Phase equilibria for the Fe2SiO4–Fe3O4 system under high pressure

High pressure phase relation of the system Fe₂SiO₄–Fe₃O₄ was investigated by synthesis experiments using multi-anvil high pressure apparatus. A complete solid solution with spinel structure along Fe₂SiO₄–Fe₃O₄ join occurs above 9 GPa at 1200 °C. Lattice constants of the solid solution show almost linear variation with composition. A spinelloid phase is stable for intermediate compositions in the pressure range from 3 to 9 GPa. the synthesized spinelloid phase is successfully indexed assuming nickel aluminosilicate V type structure. Received: October 16, 1995 / Revised, accepted: March 19, 1997     

An X-ray diffraction study of shock-wave-densified SiO<Subscript>2</Subscript> glasses

 The densification and structural changes in SiO₂ glass compressed up to 43.4 GPa by shock experiments are investigated quantitatively by the X-ray diffraction technique. Direct structural data (average Si–O and Si–Si distances and Si–O–Si angles, coordination number of the Si atom) of these shock-densified SiO₂ glasses have been obtained by analyzing the radial distribution function curves, RDF(r), calculated with X-ray diffraction data. The coordination number of all densified glasses is about 4 and shows almost no pressure variation. The SiO₂ glass has shown density increase of 11% at a shock compression of 26.3 GPa. This density evolution could not be explained by the coordination change. The reduction of the average Si–O–Si angle (144° at 0 GPa to 136° at 26.3 GPa) obtained from RDF(r) data may account for this density increase. This Si–O–Si angle change may be caused by shrinkage of the network structure and the increase of small rings of SiO₄ tetrahedra. For higher shock pressure, a decrease in the Si–O–Si angle to 140° was observed. This is consistent with the decrease in density at 32.0 and 43.2 GPa. This decrease in the Si–O–Si angle and density could be attributed to an annealing effect due to high after-shock residual temperature. This pressure dependence of average Si–O–Si angles in shock-densified SiO₂ glass agrees with the results of our previous Raman spectroscopic study. On the other hand, the pressure variation for the first sharp diffraction peak (FSDP) was analyzed to estimate the evolution of intermediate range structures. It is suggested that the mean d value (d _m ) obtained from the position of FSDP strongly depends on the shock and residual temperature, as well as shock pressure. Received: 29 June 2001 / Accepted: 14 November 2001     

Phase relations in the system fayalite–magnetite at high pressures and temperatures

The phase relations in the Fe₂SiO₄–Fe₃O₄ binary system have been determined between 900 and 1200 °C and from 2.0 to 9.0 GPa. At low to moderate pressures magnetite can accommodate significant Si, reaching X_Fe2SiO₄=0.1 and 0.2 at 3.0 and 5.0 GPa respectively, with temperature having only a secondary influence. At pressures below 3.5 GPa at 900 °C and 2.6 GPa at 1100 °C magnetite-rich spinel coexists with pure fayalite. This assemblage becomes unstable at higher pressures with respect to three intermediate phases that are spinelloid polytypes isostructural to spinelloids II, III and V in the Ni-aluminosilicate system. The phase relations between the spinelloid phases are complex. At pressures above ≈8.0 GPa at 1100 °C, the spinelloid phases give way to a complete spinel solid solution between Fe₃O₄ and Fe₂SiO₄. The presence of small amounts of Fe³⁺ stabilises the spinel structure to lower pressures compared to the Fe₂SiO₄ end member. This means that the fayalite–γ-spinel transition is generally unsuitable as a pressure calibration point for experimental apparatuses. The molar volumes of the spinel solid solutions vary nearly linearly with composition, having a small negative deviation from ideal behaviour described by W_v=−0.15(6) cm³. Extrapolation yields V°₍₂₉₈₎ = 41.981(14) cm³ for the Fe₂SiO₄-spinel end member. The cell parameters and molar volumes of the three spinelloid polytypes vary systematically with composition. Cation disorder is an important factor in stabilising the spinelloid polytypes. Each polytype exhibits a particular solid solution range that is directly influenced by the interplay between its structure and the cation distributions that are energetically favourable. In the FeO–FeO_1.5–SiO₂ ternary system Fe₇SiO₁₀ (“iscorite”) coexists with the spinelloid phases at intermediate pressures on the SiO₂-poor, or Fe³⁺-poor side of the Fe₂SiO₄–Fe₃O₄ join. On the SiO₂ and Fe³⁺-rich side of the join, orthopyroxene or high-P clinopyroxene coexists with the spinelloids and spinel solid solutions. The assemblage pyroxene+spinel+SiO₂ is stable over a wide range of bulk composition. The stability of spinelloid III is of particular petrologic interest since this phase has the same structure as (Mg,Fe)₂SiO₄–wadsleyite, indicating that Fe³⁺ can be easily incorporated in this important phase in the Earth's transition zone, in addition to silicate spinel. This has important implications for the redox state of the Earth's transition zone and for the depth at which the olivine to spinel transition occurs in the mantle, potentially leading to a shift in the “410 km” seismic discontinuity to shallower depths depending on the prevailing redox state. In addition, a coupled tetrahedral substitution of Fe³⁺+OH for Si+O could provide a further mechanism for the incorporation of H₂O in wadsleyite. Received: 10 January 2000 / Accepted: 12 May 2000     

