Melting of enstatite from 13 to 18 GPa under hydrous conditions

Experiments on MgSiO₃ enstatite were conducted in the pressure range from 13 to 18 GPa under hydrous conditions in order to clarify the effect of water on the melting phase relations of enstatite at pressures corresponding to the Earth’s mantle transition zone. In some previous experiments [Geol. Soc. Am. Bull. 79 (1968) 1685; Phys. Earth Planet. Inter. 85 (1994) 237], incongruent melting behavior to form Mg₂SiO₄ forsterite and SiO₂ enriched liquid up to 5 GPa was observed, and congruent melting behavior at pressures up to 12 GPa was observed. Under hydrous conditions, we found that the melting reaction changes from congruent to incongruent at around 13.5 GPa. Liquid formed above 13.5 GPa is enriched in MgO component relative to MgSiO₃ because it coexists with stishovite (SiO₂). Moreover, the solidus temperature decreases drastically at around 13.5 GPa, in unison with the change in the melting reaction. The solidus temperature is about 1400 °C at 13 GPa, but approximately 900 °C at 15 GPa. Our results show that the liquidus phase changes from clinoenstatite to stishovite with increasing pressure and water content above 13.5 GPa. MgSiO₃ enstatite is one of the major constituent minerals in the Earth’s mantle, and it is expected that MgO-enriched liquid will be generated in the transition zone if water is present.     

Phase relations in hydrous MORB at 18-28 GPa: implications for heterogeneity of the lower mantle

The phase relations in hydrous and anhydrous mid-ocean ridge basalt were determined at pressures of 18-28 GPa. Liquidus phase relations in hydrous and anhydrous MORB are different. Garnet is the liquidus phase at pressures below 21 GPa, Ca-Al (CAS) phase and stishovite are the liquidus phases at pressures of 22-27 GPa, and stishovite and Ca-perovskite are the liquidus phases above 27 GPa, whereas Ca-perovskite is a liquidus phase of anhydrous MORB at pressures above 23 GPa. Under subsolidus conditions, we have found that in the hydrous MORB system the stability fields of Al-bearing perovskite and Na-Al (NAL) phase might shift to lower pressure by about 1.5 GPa compared to the dry MORB system. This shift could be explained by oxidation of a garnet-bearing assemblage by hydrous fluid and formation of Fe³⁺-bearing aluminous perovskite at lower pressures relative to the anhydrous system and/or differences in water solubility of the phases existing in perovskite-bearing assemblages. Our data indicate that hydrous basaltic crust remains denser than peridotite along the geotherm of a subducting slab, i.e. there is no density crossover between peridotite and basalt. Therefore, in slabs going through the 660 km discontinuity, basalt would gravitationally sink into the lower mantle under relatively hydrous conditions. The delamination of former basaltic crust near the 660 km discontinuity might be possible under relatively dry conditions of subduction. There are no stable highly hydrous phases in MORB above 10 GPa even at lower temperatures corresponding to subducting slabs. Therefore, MORB cannot be an important carrier of water to the deep Earth interior. However, it can be constantly supplied by water-bearing fluid from the underlying peridotite part of the descending slab. Thus, it is plausible that water can control subduction of the oceanic crust into the lower mantle.     

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.     

Experimental evidence for the exsolution of cratonic peridotite from high-temperature harzburgite

