Immiscible two-liquid regions in the Fe-O-S system at high pressure: Implications for planetary cores

We have determined phase relations in the Fe-O and Fe-O-S systems in the range of 15-21 GPa and 1825-2300 °C. Below the liquidus temperatures, solid FeO and metallic liquids are observed in both the Fe-O and the Fe-O-S systems. An immiscible two-liquid region exists in the Fe-O binary system in the pressure range investigated, and the immiscibility gap between Fe-rich metallic liquid and FeO-rich ionic liquid does not greatly change with either pressure or temperature. On the other hand, an immiscible two-liquid region in the Fe-O-S ternary system narrows significantly with increasing pressure at constant temperature and vice versa, and it almost disappears at 21 GPa, and 2300 °C. Immiscible two-liquid regions are thus not expected to exist in the Fe-O-S system in the Earth's core, suggesting that both oxygen and sulfur can be incorporated into the core. Our results are consistent with a geochemical model for the core containing 5.8 wt.% oxygen and 1.9 wt.% sulfur as proposed by McDonough and Sun [McDonough, W.F., Sun, S.-S., 1995. The composition of the Earth. Chem. Geol. 120, 223-253].     

高温高压下碳酸盐熔体对地幔岩电导率的影响

为了观测含碳酸盐地幔岩部分熔融过程中电导率的变化,厘清碳酸盐熔体在金伯利岩岩浆形成过程中所起的作用,并探讨Slave克拉通中部Lac de Gras地区约80~120 km深处的高导成因,我们利用DS 3600 t六面顶压机和Solartron 1260阻抗/增益-相位分析仪在1.0~3.0 GPa、673~1873 K温压条件下分别测量了含碳酸钠（Na₂CO₃）、碳酸钙（CaCO₃）和大洋中脊玄武岩（MORB）的地幔岩样品的电导率.实验结果表明,地幔岩样品的电导率主要受到温度和组分的影响,而压力对其影响较小.在温度低于1023 K时,含Na₂CO₃地幔岩样品的电导率明显高于含同比重CaCO₃和MORB的;温度达到1023 K时,含Na₂CO₃地幔岩样品开始熔融;但在之后的200 K温度区间内,该部分熔融样品的电导率随温度的增加几乎不发生变化.这一现象或许揭示：地幔深部的碳酸质岩浆在快速上升过程中会同化吸收岩石圈地幔中的斜方辉石（Opx）,进而形成金伯利岩岩浆,期间岩浆的电导率几乎不发生变化.含CaCO₃和MORB的地幔岩样品分别在1723 K和1423 K开始熔融,其部分熔融样品的电导率随温度的增加而快速增加.依据前人的研究结果和我们的实验结果,我们认为可以用含碳酸盐的部分熔融样品来解释Slave克拉通中部Lac de Gras地区约80~120 km深处的异常高导现象,并推测熔体中碳酸盐的熔体比例小于2 wt.%.

     

高温高压下上地幔岩石电导率实验研究

为了建立具有普遍适用性的上地幔电性结构,本文利用Kawai-1000t压机和Solartron IS-1260阻抗/增益-相位分析仪,在4.0~14.0 GPa、873~1673 K的条件下,采用交流阻抗谱法（频率范围10^-1~10⁶Hz）测量了不含水的地幔岩电导率.实验结果显示,岩石的电导率随温度升高而大幅度的增大;在较大的温度范围内岩石的导电机制发生了变化,中低温时为小极化子导电,此时激活焓为0.94 eV（±0.13）eV,激活体积为0.11（±0.92）cm³·mol^-1,高温时为和镁空穴相关的离子导电,此时激活焓为1.6~3.17 eV,激活体积为6.75（±7.43）cm³·mol^-1;本次测量的电导率比低压下岩石的电导率要高,比矿物的电导率也要高.用本次的实验结果回归计算得到Fennoscandian地区的上地幔的一维电导率剖面,发现200 km以上本次实验计算的结果和大地电磁测深的电导率剖面吻合的比较好,在200 km以下本次实验得到的要比野外测量的电导率稍稍高一点,可能是因为实验过程中没有完全避免水的影响.本次的实验结果比用有效均匀介质方法计算得到的pyrolite矿物模型的电导率要高出两个数量级,这样的结果显示只用一种矿物的电导率或是几种矿物理论计算的结果有一定的不合理性.