High-pressure phase transformations in the MgFe2O4 and Fe2O3–MgSiO3 systems

 The crystal structure of MgFe₂O₄ was investigated by in situ X-ray diffraction at high pressure, using YAG laser annealing in a diamond anvil cell. Magnesioferrite undergoes a phase transformation at about 25 GPa, which leads to a CaMn₂O₄-type polymorph about 8% denser, as determined using Rietveld analysis. The consequences of the occurrence of this dense MgFe₂O₄ form on the high-pressure phase transformations in the (MgSi)_0.75(Fe^III)_0.5O₃ system were investigated. After laser annealing at about 20 GPa, we observe decomposition to two phases: stishovite and a spinel-derived structure with orthorhombic symmetry and probably intermediate composition between MgFe₂O₄ and Mg₂SiO₄. At pressures above 35 GPa, we observe recombination of these products to a single phase with Pbnm perovskite structure. We thus conclude for the formation of Mg₃Fe₂Si₃O₁₂ perovskite. Received: 27 March 2000 / Accepted: 1 October 2000     

Ab initio investigation into the elasticity of ultrahigh-pressure phases of SiO2

In this study, we report the elastic properties of three ultrahigh-pressure phases of SiO₂: pyrite, cotunnite and Fe₂P types between 300 and 1,500 GPa calculated by means of the density functional ab initio method. It is generally thought that materials tend to be more compact and isotropic with increasing pressure. These three ultrahigh-pressure phases of silica are mechanically stable in the investigated pressure range according to the Born criteria, while the cotunnite and Fe₂P types are unstable at lower pressure. The elastic azimuthal anisotropy of these ultrahigh-pressure phases of silica shows that all the structures counterintuitively have considerable anisotropies even at multimegabar pressures. Among the three investigated structures, the cotunnite type of SiO₂ is the most elastically anisotropic phase due to a soft compression along the b axis combined with a large distortion of the polyhedrons that make the structure. This might also be related to its thermodynamic unfavorability compared to the Fe₂P type under extreme pressure condition. The bond property analyses clearly show that the Si–O bond remains an ionic-covalent mixed bond even at multimegabar pressures with an invariable ionicity with pressure. This argument can explain the monotonously pressure dependence of the elastic anisotropy in the case of pyrite, while the changes in the velocity distribution patterns out of the thermodynamic instability range largely contribute to those of the cotunnite and Fe₂P types.     

