Experimental study of reaction between perovskite and molten iron to 146 GPa and implications for chemically distinct buoyant layer at the top of the core

Partitioning of oxygen and silicon between molten iron and (Mg,Fe)SiO₃ perovskite was investigated by a combination of laser-heated diamond-anvil cell (LHDAC) and analytical transmission electron microscope (TEM) to 146 GPa and 3,500 K. The chemical compositions of co-existing quenched molten iron and perovskite were determined quantitatively with energy-dispersive X-ray spectrometry (EDS) and electron energy loss spectroscopy (EELS). The results demonstrate that the quenched liquid iron in contact with perovskite contained substantial amounts of oxygen and silicon at such high pressure and temperature (P–T). The chemical equilibrium between perovskite, ferropericlase, and molten iron at the P–T conditions of the core–mantle boundary (CMB) was calculated in Mg–Fe–Si–O system from these experimental results and previous data on partitioning of oxygen between molten iron and ferropericlase. We found that molten iron should include oxygen and silicon more than required to account for the core density deficit (<10%) when co-existing with both perovskite and ferropericlase at the CMB. This suggests that the very bottom of the mantle may consist of either one of perovskite or ferropericlase. Alternatively, it is also possible that the bulk outer core liquid is not in direct contact with the mantle. Seismological observations of a small P-wave velocity reduction in the topmost core suggest the presence of chemically-distinct buoyant liquid layer. Such layer physically separates the mantle from the bulk outer core liquid, hindering the chemical reaction between them.     

下地幔矿物研究及其进展

文中综述了20世纪90年代以来对下地幔矿物高温高压研究的进展,详细评论了下地幔温压下(Mg,Fe)SiO3钙钛矿的稳定性、(Mg, Fe)SiO3 钙钛矿和(Mg, Fe)O镁方铁矿的高压状态方程和热弹性及高压熔化、核幔边界温压下铁和硅酸盐的化学反应等几个热点问题;探讨了下地幔的矿物学组成,对下地幔的地震波速异常给出了可能的矿物学解释;介绍了国内同领域的研究工作;展望了下地幔矿物研究的发展方向。     

Reaction between liquid iron and (Mg,Fe)SiO3-perovskite and solubilities of Si and O in molten iron at 27 GPa

The Earth’s core contains light elements and their identification is essential for our understanding of the thermal structure and convection in the core that drives the geodynamo and heat flow from the core to the mantle. Solubilities of Si and O in liquid iron coexisting with (Mg,Fe)SiO₃-perovskite, a major constituent of the lower mantle, were investigated at temperatures between 2,320 and 3,040 K at 27 GPa. It was observed that Si dissolved in the liquid iron up to 1.70 wt% at 3,040 K and O dissolved in the liquid iron up to 7.5 wt% at 2,800 K. It was also clearly seen that liquid iron reacts with (Mg,Fe)SiO₃-perovskite to form magnesiowüstite and it contains Si and O at 27 GPa and at 2,640 and 3,040 K. The amounts of Si and O in the liquid iron are 1.70 and 2.25 wt% at 3,040 K, respectively. The solubilities of Si and O in liquid iron coexisting with (Mg,Fe)SiO₃-perovskite have strong positive temperature dependency. Hence, they can be plausible candidates for the light elements in the core.     

上天、入地、下海:极端条件下矿物学研究

上天、入地、下海,进行极端条件下的矿物学研究,研究微矿物,发现新矿物。主要利用金刚石压机,结合使用国内外同步辐射X-光源、中子源,以及其他多种物理的、化学的、光学的测试手段(如岩石矿物化学分析,光薄片测定,电子探针,离子探针,扫描电镜,透射电镜,红外、紫外、拉曼光谱,激光加热等),对来自天外的陨石、陨石坑样品、地球深处地幔源矿物以及海底甲烷水合物进行了一些研究。模拟不同温度和压力下各种不同成分的矿物材料的晶体结构、物理和化学性质。文章着重研究从地球内核到地壳海底的各种不同组分在不同温度、压力极端环境下形成的各种各样的典型矿物:从金属固体内核和金属液体外核中的ε-Fe到核幔边界(CMB)地球D″层的后钙钛矿(Post-Perovskite)结构(ppv)镁铁硅酸盐(Mg,Fe)SiO₃,从下地幔中的铁磁性钙钛矿(Perovskite)结构(pv)镁铁硅酸盐布里奇曼石(Bridgmanite)(Mg,Fe)SiO₃、镁铁氧化物(Fe,Mg)O和后尖晶石(Post-Spinel)结构的含Fe³⁺毛河光矿(Maohokite)(HP-Mg$Fe^{3+}_{2}O_{4}$)到过渡带、上地幔和地壳中的镁铁硅酸盐、硅氧化物、铬铁氧化物和金刚石及其内含物以及甲烷水合物(CH₄·H₂O)等。进行高温高压极端条件下的矿物学研究,为探索地球结构性质、形成动力和发展历史提供了新的窗口。     