     

高温高压下上地幔岩石电导率实验研究

为了建立具有普遍适用性的上地幔电性结构,本文利用Kawai-1000t压机和Solartron IS-1260阻抗/增益-相位分析仪,在4.0~14.0 GPa、873~1673 K的条件下,采用交流阻抗谱法（频率范围10^-1~10⁶Hz）测量了不含水的地幔岩电导率.实验结果显示,岩石的电导率随温度升高而大幅度的增大;在较大的温度范围内岩石的导电机制发生了变化,中低温时为小极化子导电,此时激活焓为0.94 eV （±0.13） eV,激活体积为0.11（±0.92） cm³·mol^-1,高温时为和镁空穴相关的离子导电,此时激活焓为1.6~3.17 eV,激活体积为6.75（±7.43） cm³·mol^-1;本次测量的电导率比低压下岩石的电导率要高,比矿物的电导率也要高.用本次的实验结果回归计算得到Fennoscandian地区的上地幔的一维电导率剖面,发现200 km以上本次实验计算的结果和大地电磁测深的电导率剖面吻合的比较好,在200 km以下本次实验得到的要比野外测量的电导率稍稍高一点,可能是因为实验过程中没有完全避免水的影响.本次的实验结果比用有效均匀介质方法计算得到的pyrolite矿物模型的电导率要高出两个数量级,这样的结果显示只用一种矿物的电导率或是几种矿物理论计算的结果有一定的不合理性.     

高温高压下麻粒岩电导率研究

麻粒岩是下地壳的重要组成物质,模拟其在下地壳温压条件下的电导率对于认识下地壳的电导率分布具有十分重要的意义.本文用交流法在1 GPa下,373~1002 K范围内研究了麻粒岩样品的复阻抗,并且对测量结果进行了阻抗谱分析.研究结果表明,复阻抗对频率具有依赖性,且随温度的升高,复阻抗的实部、虚部均变小.在实验给出的温度范围内,电导率结果符合Arrhenius关系式.当温度在373~663 K范围内时,实验所获得的激化焓为0.31 eV,表明样品的电导率由低能带杂质离子所控制;当温度在673~1002 K范围内时,激化焓为0.67 eV,此时可能为小极化子导电.将所得电导率结果与西南峨边—马边地区以及华北应县―商河地区的大地电磁结果进行了对比,发现在所模拟的下地壳温压范围内,实验室测得的电导率位于野外MT数据范围内.     

Pyroxenite melting at subduction zone: Implications for the origin of mafic arc magmas

<正>1. Introduction The oceanic arc basalts and continental arc andesites are typical products of subduction zone magmatism(Straub et al., 2011; Zheng et al., 2020). However, there has been controversy over the lithology of their magma sources. As this issue is closely related to both physicochemical and geodynamic mechanisms of subduction zone magmatism, it has become one of the key issues in the study of convergent plate margins(Zheng et al., 2022).     

Impedance spectroscopy analysis on electrical properties of serpentine at high pressure and high temperature

The electrical conductivity of serpentine is measured and the microscopic conductance mechanisms are investigated with impedance spectroscopy at 2.5–4.0 GPa and 220–780°C. The results show that the electrical conductivity is strongly dependent on the frequencies used, and that only arc I, which reflects grain interior conductance, occurs and dominates the whole conductance processes over 12-10⁵Hz at high pressure before dehydration. The arc II, which indicates the grain boundary process, begins to occur at the initial stage of dehydration. After dehydration, due to the presence of highly conductive networks of free water, the electrical conductivity is not dependent on frequencies any longer and the total electrical conductivity is dominated by process of ionic conductance of free water in interconnected networks. Dehydration of serpentine enhances pronouncedly the total electrical conductivity, through which highly conductive layers (HCL) may be formed in the earth’s interior.     

Convection at the melting point: A thermal history of the earth's core

Abstract

Higgins and Kennedy (1971) concluded that the Earth's fluid core has a stable stratification if it is at its melting point. Busse (1972) and Elsasser suggested as an alternative that a hydrostatic-isentropic distribution of particulate solid can produce neutral stability in a partially molten core. Here this suggestion is quantified and a determination is made of the efficiency of the production of fluid motion from the heat flux. This is used to establish that macroscopic convection can exist only if the particulate solid is of sufficiently small size. A thermal history of the core compatible with upper mantle heat flux is advanced in which it is suggested that the inner core is a fairly recent feature. The implication of these results for convection-driven and precession-driven dynamos is that both can function for a small enough suspended particulate, that the convection-dynamo will fail for particles greater than one micron in diameter, and that the precession-driven dynamo probably cannot survive particles greater than ten microns in diameter.     