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

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

Single crystal hydrostatic compression of (Mg,Mn,Fe,Co)2SiO4 olivines

Four synthetic endmember olivines (Mg,Mn, Fe,Co)₂SiO₄ with space group Pbnm were loaded together in one diamond cell mount. Their unit-cell parameters were determined by single crystal X-ray diffraction to 10 GPa. The linear compressibilities β_a, β_b, β_c were 1.53, 2.90, 2.32; 1.45, 3.48, 1.98; 1.35, 3.29, 1.76; and 1.25, 2.82, 2.01×10⁻³ GPa⁻¹ for Mg₂SiO₄, Mn₂SiO₄, Fe₂SiO₄ and Co₂SiO₄, respectively. The b axis is the most compressible direction in all crystals studied. Bulk modulus K_T0 and its first pressure derivative were simultaneously determined for Mg₂SiO₄, Fe₂SiO₄ and Co₂SiO₄ crystals respectively by fitting volume data to a third order Birch-Murnaghan equation of state. They are 127(4) and 4.2(8), 136(3) and 4.1(7), and 144(2) and 4.1(5). The K_T0 and could not simultaneously be determined unambiguously for Mn₂SiO₄. Direct comparisons of unit-cell volumes at high pressure among pairs of olivines reveal anomalous compression behavior of the Mg₂SiO₄ crystal regarding the bulk modulus-volume relationship. This behavior, however, could not be observed in the transition metal olivines (Mn,Fe,Co)₂SiO₄. The distinct electronic configurations of Mg²⁺ and the transition metal cations Mn²⁺, Fe²⁺, and Co²⁺ result in the different compression behaviors of Mg₂SiO₄ and (Mn,Fe,Co)₂SiO₄. Received: 14 April 1997 / Revised, accepted: 29 July 1997     

Electric conductivity of Fe2SiO4–Fe3O4 spinel solid solutions

 The spinel solid solution was found to exist in the whole range between Fe₃O₄ and γ-Fe₂SiO₄ at over 10 GPa. The resistivity of Fe_{3− x} Si _x O₄ (0.0<x<0.288) was measured in the temperature range of 80∼300 K by the AC impedance method. Electron hopping between Fe³⁺ and Fe²⁺ in the octahedral site of iron-rich phases gives a large electric conductivity at room temperature. The activation energy of the electron hopping becomes larger with increasing γ-Fe₂SiO₄ component. A nonlinear change in electric conductivity is not simply caused by the statistical probability of Fe³⁺–Fe²⁺ electron hopping with increasing the total Si content. This is probably because a large number of Si⁴⁺ ions occupies the octahedral site and the adjacent Fe²⁺ keeping the local electric neutrality around Si⁴⁺ makes a cluster, which generates a local deformation by Si substitution. The temperature dependence of the conductivity of solid solutions indicates the Verwey transition temperature, which decreases from 124(±2) K at x=0 (Fe₃O₄) to 102(±5) K at x=0.288, and the electric conductivity gap at the transition temperature decreases with Si⁴⁺ substitution. Received: 15 March 2000 / Accepted: 4 September 2000     

Single-crystal hydrostatic compression of synthetic pyrope, almandine, spessartine, grossular and andradite garnets at high pressures

The compression of synthetic pyrope Mg₃Al₂ (SiO₄)₃, almandine Fe₃Al₂(SiO₄)₃, spessartine Mn₃Al₂ (SiO₄)₃ grossular Ca₃Al₂(SiO₄)₃ and andradite Ca₃Fe₂ (SiO₄)₃ was studied by loading the crystals together in a diamond anvil cell. The unit-cell parameters were determined as a function of pressure by X-ray diffraction up to 15 GPa using neon as a pressure transmitting medium. The unit-cell parameters of pyrope and almandine were measured up to 33 and 21 GPa, respectively, using helium as a pressure medium. The bulk moduli, K _{T 0}, and their first pressure derivatives, K _{T 0} ^′, were simultaneously determined for all five garnets by fitting the volume data to a third order Birch-Murnaghan equation of state. Both parameters can be further constrained through a comparison of volume compressions between pairs of garnets, giving for K _{T 0} and K _{T 0} ^′ 171(2) GPa and 4.4(2) for pyrope, 185(3) GPa and 4.2(3) for almandine, 189(1) GPa and 4.2 for spessartine, 175(1) GPa and 4.4 for grossular and 157(1) GPa and 5.1 for andradite, where the K _{T 0} ^′ are fixed in the case of spessartine, grossular and andradite. Direct comparisons of the unit-cell volumes determined at high pressures between pairs of garnets reveal anomalous compression behavior for Mg²⁺ in the 8-fold coordinated triangular dodecahedron in pyrope. This agrees with previous studies concerning the compression behaviors of Mg²⁺ in 6-fold coordinated polyhedra at high pressures. The results show that simple bulk modulus–volume systematics are not obeyed by garnets. Received: 29 July 1998 / Revised, accepted: 7 April 1999     