Magmatic evolution of the material of the Earth’s lower mantle: Stishovite paradox and origin of superdeep diamonds (Experiments at 24–26 GPa)

The ultrabasic–basic magmatic evolution of the lower mantle material includes important physicochemical phenomena, such as the stishovite paradox and the genesis of superdeep diamonds. Stishovite SiO₂ and periclase–wüstite solid solutions, (MgO · FeO)_ss, associate paradoxically in primary inclusions of superdeep lower mantle diamonds. Under the conditions of the Earth’s crust and upper mantle, such oxide assemblages are chemically impossible (forbidden), because the oxides MgO and FeO and SiO₂ react to produce intermediate silicate compounds, enstatite and ferrosilite. Experimental and physicochemical investigations of melting phase relations in the MgO–FeO–SiO₂–CaSiO₃ system at 24 GPa revealed a peritectic mechanism of the stishovite paradox, (Mg, Fe)SiO₃ (bridgmanite) + L = SiO₂ + (Mg, Fe)O during the ultrabasic–basic magmatic evolution of the primitive oxide–silicate lower mantle material. Experiments at 26 GPa with oxide–silicate–carbonate–carbon melts, parental for diamonds and primary inclusions in them, demonstrated the equilibrium formation of superdeep diamonds in association with ultrabasic, (Mg, Fe)SiO₃ (bridgmanite) + (MgO · FeO)_ss (ferropericlase), and basic minerals, (FeO · MgO)_ss (magnesiowüstite) + SiO₂ (stishovite). This leads to the conclusion that a peritectic mechanism, similar to that responsible for the stishovite paradox in the pristine lower mantle material, operates also in the parental media of superdeep diamonds. Thus, this mechanism promotes both the ultrabasic–basic evolution of primitive oxide–silicate magmas in the lower mantle and oxide–silicate–carbonate melts parental for superdeep diamonds and their paradoxical primary inclusions.     

http://www.sciencedirect.com/science/article/pii/S1674987111000909

We have performed measurements of minerals based on the synchrotron source for single crystal and powder X-ray diffraction,inelastic scattering,spectroscopy and radiography by using diamond anvil cells.We investigated the properties of iron（Fe）,iron-magnesium oxides（Fe,Mg）O, silica（SiO₂）,iron-magnesium silicates（Fe,Mg）SiO₃ under simulated high pressure-high temperature extreme conditions of the Earth’s crust,upper mantle,low mantle,core-mantle boundary,outer core, and inner core.The results provide a new window on the investigation of the mineral properties at Earth’s conditions.     

西藏蛇绿岩中硅铁合金组合及成因探讨

在雅鲁藏布江蛇绿岩带的东端罗布莎蛇绿岩的铬铁矿中发现不寻常的硅铁合金组合。4种硅铁合金的理论分子式分别为Fe0.84Si2.00(Fe3Si7)、Fe7Si3、Fe6Si4以及Fe4Ti3Si2P。这些合金均选自铬铁矿石的人工重砂中，在少数颗粒中见到由3种硅铁合金组成的交生结构，明显表明这些合金的同生和同成因性。推测它们为化学反应成因,来自于核幔边界地带。     

