcritical crack growth at velocities from 10^–3 m·s^–1 to 10^–9 m·s^–1 at temperatures from 20°C to 80°C is believed to be facilitated by chemical reaction between the siloxane bonds of the quartz and the water or water vapour of the environment (stress corrosion). The slopes, of isotherms in theK-v diagrams are dependent upon crystallographic orientation. The isotherms have a slope of 12±0.6 for cracking normal tor and 19.9±1.7 for cracking normal toz. The activation enthalpy for crack propagation in the former orientation in liquid water at temperatures from 20°C to 80°C is 52.5±3.8 kJ·mole^–1.A discussion is presented of the characteristics of theK-v diagrams for quartz.     

Determination of phase transition pressures of ZnTe under quasihydrostatic conditions

Pressure behavior of ZnTe at room temperature was studied using an X-ray energy dispersive method on a DIA type cubic anvil apparatus (SAM-85) at NSLS-X17B1. By using powdered polyethylene, the sample and NaCl for a pressure scale were held under quasihydrostatic conditions, which were confirmed by X-ray diffraction method. Two high-pressure phase transitions were confirmed using X-ray powder diffraction simultaneously with electrical resistance measurements. The phase transition pressures under quasihydrostatic conditions were determined to be 9.6 GPa, at which the resistance increased, and 12.0 GPa, which was the midpoint of a large resistance decrease. Errors in the pressure determinations were estimated to be less than 0.2 GPa. These pressure values may depend on grain size and anisotropic stress effects on the calibrant. From X-ray observation of ZnTe, the bulk modulus of the zinc blende structure was calculated to beK ₀=51(3) GPa andK ₀ =3.6(0.8), and the first transition at 9.6 GPa was found to have about 9% volume change. It was consistent with an anomaly in the pressure generating curves.     

High-pressure studies of ferroelectric phases related to the earth and planetary interiors

To determine the effects of high-pressure constraints on the overall behaviour of ferroelectrics (FE) of both the perovskite “soft-mode” and hydrogen-bonded types, the authors have conducted dielectric property measurements to 5.5 GPa on single crystals and polycrystalline aggregates of several ferroelectrics (BaTiO₃, Pb(Zr,Ti)O₃, triglycine sulphate, Rochelle salt). The results of the experiments indicate: (1) dielectric hysteresis is possible in ferroelectrics which are under high-pressure conditions of deviatoric stresses and strains in which the FE phase forms part of a composite system; that is, under the conditions it would encounter if it formed part of a planetary interior; (2) the continued stability of these FE phases is not restricted to a particular polarization mechanism; (3) existing FE states, occurring as elastic and dielectric inhomogeneities, can persist to much higher pressures than expected on the basis of the pressure dependence of isolated and unconstrained FE crystals.     

Experimental and theoretical study of stability of dense hydrous magnesium silicates in the deep upper mantle

Fluid-undersaturated experiments were conducted to determine the phase relations in the simplified peridotite system MgO-SiO₂-H₂O (MSH) at 11.0-14.5 GPa and 800-1400 °C. Stability relations of dense hydrous magnesium silicates (DHMSs) under fluid-undersaturated conditions were experimentally examined. From the fluid-absent experimental results, we retrieved thermodynamic data for clinohumite, phase A, phase E, and hydrous wadsleyite, consistent with the published data set for dry mantle minerals. With this new data set, we have calculated phase equilibria in the MSH system including dehydration reactions. The dehydration reactions calculated with lower water activities of 0.68-0.60 match the fluid-present experiments of this study above 11.0 GPa and 1000 °C, indicating that considerable amounts of silicate component were dissolved into the fluid phase. The calculated phase equilibria illustrate the stability of the post-antigorite phase A-bearing assemblages. In the cold subducting slab peridotite, phase A + enstatite assemblage survives into the transition zone, whereas phase A + forsterite + enstatite assemblage forms hydrous wadsleyite at a much shallower depth of about 360-km. The slab is subducted with no dehydration reactions occurring when entering the transition zone. The phase equilibria also show the high temperature stability of phase E. Phase E is stable up to 1200 °C at 13.5 GPa, a plausible condition in the mantle of relatively low temperature, i.e., beneath subduction zones. Phase E is a possible water reservoir in the mantle as well as wadsleyite and ringwoodite.     