Tetrahedral compression in (Mg,Fe)SiO3 orthopyroxenes

Single-crystal structure determinations at pressure have shown that the structural response of synthetic (Mg_0.6Fe_0.4)SiO₃ orthopyroxene to compression is the same as that previously observed in MgSiO₃ orthoenstatite. At pressure below ～4?GPa there is no significant compression of the SiO₄ tetrahedra, while above ～4?GPa the tetrahedra decrease in volume as a result of Si?O bond shortening. A study of the compressional behaviour of synthetic FeSiO₃ orthoferrosilite also shows the same behaviour below 4?GPa, but studies at higher pressures are precluded due to the transformation of the sample to the higher density C2/c high-clinoferrosilite polymorph. A further single-crystal study to 6?GPa of a Ca²⁺-containing natural orthopyroxene shows that chemical substitution of, primarily, Al³⁺ and Ca²⁺ into the structure of orthopyroxene inhibits the initial rapid compression of the M2?O3 bonds observed in the synthetic samples, and no significant tetrahedral compression is observed in this sample. Raman data collected from synthetic MgSiO₃ orthoenstatite show that there is a change in the rate of change of frequency with pressure, δν/δP, between 3.5 and 6.0?GPa, but no changes in the number of observed bands. These observations indicate a non-symmetry-breaking change in the properties of the orthoenstatite, which is associated with the change in compression mechanism observed using X-ray diffraction techniques at this pressure.     

Subsolidus and melting phase relations of basaltic composition in the uppermostlower mantle

The phase relations and the element partitioning in a mid-oceanic ridge basalt composition were determined for both above-solidus and subsolidus conditions at 22 to 27.5 GPa by means of a multianvil apparatus. The mineral assemblage at the solidus changes remarkably with pressure; majorite and stishovite at 22 GPa, joined by Ca-perovskite at 23 GPa, further joined by CaAl₄Si₂O₁₁-rich CAS phase at 25.5 GPa, and Mg-perovskite, stishovite, Ca-perovskite, CF phase (approximately on the join NaAlSiO₄-MgAl₂O₄), and NAL phase ([Na,K,Ca]₁[Mg,Fe²⁺]₂[Al,Fe³⁺,Si]_5.5-6.0O₁₂) above 27 GPa. The liquidus phase is Ca-perovskite, and stishovite, a CAS phase, a NAL phase, Mg-perovskite, and a CF phase appear with decreasing temperature at 27.5 GPa. Partial melt at 27 to 27.5 GPa is significantly depleted in SiO₂ and CaO and enriched in FeO and MgO compared with those formed at lower pressures, reflecting the narrow stability of (Fe,Mg)-rich phases (majorite or Mg-perovskite) above solidus temperature. The basaltic composition has a lower melting temperature than the peridotitic composition at high pressures except at 13 to 18 GPa (Yasuda et al., 1994) and therefore can preferentially melt in the Earth’s interior. Recycled basaltic crusts were possibly included in hot Archean plumes, and they might have melted in the uppermost lower mantle. In this case, Ca-perovskite plays a dominant role in the trace element partitioning between melt and solid. This contrasts remarkably with the case of partial melting of a peridotitic composition in which magnesiowüstite is the liquidus phase at this depth.     

Pressure dependence of electrical conductivity of (Mg,Fe)SiO<Subscript>3</Subscript> ilmenite

The electrical conductivity of (Mg_0.93Fe_0.07)SiO₃ ilmenite was measured at temperatures of 500–1,200 K and pressures of 25–35 GPa in a Kawai-type multi-anvil apparatus equipped with sintered diamond anvils. In order to verify the reliability of this study, the electrical conductivity of (Mg_0.93Fe_0.07)SiO₃ perovskite was also measured at temperatures of 500–1,400 K and pressures of 30–35 GPa. The pressure calibration was carried out using in situ X-ray diffraction of MgO as pressure marker. The oxidation conditions of the samples were controlled by the Fe disk. The activation energy at zero pressure and activation volume for ilmenite are 0.82(6) eV and −1.5(2) cm³/mol, respectively. Those for perovskite were 0.5(1) eV and −0.4(4) cm³/mol, respectively, which are in agreement with the experimental results reported previously. It is concluded that ilmenite conductivity has a large pressure dependence in the investigated P–T range.     