高温高压下角闪片麻岩的电导率研究

在1.0 GPa压力、343～962 K温度和0.1～106Hz频率的条件下,使用Solartron 1260阻抗-增益/相位分析仪对含角闪石的片麻岩从平行和垂直面理两个不同方向分别进行了电阻抗的测定,并且进一步分析了片麻岩的微观导电机制.高温高压实验结果表明:片麻岩的复阻抗对温度、频率表现出明显的依赖性.片麻岩的电导...     

Experimental studies on elastic and rheological properties of amphibolites at high pressure and high temperature

The experimental studies done at high temperature and high pressure find that increased temperature can lead to dramatic velocity and strength reductions of most of rocks at high confining pressure[1,2]. What causes this phenomenon? Is it due to dehydrati…     

高温高压下地幔岩和苦橄质榴辉岩的电导率实验

为了探讨地幔岩模型和苦橄质榴辉岩模型在上地幔存在的合理性,建立上地幔的电性结构,本文利用YJ-3000t紧装式六面顶压机和Solartron IS-1260阻抗/增益-相位分析仪,在1.0~4.0 GPa、700~1150℃的条件下,采用交流阻抗谱法(频率范围10-1~106 Hz)分别测量了地幔岩和苦橄质榴辉岩的电导率.实验结果表明:随着温度的升高,地幔岩和苦橄质榴辉岩的电导率大幅增加;随着压力的增大,地幔岩的电导率略有增加,活化体积ΔV为-4.73 cm3·mol-1,而苦橄质榴辉岩的电导率几乎没有变化,活化体积ΔV为-0.11 cm3·mol-1;在电性方面,用苦橄质榴辉岩来表示深部的物质较为合理,地幔岩解释浅部可能更恰当,但浅部物质的分布不均匀,电导率随深度的变化主要受控于温度的影响,其次才是成分.     

Fugacity-concentration relationship of dilute hydrogen in water at elevated temperature and pressure

The fugacity vs. concentration ratio(Y) of dilute hydrogen dissolved in water was determined at temperatures below 500°C and pressures below 1000 bar by measuring H₂ concentrations in magnetite-hematite-water and palladium hydride-water systems. Combining these results with reported solubility data of H₂ in water and with the Shaw's expression for the activity-composition relationship of H₂H₂O mixture at higher temperatures, theP-T-Y diagram was constructed over theP-T range below 900°C and 1000 bar.     

高温高压条件下纳米材料强度的测试和分析方法

基于高温高压同步辐射X射线衍射和飞行时间中子衍射实验,我们提出了一种通过衍射研究纳米材料本征力学性能的方法.实验通过高压压缩实验对纳米晶和微米晶Ni的变形行为进行了对比研究;二者在不同压力下的晶胞体积数据表明,纳米晶Ni具有明显的弹性软化现象,体弹模量比微米晶Ni减小约10%.研究结果表明,纳米晶Ni的整体抗压缩性减小是由于该材料纳米晶壳层呈现为张应力状态,具有较低的抗压缩性,这与分子动力学模拟结果一致.基于该方法,通过定量分析衍射峰的宽化和偏移,我们可以获得晶粒之间的高应力聚集区所产生的"微观/局部"屈服,以及整个样品在应力下所产生的"宏观/整体"屈服.我们的应变/应力图形分析方法还可以研究材料的屈服强度、高温高压条件下的晶粒破碎/长大、加工硬化/软化,以及多晶体中的固有残余/表面应变.本文提出的方法可以用于岩石矿物的高温高压流变强度的定量测定,为研究岩石圈以及地幔物质的蠕变对流提供了高科技的研究手段.     

First-principles calculations of elasticity of minerals at high temperature and pressure

