First-principles simulation of high-pressure polymorphs in MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>

We have used density functional theory to investigate the stability of MgAl₂O₄ polymorphs under pressure. Our results can reasonably explain the transition sequence of MgAl₂O₄ polymorphs observed in previous experiments. The spinel phase (stable at ambient conditions) dissociates into periclase and corundum at 14 GPa. With increasing pressure, a phase change from the two oxides to a calcium-ferrite phase occurs, and finally transforms to a calcium-titanate phase at 68 GPa. The calcium-titanate phase is stable up to at least 150 GPa, and we did not observe a stability field for a hexagonal phase or periclase + Rh₂O₃(II)-type Al₂O₃. The bulk moduli of the phases calculated in this study are in good agreement with those measured in high-pressure experiments. Our results differ from those of a previous study using similar methods. We attribute this inconsistency to an incomplete optimization of a cell shape and ionic positions at high pressures in the previous calculations.     

High-pressure stability, structure and compressibility of Cmcm -MgAl2O4: an ab initio study

 Quantum-mechanical solid-state calculations have been performed on the highest-pressure polymorph of magnesium aluminate (CaTi₂O₄-type structure, Cmcm space group), as well as on the low-pressure (Fd3ˉm) spinel phase and on MgO and Al₂O₃. An ab initio all-electron periodic scheme with localized basis functions (Gaussian-type atomic orbitals) has been used, employing density-functional-theory Hamiltonians based on LDA and B3LYP functionals. Least-enthalpy structure optimizations in the pressure range 0 to 60 GPa have allowed us to predict: (1) the full crystal structure, the pV equation of state and the compressibility of Cmcm-MgAl₂O₄ as a function of pressure; (2) the phase diagram of the MgO–Al₂O₃–MgAl₂O₄ system (with exclusion of CaFe₂O₄-type Pmcn-MgAl₂O₄), and the equilibrium pressures for the reactions of formation/decomposition of the Fd3ˉm and Cmcm polymorphs of MgAl₂O₄ from the MgO + Al₂O₃ assemblage. Cmcm-MgAl₂O₄ is predicted to form at 39 and 57 GPa by LDA and B3LYP calculations, with K ₀=248 (K′=3.3) and 222 GPa (K′=3.8), respectively. Results are compared to experimental data, where available, and the performance of different DFT functionals is discussed. Received: 31 January 2001 / Accepted: 16 May 2001     

Low-temperature heat capacities of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and spinels of the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution

We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl₂O₄ and MgCr₂O₄. The data also include new low-temperature heat capacity measurements for MgAl₂O₄ spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results. No heat capacity anomaly was observed for MgAl₂O₄ spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)₂O₄ spinels. We suggest a standard entropy for MgAl₂O₄ of 80.9 ± 0.6 J mol⁻¹ K⁻¹. For the solid solution between MgAl₂O₄ and MgCr₂O₄, we observe a linear increase of the standard entropies from 80.9 J mol⁻¹ K⁻¹ for MgAl₂O₄ to 118.3 J mol⁻¹ K⁻¹ for MgCr₂O₄.     

New high-pressure phases in BaCO<Subscript>3</Subscript>

Barium carbonate (BaCO₃) was examined in a diamond anvil cell up to a pressure of 73 GPa using an in situ angle-dispersive X-ray diffraction technique. Three new phases of BaCO₃ were observed at pressures >10 GPa. From 10 to 24 GPa, BaCO₃-IV had a post-aragonite structure with space group Pmmn. There are two molecules in a single unit cell (Z = 2) of the orthorhombic phase, which is same as the high-pressure phases of CaCO₃ and SrCO₃. The isothermal bulk modulus of BaCO₃-IV is K ₀ = 84(4) GPa, with V ₀ = 129.0(7) Å³ when K ₀′ = 4. The c axis of the unit cell parameter is less compressible than the a and b axes. The relative change in volume that accompanies the transformation between BaCO₃-III and BaCO₃-IV is ～6%. BaCO₃-V, which has an orthorhombic symmetry, was synthesized at 50 GPa. As the pressure increases, BaCO₃-V is transformed into tetragonal BaCO₃-VI. This transformation is likely to be second order, because the diffraction pattern of BaCO₃-V is similar to that of BaCO₃-VI, and some single peaks in BaCO₃-VI become doublets in BaCO₃-V. After decompression, the new high-pressure phases transform into BaCO₃-II. Our findings resolve a dispute regarding the stable high-pressure phases of BaCO₃.     

