Water content in the transition zone from electrical conductivity of wadsleyite and ringwoodite

The distribution of water in the Earth's interior reflects the way in which the Earth has evolved, and has an important influence on its material properties. Minerals in the transition zone of the Earth's mantle (from approximately 410 to approximately 660 km depth) have large water solubility, and hence it is thought that the transition zone might act as a water reservoir. When the water content of the transition zone exceeds a critical value, upwelling flow might result in partial melting at approximately 410 km, which would affect the distribution of certain elements in the Earth. However, the amount of water in the transition zone has remained unknown. Here we determined the effects of water and temperature on the electrical conductivity of the minerals wadsleyite and ringwoodite to infer the water content of the transition zone. We find that the electrical conductivity of these minerals depends strongly on water content but only weakly on temperature. By comparing these results with geophysically inferred conductivity, we infer that the water content in the mantle transition zone varies regionally, but that its value in the Pacific is estimated to be approximately 0.1-0.2 wt%. These values significantly exceed the estimated critical water content in the upper mantle, suggesting that partial melting may indeed occur at approximately 410 km depth, at least in this region.     

Seismic evidence of negligible water carried below 400-km depth in subducting lithosphere

Strong evidence exists that water is carried from the surface into the upper mantle by hydrous minerals in the uppermost 10-12?km of subducting lithosphere, and more water may be added as the lithosphere bends and goes downwards. Significant amounts of that water are released as the lithosphere heats up, triggering earthquakes and fluxing arc volcanism. In addition, there is experimental evidence for high solubility of water in olivine, the most abundant mineral in the upper mantle, for even higher solubility in olivine's high-pressure polymorphs, wadsleyite and ringwoodite, and for the existence of dense hydrous magnesium silicates that potentially could carry water well into the lower mantle (deeper than 1,000?km). Here we compare experimental and seismic evidence to test whether patterns of seismicity and the stabilities of these potentially relevant hydrous phases are consistent with a wet lithosphere. We show that there is nearly a one-to-one correlation between dehydration of minerals and seismicity at depths less than about 250?km, and conclude that the dehydration of minerals is the trigger of instability that leads to seismicity. At greater depths, however, we find no correlation between occurrences of earthquakes and depths where breakdown of hydrous phases is expected. Lastly, we note that there is compelling evidence for the existence of metastable olivine (which, if present, can explain the distribution of deep-focus earthquakes) west of and within the subducting Tonga slab and also in three other subduction zones, despite metastable olivine being incompatible with even extremely small amounts of water (of the order of 100?p.p.m. by weight). We conclude that subducting slabs are essentially dry at depths below 400?km and thus do not provide a pathway for significant amounts of water to enter the mantle transition zone or the lower mantle.     

An experimental study of phase transformations in olivine under pressure and temperature conditions corresponding to the mantle transition zone

High-pressure polymorphs of olivine (wadsleyite and ringwoodite) are major minerals in the mantle transition zone (MTZ).Phase transformations in olivine are important for a series of geodynamic problems such as the mineralogical and evolutionary history of the mantle,mantle convection patterns,and deep focus earthquakes in subduction zones.In this study,we examine phase transformations in olivine with two compositions,namely Mg 2 SiO 4 (Fo 100) and (Mg 0.9 Fe 0.1) 2 SiO 4 (Fo 90),at pressures between 14.1 and 20 GPa and a constant temperature of 1400°C,using the newly installed multi-anvil system at the Laboratory for Studies of the Earth’s Deep Interior (SEDI),China University of Geosciences (Wuhan).At 14.1 GPa,Fo 90 transformed completely into the wadsleyite structure (β),while Fo 100 remained as olivine (α).Between 14.8 and 15.6 GPa,both Fo 100 and Fo 90 transformed into the wadsleyite structure.Wadsleyite crystals were identified by two characteristic Raman peaks between 722 and 723 and 917 and 919 cm 1.They exhibit a bimodal grain size distribution:large-crystals with average grain sizes greater than 100 μm and microcrystals less than 10 μm.The population of microcrystals increased with pressure,apparently due to the increase in over-pressure (the difference between the experimental pressure condition and the equilibrium transformation pressure at 1400°C),which promotes nucleation and retards grain growth.All run charges contained large numbers of wadsleyite microcrystals,because of the low activation energy of the nucleation process.The experimentally observed microstructure may shed light on the morphology of wadsleyite observed in shocked meteorites.At 19.5 GPa,wadsleyite coexisted with ringwoodite (γ) in Fo 100,but was absent in Fo 90.At 20 GPa,both samples transformed completely into ringwoodite,which was characterized by the 798 and 840 cm 1 Raman lines.Ringwoodite crystals are euhedral grains (average grain size 10-20 μm),with well-developed triple junctions.The complex upper mantle structure in eastern China determined from seismological studies cannot be explained by the simple transformation sequence of the olivine system alone.Phase transformations in other pyroxene-normative components (including pyroxenes and garnets) and the interaction of these components with olivine may be responsible for the complex structure.High-pressure and high-temperature experimental studies on complex systems (e.g.olivine-pyroxene),combined with data from geophysical exploration,may help in establishing a more realistic geological-petrological model for eastern China and further our understanding of the possible physical mechanisms that are responsible for the complex structure.Such studies will have profound implications for understanding the dynamic processes in the deep Earth interior.     

