Melting relationships in CaO-CO2 and MgO-CO2 to 36 kilobars with comments on CO2 in the mantle

The melting curves of CaCO₃ and MgCO₃ have been extended to pressures of 36 kb by experiments in piston-cylinder apparatus. At 30 kb, the melting temperatures of calcite and magnesite are 1610°C and 1585°C, respectively. New data for the magnesite dissociation reaction permit the location of an invariant point for the assemblage magnesite + periclase + liquid + vapor near 26 kb-1550°C. New data are also presented for the calcite-aragonite transition at 800°C, 950°C and 1100°C. At pressures above 36–50 kb, calcite and magnesite melt at temperatures lower than the solidus of dry mantle peridotite. Natural and experimental evidence suggests that carbon dioxide in the Earth's mantle could be present in a variety of forms: (a) a free vapor phase, (b) vapor dissolved in silicate magma, (c) crystalline carbonate, (d) carbonatite liquid, (e) carbon-bearing silicate analogs, or (f) carbonato-silicates (such as scapolite, spurrite, tilleyite, and related compounds).     

Interfacial tension between CO2 and brine (NaCl + CaCl2) at elevated pressures and temperatures: The additive effect of different salts

An extensive laboratory study was conducted to measure the interfacial tension (IFT) between CO₂ and brine consisting in equal molal concentrations of NaCl and CaCl₂. The experiments were repeated at various pressures, temperatures and salinities that are representative of conditions prevailing during CO₂ storage in deep saline aquifers. The dependence of CO₂/brine IFT on pressure and temperature is similar to that previously reported for the systems: CO₂/NaCl solution and CO₂/CaCl₂ solution. CO₂/brine IFT increases linearly with water salinity and the magnitude of this increase was found equal to the sum of the individual CO₂/NaCl solution and CO₂/CaCl₂ solution IFT increments, indicating a strong additive effect on IFT when the brine is composed of various salts.     

Disproportionation of Ni2SiO4 to stishovite plus bunsenite at high pressures and temperatures

Samples of Ni₂SiO₄ in both olivine and spinel phases have been compressed to pressures above 140 kbar in a diamond-anvil cell and heated to temperatures of 1400–1800°C using a continuous YAG laser. After quenching and releasing pressure, X-ray diffraction examination indicates that the samples disproportionate to a mixture of stishovite (SiO₂) and bunsenite (NiO) at pressures between 140 and 190 kbar. The exact disproportionation pressure is not certain due to transient increases in pressure during the local and rapid heating. However, thermodynamic calculations suggest that the transition pressure is about 192 ± 4 kbar at 1545°C and that the equation of the spinel-mixed oxides phase boundary isP(kbar) = 121 + (0.046 ± 0.020) T (°C).     

High-temperature elasticity of the fluorite-structure compounds CaF2, SrF2 and BaF2

The elastic moduli of single-crystal CaF₂, SrF₂ and BaF₂ have been determined by the ultrasonic pulse superposition technique as a function of temperature from T = 298 to T = 650°K. These new data are consistent with other data obtained by ultrasonic pulse techniques in the region of room temperature and are superior to previous high-temperature data from resonance experiments. The elastic moduli (c) are represented by quadratic functions in T over the experimental temperature range with the curvature in the same sense for all the moduli. Evaluation of the temperature derivatives of the elastic moduli at constant volume indicates that the dominant temperature effect is extrinsic for (?K_S/?T)_P and intrinsic for (?μ/?T)_P, where K_S and μ are the isotropic bulk and shear moduli, respectively. For the series CaF₂SrF₂BaF₂, |(?c/?T)_p| decreases with increasing molar volume for all moduli; however there are no theoretical or empirical grounds on which to derive a simple relationship between (?c/?T)_P and crystallographic parameters.     