Heat capacity and phase equilibria of wadeite-type K2Si4O9

The low-temperature heat capacity (C _p) of Si-wadeite (K₂Si₄O₉) synthesized with a piston cylinder device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system. The entropy of Si-wadeite at standard temperature and pressure calculated from the measured heat capacity data is 253.8 ± 0.6 J mol⁻¹ K⁻¹, which is considerably larger than some of the previous estimated values. The calculated phase transition boundaries in the system K₂O–Al₂O₃–SiO₂ are generally consistent with previous experimental results. Together with our calculated phase boundaries, seven multi-anvil experiments at 1,400 K and 6.0–7.7 GPa suggest that no equilibrium stability field of kalsilite + coesite intervenes between the stability field of sanidine and that of coesite + kyanite + Si-wadeite, in contrast to previous predictions. First-order approximations were undertaken to calculate the phase diagram in the system K₂Si₄O₉ at lower pressure and temperature. Large discrepancies were shown between the calculated diagram compared with previously published versions, suggesting that further experimental or/and calorimetric work is needed to better constrain the low-pressure phase relations of the K₂Si₄O₉ polymorphs. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synchrotron IR study of hydrous ringwoodite (γ-Mg2SiO4) up to 30 GPa

High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm⁻¹ at ambient temperature for hydrous Mg-ringwoodite (γ-Mg₂SiO₄) up to 30 GPa. The main feature in the OH⁻ stretching region is an extremely broad band centred at 3,150 cm⁻¹. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm⁻¹ and an absorption plateau persist with a maximum wavenumber of 3,800 cm⁻¹. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.     

Decomposition of kyanite and solubility of Al2O3 in stishovite at high pressure and high temperature conditions

In order to constrain the high-pressure behavior of kyanite, multi-anvil experiments have been carried out from 15 to 25 GPa, and 1,350 to 2,500°C. Both forward and reversal approaches to phase equilibria were adopted in these experiments. We find that kyanite breaks down to stishovite + corundum at pressures above ∼15 GPa, and stishovite + corundum should be the stable phase assemblage at the pressure–temperature conditions of the transition zone and the uppermost part of the lower mantle of the Earth, in agreement with previous multi-anvil experimental studies and ab initio calculation results, but in disagreement with some of the diamond-anvil cell experimental studies in the literature. The Al₂O₃ solubility in nominally dry stishovite has been tightly bracketed by forward and reversal experiments; it is slightly but consistently reduced by pressure increase. Its response to temperature increase, however, is more complicated: increases at low temperatures, maximizes at around 2,000°C, and perhaps decreases at higher temperatures. Consequently, the Al₂O₃ solubility in dry stishovite at conditions of high temperature–high pressure is very limited.     

Elastic behavior of vanadinite,Pb<Subscript>10</Subscript>(VO<Subscript>4</Subscript>)<Subscript>6</Subscript>Cl<Subscript>2</Subscript>, a microporous non-zeolitic mineral

The high-pressure behavior of a vanadinite (Pb₁₀(VO₄)₆Cl₂, a = b = 10.3254(5), c = 7.3450(4) Å, space group P6₃/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 681(1) Å³, K ₀ = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a ₀ = 10.3302(2) Å, K ₀(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c ₀ = 7.3520(3) Å, K ₀(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K ₀(a):K ₀(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe _a (0) = 35(2) GPa for the a-axis, Fe _c (0) = 98(4) GPa for the c-axis and Fe _V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.     