Phase equilibrium experiments were performed on typical ‘oceanic’ and ‘cratonic’ peridotite compositions and a Ca, Al-rich orthopyroxene composition, to test the proposal that garnet lherzolites exsolved from high-temperature harzburgites, and to further our understanding of the origin of ancient cratonic lithospheres. ‘Oceanic’ peridotites crystallize a garnet harzburgite assemblage at pressures above 5 GPa in the temperature range 1450–1600°C, but at 5 GPa and temperatures less than 1450°C, crystallize clinopyroxene to become true lherzolites. ‘Cratonic’ peridotites crystallize a garnet harzburgite assemblage at pressures above 5 GPa in the temperature range 1300–1600°C. Garnet-free harzburgite crystallizes from both ‘cratonic’ and ‘oceanic’ peridotite at temperatures above 1450°C and pressures below 4.5–5 GPa. Phase relations for the high Ca, Al-rich orthopyroxene composition essentially mirror those for ‘oceanic’ peridotite.The complete solution of garnet and clinopyroxene into orthopyroxene observed in all three starting compositions at temperatures near or above the mantle solidus at pressures less than 6 GPa supports the hypothesis that garnet lherzolite could have exsolved from harzburgite. The inferred cooling path for the original high-temperature harzburgite protoliths of garnet lherzolites differs depending on bulk composition. The precursor harzburgite protoliths of garnet lherzolites and harzburgites with ‘cratonic’ bulk compositions apparently experienced simple isobaric cooling from formation temperatures near the peridotite solidus to those at which most of these peridotites were sampled in the mantle (< 1200°C). The cooling histories for harzburgite protoliths of sheared garnet lherzolites with ‘oceanic’ compositional affinity are speculated to have involved convective circulation of mantle material to depths deeper than those at which it was originally formed.Phase equilibria and compositional relationships for orthopyroxenes produced in phase equilibrium experiments on peridotite and komatiite are consistent with an origin for ‘cratonic’ peridotite as a residue of Archean komatiite extraction, which has since cooled and exsolved clinopyroxene and garnet to become the common low-temperature, coarse-grained peridotite thought to comprise the bulk of the mantle lithosphere beneath the Archean Kaapvaal craton.     

Melting of hydrous upper mantle and possible generation of andesitic magma: An approach from synthetic systems

Phase equilibria in a portion of the system forsterite-plagioclase (An₅₀Ab₅₀ by weight)-silica-H₂O have been determined at 15 kbar pressure under H₂O-saturated conditions. The composition of the liquid pertinent to the piercing point forsterite + enstatite solid solution + amphibole + liquid + vapor is similar to that of calc-alkaline andesite. The electron microprobe analysis of the glass coexisting with the above three crystalline phases is very close to that of the piercing point determined by phase assemblage observations; however, the glass near (< 8 μm) forsterite crystals is significantly depleted in the normative forsterite component. With the addition of 10 wt.% KAlSi₃O₈, the composition of this piercing point becomes even closer to the compositions of calc-alkaline andesites. It is also shown that the liquid coexisting with forsterite and enstatite solid solution remains silica-rich (60–62 wt.%) over a wide (～ 100°C) temperature range. The present experimental studies support the view that liquids similar in composition to calc-alkaline andesites can be generated by direct partial melting of hydrous upper mantle at least at or near 15 kbar.     

Experimental investigation of phase transformations of olivine and enstatite at the lower part of the mantle transition zone: Implications for structure of the 660 km seismic discontinuity

High-pressure polymorphs of olivine and enstatite are major constituent minerals in the mantle transition zone(MTZ).The phase transformations of olivine and enstatite at pressure and temperature conditions corresponding to the lower part of the MTZ are import for understanding the nature of the 660 km seismic discontinuity.In this study,we determine phase transformations of olivine(MgSi2O4) and enstatite(MgSiO3) systematiclly at pressures between 21.3 and 24.4 GPa and at a constant temperature of 1600℃.The most profound discrepancy between olivine and enstatite phase transformation is the occurency of perovskite.In the olivine system,the post-spinel transformation occures at 23.8 GPa,corresponding to a depth of 660 km.In contrast,perovskite appears at 23 GPa(640 km) in the enstatite system.The ~1 GPa gap could explain the uplifting and/or splitting of the 660 km seismic discountinuity under eastern China.     