The elasticity of minerals at high temperature and pressure(PT) is critical for constraining the composition and temperature of the Earth's interior and understand better the deep water cycle and the dynamic Earth. First-principles calculations without introducing any adjustable parameters, whose results can be comparable to experimental data, play a more and more important role in investigating the elasticity of minerals at high PT mainly because of(1) the quick increasing of computational powers and(2) advances in method. For example, the new method reduces the computation loads to one-tenth of the traditional method with the comparable precise as the traditional method. This is extraordinarily helpful because first-principles calculations of the elasticity of minerals at high PT are extremely time-consuming. So far the elasticity of most of lower mantle minerals has been investigated in detail. We have good idea on the effect of temperature, pressure, and iron concentration on elasticity of main minerals of the lower mantle and the unusual softening in bulk modulus by the spin crossover of iron in ferropericlase. With these elastic data the lower mantle has been constrained to have 10–15 wt% ferropericlase, which is sufficient to generate some visible effects of spin crossover in seismic tomography. For example, the spin crossover causes that the temperature sensitivity of P wave at the depth of ~1700 km is only a fraction of that at the depth of ~2300 km. The disruptions of global P wave structure and of P wave image below hotspots such as Hawaii and Iceland at similar depth are in consistence with the spin crossover effect of iron in ferropericlase. The spin crossover, which causes anomalous thermodynamic properties of ferropericlase, has also been found to play a control role for the two features of the large low shear velocity provinces(LLSVPs): the sharp edge and high elevation up to 1000 km above core-mantle boundary. All these results clearly suggest the spin crossover of iron in the lower mantle. The theoretical investigations for the elasticity of minerals at the upper mantle and water effect on elasticity of minerals at the mantle transition zone and subducting slab have also been conducted extensively. These researches are critical for understanding better the composition of the upper mantle and water distribution and transport in the Earth's mantle. Most of these were static calculations, which did not include the vibrational(temperature) effect on elasticity, although temperature effect on elasticity is basic because of high temperature at the Earth's interior and huge temperature difference between the ambient mantle and the subducting slab. Including temperature effect on elasticity of minerals should be important future work. New method developed is helpful for these directions. The elasticity of iron and iron-alloy with various light elements has also been calculated extensively. However, more work is necessary in order to meet the demand for constraining the types and amount of light elements at the Earth's core.     

高温高压下斜长角闪岩电导率研究及其地球物理启示

中下地壳和俯冲带区域的高电导率异常（0.01~1 S·m^-1）可能与地球内部的特定物质及其变化有关.斜长角闪岩是中下地壳以及俯冲带区域的重要组成之一,高温高压下斜长角闪岩的电导率研究对认识电导率异常具有重要意义.本研究采用交流阻抗谱法,在0.5,1.0,1.5 GPa和473~1073 K条件下测量了天然斜长角闪岩样品的复阻抗,实验结果表明压力对斜长角闪岩的电导率影响非常小,而温度对于电导率影响非常显著,其电导率在1073 K可以达到10^-0.5 S·m^-1;实验获得的活化能值为52.21 kJ·mol^-1,推断其导电机制可能为小极化子传导（Fe²⁺的氧化）主导.结合本实验获得的结果与大陆岩石圈和俯冲带的温度结构,我们计算得到相应的电性结构剖面,并与三种不同构造背景下的大陆岩石圈（克拉通、大陆裂谷和活动造山带）和俯冲带区域的电磁剖面结构进行了对比研究,结果发现斜长角闪岩可以解释大陆裂谷和活动造山带构造背景下的莫霍面附近的高电导率异常现象,同时可能是导致较热的俯冲带区域（例如卡斯卡迪地区）高电导率异常现象的原因.     

高温高压下斜长角闪岩电导率研究及其地球物理启示

中下地壳和俯冲带区域的高电导率异常（0.01~1 S·m^-1）可能与地球内部的特定物质及其变化有关.斜长角闪岩是中下地壳以及俯冲带区域的重要组成之一,高温高压下斜长角闪岩的电导率研究对认识电导率异常具有重要意义.本研究采用交流阻抗谱法,在0.5,1.0,1.5 GPa和473~1073 K条件下测量了天然斜长角闪岩样品的复阻抗,实验结果表明压力对斜长角闪岩的电导率影响非常小,而温度对于电导率影响非常显著,其电导率在1073 K可以达到10^-0.5 S·m^-1;实验获得的活化能值为52.21 kJ·mol^-1,推断其导电机制可能为小极化子传导（Fe²⁺的氧化）主导.结合本实验获得的结果与大陆岩石圈和俯冲带的温度结构,我们计算得到相应的电性结构剖面,并与三种不同构造背景下的大陆岩石圈（克拉通、大陆裂谷和活动造山带）和俯冲带区域的电磁剖面结构进行了对比研究,结果发现斜长角闪岩可以解释大陆裂谷和活动造山带构造背景下的莫霍面附近的高电导率异常现象,同时可能是导致较热的俯冲带区域（例如卡斯卡迪地区）高电导率异常现象的原因.