碳酸岩岩浆演化的指示性矿物—环带金云母——以山东西部雪野碳酸岩为例

山东西部莱芜－淄博地区的中生代雪野碳酸岩中发育有大量罕见的反环带云母，云母的电子探针分析表明，云母斑晶的核心为黑云母，过渡带和边缘是金云母，基质中云母为金云母，核心黑云母与过渡带的金云母界限清晰，成分突变以及核心黑云母的溶蚀结构表明，核心黑云母和过渡带与边缘带金云母不是同一岩浆体系结晶的产物，核心黑云母可能是碳酸岩岩浆捕获的外来黑云母，过渡带与边缘带金云母同基质中金云母具有相似的化学成分，从过渡带到边缘带，金云母的Mg(Mg Fe)逐渐降低，反映了碳酸岩岩浆的不断结晶演化过程，TiO2的不断降低，一方面是由于岩浆的分异结晶，另一方面则是岩浆上升期间去气作用导致岩浆内CO2／H2O值降低所致。云母斑晶从过渡带向边缘带Al2O3含量逐渐减少，表明碳酸岩浆自过渡带云母结晶后没有富Al的圈岩物质加入。     

Combined iron and magnesium isotope geochemistry of pyroxenite xenoliths from Hannuoba,North China Craton: implications for mantle metasomatism

We present high-precision iron and magnesium isotopic data for diverse mantle pyroxenite xenoliths collected from Hannuoba, North China Craton and provide the first combined iron and magnesium isotopic study of such rocks. Compositionally, these xenoliths range from Cr-diopside pyroxenites and Al-augite pyroxenites to garnet-bearing pyroxenites and are taken as physical evidence for different episodes of melt injection. Our results show that both Cr-diopside pyroxenites and Al-augite pyroxenites of cumulate origin display narrow ranges in iron and magnesium isotopic compositions (δ⁵⁷Fe = ?0.01 to 0.09 with an average of 0.03 ± 0.08 (2SD, n = 6); δ²⁶Mg = ? 0.28 to ?0.25 with an average of ?0.26 ± 0.03 (2SD, n = 3), respectively). These values are identical to those in the normal upper mantle and show equilibrium inter-mineral iron and magnesium isotope fractionation between coexisting mantle minerals. In contrast, the garnet-bearing pyroxenites, which are products of reactions between peridotites and silicate melts from an ancient subducted oceanic slab, exhibit larger iron isotopic variations, with δ⁵⁷Fe ranging from 0.12 to 0.30. The δ⁵⁷Fe values of minerals in these garnet-bearing pyroxenites also vary widely (?0.25 to 0.08 in olivines, ?0.04 to 0.25 in orthopyroxenes, ?0.07 to 0.31 in clinopyroxenes, 0.07 to 0.48 in spinels and 0.31–0.42 in garnets). In addition, the garnet-bearing pyroxenite shows light δ²⁶Mg (?0.43) relative to the mantle. The δ²⁶Mg of minerals in the garnet-bearing pyroxenite range from ?0.35 for olivine and orthopyroxene, to ?0.34 for clinopyroxene, 0.04 for spinel and ?0.68 for garnet. These measured values stand in marked contrast to calculated equilibrium iron and magnesium isotope fractionation between coexisting mantle minerals at mantle temperatures derived from theory, indicating disequilibrium isotope fractionation. Notably, one phlogopite clinopyroxenite with an apparent later metasomatic overprint has the heaviest δ⁵⁷Fe (as high as 1.00) but the lightest δ²⁶Mg (as low as ?1.50) values of all investigated samples. Overall, there appears to be a negative co-variation between δ⁵⁷Fe and δ²⁶Mg in the Hannuoba garnet-bearing pyroxenite and in the phlogopite clinopyroxenite xenoliths and minerals therein. These features may reflect kinetic isotopic fractionation due to iron and magnesium inter-diffusion during melt–rock interaction. Such processes play an important role in producing inter-mineral iron and magnesium isotopic disequilibrium and local iron and magnesium isotopic heterogeneity in the subcontinental mantle.     

