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.     

High-pressure Raman studies and heat capacity measurements on the MgSiO<Subscript>3</Subscript> analogue CaIr<Subscript>0.5</Subscript>Pt<Subscript>0.5</Subscript>O<Subscript>3</Subscript>

Raman spectroscopy and heat capacity measurements have been used to study the post-perovskite phase of CaIr_0.5Pt_0.5O₃, recovered from synthesis at a pressure of 15 GPa. Laser heating CaIr_0.5Pt_0.5O₃ to 1,900 K at 60 GPa produces a new perovskite phase which is not recoverable and reverts to the post-perovskite polymorph between 20 and 9 GPa on decompression. This implies that Pt-rich CaIr_1−xPt_xO₃ perovskites including the end member CaPtO₃ cannot easily be recovered to ambient pressure from high P–T synthesis. We estimate an increase in the thermodynamic Grüneisen parameter across the post-perovskite to perovskite transition of 34%, of similar magnitude to those for (Mg,Fe)SiO₃ and MgGeO₃, suggesting that CaIr_0.5Pt_0.5O₃ is a promising analogue for experimental studies of the competition in energetics between perovskite and post-perovskite phases of magnesium silicates in Earth’s lowermost mantle. Low-temperature heat capacity measurements show that CaIrO₃ has a significant Sommerfeld coefficient of 11.7 mJ/mol K² and an entropy change of only 1.1% of Rln2 at the 108 K Curie transition, consistent with the near-itinerant electron magnetism. Heat capacity results for post-perovskite CaIr_0.5Rh_0.5O₃ are also reported.     

Raman spectroscopic study of hydroxyl-clinohumite at various pressures and temperatures

 Variations of Raman spectra of hydroxyl-clinohumite were studied up to ∼370 kbar at room temperature, and in the range 81–873 K at atmospheric pressure. With the exception of the symmetric OH-stretch bands, the Raman frequencies of all bands were observed to increase monotonically with increasing pressure, and decrease with increasing temperature. This behavior is in line with those observed for other humite members (norbergite and chondrodite) so far studied. The symmetric OH-stretching band shows a mode softening with increasing pressure, and splits into two bands at either high pressure or low temperature. In the quasihydrostatic experiment, the compression and decompression paths of one of the asymmetric OH-stretch bands form a hysteresis loop, but the same behavior was not observed in the nonhydrostatic experiment. These results indicate that the two kinds of OH groups in hydroxyl-clinohumite have nonequivalent movement paths on compression, and with one OH group experiencing a release of spatial hindrance during compression. This behavior appears to be modified by shear stress. The same complication of the OH groups was not observed in the temperature variation study. The pressure and temperature variations of the Raman frequencies for the various vibrations involving the SiO₄ tetrahedra and MgO₆ octahedra below ∼1000 cm⁻¹ for clinohumite behave similarly to other hydrous magnesium silicates. On the basis of the relationship between isothermal bulk modulus and Raman data, it is suggested that the linear pressure dependences of vibrational frequencies of various Raman bands reported in the literature are inadequate. Received: 20 March 1999 / Revised, accepted: 24 August 1999     

Fe-Mg interdiffusion in magnesiowüstite up to 35 GPa

Fe-Mg interdiffusivities in (Fe,Mg)O magnesiowüstite have been measured in experiments conducted at pressures of 7-35 GPa and temperatures of 1573-1973 K using a Kawai-type high-pressure apparatus. The diffusion profiles were measured across the interface between MgO and (Fe_0.5,Mg_0.5)O samples by electron microprobe analysis, and the Fe-Mg interdiffusivities were determined as D_Fe-Mg=D₀exp{−E*(1+PV*_Mg/E*_Mg)/RT}, where D₀=4.1(^+16.1_−3.3)×10⁻⁷ m²/s, E*=(1−C_Mg)E*_Fe+C_MgE*_Mg (activation energy for the concentration of Mg, where E*_Fe=113(±74) kJ/mol and E*_Mg=226(±32) kJ/mol), the activation volume V*_Mg=1.8(±1.2)×10⁻⁶ m³/mol. By extrapolating these results to the P-T conditions of the core-mantle boundary, we conclude that the interdiffusivity of Fe-Mg in magnesiowüstite at the bottom of the lower mantle is at least one order of magnitude larger than that at the top of the lower mantle.     