Melting of forsterite Mg2SiO4 up to 15 GPa

The melting curve of forsterite has been studied by static experiment up to a pressure of 15 GPa. Forsterite melts congruently at least up to 12.7 GPa. The congruent melting temperature is expressed by the Kraut-Kennedy equation in the following form: T_m(K)=2163 (1+3.0(V₀ ? V)/V₀), where the volume change with pressure was calculated by the Birch-Managhan equation of state with the isothermal bulk modulus K₀ = 125.4 GPa and its pressure derivative K′ = 5.33. The triple point of forsterite-β-Mg₂SiO₄-liquid will be located at about 2600°C and 20 GPa, assuming that congruent melting persists up to the limit of the stability field of forsterite. The extrapolation of the previous melting data on enstatite and periclase indicates that the eutectic composition of the forsterite-enstatite system should shift toward the forsterite component with increasing pressure, and there is a possibility of incongruent melting of forsterite into periclase and liquid at higher pressure, although no evidence on incongruent melting has been obtained in the present experiment.     

Phosphate in Angra dos Reis: Structure and composition of the Ca3(PO4)2 minerals

Extraterrestrial calcium phosphates (“whitlockites”) have the anhydrous β-Ca₃(PO₄)₂ structure, which is different from that of hydrous terrestrial whitlockite. This has been confirmed by X-ray refinement of the structure of a phosphate from the achondrite Angra dos Reis. In the β-Ca₃(PO₄)₂ structure, there is one crystallographic site, Ca(IIA), which is half-occupied by calcium, and which seems to have an energetically unfavorable configuration; natural phosphates with this configuration (including Angra dos Reis) have composition Ca₁₉(Mg,Fe)₂(PO₄)₁₄. Stability of the structure is probably increased by substitution of Na for Ca in Ca(IIA) giving composition Ca₁₈ (Mg,Fe)₂Na₂(PO₄)₁₄, which occurs in chondrites; by vacancy of Ca(IIA), with rare earths and yttrium substituting for calcium in other sites for charge balance, giving composition Ca₁₆(Y,RE)₂(Mg,Fe)₂(PO₄)₁₄, found in lunar rocks; or by replacing Ca with hydrogen, giving composition Ca₁₈(Mg,Fe)₂H₂(PO₄)₁₄, which is terrestrial whitlockite. Lack of the favorable substitutions of Na, (Y, RE) or H in Angra dos Reis phosphate implies that these elements were relatively scarce in its environment of formation.     

Phase relations in the system LiFMgF2 at elevated pressures: Implications for the proposed mixed-oxide zone of the earth's mantle

Solvi and liquidi for various LiFMgF₂ mixtures have been determined at pressures up to 40 kbar by differential-thermal-analysis in a piston-cylinder high-pressure device. The melting curves of pure LiF and MgF₂ were also studied and the initial slopes (dT_m/dP)_{P = 0} were found to be 11.2 and 8.3°C/kbar, respectively. The eutectic composition (LiF)_0.64(MgF₂)_0.36 is independent of pressure to 35 kbar and the eutectic temperature rises approximately 6.3°C per kbar. Initial slopes of 11°C/kbar and 35°C/kbar are inferred for the melting curves of MgO and SiO₂ (stishovite) respectively, on the basis of data for their structural analogue compounds. The observed solid solution of LiF in MgF₂ and other evidence suggest the possibility of solid solution in the system (Mg,Fe)OSiO₂ (stishovite) under mantle conditions which may have important consequences for the elastic properties of a “mixed-oxide” zone of the earth's mantle.     

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

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

Phase relations of titan-phlogopite,K2Mg4TiAl2Si6O20(OH)4: a refractory phase in the upper mantle?

Experimental data on the stability of titan-phlogopite [K₂Mg₄TiAl₂Si₆O₂₀(OH)₄] are presented which show it to be stable to substantially higher temperatures than normal phlogopite [K₂Mg₆Al₂Si₆O₂₀(OH)₄]. A qualitative model to explain the role of titan-phlogopite during magma generation is put forward. Breakdown of titan-phlogopite during melting at depth (> 150km) on subducted lithospheric slabs is believed responsible for the concomitant increase of K and Ti observed in magmas erupted during orogenic volcanism. At lower pressures (up to about 10 kbar) beneath mid-oceanic ridges, titan-phlogopite is predicted to behave as a refractory phase during partial melting in the mantle, especially if H₂O-excess conditions pertain, although at higher pressures in this environment it would almost certainly behave as a low-melting component.     