High pressure polymorphism of dicalcium silicate Ca2SiO4. A transmission electron microscopy study

Ca₂SiO₄ dicalcium silicate has been transformed at high pressure in a diamond-anvil cell (DAC) coupled with a YAG laser heater, in order to study the high-pressure modifications of this compound. Starting material was the olivine form of Ca₂SiO₄ (γ-polymorph). Several samples have been synthesized at loading pressures of 4.5, 10 and 15 GPa respectively, at room temperature. Other samples have been obtained at pressures ranging between 4.5 and 45 GPa and temperatures estimated to be about 2500 °C. The study of the quenched high pressure and/or high temperature phases has been performed using analytical transmission electron microscopy (ATEM) and X-ray diffraction (XRD). All the polymorphs of Ca₂SiO₄ usually produced with high temperatures, including α-Ca₂SiO₄, have been observed in the samples recovered from the high-pressure experiments. The α′-Ca₂SiO₄ and α-Ca₂SiO₄ polymorphs have been obtained at ambient conditions for the first time without stabilizing impurities. A new modification of α′-Ca₂SiO₄ has also been synthesized. Finally, the breakdown at high-pressure and temperature of Ca₂SiO₄ into CaSiO₃ and CaO is reported.     

Mg-Fe partitioning between silicate spinel and magnesiowüstite at high pressure: experimental determination and calculation of phase relations in the system Mg2SiO4-Fe2SiO4

 Mg-Fe partitioning experiments between (Mg,Fe)₂SiO₄ spinel and (Mg,Fe)O magnesiowüstite were carried out at pressures of 17–21.3 GPa at temperatures of 1400 and 1600 °C, using a multi-anvil apparatus, in order to determine interaction parameters of spinel and magnesiowüstite solid solutions and also to constrain the equilibrium boundaries of the postspinel transition in the Fe-rich side in the system Mg₂SiO₄-Fe₂SiO₄. The obtained values of the interaction parameters were 3.4 ± 1.5 and 13.9 ± 1.4 kJ mol⁻¹, respectively, for spinel and magnesiowüstite solid solutions at 19 GPa and 1600 °C. The partitioning data in the system Mg₂SiO₄-Fe₂SiO₄ at 1400 and 1600 °C showed that the transition boundary between spinel and the mixture of magnesiowüstite and stishovite has a negative dP/dT slope. Using the above interaction parameters and available thermodynamic data of the Mg₂SiO₄ and Fe₂SiO₄ end members, the transition boundaries of spinel to the mixture of magnesiowüstite and stishovite were calculated. Within the uncertainties of the data used, the calculated boundaries are in good agreement with the boundaries at 1400 and 1600 °C experimentally determined in this study. The dissociation boundary of Fe₂SiO₄ spinel to wüstite and stishovite, calculated from the thermodynamic data, has a negative slope of −1.5 ± 0.6 MPa K⁻¹. Received: 18 February 1998 / Revised, accepted: 18 October 1999     

Experiments on liquid immiscibility in silicate melts with H2O, P, S, F and Cl: implications for natural magmas