Electrical conductivity measurements on synthetic olivines and on olivine,enstatite and diopside from Dreiser Weiher,Eifel (Germany) under defined thermodynamic activities as a function of temperature and pressure

Results of electrical conductivity measurments on synthetic olivines of the system Mg₂SiO₄Fe₂SiO₄ and on minerals of Dreiser Weiher peridotite nodule Ib-8 (Eifel, Germany) are discussed in relation to the measuring procedure and to the variation of thermodynamic parameters.The measurements were performed in solid state high-pressure vessels between 340 and 1100°C and at a pressure of 10 kbar. It is shown that for ternary olivines and for pyroxenes, the control of two further variables, like the chemical activities of the components, is needed besides temperature and pressure control. The experimental set-up for the control of chemical activities and oxygen partial pressure is shown. From the slopes of the lines of log σ against 1/T the activation energies were calculated. Though in most cases the same oxygen fugacity ?_O2 is applied, the results reveal different values for synthetic and natural samples since the chemical activities of SiO₂ are different.     

Prograde P–T path of kyanite eclogites from Junan in the Sulu ultrahigh-pressure province, eastern China

Kyanite-bearing ultrahigh-pressure (UHP) eclogites occur as blocks in orthogneisses at Yangzhuang, in the Junan area of the southwestern Sulu province, eastern China. Eclogites have variable bulk rock compositions, with Al₂O₃ = 16–27 wt%, FeO* + MgO = 6–22 wt% and CaO = 9–13 wt%. Major minerals are garnet, omphacite, phengitic white mica, zoisite, kyanite, rutile and an SiO₂ phase. Fe-rich staurolite (Mg ? Mg# = 0.24 ± 0.01) and paragonite–margarite aggregates are rarely included in the cores of prograde zoned garnet. Metamorphic conditions ranged from 520 to 650°C and <1.4 GPa at an early prograde stage, and mostly reached 660–830°C and 2.7–3.5 GPa at the peak UHP stage. The estimated dP/dT of the prograde P–T path is less than 0.25 GPa/100°C at earlier stages and increases to 0.7–1.4 GPa/100°C just before the UHP stage. The kink of the prograde P–T path closely resembles the steady-state P–T paths proposed, assuming a two-parameter brittle-plastic shear stress model. The estimated P–T path adequately explains the absence of prograde lawsonite and sodic amphibole and the common occurrence of coexisting zoisite, kyanite and sodic-calcic amphibole in the UHP eclogites throughout the Sulu province. Simple clockwise prograde P–T paths for Sulu UHP eclogites proposed in earlier studies should be carefully re-examined.     

Effect of high-pressures on the electrical resistivity of natural zeolites from Deccan Trap, Maharashtra, India

We report here the electrical resistivity measurements on two natural zeolites–natrolite and scolecite (from the Killari borehole, Maharashtra, India) as a function of pressure up to 8 GPa at room temperature. High-pressure electrical resistivity studies on hydrous alumino-silicate minerals are very helpful in understanding the role of water in deep crustal conductivities obtained from geophysical models. The results obtained by magneto-telluric (MT) soundings and direct current resistivity surveys, along with the laboratory data on the electrical resistivity of minerals and rocks at high-pressure–temperature are used to determine the electrical conductivity distribution in continental lithosphere. The electrical resistivity of natural natrolite decreases continuously from 2.9 × 10⁹ Ω cm at ambient condition to 7.64 × 10² Ω cm at 8 GPa, at room temperature. There is no pressure-induced first order structural phase transitions in natrolite, when it is compressed in non-penetrating pressure transmitting medium up to 8 GPa. On the other hand scolecite exhibits a pressure-induced transition, with a discontinuous decrease of the electrical resistivity from 2.6 × 10⁶ to 4.79 × 10⁵ Ω cm at 4.2 to 4.3 GPa. The observed phase transition in scolecite is found to be irreversible. Vibrational spectroscopic and X-ray diffraction studies confirm the amorphous nature of the high-pressure phase. The results of the present high-pressure studies on scolecite are in good agreement with the high-pressure Raman spectroscopic data on scolecite. The thermo gravimetric studies on the pressure-quenched samples show that the samples underwent a pressure-induced partial dehydration. Such a pressure-induced partial dehydration, which has been observed in natural scolecite could explain the presence of high conductive layers in the earth's deep-crust.     