Viscosity and structural changes of albite (NaAlSi3O8) melt at high pressures

Viscosity of anhydrous albite melt, determined by the falling-sphere method in the solid-media, piston-cylinder apparatus, decreases with increasing pressure from 1.13 × 10⁵ P at 1 atm to 1.8 × 10⁴ P at 20 kbar at 1400°C. The rate of decrease in viscosity is larger between 12 and 15 kbar than in other pressure ranges examined. The density of the quenched albite melt increases with increasing pressure of quenching from 2.38 g/cm³ at 1 atm to 2.53 g/cm³ at 20 kbar. The rate of increase in density is largest at pressures between 15 and 20 kbar. The melting curve of albite shows an inflexion at about 16 kbar. These observations strongly suggest that structural changes of albite melt would take place effectively at pressures near 15 kbar. Melt of jadeite (NaAlSi₂O₆) composition shows very similar changes in viscosity and density and a melting curve inflexion at pressures near 10 kbar. Difference in pressure for the suggested effective structural changes of albite and jadeite melts is 5–6 kbar, which is nearly the same as that between the subsolidus reaction curves nepheline + albite= 2jadeite and albite=jadeite + quartz. The structural changes of the melts are, however, continuous and begin to take place at pressures lower than those of the crystalline phases.     

Melting of some alkaline-earth and transition-metal fluorides and alkali fluoroberyllates at elevated pressures: A search for melting systematics

The melting curves of the fluorides ZnF₂ and NiF₂ (rutile structure), CaF₂, SrF₂ and BaF₂ (fluorite structure), and of the fluoroberyllates Na₂BeF₄ and Li₂BeF₄ have been studied at pressures ? 40 kbar by differential thermal analysis in a piston-cylinder high-pressure device. The initial slopes (dT_m/dP)₀ of these melting curves are respectively 7.2, 5.8, 16.7, 15.2, 15.7, 15.1 and <0°C/kbar. A new Li₂BeF₄ polymorph, apparently of the olivine structure type, is stable at pressures > 10 kbar and its melting curve has an average slope of ～6.7°C/kbar. These new data and those for SiO₂, BeF₂, GeO₂, LiF and MgF₂, recently studied by Jackson, are combined with existing data for elements, ionic compounds and silicates to assess the influence of crystal structure, molar volume and the nature of interatomic bonding on the initial slopes of melting curves. It is found that the entropy of fusion (ΔS_m) is primarily a function of crystal structure while the volume change on fusion (ΔV_m) is controlled by crystal molar volume within each isostructural series. Such systematics have recently facilitated estimation of the initial slopes of the melting curves of periclase and stishovite. New and existing melting data for silicates and their analogues have been analysed and a systematic dependence of (dT_m/dP)₀ on SiO₂ concentration has been demonstrated. Possible implications of this trend for partial melting of upper-mantle garnet lherzolite are illustrated. Finally, the use of the traditional silicate-germanate and oxide-fluoride modelling schemes is reviewed in the light of information from this present study.     

Effects of elevated CO2 on the reproduction of two calanoid copepods

Some planktonic groups suffer negative effects from ocean acidification (OA), although copepods might be less sensitive. We investigated the effect of predicted CO₂ levels (range 480–750 ppm), on egg production and hatching success of two copepod species, Centropages typicus and Temora longicornis. In these short-term incubations there was no significant effect of high CO₂ on these parameters. Additionally a very high CO₂ treatment, (CO₂ = 9830 ppm), representative of carbon capture and storage scenarios, resulted in a reduction of egg production rate and hatching success of C. typicus, but not T. longicornis. In conclusion, reproduction of C. typicus was more sensitive to acute elevated seawater CO₂ than that of T. longicornis, but neither species was affected by exposure to CO₂ levels predicted for the year 2100. The duration and seasonal timing of exposures to high pCO₂, however, might have a significant effect on the reproduction success of calanoid copepods.     

The system Mg2SiO4MgOH2O at high pressures and temperatures — Possible hydrous magnesian silicates in the mantle transition zone

The system Mg₂SiO₄MgOH₂O was investigated at pressures between 85 and 160 kbar and at temperatures between 750 and 1200°C. In runs for a gel with Mg/Si ratio of 3 and with 4.0 wt.-percent H₂O, a dense hydrous magnesian silicate, denoted phase B by Ringwood and Major, was found at pressures from about 100 kbar to at least 160 kbar in the whole temperature range studied. In the following table the crystallographic parameters and chemical formula of phase B, determined in this study, are compared with those of the other dense hydrous silicates in Mg₂SiO₄MgOH₂O.