葡萄石的热膨胀性与压缩性及其地质意义

利用同步辐射X射线衍射及拉曼光谱技术对葡萄石分别进行了原位高温及原位高压实验。原位高温实验结果表明葡萄石的热膨胀系数为K=1. 77(3)×10~(-5)K~(-1),轴向热膨胀系数具有各向异性(α_aα_bα_c),葡萄石在1073K时开始发生脱水反应,分解为钙长石及硅灰石。原位高压X射线衍射实验结果表明,在大于12. 4GPa时,葡萄石的晶胞参数发生不连续变化,可能发生了相变;在24. 0GPa左右,葡萄石发生不可逆的非晶化转变。原位高压拉曼光谱表明,葡萄石在12. 6GPa左右发生相变,这一相变很可能与其[(Si,Al)O_4]四面体中的Si发生有序排列有关。结合葡萄石的热膨胀性及压缩性,我们确定了葡萄石在高温高压下的稳定范围,这一结果对认识上地幔中含水矿物的状态以及地幔中水的来源有重要意义。     

Ab initio study of the high-pressure behavior of CaSiO3 perovskite

Using density functional simulations, within the generalized gradient approximation and projector-augmented wave method, we study structures and energetics of CaSiO₃ perovskite in the pressure range of the Earths lower mantle (0–150 GPa). At zero Kelvin temperature the cubic CaSiO₃ perovskite structure is unstable in the whole pressure range, at low pressures the orthorhombic (Pnam) structure is preferred. At 14.2 GPa there is a phase transition to the tetragonal (I4/mcm) phase. The CaIrO₃-type structure is not stable for CaSiO₃. Our results also rule out the possibility of decomposition into oxides.

A computer simulation study of OH defects in Mg2SiO4 and Mg2GeO4 spinels

Classical atomistic simulation techniques have been used to investigate the energies of hydrogen defects in Mg₂SiO₄ and Mg₂GeO₄ spinels. Ringwoodite (γ-Mg₂SiO₄) is considered to be the most abundant mineral in the lower part of the transition zone and can incorporate large amounts of water in the form of hydroxyls, whereas the germanate spinel (γ-Mg₂GeO₄) corresponds to a low-pressure structural analogue for ringwoodite. The calculated defect energies indicate that the most favourable mechanisms for hydrogen incorporation are coupled either with the reduction of ferric iron or with the creation of tetrahedral vacancies. Hydrogen will go preferentially into tetrahedral vacancies, eventually leading to the formation of the hydrogarnet defect, before associating with other negatively charged point defects. The presence of isolated hydroxyls is not expected. The same trend is observed for germanate, and thus γ-Mg₂GeO₄ could be used as a low-pressure analogue for ringwoodite in studies of water-related defects and their effect on physical properties.     

Fate of carbonates within oceanic plates subducted to the lower mantle, and a possible mechanism of diamond formation

We report on high-pressure and high-temperature experiments involving carbonates and silicates at 30–80 GPa and 1,600–3,200 K, corresponding to depths within the Earth of approximately 800–2,200 km. The experiments are intended to represent the decomposition process of carbonates contained within oceanic plates subducted into the lower mantle. In basaltic composition, CaCO₃ (calcite and aragonite), the major carbonate phase in marine sediments, is altered into MgCO₃ (magnesite) via reactions with Mg-bearing silicates under conditions that are 200–300°C colder than the mantle geotherm. With increasing temperature and pressure, the magnesite decomposes into an assemblage of CO₂ + perovskite via reactions with SiO₂. Magnesite is not the only host phase for subducted carbon—solid CO₂ also carries carbon in the lower mantle. Furthermore, CO₂ itself breaks down to diamond and oxygen under geotherm conditions over 70 GPa, which might imply a possible mechanism for diamond formation in the lower mantle.     