Deep carbon cycle and geodynamics: the role of the core and carbonatite melts in the lower mantle

Carbon, though being abundant in the Solar system, barely exceeds 0.01 wt.% in the silicate mantle, whereas it is ~ 3.6 wt.% in primitive chondritic meteorites that most likely formed our planet. This deficit may be due to redistribution of carbon in the liquid metal phase and then in the core at the stage of magma ocean fractionation, because carbon is much more soluble in Fe–Ni ± S melt than in silicate melts. The terrestrial heat and mass transfer are controlled mainly by layered convection and periodic peaks of plume activity as fast mantle jets that rise from the core. Plumes carry significant amounts of CO₂, H₂O, and K₂O (most probably in the form of carbonatite or hydrous carbonatite melts) released by the degassing core on its interaction with oxidized silicate material. There are two mechanisms that may maintain fast plume ascent: (1) local melting at the plume front as a result of doping with volatiles (H₂O, CO₂) as in a gas burner (rise rate 60–110 cm/yr) or (2) flow controlled by diffusion transport of silicate components in carbonatite melt (rise rate ~ 100 cm/yr).     

Phase relations in the carbon-saturated C–Mg–Fe–Si–O system and C and Si solubility in liquid Fe at high pressure and temperature: implications for planetary interiors

The phase and melting relations of the C-saturated C–Mg–Fe–Si–O system were investigated at high pressure and temperature to understand the role of carbon in the structure of the Earth, terrestrial planets, and carbon-enriched extraterrestrial planets. The phase relations were studied using two types of experiments at 4 GPa: analyses of recovered samples and in situ X-ray diffractions. Our experiments revealed that the composition of metallic iron melts changes from a C-rich composition with up to about 5 wt.% C under oxidizing conditions (ΔIW = ?1.7 to ?1.2, where ΔIW is the deviation of the oxygen fugacity (fO₂) from an iron-wüstite (IW) buffer) to a C-depleted composition with 21 wt.% Si under reducing conditions (ΔIW < ?3.3) at 4 GPa and 1,873 K. SiC grains also coexisted with the Fe–Si melt under the most reducing conditions. The solubility of C in liquid Fe increased with increasing fO₂, whereas the solubility of Si decreased with increasing fO₂. The carbon-bearing phases were graphite, Fe₃C, SiC, and Fe alloy melt (Fe–C or Fe–Si–C melts) under the redox conditions applied at 4 GPa, but carbonate was not observed under our experimental conditions. The phase relations observed in this study can be applicable to the Earth and other planets. In hypothetical reducing carbon planets (ΔIW < ?6.2), graphite/diamond and/or SiC exist in the mantle, whereas the core would be an Fe–Si alloy containing very small amount of C even in the carbon-enriched planets. The mutually exclusive nature of C and Si may be important also for considering the light elements of the Earth’s core.     

An alternative interpretation of lower mantle mineral associations in diamonds

Diamonds containing ferropericlase (Mg,Fe)O and other silicate (enstatite [(Mg,Fe)SiO₃], in particular) assemblages are generally believed to be derived from the Earth's lower mantle. On the basis of the observed ratio between ferropericlase and enstatite inclusions and the FeO content of these ferropericlases, it is concluded that most of these minerals entrapped in diamonds may not represent the lithology of the lower mantle itself as has been suggested by many investigators. Instead, ferropericlases in these diamonds represent most likely the disproportionate product of ferromagnesite [(Mg,Fe)CO₃], which underwent a decarbonation reaction to form both diamond and ferropericlase simultaneously in the lower mantle. The wide variation in the Mg# of ferropericlase inclusions in diamonds is attributed to the decarbonation "loop" of the MgCO₃-FeCO₃ solid solutions. Some of the enstatite inclusions coexisting with these ferropericlases in the same diamond may represent the most abundant mineral species of (Mg,Fe)SiO₃-perovskite in the lower mantle. The latter mineral phase experienced a retrogressive transition into enstatite during the transport of diamonds to the Earth's surface.     