Water and magma generation at subduction zones

The basaltic ocean crust, metasomatized and metamorphosed during and after generation at the ocean ridge, contains H₂O stored in minerals and pore fluid. Phase equilibrium data establish the conditions for dehydration, and the conditions for melting of amphibole-gabbro or amphibole-quartz-eclogite, or for quartz-eclogite or mantle peridotite if aqueous fluids are available. But there is no concensus about the temperature distribution through the subducted crust, or within the overlying mantle wedge. Therefore, a variety of magmatic models can be derived from the experimental data. According to some calculations, endothermic dehydration reactions in the depth interval 75–125 km cool the oceanic crust to such an extent that it cannot be a major source of magmas; instead, concentrated aqueous fluids released from the crust generate magmas in the overlying peridotite. However, according to most existing thermal models, if temperatures in ocean crust are cool enough to prohibit melting of amphibolite, then temperatures in the mantle above the main sources of expelled fluids are too low for hydrous melting. The ocean crust appears to be effectively dehydrated by 100–125 km depth. Dense hydrous magnesian silicates are not likely candidates for deeper H₂O transport. The extent to which H₂O can be fixed in metasomatic phlogopite in crust or mantle is a significant but undetermined factor. Experimental data on minerals and liquid compositions do not support the concept of primary magmas for andesites and associated lavas from mantle or subducted crust. Complex, multi-stage processes appear to be more likely, which is consistent with recent interpretations of geochemical data.     

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

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

Grain growth in the forsterite-diopside system

Grain growth experiments in dunite, clinopyroxenite, and wehrlites with various forsterite/diopside ratios were performed to investigate the effect of modal composition on grain growth kinetics in the Earth's uppermost mantle. The experiments were conducted using a piston-cylinder apparatus at 1200 °C and 1.2 GPa for 2-763 h under dry conditions. Normal grain growth (NGG) occurred in dunite, clinopyroxenite, and relatively forsterite-poor wehrlites (≤70 vol.% of forsterite). Grain growth rates of forsterite and diopside in relatively forsterite-poor wehrlites were much slower than those in dunite and clinopyroxenite. In the forsterite-rich wehrlites (≥80 vol.% of forsterite), NGG of diopside and abnormal grain growth (AGG) of forsterite occurred. The growth rate of diopside was significantly slower than that in clinopyroxenite, while the growth rate of forsterite by AGG was found to be similar to that by NGG in dunite. The presence of ≤20 vol.% diopside had the effect of inhibiting the forsterite grain growth during the initial stage, resulting in AGG of forsterite, thus overtaking the growth rate in dunite. Our experimental results suggest that there would be a significant difference in grain growth rate and consequently in effective viscosity between olivine-rich peridotites (depleted mantle) and relatively olivine-poor peridotites (fertile mantle) in the case of grain size-sensitive creep. Variation of mean grain sizes in the upper mantle would result not only from differences in temperature and phase assemblage, but also from the variation of modal compositions.     

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.     

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.     

The effect of mantle composition on density in the extending lithosphere

The density distribution of the lithosphere is non-linear and discontinuous due to complex mineralogy and, most importantly, phase transitions. We evaluate the influence of changes in mantle composition on lithospheric density and its evolution during horizontal stretching, using thermodynamic calculations of the density as a function of pressure, temperature and composition. We also develop a simple parameterization based on end-member mineral reactions and geometric relationships between the geotherm and the phase boundary for comparison. The garnet–spinel peridotite transition leads to a moderate decrease in density of the mantle part of the lithospheric column at the initial stages of stretching. When the crust is sufficiently thinned and temperature is relatively high, plagioclase peridotite becomes stable in the upper part of the mantle. The density reduction due to the plagioclase-in reaction is controlled by bulk Al₂O₃ in the mantle and by the depth of the plagioclase-in reaction, which is mainly governed by the Na₂O/Al₂O₃ ratio. Since Na₂O and Al₂O₃ increase with the fertility of the mantle the phase transition effect is most pronounced for relatively fertile mantle (and strong extension) and can lead to 2.3% density reduction. This is equivalent to heating the entire lithosphere by 700 °C if only the effect of thermal expansion on density is taken into account. The formation of plagioclase peridotite can explain syn-rift uplift in sedimentary basins that experienced large mantle stretching without invoking an unrealistically strong increase in temperature. It might also be responsible for the break-up unconformity observed at continental margins.     