Isobaric (200 MPa) experiments have been performed to investigate the effects of H₂O alone or in combination with P, S, F or Cl on liquid-phase separation in melts in the systems Fe₂SiO₄–Fe₃O₄–KAlSi₂O₆–SiO₂, Fe₃O₄–KAlSi₂O₆–SiO₂ and Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ with or without plagioclase (An₅₀). Experiments were heated in a rapid-quench internally heated pressure vessel at 1,075, 1,150 or 1,200 °C for 2 h. Experimental fO₂ was maintained at QFM, NNO or MH oxygen buffers. H₂O alone or in combination with P, S or F increases the temperature and composition range of two-liquid fields at fO₂ = NNO and MH buffers. P, S, F and Cl partition preferentially into the Fe-rich immiscible liquid. Two-liquid partition coefficients for Fe, Si, P and S correlate well with the degree of polymerization of the SiO₂-rich liquid and plot on similar but distinct power-law curves compared with equivalent anhydrous or basaltic melts. The addition of 2 wt% S to the system Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ stabilizes three immiscible melts with Fe-, FeS- and Si-rich compositions. H₂O-induced suppression of liquidus temperatures in the experimental systems, considered with the effects of pressure on the temperature and composition ranges of two-liquid fields in silicate melts, suggests that liquid-phase separation may be stable in some H₂O-rich silicate magmas at pressures in excess of 200 MPa.     

High pressure single-crystal synthesis, structure and compressibility of the garnet Mn2+ 3Mn3+ 2[SiO4]3

Single crystals of the garnet Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ and coesite were synthesised from MnO₂-SiO₂ oxide mixtures at 1000°C and 9 GPa in a multianvil press. The crystal structure of the garnet [space group Ia3¯d, a=11.801(2) Å] was refined at room temperature and 100 K from single-crystal X-ray data to R1=2.36% and R1=2.71%, respectively. In contrast to tetragonal Ca₃Mn³⁺ ₂[GeO₄]₃ (space group I4₁/a), the high-pressure garnet is cubic and does not display an ordered Jahn-Teller distortion of octahedral Mn³⁺. A disordered Jahn-Teller distortion either dynamic or static is evidenced by unusual high anisotropic displacement parameters. The room temperature structure is characterised by following bond lengths: Si-O=1.636(4) Å (tetrahedron), Mn³⁺-O=1.995 (4) Å (octahedron), Mn²⁺-O=2.280(5) and 2.409(4) Å (dodecahedron). The cubic structure was preserved upon cooling to 100 K [a=11.788(2) Å] and upon compressing up to 11.8 GPa in a diamond-anvil cell. Pressure variation of the unit cell parameter expressed by a third-order Birch-Murnaghan equation of state led to a bulk modulus K ₀=151.6(8) GPa and its pressure derivatives K′=6.38(19). The peak positions of the Raman spectrum recorded for Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ were assigned based on a calderite Mn²⁺ ₃Fe³⁺ ₂[SiO₄]₃ model extrapolated from andradite and grossular literature data.     

Equation of state of synthetic qandilite Mg<Subscript>2</Subscript>TiO<Subscript>4</Subscript> at ambient temperature

Using a diamond-anvil cell and synchrotron X-ray diffraction, the compressional behavior of a synthetic qandilite Mg_2.00(1)Ti_1.00(1)O₄ has been investigated up to about 14.9 GPa at 300 K. The pressure–volume data fitted to the third-order Birch–Murnaghan equation of state yield an isothermal bulk modulus (K _T0) of 175(5) GPa, with its first derivative \(K_{T0}^{{\prime }}\) attaining 3.5(7). If \(K_{T0}^{{\prime }}\) is fixed as 4, the K _T0 value is 172(1) GPa. This value is substantially larger than the value of the adiabatic bulk modulus (K _S0) previously determined by an ultrasonic pulse echo method (152(7) GPa; Liebermann et al. in Geophys J Int 50:553–586, 1977), but in general agreement with the K _T0 empirically estimated on the basis of crystal chemical systematics (169 GPa; Hazen and Yang in Am Miner 84:1956–1960, 1999). Compared to the K _T0 values of the ulvöspinel (Fe₂TiO₄; ~148(4) GPa with \(K_{T0}^{{\prime }} = 4\)) and the ringwoodite solid solutions along the Mg₂SiO₄–Fe₂SiO₄ join, our finding suggests that the substitution of Mg²⁺ for Fe²⁺ on the T sites of the 4–2 spinels can have more significant effect on the K _T0 than that on the M sites.     