     

15.

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

Daniel J. Frost 《Earth and Planetary Science Letters》2003,216(3):313-328

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.     

16.

Phase transformations in MSiO₄ compounds at high pressures and their geophysical implications     

Lin-gun Liu 《Earth and Planetary Science Letters》1982,57(1):110-116

The phase behaviour of MSiO₄ compounds (MHf, Zr, U and Th0 has been investigated at high pressures and temperatures in a diamond-anvil press coupled with laser heating. All of these compounds have been found to undergo two or perhaps three phase transformations at pressures below 300 kbar. The high-pressure phase transformations of these compounds differ from one another, with the exception of HfSiO₄ and ZrSiO₄, which undergo identical phase transformations. The ultimate phase assemblages of these compounds are of dense component dioxides (although this is yet to be confirmed in ThSiO₄). It is suggested that the heat-producing elements U and Th would exist as dioxide solid solutions rather than silicates in the deep interior of the earth. Moreover, the densities of these dioxides are more than twice as great as mantle silicates and even slightly greater than pure iron under similar P, T conditions. Gravitational separation due to mandle convection may transport these dioxides to the deep interior of the earth to form deep heat sources. It is also suggested, however, that these deep heat sources are located in the inner-outer core boundary instead of in the lower mantle.     

17.

High-pressure phases of Co₂GeO₄, Ni₂GeO₄, Mn₂GeO₄ and MnGeO₃: implications for the germanate-silicate modeling scheme and the Earth's mantle     

Lin-Gun Liu 《Earth and Planetary Science Letters》1976,31(3):393-396

In a diamond-anvil press coupled with YAG laser heating, the spinels of Co₂GeO₄ and Ni₂GeO₄ have been found to disproportionate into their isochemical oxide mixtures at about 250 kbar and 1400–1800°C in the same manner as their silicate analogues. At about the same P-T conditions MnGeO₃ transforms to the orthorhombic perovskite structure (space group Pbnm); the lattice parameters at room temperature and 1 bar are a₀ = 5.084 ± 0.002, b₀ = 5.214 ± 0.002, and c₀ = 7.323 ± 0.003Å with Z = 4 for the perovskite phase. The zero-pressure volume change associated with the ilmenite-perovskite phase transition in MnGeO₃ is ?6.6%. Mn₂GeO₄ disproportionates into a mixture of the perovskite phase of MnGeO₃ plus the rocksalt phase of MnO at P = 250kbar and T = 1400–1800°C. The concept of utilizing germanates as high-pressure models for silicates is valid in general. The results of this study support the previous conclusion that the lower mantle comprises predominantly the orthorhombic perovskite phase of ferromagnesian silicate.     

18.

Pyroxenes in the system Mg₂Si₂O₆-CaMgSi₂O₆ at high pressure     

Takeshi Mori  David H. Green 《Earth and Planetary Science Letters》1975,26(3):277-286

The enstatite-diopside solvus in the system Mg₂Si₂O₆-CaMgSi₂O₆ has been experimentally determined within the pressure range 5–40 kbars and the temperature range 900–1500°C. Experiments involving reversal of the phase boundaries by unmixing from glass starting material and by reaction of pure clinoenstatite and diopside showed difficulty in achieving equilibration due to persistence of metastable, subcalcic clinopyroxene and to the sluggishness of reaction rate. The experimental data showed that the temperature dependence of the diopside limb is less than previously accepted. At 1500°C and 30 kbars subcalcic diopside found by Davis and Boyd (1966) is shown to be metastable with respect to enstatite and more calcic diopside of composition En_42.3Di_57.7. The solvus widens with increasing pressure between 5 and 40 kbars at 1200°C, but at 900°C the pressure effect on the solvus is very small. The stability relationships of the four pyroxenes, protoenstatite, enstatite, iron-free pigeonite and diopside are summarized, based on data from the literature and the present study.     

19.

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

Masaki Akaogi  Akira TanakaEiji Ito 《Physics of the Earth and Planetary Interiors》2002,132(4):303-324

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.     

20.