Estimates of the transition zone temperature in a mechanically mixed upper mantle

Partial melting of mantle peridotite generates a physically and chemically layered oceanic lithosphere that is cycled back into the mantle in subduction zones. Stirring times of the mantle are too long to allow for complete re-homogenization of subducted basalt and harzburgite, given the low chemical diffusivity of the solid mantle. This suggests that the Earth's mantle is a mechanical mixture of basaltic and harzburgitic components. Using a recently developed thermodynamic formulism we determine the phase equilibria and the seismic properties of a mantle comprised of a mechanical mixture of basalt and harzburgite (MM) and a homogeneous mantle (EA) with identical pyrolitic bulk chemistry. We use the theoretical shear velocity profiles as a new thermometer of the mantle below the magma-genetic zone by modeling the difference ΔT_410-660 between traveltimes of shear wave reflections off the 410-km and 660-km with the potential temperature T_P. ΔT_410-660 are measured from waveform stacks. They indicate that, over 1000+ km wave lengths, the temperature varies by about 200 K. Lowest and highest temperatures are resolved for the western Pacific subduction zones and the central Pacific, respectively. This variation is similar for the EA and MM and is in excellent agreement with estimates of transition zone thickness and shear velocity variations. The median value of T_P for the EA is 1720 K. It is about 1625 K for the MM, a value that is in better agreement with the Normal-MORB values of 1610 ± 40 K inferred from olivine-liquid equilibria given that our sampling region encompasses the Western Pacific subduction zones and the oldest parts of the Pacific Plate. We argue therefore that a mechanical mixed mantle, with generally higher velocities and steeper velocities gradients, represents a better physical reference model than a model based on a fully equilibrated assemblage.     

Spinifex-like textured metaperidotites from the Higo Metamorphic Rocks,Japan, a possible high-pressure dehydration product of antigorite serpentinite

Spinifex-like textured metaperidotites from the Higo Metamorphic Rocks (HMR), west-central Kyushu, Japan, may be formed by high-pressure dehydration of antigorite, and may indicate deep subduction of serpentinite reaching a pressure–temperature condition of 1.6 GPa and 740–750 °C. Three rock types have been identified based on mineral assemblage and rock texture: Type I (L) consisting of medium-grained (1–5 cm long) olivine + enstatite + chromite ±tremolite with secondary talc and anthophyllite that occurs in low-grade metamorphic rocks of the biotite zone, Type I (H) of coarse-grained (up to 10 cm long) olivine + enstatite (with clinoenstatite lamella) + chromite ±tremolite with secondary talc that occurs in high-grade metamorphic rocks of the garnet-cordierite zone, and Type II composed of Al-spinel + chlorite + olivine + apatite + ilmenite with minor sodic gedrite in the garnet-cordierite zone together with Type I (H). Olivines in all rock types are mostly serpentinized during exhumation. The chromite-olivine thermometer gives 560–690 °C for Type I (L) rocks, and the spinel-olivine thermometer gives 610–740 °C for Type II rocks. The peak metamorphic pressure will be higher than 1.6 GPa based on the location of the experimentally determined invariant point (P = 1.6 GPa and T = 670 °C) of antigorite + forsterite + enstatite + talc + H₂O. This estimate is consistent with the occurrence of chlorite in Type II rocks, which is stable up to 890 °C at 2.0 GPa. The spinifex-like textured metaperidotites occur as small bodies in the low P/T type gneisses, implying tectonic juxtaposition of them probably during exhumation of the HMR. Recent findings of medium pressure (0.9–1.2 GPa) granulites and gneisses from the HMR may indicate that the HMR has a deep root into the wedge mantle from which the spinifex-like textured metaperidotites have derived.     