Compressibility and crystal structure of sillimanite, Al2SiO5, at high pressure

The unit-cell dimensions and crystal structure of sillimanite at various pressures up to 5.29 GPa have been refined from single-crystal X-ray diffraction data. As pressure increases, a and b decrease linearly, whereas c decreases nonlinearly with a slightly positive curvature. The axial compression ratios at room pressure are β_a:β_b:β_c=1.22:1.63:1.00. Sillimanite exhibits the least compressibility along c, but the least thermal expansivity along a (Skinner et al. 1961; Winter and Ghose 1979). The bulk modulus of sillimanite is 171(1) GPa with K′=4 (3), larger than that of andalusite (151 GPa), but smaller than that of kyanite (193 GPa). The bulk moduli of the [Al1O₆], [Al2O₄], and [SiO₄] polyhedra are 162(8), 269(33), and 367(89) GPa, respectively. Comparison of high-pressure data for Al₂SiO₅ polymorphs reveals that the [SiO₄] tetrahedra are the most rigid units in all these polymorphic structures, whereas the [AlO₆] octahedra are most compressible. Furthermore, [AlO₆] octahedral compressibilities decrease from kyanite to sillimanite, to andalusite, the same order as their bulk moduli, suggesting that [AlO₆] octahedra control the compression of the Al₂SiO₅ polymorphs. The compression of the [Al1O₆] octahedron in sillimanite is anisotropic with the longest Al1-OD bond shortening by ～1.9% between room pressure and 5.29 GPa and the shortest Al1-OB bond by only 0.3%. The compression anisotropy of sillimanite is primarily a consequence of its topological anisotropy, coupled with the compression anisotropy of the Al-O bonds within the [Al1O₆] octahedron.     

High temperature structural investigation of Na2O·0.5Fe2O3·3SiO2 and Na2O·FeO·3SiO2 melts and glasses

The structure of glasses and melts of Na₂O· 0.5Fe₂O₃·3SiO₂ and Na₂O·FeO·3SiO₂ compositions have been measured using high temperature Raman spectroscopy. For the oxidized sample it has been demonstrated that there is a close structural relationship between melt and glass. No coordination changes of Fe³⁺ with temperature and no new anionic species have been observed in the oxidized melt. The Raman spectra of the reduced sample clearly show a decrease in the degree of polymerization, as determined by the observation of the polarization character of the spectra and the details of the change of the Raman intensities during heating in hydrogen. Mössbauer spectra suggest that Fe³⁺ is tetrahedrally coordinated in the oxidized glass and part of the Fe²⁺ is tetrahedrally coordinated in the reduced glass.     

Carbonatitic melts along the solidus of model lherzolite in the system CaO-MgO-Al2O3-SiO2-CO2 from 3 to 7 GPa

We have experimentally determined the solidus position of model lherzolite in the system CaO-MgO-Al₂O₃-SiO₂-CO₂ (CMAS.CO₂) from 3 to 7 GPa by locating isobaric invariant points where liquid coexists with olivine, orthopyroxene, clinopyroxene, garnet and carbonate. The intersection of two subsolidus reactions at the solidus involving carbonate generates two invariant points, I_1A and I_2A, which mark the transition from CO₂-bearing to dolomite-bearing and dolomite-bearing to magnesite-bearing lherzolite respectively. In CMAS.CO₂, we find I_1A at 2.6 GPa/1230 °C and I_2A at 4.8 GPa/1320 °C. The variation of all phase compositions along the solidus has also been determined. In the pressure range investigated, solidus melts are carbonatitic with SiO₂ contents of <6 wt%, CO₂ contents of ˜45 wt%, and Ca/(Ca+Mg) ratios that range from 0.59 (3 GPa) to 0.45 (7 GPa); compositionally they resemble natural magnesiocarbonatites. Volcanic magnesiocarbonatites may well be an example of the eruption of such melts directly from their mantle source region as evidenced by their diatremic style of activity and lack of associated silicate magmas. Our data in the CMAS.CO₂ system show that in a carbonate-bearing mantle, solidus and near-solidus melts will be CO₂-rich and silica poor. The widespread evidence for the presence of CO₂ in both the oceanic and continental upper mantle implies that such low degree SiO₂-poor carbonatitic melts are common in the mantle, despite the rarity of carbonatites themselves at the Earth's surface. Received: 9 April 1997 / Accepted: 25 November 1997