The structure and sharpness of (Mg,Fe)2SiO4 phase transformations in the transition zone

To calculate accurately the pressure interval and mineral proportions (i.e. yields) across the olivine to wadsleyite and wadsleyite to ringwoodite transformations requires a detailed knowledge of the non-ideality of Fe-Mg mixing in these (Mg,Fe)₂SiO₄ solid solutions. In order to constrain the activity-composition relations that describe non-ideal mixing, Fe-Mg partitioning experiments have been conducted between magnesiowüstite and (Mg,Fe)₂SiO₄ olivine, wadsleyite and ringwoodite as a function of pressure at 1400°C. Using known activity-composition relations for magnesiowüstite the corresponding relations for the three polymorphs were determined from the partitioning data. In all experiments the presence of metallic iron ensured redox conditions compatible with the Earth’s transition zone. The non-ideality of the (Mg,Fe)₂SiO₄ solid solutions was found to decrease in the order W^wadsleyite_FeMg>W^ringwoodite_FeMg>W^olivine_FeMg. These partitioning data were used, along with published phase equilibria measurements for the Mg₂SiO₄ and Fe₂SiO₄ end-member transformations, to produce an internally consistent thermodynamic model for the Mg₂SiO₄-Fe₂SiO₄ system at 1400°C. Using this model the pressure interval of the olivine to wadsleyite transformation is calculated to be significantly smaller than previous determinations. By combining these results with Fe-Mg partitioning data for garnet, the widths of transition zone phase transformations in a peridotite composition were calculated. The olivine to wadsleyite transformation at 1400°C in dry peridotite was found to occur over a pressure interval equivalent to approximately 6 km depth and the mineral yields were found to vary almost linearly with depth across the transformation. This transformation is likely to be even sharper at higher temperatures or could be significantly broader in wet mantle or in regions with a significant vertical component of mantle flow. The entire range of estimated widths for the 410 km discontinuity (4-35 km) could, therefore, be explained by the olivine to wadsleyite transformation in a peridotite composition over a range of quite plausible mantle temperatures and H₂O contents. The wadsleyite to ringwoodite transformation in peridotite mantle was calculated to take place over an interval of 20 km at 1400°C. This transformation yield was also found to be near linear.     

High-pressure decompositions in cobalt and nickel silicates

High-pressure stability relations in cobalt and nickel silicates have been studied over the pressure range 130–330 kbar employing a double-staged split-sphere-type high-pressure apparatus.γ-Co₂SiO₄ and γ-Ni₂SiO₄ decompose directly into their constituent oxide mixtures (rocksalt plus stishovite) 175 kbar and 280 kbar, respectively. The result that γ-Ni₂SiO₄ has a wider stability field in pressure than γ-Co₂SiO₄, is consistent with simple crystal-field theory.The experimental precision is high enough to show that the decomposition boundary of γ-Co₂SiO₄ has a positive slope (dP/dT > 0) and a preliminary determination of the boundary curve is P(kbar) = 0.065 T (°C) + 110.No positive evidence for the existence of high-pressure forms of CoSiO₃ and NiSiO₃ has been obtained in these quenching experiments, and they finally decompose into constituent oxide mixtures as in the cases of orthosilicates.     

Elasticity of the ilmenite - perovskite phase transformation in CdTiO3

Ultrasonic data for the velocities of the ilmenite and perovskite polymorphs of CdTiO₃ have been determined as a function of pressure to 7.5 kbar at room temperature for polycrystalline specimens hot-pressed at pressures up to 25 kbar. This transition is characterized by the following velocity (ν)-density (?) relationships: (1) the changes in compressional (ν_p) and bulk sound (ν_?) velocities are comparable in percentage magnitude to the density jump, while the shear (ν_s) velocity jump is three times greater than that for ?; (2) (ν_p/ν_s) decreases across the transition from the low- to high-pressure phase; and (3) low slopes (linear or logarithmic) on ν-? diagrams. The (ν_p/ν_s) behaviour for the ilmenite-perovskite transformation is unusual for the transitions studied in our laboratory. The observed relationships (1) and (2) are typical of the elasticity behaviour across phase transformations which involve increases in cation-anion co-ordination and in nearest-neighbour interatomic distances, such as those exhibited by CdTiO₃ in transforming from the ilmenite to the perovskite phase. Elasticity systematics for isostructural sequences are used to estimate the bulk moduli of the perovskite polymorphs of CaSiO₃ (2.7 Mbar) and MgSiO₃ (2.8 Mbar).     