No mushy zones in the Earth’s core

Mushy zones, assemblages of crystals and their pore-space liquids, have been invoked for both the upper and lower boundaries of the liquid outer core. The timescale of very slow accumulation compared with solidification at either of these interfaces militates against such zones, where instead hard ground should be expected to form by solidification at the interface. Such adcumulus growth involves isothermal, isocompositional solidification by successful exchange of evolving solute with fresh melt from an infinite reservoir. At both boundaries of the outer core, the removal of rejected material is significantly aided by compositional convection. The accumulation rates at the outer core boundaries are orders of magnitude slower than required for adcumulus growth, as calibrated both by field and experimental evidence in silicate melts. A conceptual phase diagram for the core-mantle boundary helps to visualize the relevant equilibria. Capture of core metal into the mantle has been suggested to occur via a mushy zone, to explain a high electrical conductivity there, as plausibly required by the secular behavior of the Earth’s nutation. One conjecture is that the rejected light elements from the freezing of the inner core might be able to congregate as a porous flotation sediment at the top of the core. The idea of porosity in such a mushy zone must be rejected from experience with solidification of cumulates from magmas.A high electrical conductivity might instead be caused by solution of core metal by mantle, followed by exsolution. The hottest part of the mantle lies in contact with the molten outer core, where the maximum solubility of Fe must occur in the major mantle phases. On leaving the core-mantle boundary, the mantle must cool and may exsolve metal on the metal-silicate solvus. If the iron-rich metal resides chiefly in the rheologically weaker metal oxide phase, which coats the deforming perovskite grains, it may furnish a short circuit for mantle conductivity in the basal mantle. At still cooler and higher levels, the mantle encounters more normal mantle redox conditions, and any exsolved Fe metal should oxidize to FeO in the metal oxide and perovskite phases, ceasing to be a conductor.     

Melting relationships in the system Fe-Feo at high pressures: Implications for the composition and formation of the earth's core

A reconnaissance investigation has been carried out on melting relationships in the system Fe-FeO at pressures up to 25 GPa and temperatures up to 2200° C using an MA-8 apparatus. Limited studies were also made of the Co-CoO and Ni-NiO systems. In the system FeFeO, the rapid exsolution of FeO from liquids during quenching causes some difficulties in interpretation of textures and phase relationships. The Co-CoO and Ni-NiO systems are more tractable experimentally and provide useful analogues to the Fe-FeO system. It was found that the broad field of liquid immiscibility present at ambient pressure in the Co-CoO system had disappeared at 18 GPa, 2200° C and that the system displayed complete miscibility between molten Co and CoO, analogous to the behaviour of the Ni-NiO system at ambient pressure. The phase diagram of the system Fe-FeO at 16 GPa and from 1600–2200° C was constructed from interpretations based on the textures of quenched run products. The solubility of FeO in molten iron is considerably enhanced by high pressures. At 16 GPa, the Fe-FeO eutectic contains about 10–15 mol percent FeO and the eutectic temperature in this iron-rich region of the system occurs at 1700±25° C, some 350° C below the melting point of pure iron at the same pressure. The solubility of FeO in molten Fe increases rapidly as temperature increases from 1700 to 2200° C. A relatively small liquid immiscibility field is present above 1900° C but is believed to be eliminated above 2200° C. This inference is supported by thermodynamic calculations on the positions of key phase boundaries. A single run carried out on an Fe₅₀ FeO₅₀ composition at 25 GPa and 2200° C demonstrated extensive and probably complete miscibility between Fe and FeO liquids under these conditions. The melting point of iron is decreased considerably by solution of FeO at high pressures; moreover, the melting point gradient (dP/dT) of the Fe-FeO eutectic is much smaller than that of pure iron and is also smaller than that of mantle pyrolite under the P, T conditions studied. These characteristics make it possible for melting of metal phase and segregation of the core to proceed within the Earth under conditions where most of the mantle remains below solidus temperatures. Under these conditions, the core would inevitably contain a large proportion of dissolved FeO. It is concluded therefore, that oxygen is likely to be the principal light element in the core. The inner core may not be composed of pure iron, as often proposed. Instead, it may consist of a crystalline oxide solid solution (Ni, Fe)₂O.     