High-pressure Raman spectroscopic study of chondrodite

Variation of Raman spectra of both natural (F-bearing) and synthetic (F-free) chondrodite samples were studied up to 400 kbar at room temperature. Ambient Raman frequencies for the synthetic sample are in general lower than those for the natural one. This is correlated with a slight expansion of the volume of the synthetic sample due to substitution of OH for F. The frequencies of all Raman bands for both samples increase monotonically with increasing pressure. The positive pressure dependences in the O−H stretch frequencies for both F-free and F-bearing samples are contrary to those for other dense hydrous magnesium silicates. A mechanism involving both the hydrogen-hydrogen repulsion and hydrogen bondings is proposed to explain the abnormal behavior. The effects of substitution of F for OH on both the ambient and high-pressure Raman spectra of chondrodite are also discussed. Received: 19 February 1998 / Revised accepted: 26 June 1998     

Raman spectra of MgSiO3·10% Al2O3-perovskite at various pressures and temperatures

Variations of Raman spectra of MgSiO₃·10% Al₂O₃-perovskite were investigated up to about 270 kbar at room temperature and in the range 108–425 °K at atmospheric pressure. Like MgSiO₃-perovskite, the Raman frequencies of MgSiO₃·10% Al₂O₃-perovskite increase nonlinearly with increasing pressure and decrease linearly with increasing temperature within the experimental uncertainties and the range investigated. A comparison of these data with those of MgSiO₃-perovskite suggests that MgSiO₃·10% Al₂O₃-perovskite is slightly more compressible than MgSiO₃-perovskite, and that the volume thermal expansion for MgSiO₃·10% Al₂O₃-perovskite is also slightly greater than that for MgSiO₃-perovskite.     

Compressibility of calcium ferrite-type MgAl2O4

 In situ X-ray diffraction experiments of calcium ferrite-type MgAl₂O₄ have been carried out using a diamond anvil cell combined with synchrotron radiation and an imaging plate X-ray detector under hydrostatic pressures up to 9 GPa. The observed unit-cell volumes at various pressures were fitted to the Birch-Murnaghan equation of state, yielding a bulk modulus of K _{T 0}= 241(3) GPa when K′ _{T 0}=4 is assumed. This relatively large bulk modulus of calcium ferrite-type MgAl₂O₄ is consistent with that expected from the systematic relation between bulk modulus and molar volume for the most compounds possessing fcc oxygen packing. Received March 5, 1996/Revised, accepted October 15, 1996     

The phase boundary between wadsleyite and ringwoodite in Mg2SiO4 determined by in situ X-ray diffraction

The phase boundary between wadsleyite and ringwoodite in Mg₂SiO₄ has been determined in situ using a multi-anvil apparatus and synchrotron X-rays radiation at SPring-8. In spite of the similar X-ray diffraction profiles of these high-pressure phases with closely related structures, we were able to identify the occurrence of the mutual phase transformations based on the change in the difference profile by utilizing a newly introduced press-oscillation system. The boundary was located at ~18.9 GPa and 1,400°C when we used Shim’s gold pressure scale (Shim et al. in Earth Planet Sci Lett 203:729–739, 2002), which was slightly (~0.8 GPa) lower than the pressure as determined from the quench experiments of Katsura and Ito (J Geophys Res 94:15663–15670, 1989). Although it was difficult to constrain the Clapeyron slope based solely on the present data due to the kinetic problem, the phase boundary [P (GPa)=13.1+4.11×10⁻³×T (K)] calculated by a combination of a P–T position well constrained by the present experiment and the calorimetric data of Akaogi et al. (J Geophys Res 94:15671–15685, 1989) reasonably explains all the present data within the experimental error. When we used Anderson’s gold pressure scale (Anderson et al. in J Appl Phys 65:1535–1543, 1989), our phase boundary was located in ~18.1 GPa and 1,400°C, and the extrapolation boundary was consistent with that of Kuroda et al. (Phys Chem Miner 27:523–532, 2000), which was determined at high temperature (1,800–2,000°C) using a calibration based on the same pressure scale. Our new phase boundary is marginally consistent with that of Suzuki et al. (Geophys Res Lett 27:803–806, 2000) based on in situ X-ray experiments at lower temperatures (<1,000°C) using Brown’s and Decker’s NaCl pressure scales.