Elasticity of pyrope and majorite-pyrope solid solutions to high temperatures

Majorite-garnet solid solutions are major mineral phases in the Earth’s upper mantle and transition zone. Here we present the first Brillouin scattering measurements of the elasticity of majorite (Mj, Mg₄Si₄O₁₂)-pyrope (Py, Mg₃Al₂Si₃O₁₂) solid solutions (Mj₅₀Py₅₀ and Mj₈₀Py₂₀) and single-crystal elasticity of pure synthetic pyrope at temperatures up to 800°C. The temperature derivatives of the adiabatic bulk (K_S) and shear (μ) moduli for all compositions along the Mj-Py join are the same within the experimental uncertainties (−∂K_S/∂T=14.0-14.5(20) MPa/K, −∂μ/∂T=8.3-9.2(10) MPa/K). The temperature dependence of the acoustic velocities for Mj-Py solid solutions is about half that of other major transition zone minerals. This implies that temperature variations in the transition zone, inferred from lateral velocity heterogeneity, can be significantly underestimated if the properties of majoritic garnet are not taken into account.     

Ray parameters of diffracted long period P and S waves and the velocities at the base of the mantle

The derivation of P and S velocities at the core-mantle boundary (CMB) from long-period diffracted waves by the use of the simple ray-theoretical formulav _CMB=r _c /p (v _CMB=velocity at the CMB;r _c =core radius;p=ray parameter) yields apparent velocity values which differ from the true velocities. Using a dominant period of about 20 sec for calculating theoretical seismograms, we found a linear relation between the apparent velocity and the average velocity in a transition zone at the base of the mantle with fixed velocity on top.The ray parameters determined from long-period earthquake data are found to be 4.540±0.035 and 8.427±0.072 sec/deg for P_diff and S_diff, respectively. These values yield apparent velocities of 13.378±0.103 for P and 7.207±0.062 km/sec for S waves. By means of the theoretical relation between apparent and average velocity and under the assumption of linear variation of velocity with depth, one can invert the apparent velocities into true CMB velocities of 13.736±0.170 and 7.320±0.124 km/sec. These results imply positive velocity gradients at the base of the mantle and hence no significant departures from adiabaticity and homogeneity.Contribution No. 211 of the Geophysical Institute, University of Karlsruhe.     

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.     

Laboratory measurements of ‘porosity‐free’ intrinsic Vp and Vs in an olivine gabbro of the Oman ophiolite: Implication for interpretation of the seismic structure of lower oceanic crust

In order to determine ‘porosity‐free’ intrinsic ultrasonic compressional (Vp) and shear wave (Vs) velocities and Vp/Vs of an olivine gabbro from the Oman ophiolite, we developed a new experimental system using a piston‐cylinder type high‐pressure apparatus. The new system allowed us to measure velocities at pressures ranging from 0.20 to 1.00 GPa and at temperatures up to 300°C for Vp and 400°C for Vs. At room temperature, the Vp and Vp/Vs increase rapidly with pressure up to 0.40 GPa, while between 0.45 and 1.00 GPa the increase is more gradual. The change in increasing rate is attributed to closure of porosity at pressures above 0.45 GPa. Based on the linear regression of data obtained at higher pressures (0.45–1.00 GPa) and extrapolation to the lower pressures, combined with temperature derivatives of velocities of the sample measured at 1.00 GPa, we determined the intrinsic Vp and Vs of the sample as a function of pressure (P, in GPa) and temperature (T, in °C). The intrinsic velocities can be expressed as Vp (km/s) = 7.004 + 0.096 × P ? 0.00015 × T, and Vs (km/s) = 3.827 + 0.007 × P ? 0.00008 × T. We evaluated the intrinsic Vp and Vs of the olivine gabbro at oceanic crustal conditions and compared them with a velocity depth‐profile of the borehole seismic observatory WP‐2 area in the northwestern Pacific Basin. Although the intrinsic Vp (～7.0 km/s) and Vs (～3.8 km/s) for the olivine gabbro studied are comparable to those of seismic layer 3 in the WP‐2 area, the estimated vertical gradients of intrinsic velocities are significantly smaller than those reported from layer 3. These results suggest that velocity profiles of layer 3 in the WP‐2 area may reflect the presence of a minor porosity in lower oceanic crust, which closes with increasing depth and/or continuous changes in mineralogy of layer 3 rocks.