Study on correlativity among capacity dimension D ₀, information dimension D ₁, algorithmic complexity C ( n ) and b value     

Wei-Bin Han  Gui-Xi Yi  Hua Xin 《地震学报(英文版)》1998,11(4):507-510

     

Phase	Composition	Space group	Cell parameters				Density (g cm?3)
			$\text{a}$	$\text{b}$	$\text{c}$	β
			(Å)	(Å)	(Å)	(°)
Chondrodite	Mg5Si2O10H2	$\text{P2}{}_1\text{/c}$	7.914	4.752	10.350	108.71	3.06
Clinohumite	Mg9Si4O18H2	$\text{P2}{}_1\text{/c}$	13.695	4.747	10.284	100.64	3.14
Phase A	Mg7Si2O14H6	$\text{P6}{}_3$	7.860		9.573		2.96
Phase B	Mg23Si8O42H6	$\text{P2}{}_1\text{/c}$	10.600	14.098	10.092	104.05	3.32

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.     

Phase transformations in MSiO4 compounds at high pressures and their geophysical implications

The phase behaviour of MSiO₄ compounds (MHf, Zr, U and Th0 has been investigated at high pressures and temperatures in a diamond-anvil press coupled with laser heating. All of these compounds have been found to undergo two or perhaps three phase transformations at pressures below 300 kbar. The high-pressure phase transformations of these compounds differ from one another, with the exception of HfSiO₄ and ZrSiO₄, which undergo identical phase transformations. The ultimate phase assemblages of these compounds are of dense component dioxides (although this is yet to be confirmed in ThSiO₄). It is suggested that the heat-producing elements U and Th would exist as dioxide solid solutions rather than silicates in the deep interior of the earth. Moreover, the densities of these dioxides are more than twice as great as mantle silicates and even slightly greater than pure iron under similar P, T conditions. Gravitational separation due to mandle convection may transport these dioxides to the deep interior of the earth to form deep heat sources. It is also suggested, however, that these deep heat sources are located in the inner-outer core boundary instead of in the lower mantle.     

High-pressure phases of Co2GeO4, Ni2GeO4, Mn2GeO4 and MnGeO3: implications for the germanate-silicate modeling scheme and the Earth's mantle

In a diamond-anvil press coupled with YAG laser heating, the spinels of Co₂GeO₄ and Ni₂GeO₄ have been found to disproportionate into their isochemical oxide mixtures at about 250 kbar and 1400–1800°C in the same manner as their silicate analogues. At about the same P-T conditions MnGeO₃ transforms to the orthorhombic perovskite structure (space group Pbnm); the lattice parameters at room temperature and 1 bar are a₀ = 5.084 ± 0.002, b₀ = 5.214 ± 0.002, and c₀ = 7.323 ± 0.003Å with Z = 4 for the perovskite phase. The zero-pressure volume change associated with the ilmenite-perovskite phase transition in MnGeO₃ is ?6.6%. Mn₂GeO₄ disproportionates into a mixture of the perovskite phase of MnGeO₃ plus the rocksalt phase of MnO at P = 250kbar and T = 1400–1800°C. The concept of utilizing germanates as high-pressure models for silicates is valid in general. The results of this study support the previous conclusion that the lower mantle comprises predominantly the orthorhombic perovskite phase of ferromagnesian silicate.     

Pyroxenes in the system Mg2Si2O6-CaMgSi2O6 at high pressure

The enstatite-diopside solvus in the system Mg₂Si₂O₆-CaMgSi₂O₆ has been experimentally determined within the pressure range 5–40 kbars and the temperature range 900–1500°C. Experiments involving reversal of the phase boundaries by unmixing from glass starting material and by reaction of pure clinoenstatite and diopside showed difficulty in achieving equilibration due to persistence of metastable, subcalcic clinopyroxene and to the sluggishness of reaction rate. The experimental data showed that the temperature dependence of the diopside limb is less than previously accepted. At 1500°C and 30 kbars subcalcic diopside found by Davis and Boyd (1966) is shown to be metastable with respect to enstatite and more calcic diopside of composition En_42.3Di_57.7. The solvus widens with increasing pressure between 5 and 40 kbars at 1200°C, but at 900°C the pressure effect on the solvus is very small. The stability relationships of the four pyroxenes, protoenstatite, enstatite, iron-free pigeonite and diopside are summarized, based on data from the literature and the present study.     

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.