Dynamics and evolution of the deep mantle resulting from thermal,chemical, phase and melting effects

The core–mantle boundary (CMB) – the interface between the silicate mantle and liquid iron alloy outer core – is the most important boundary inside our planet, with processes occurring in the deep mantle above it playing a major role in the evolution of both the core and the mantle. The last decade has seen an astonishing improvement in our knowledge of this region due to improvements in seismological data and techniques for mapping both large- and small-scale structures, mineral physics discoveries such as post-perovskite and the iron spin transition, and dynamical modelling. The deep mantle is increasingly revealed as a very complex region characterised by large variations in temperature and composition, phase changes, melting (possibly at present and certainly in the past), and anisotropic structures. Here, some fundamentals of the relevant processes and uncertainties are reviewed in the context of long-term Earth evolution and how it has led to the observed present-day structures. Melting has been a dominant process in Earth's evolution. Several processes involving melting, some of which operated soon after Earth's formation and some of which operated throughout its history, have produced dense, iron rich material that has likely sunk to the deepest mantle to be incorporated into a heterogeneous basal mélange (BAM) that is now evident seismically as two large low-velocity regions under African and the Pacific, but was probably much larger in the past. This BAM modulates core heat flux, plume formation and the separation of different slab components, and may contain various trace-element cocktails required to explain geochemical observations. The geographical location of BAM material has, however, probably changed through Earth's history due to the inherent time-dependence of plate tectonics and continental cycles.     

Unique Clinkers and Paralavas from a New Nyalga Combustion Metamorphic Complex in Central Mongolia: Mineralogy,Geochemistry, and Genesis

The paper presents mineralogical and geochemical data on clinkers and paralavas and on conditions under which they were formed at the Nyalga combustion metamorphic complex, which was recently discovered in Central Mongolia. Mineral and phase assemblages of the CM rocks do not have analogues in the world. The clinkers contain pyrogenically modified mudstone relics, acid silicate glass, partly molten quartz and feldspar grains, and newly formed indialite microlites (phenocrysts) with a ferroindialite marginal zone. In the paralava melts, spinel microlites with broadly varying Fe concentrations and anorthite–bytownite were the first to crystallize, and were followed by phenocrysts of Al-clinopyroxene ± melilite and Mg–Fe olivine. The next minerals to crystallize were Ca-fayalite, kirschsteinite, pyrrhotite, minerals of the rhönite–kuratite series, K–Ba feldspars (celsian, hyalophane, and Ba-orthoclase, Fe³⁺-hercynite ± (native iron, wüstite, Al-magnetite, and fresnoite), nepheline ± (kalsilite), and later calcite, siderite, barite, celestine, and gypsum. The paralavas contain rare minerals of the rhönite–kuratite series, a new end-member of the rhönite subgroup Ca₄Fe ₈ ²⁺ Fe ₄ ³⁺ O₄ [Si₈Al₄O₃₆], a tobermorite-like mineral Ca₅Si₅(Al,Fe)(OH)O₁₆ · 5H₂O, and high- Ba F-rich mica (K,Ba)(Mg,Fe)₃(Al,Si)₄O₁₀F₂. The paralavas host quenched relics of microemulsions of immiscible residual silicate melts with broadly varying Si, Al, Fe, Ca, K, Ba, and Sr concentrations, sulfide and calcitic melts, and water-rich silicate–iron ± (Mn) fluid media. The clinkers were formed less than 2 Ma ago in various parts of the Choir–Nyalga basin by melting Early Cretaceous mudstones with bulk composition varies from dacitic to andesitic. The pyrogenic transformations of the mudstones were nearly isochemical, except only for volatile components. The CM melt rocks of basaltic andesitic composition were formed via melting carbonate–silicate sediments at temperatures above 1450°C. The Ca- and Fe-enriched and silicaundersaturated paralavas crystallized near the surface at temperatures higher than 900–1100°C and oxygen fugacity \(f_{O_2 }\) between the IW and QFM buffers. In local melting domains of the carbonate–silicate sedimentary rocks and in isolations of the residual melts among the paralava matrix the fluid pressure was higher than the atmospheric one. The bulk composition, mineral and phase assemblages of CM rocks of the Nyalga complex are very diverse (dacitic, andesitic, basaltic andesitic, basaltic, and silica-undersaturated mafic) because the melts crystallized under unequilibrated conditions and were derived by the complete or partial melting of clayey and carbonate–silicate sediments during natural coal fires.     