Hydration effects on crystal structures and equations of state for silicate minerals in the subducting slabs and mantle transition zone

There are potentially huge amounts of water stored in Earth’s mantle, and the water solubilities in the silicate minerals range from tens to thousands of part per minion (ppm, part per million). Exploring water in the mantle has attracted much attention from the societies of mineralogy and geophysics in recent years. In the subducting slab, serpentine breaks down at high temperature, generating a series of dense hydrous magnesium silicate (DHMS) phases, such as phase A, chondrodite, clinohumite, etc. These phases may serve as carriers of water as hydroxyl into the upper mantle and the mantle transition zone (MTZ). On the other hand, wadsleyite and ringwoodite, polymorphs of olivine, are most the abundant minerals in the MTZ, and able to absorb significant amount of water (up to about 3 wt.% H₂O). Hence, the MTZ becomes a very important layer for water storage in the mantle, and hydration plays important roles in physics and chemistry of the MTZ. In this paper, we will discuss two aspects of hydrous silicate minerals: (1) crystal structures and (2) equations of state (EoSs).     

Lead isotopes and age of Hawaiian lherzolite nodules

The reaction between enstatite (En_95.3Fs_4.7) and CaCO₃ has been studied at pressures between 23 and 77 kbars and at temperatures between 800° and 1400°C. At 1000°C enstatite and CaCO₃ react to form dolomite and diopside solid solutions at pressures below approximately 45 kbars and magnesite and diopside solid solutions at higher pressures. The curve for the reaction dolomite_ss + enstatite_ss ? magnesite_ss + diopside_ss lies between 40 to 45 kbars at 1000°C and between 45 and 50 kbars at 1200°C. It is very close to the graphite-diamond transition curve. These experimental results indicate that calcite (or aragonite) is unstable in the presence of enstatite, and that dolomite and magnesite are the stable carbonates at high pressures. The forsterite + aragonite assemblage is, however, stable to at least 80 kbars at 800°C. It is suggested that in the upper mantle where enstatite is present, dolomite is stable to depths of about 150 km and magnesite is stable at greater depths in the continental regions, assuming that the partial pressure of CO₂ is equal or close to the total pressure. It is also suggested that carbonate inclusions in pyroxene can be used as an indicator of the depth of their equilibration; dolomite inclusions in enstatite would be formed at depths shallower than 150 km and magnesite inclusions in diopside at greater depths. Eclogite and peridotite inclusions in kimberlite may be classified on this basis.     

Iron isotope fractionation during planetary differentiation

The Fe isotope composition of samples from the Moon, Mars (SNC meteorites), HED parent body (eucrites), pallasites (metal and silicate) and the Earth's mantle were measured using high mass resolution MC-ICP-MS. These high precision measurements (δ⁵⁶Fe ≈ ± 0.04‰, 2 S.D.) place tight constraints on Fe isotope fractionation during planetary differentiation.Fractionation during planetary core formation is confined to < 0.1‰ for δ⁵⁶Fe by the indistinguishable Fe isotope composition of pallasite bulk metal (including sulfides and phosphides) and olivine separates. However, large isotopic variations (≈ 0.5‰) were observed among pallasite metal separates, varying systematically with the amounts of troilite, schreibersite, kamacite and taenite. Troilite generally has the lightest (δ⁵⁶Fe ≈ − 0.25‰) and schreibersite the heaviest (δ⁵⁶Fe ≈ + 0.2‰) Fe isotope composition. Taenite is heavier then kamacite. Therefore, these variations probably reflect Fe isotope fractionation during the late stage evolution and differentiation of the S- and P-rich metal melts, and during low-temperature kamacite exsolution, rather than fractionation during silicate-metal separation.Differentiation of the silicate portion of planets also seems to fractionate Fe isotopes. Notably, magmatic rocks (partial melts) are systematically isotopically heavier than their mantle protoliths. This is indicated by the mean of 11 terrestrial peridotite samples from different tectonic settings (δ⁵⁶Fe = + 0.015 ± 0.018‰), which is significantly lighter than the mean of terrestrial basalts (δ⁵⁶Fe = + 0.076 ± 0.029‰). We consider the peridotite mean to be the best estimate for the Fe isotope composition of the bulk silicate Earth, and probably also of bulk Earth. The terrestrial basaltic mean is in good agreement with the mean of the lunar samples (δ⁵⁶Fe = + 0.073 ± 0.019‰), excluding the high-Ti basalts. The high-Ti basalts display the heaviest Fe isotope composition of all rocks measured here (δ⁵⁶Fe ≈ + 0.2‰). This is interpreted as a fingerprint of the lunar magma ocean, which produced a very heterogeneous mantle, including the ilmenite-rich source regions of these basalts.Within uncertainties, samples from Mars (SNC meteorites), HED (eucrites) and the pallasites (average olivine + metal) have the same Fe isotope compositions as the Earth's mantle. This indicates that the solar system is very homogeneous in Fe isotopes. Its average δ⁵⁶Fe is very close to that of the IRMM-014 standard.     