Phase transition and compression behavior of gibbsite under high-pressure

In situ high-pressure synchrotron X-ray diffraction and infrared absorption experiments for gibbsite were performed at room temperature up to 53 and 25 GPa, respectively. A phase transition was confirmed at about 2.5 GPa. The high-pressure phase is indexed as an orthorhombic structure, rather than a triclinic structure as reported in previous studies. The compressibility of gibbsite and its high-pressure polymorph were studied, and their bulk moduli K₀ were determined to be 49 and 75 GPa, respectively with K₀ as 4. The in situ high-pressure infrared absorption spectra revealed the gradual disordering of hydrogen substructure above 15 GPa in quasihydrostatic compression.     

Phase transition of synthetic zinc ferrite spinel (ZnFe2O4) at high pressure, from synchrotron X-ray powder diffraction

 Synthetic Zn-ferrite (ideally ZnFe₂O₄; mineral name: franklinite) was studied up to 37 GPa, by X-ray powder diffraction at ESRF (Grenoble, France), on the ID9 beamline; high pressure was achieved by means of a DAC. The P-V equation of state of franklinite was investigated using the Birch-Murnaghan function, and the elastic properties thus inferred [K₀ = 166.4(±3.0) GPa K₀ ^′ = 9.3(±0.6) K₀ ^″ = −0.22 GPa⁻¹] are compared with earlier determinations for MgAl-spinel and magnetite. The structural behaviour of Zn-ferrite as a function of pressure was studied by Rietveld refinements, and interpreted in the light of a phase transition from spinel to either CaTi₂O₄- or MnFe₂O₄-like structure; this transformation occurs above 24 GPa. Received: 15 March 1999 / Accepted: 22 April 2000     

New measurement of melting and thermal conductivity of iron close to outer core conditions

The amount of literature on both melting and thermal conductivity of iron at Earth’s core conditions is overwhelming and the discrepancies are very large.There is a broad range of experimental techniques each of which is flawed to a certain degree,which may explain the discrepancy.In this report,we present new data using a different method for determining the phase behavior and resistivity of iron in the laser-heated diamond cell by measuring the electrical resistance of both solid and liquid iron wires.The experiment avoids some of the major flaws of previous experiments,the most important of which is the detection of the onset of melting.These measurements confirm a shallow melting curve found earlier and the resistivity data imply a trend towards low thermal conductivity in the liquid outer core.     

Equation of state,structural behaviour and phase diagram of synthetic MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as a function of pressure and temperature

The behaviour of synthetic Mg-ferrite (MgFe₂O₄) has been investigated at high pressure (in situ high-pressure synchrotron radiation powder diffraction at ESRF) and at high temperature (in situ high-temperature X-ray powder diffraction) conditions. The elastic properties determined by the third-order Birch–Murnaghan equation of state result in K₀=181.5(± 1.3) GPa, K=6.32(± 0.14) and K= –0.0638 GPa^–1. The symmetry-independent coordinate of oxygen does not show significant sensitivity to pressure, and the structure shrinking is mainly attributable to the shortening of the cell edge (homogeneous strain). The lattice parameter thermal expansion is described by _a0+_a1*(T–298)+_a2/(T–298)², where _a0=9.1(1) 10^–6 K^–1, _a1=4.9(2) 10^–9 K^–2 and _a2= 5.1(5) 10^–2 K. The high-temperature cation-ordering reaction which MgFe-spinel undergoes has been interpreted by the ONeill model, whose parameters are = 22.2(± 1.8) kJ mol^–1 and =–17.6(± 1.2) kJ mol^–1. The elastic and thermal properties measured have then been used to model the phase diagram of MgFe₂O₄, which shows that the high-pressure transition from spinel to orthorombic CaMn₂O₄-like structure at T < 1700 K is preceded by a decomposition into MgO and Fe₂O₃.     