The stishovite paradox in the evolution of lower mantle magmas and diamond-forming melts (experiment at 24 and 26 GPa)

Experimental studies of phase relations in the oxide–silicate system MgO–FeO–SiO₂ at 24 GPa show that the peritectic reaction of bridgmanite controls the formation of stishovite as a primary in situ mineral of the lower mantle and as an effect of the stishovite paradox. The stishovite paradox is registered in the diamond-forming system MgO–FeO–SiO₂–(Mg–Fe–Ca–Na carbonate)–carbon in experiments at 26 GPa as well. The physicochemical mechanisms of the ultrabasic–basic evolution of deep magmas and diamondforming media, as well as their role in the origin of the lower mantle minerals and genesis of ultradeep diamonds, are studied.     

Experimental and thermodynamic study of the crystallization of diamond and silicates in a metal-silicate-carbon system

Silicate inclusions are widespread in natural diamonds, which also may contain rare inclusions of native iron. This suggests that some natural diamonds crystallized in metal-silicate-carbon systems. We experimentally studied the crystallization of diamond and silicate phases from the starting composition Fe_0.36Ni_0.64 + silicate glass + graphite and calculated the Fe mole fractions of the silicate phases crystallizing under these conditions. The silicates synthesized together with diamond had low Fe mole fractions [Fe/(Fe + Mg + Ca)] in spite of strong Fe predominance in the system. The Fe mole fractions of the silicates decreased in the sequence garnet-pyroxene-olivine, which is consistent with the results of our thermodynamic calculations. The Fe mole fraction of silicates under various redox conditions under which metal-carbon melts are stable drastically decreases with decreasing fo₂. The low Fe mole fractions of silicate inclusions in diamond from the Earth’s mantle can be explained by the highly reducing crystallization conditions, under which Fe was concentrated as a metallic phase of the magmatic melts and could be only insignificantly incorporated in the structures of silicates.     

Prediction of high-temperature oxygen isotope fractionation factors between mantle minerals

The increment method is adopted to calculate oxygen isotope fractionation factors for mantle minerals, particularly for the polymorphic phases of MgSiO₃ and Mg₂SiO₄. The results predict the following sequence of ¹⁸O-enrichment: pyroxene (Mg,Fe,Ca)₂Si₂O₆>olivine (Mg,Fe)₂SiO₄>spinel (Mg,Fe)₂SiO₄>ilmenite (Mg,Fe, Ca)SiO₃>perovskite (Mg,Fe,Ca)SiO₃. The calculated fractionations for the calcite-perovskite (CaTiO₃) system are in excellent agreement with experimental calibrations. If there would be complete isotopic equilibration in the mantle, the spinel-structured silicates in the transition zone are predicted to be enriched in ¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in ¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle would essentially result from differences in the chemical composition and crystal structure of mineral phases at different mantle depths. Assuming isotopic equilibrium on a whole earth scale, the chemical structure of the Earth's interior can be described by the following sequence of ¹⁸O-enrichment: uppr crust>lower crust>upper mantle>transition zone>lower mantle >core.     

On the implications of the coupled evolution of the deep planetary interior and the presence of surface ocean water in hydrous mantle convection

We investigate the influence of the deep mantle water cycle incorporating dehydration reactions with subduction fluxes and degassing events on the thermal evolution of the Earth as a consequence of core–mantle thermal coupling. Since, in our numerical modeling, the mantle can have ocean masses ∼12 times larger than the present-day surface ocean, it seems that more than 13 ocean masses of water are at the maximum required within the planetary system overall to partition one ocean mass at the surface of the present-day Earth. This is caused by effects of water-dependent viscosity, which works at cooling down the mantle temperature significantly so that the water can be absorbed into the mantle transition zone and the uppermost lower mantle. This is a result similar to that without the effects of the thermal evolution of the Earth's core (Nakagawa et al., 2018). For the core's evolution, it seems to be expected for a partially molten state in the deep mantle over 2 billion years. Hence, the metal–silicate partitioning of hydrogen might have occurred at least 2 billion years ago. This suggests that the hydrogen generated from the phase transformation of hydrous-silicate-hosted water may have contributed to the partitioning of hydrogen into the metallic core, but it is still quite uncertain because the partitioning mechanism of hydrogen in metal–silicate partitioning is still controversial. In spite of many uncertainties for water circulation in the deep mantle, through this modeling investigation, it is possible to integrate the co-evolution of the deep planetary interior within that of the surface environment.