     

The experimental studies on electrical con-ductivities and P-wave velocities of anortho-site at high pressure and high temperature

Introduction The measurements of the compressional wave velocity and electrical conductivity of minerals and rocks are of fundamental importance to look into the earths interior, including composition, geotherm, generation and distribution of fluids and melts. Hydrous minerals formed by metamatu-siom are abundant within the earth. Previous studies have been carried out on the dehydration effect on the electrical conductivity and wave velocity of rocks such as serpentine, amphibole, most of whi…     

Potassium partitioning into molten iron alloys at high-pressure: Implications for Earth's core

The partition coefficients of potassium, D_K, between molten sanidine, KAlSi₃O₈, and molten roedderite, K₂Mg₅Si₁₂O₃₀, with FeS-rich alloy and pure Fe metal liquids have been investigated in a multi-anvil press, between 5 and 15 GPa, at a temperature of 2173 K, and at an oxygen fugacity between 0.5 and 3 log units below the iron-wüstite (IW) buffer. No pressure dependence of the D_K coefficients in sulphur-free and sulphur-bearing systems was found within the investigated pressure range. We also observed minor effect of the silicate melt composition for an nbo/t (non-bridging oxygen to tetrahedral cation ratio) higher than 0.8 ± 0.4. In contrast, the partitioning of potassium varies strongly with the metallic phase composition, with an increase of K-solubility in the metallic liquid for high sulphur and oxygen contents.We review all available high-pressure data to obtain reliable D_K coefficients for the interaction between molten silicates and Fe-alloy liquids at pressures and temperatures relevant to those of core formation in a terrestrial magma ocean. The dominant controlling parameters appear to be the temperature and the chemical composition of the metallic phase, with D_K coefficients significantly increased with temperature, and with the sulphur and oxygen contents of the Fe-alloy liquid. Our considerations distinguish two extreme cases, with an S-free or S-bearing iron core, which yield K contents of ∼25 or ∼250 ppm, respectively. These two extreme values have very different consequences for thermal budget models of the Earth's core since its formation.     

Performance of the complete travel-time equation of state at simultaneous high pressure and temperature

The complete travel-time equation of state (CT-EOS) is presented by utilizing thermodynamics relations, such as; $$K_T = K_S (1 + \alpha \gamma T)^{ - 1} , \gamma = \frac{{\alpha K_S }}{{\rho C_P }}, \left. {\frac{{\partial C_P }}{{\partial P}}} \right)_T = - \frac{T}{\rho }\left[ {\alpha ^2 + \left. {\frac{{\partial \alpha }}{{\partial T}}} \right)_P } \right], etc.$$ The CT-EOS enables us to analyze ultrasonic experimental data under simultaneous high pressure and high temperature without introducing any assumption, as long as the density, or thermal expansivity, and heat capacity are also available as functions of temperature at zero pressure. The performance of the CT-EOS was examined by using synthesized travel-time data with random noise of 10^?5 and 10^?4 amplitude up to 4 GPa and 1500 K. Those test conditions are to be met with the newly developed GHz interferometry in a gas medium piston cylinder apparatus. The results suggest that the combination of the CT-EOS and accurate experimental data (10^?4 in travel time) can determine thermodynamic and elastic parameters, as well as their derivatives with unprecedented accuracy, yielding second-order pressure derivatives (?² M/?P ²) of the elastic moduli as well as the temperature derivatives of their first-order pressure derivatives ?² M/?P?T). The completeness of the CT-EOS provides an unambiguous criterion to evaluate the compatibility of empirical EOS with experimental data. Furthermore because of this completeness, it offers the possibility of a new and absolute pressure calibration when X-ray (i.e., volume) measurements are made simultaneously with the travel-time measurements.     

Disproportionation of kyanite to corundum plus stishovite at high pressure and temperature

Natural kyanite (Al₂SiO₅) has been found to disproportionate into a mixture of its component oxides, corundum and stishovite, at a loading pressure of about 160 kbar and temperature between 1000–1400°C in a diamond-anvil press. The exact transition pressure is not certain due to transient increases in pressure during the local and rapid heating by a continuous YAG laser. The phase boundary, however, has been estimated to be P(kbar) = (138 ～ 174) + 0.011 T (°C) on the basis of the available thermodynamic data. The shock-wave Hugoniot data above 650 kbar for andalusite (Al₂SiO₅) and sillimanite (Al₂SiO₅) as starting materials are consistent with the present results.