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

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

On the origin of El Chichón volcano and subduction of Tehuantepec Ridge: A geodynamical perspective

The origin of El Chichón volcano is poorly understood, and we attempt in this study to demonstrate that the Tehuantepec Ridge (TR), a major tectonic discontinuity on the Cocos plate, plays a key role in determining the location of the volcano by enhancing the slab dehydration budget beneath it. Using marine magnetic anomalies we show that the upper mantle beneath TR undergoes strong serpentinization, carrying significant amounts of water into subduction. Another key aspect of the magnetic anomaly over southern Mexico is a long-wavelength (∼ 150 km) high amplitude (∼ 500 nT) magnetic anomaly located between the trench and the coast. Using a 2D joint magnetic-gravity forward model, constrained by the subduction P–T structure, slab geometry and seismicity, we find a highly magnetic and low-density source located at 40–80 km depth that we interpret as a partially serpentinized mantle wedge formed by fluids expelled from the subducting Cocos plate. Using phase diagrams for sediments, basalt and peridotite, and the thermal structure of the subduction zone beneath El Chichón we find that ∼ 40% of sediments and basalt dehydrate at depths corresponding with the location of the serpentinized mantle wedge, whereas the serpentinized root beneath TR strongly dehydrates (∼90%) at depths of 180-200 km comparable with the slab depths beneath El Chichón (200-220 km). We conclude that this strong deserpentinization pulse of mantle lithosphere beneath TR at great depths is responsible for the unusual location, singularity and, probably, the geochemically distinct signature (adakitic-like) of El Chichón volcano.     

Stability relation of (Mg,Fe)SiO3 garnets, major constituents in the Earth's interior

High-pressure and high temperature experiments at 20 GPa on (Mg,Fe)SiO₃ have revealed stability fields of two types of aluminium-free ferromagnesian garnets; non-cubic garnet and cubic garnet (majorite). Majorite garnet is stable only within a limited compositional variation, 0.2 < Fe/(Mg + Fe)< 0.4, and in the narrow temperature interval of 200°C around 2000°C, while the stability of non-cubic garnet with more iron-deficient compositions persists up to higher temperatures. These two garnets show fractional melting into iron-deficient garnet and iron-rich liquid, and the crystallization field of cubic garnet extends over Fe/(Mg + Fe)= 0.5. The assemblage silicate spinel and stishovite is a low-temperature phase, which also occurs in the iron-rich portion of the MgSiO₃—FeSiO₃ system. The sequence as given by the Fe/(Mg + Fe) value for the coexisting phases with the two garnets at 2000°C and 20 GPa is: silicate modified spinel aluminium-free garnets silicate spinel.Natural majorite in shock-metamorphosed chondrites is clarified to be produced at pressures above 20 GPa and temperatures around 2000°C. Similar shock events may cause the occurrence of non-cubic garnet in iron-deficient meteorites. Non-cubic garnet could be a stable phase in the Earth's mantle if a sufficiently low concentration of aluminium is present in the layer corresponding to the stable pressure range of non-cubic garnet. The chemical differentiation by melting in the deep mantle is also discussed on the basis of the present experimental results and the observed coexistence of majorite garnet with magnesiowüstite in chondrites.