Compressional behaviour of CaNiSi2O6 clinopyroxene: bulk modulus systematic and cation type in clinopyroxenes

A single-crystal of composition CaNiSi₂O₆ (space group C2/c) was investigated at high pressure up to about 7.8 GPa by X-ray diffraction. The unit-cell parameters were measured at 18 different pressures. The P-V data were fitted by a third-order Birch-Murnaghan equation of state V₀=435.21(1) ų, K ₀=117.6(3) GPa and K^=6.4(1). The linear axial compressibilities _a, _b, _c and a sin are 2.14(1), 3.00(1), 2.43(1) and 1.63(1) × 10–3 GPa^–1. Comparing the compressibility data with other CaM1Si₂O₆ pyroxenes we suggest that the empirical K × V = constant relationships are followed in C2/c pyroxenes only if the same valence electron character is shared.     

Low-temperature heat capacities,entropies and enthalpies of Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> polymorphs,and α−β−γ and post-spinel phase relations at high pressure

The low-temperature isobaric heat capacities (C _p) of β- and γ-Mg₂SiO₄ were measured at the range of 1.8–304.7 K with a thermal relaxation method using the Physical Property Measurement System. The obtained standard entropies (S°₂₉₈) of β- and γ-Mg₂SiO₄ are 86.4 ± 0.4 and 82.7 ± 0.5 J/mol K, respectively. Enthalpies of transitions among α-, β- and γ-Mg₂SiO₄ were measured by high-temperature drop-solution calorimetry with gas-bubbling technique. The enthalpies of the α−β and β−γ transitions at 298 K (ΔH°₂₉₈) in Mg₂SiO₄ are 27.2 ± 3.6 and 12.9 ± 3.3 kJ/mol, respectively. Calculated α−β and β−γ transition boundaries were generally consistent with those determined by high-pressure experiments within the errors. Combining the measured ΔH°₂₉₈ and ΔS°₂₉₈ with selected data of in situ X-ray diffraction experiments at high pressure, the ΔH°₂₉₈ and ΔS°₂₉₈ of the α−β and β−γ transitions were optimized. Calculation using the optimized data tightly constrained the α−β and β−γ transition boundaries in the P, T space. The slope of α−β transition boundary is 3.1 MPa/K at 13.4 GPa and 1,400 K, and that of β−γ boundary 5.2 MPa/K at 18.7 GPa and 1,600 K. The post-spinel transition boundary of γ-Mg₂SiO₄ to MgSiO₃ perovskite plus MgO was also calculated, using the optimized data on γ-Mg₂SiO₄ and available enthalpy and entropy data on MgSiO₃ perovskite and MgO. The calculated post-spinel boundary with a Clapeyron slope of −2.6 ± 0.2 MPa/K is located at pressure consistent with the 660 km discontinuity, considering the error of the thermodynamic data.     

流体包裹体压力计研究之二:高温高压下碳氢化合物的拉曼光谱

在温度23～315℃、压力高达近2000MPa下用金刚石压腔下研究了正庚烷、环己烷及其混合物的拉曼光谱特征。结果表明：环己烷和正庚烷混合,只是改变了环己烷及正庚烷的平均C-H伸缩振动的拉曼位移,但是并不影响其P-△^-vp关系式。另外,经过数据拟合,得到了平均C-H伸缩振动的拉曼位移与压力的关系为：P=78．21（△^-vp）＋71．56。该公式可以用来作为流体包裹体尤其是油气包裹体的压力计。     

The rise of trees and their effects on Paleozoic atmospheric CO2 and O2

The rise of large vascular plants during the mid-Paleozoic brought about a major increase in the rates of weathering of silicate minerals that induced a drop in the level of atmospheric CO₂ and contributed, via the atmospheric greenhouse effect, to global cooling and the initiation of the most long lived and a really extensive glaciation of the past 550 million years. Sedimentary burial of the microbiologically resistant remains of the plants resulted during the Permo-Carboniferous in both further lowering of CO₂ and in elevation of atmospheric O₂. Evidence of changes in CO₂ and O₂ are provided by mathematical models, studies of paleosols, fossil plants, fossil insects, and the effects of modern plants on silicate weathering, and by laboratory studies of the effects of changes in O₂ on plants and insects. To cite this article: R.A. Berner, C. R. Geoscience 335 (2003).