Sound velocities of majorite garnet and the composition of the mantle transition region

The composition of the mantle transition region, characterized by anomalous seismic-wave velocity and density changes at depths of approximately 400 to 700 km, has remained controversial. Some have proposed that the mantle transition region has an olivine-rich 'pyrolite' composition, whereas others have inferred that it is characterized by pyroxene- and garnet-rich compositions ('piclogite'), because the sound velocities in pyrolite estimated from laboratory data are substantially higher than those seismologically observed. Although the velocities of the olivine polymorphs at these pressures (wadsleyite and ringwoodite) have been well documented, those of majorite (another significant high-pressure phase in the mantle transition region) with realistic mantle compositions have never been measured. Here we use combined in situ X-ray and ultrasonic measurements under the pressure and temperature conditions of the mantle transition region to show that majorite in a pyrolite composition has sound velocities substantially lower than those of earlier estimates, owing to strong nonlinear decreases at high temperature, particularly for shear-wave velocity. We found that pyrolite yields seismic velocities more consistent with typical seismological models than those of piclogite in the upper to middle parts of the region, except for the potentially larger velocity jumps in pyrolite relative to those observed at a depth of 410 km. In contrast, both of these compositions lead to significantly low shear-wave velocities in the lower part of the region, suggesting possible subadiabatic temperatures or the existence of a layer of harzburgite-rich material supplied by the subducted slabs stagnant at these depths.     

High-pressure polymorphs of olivine and the 660-km seismic discontinuity

It had long been accepted that the 400-km seismic discontinuity in the Earth's mantle results from the phase transition of (Mg,Fe)2-SiO4-olivine to its high-pressure polymorph beta-spinel (wadsleyite), and that the 660-km discontinuity results from the breakdown of the higher-pressure polymorph gamma-spinel (ringwoodite) to MgSiO3-perovskite and (Mg,Fe)O-magnesiowüstite. An in situ multi-anvil-press X-ray study indicated, however, that the phase boundary of the latter transition occurs at pressures 2 GPa lower than had been found in earlier studies using multi-anvil recovery experiments and laser-heated diamond-anvil cells. Such a lower-pressure phase boundary would be irreconcilable with the accuracy of seismic measurements of the 660-km discontinuity, and would thus require a mineral composition of the mantle that is significantly different from what is currently thought. Here, however, we present measurements made with a laser-heated diamond-anvil cell which indicate that gamma-Mg2SiO4 is stable up to pressure and temperature conditions equivalent to 660-km depth in the Earth's mantle (24 GPa and 1,900 K) and then breaks down into MgSiO3-perovskite and MgO (periclase). We paid special attention to pressure accuracy and thermal pressure in our experiments, and to ensuring that our experiments were performed under nearly hydrostatic, inert pressure conditions using a variety of heating methods. We infer that these factors are responsible for the different results obtained in our experiments compared to the in situ multi-anvil-press study.     

The effect of water on the electrical conductivity of olivine

It is well known that water (as a source of hydrogen) affects the physical and chemical properties of minerals--for example, plastic deformation and melting temperature--and accordingly plays an important role in the dynamics and geochemical evolution of the Earth. Estimating the water content of the Earth's mantle by direct sampling provides only a limited data set from shallow regions (<200 km depth). Geophysical observations such as electrical conductivity are considered to be sensitive to water content, but there has been no experimental study to determine the effect of water on the electrical conductivity of olivine, the most abundant mineral in the Earth's mantle. Here we report a laboratory study of the dependence of the electrical conductivity of olivine aggregates on water content at high temperature and pressure. The electrical conductivity of synthetic polycrystalline olivine was determined from a.c. impedance measurements at a pressure of 4 GPa for a temperature range of 873-1,273 K for water contents of 0.01-0.08 wt%. The results show that the electrical conductivity is strongly dependent on water content but depends only modestly on temperature. The water content dependence of conductivity is best explained by a model in which electrical conduction is due to the motion of free protons. A comparison of the laboratory data with geophysical observations suggests that the typical oceanic asthenosphere contains approximately 10(-2) wt% water, whereas the water content in the continental upper mantle is less than approximately 10(-3) wt%.     

矿物电导率Meyer-Neldel补偿规律及其应用研究

大量矿物电导率数据分析表明,矿物电导率存在Meyer-Neldel补偿规律,即同一矿物在不同物理、化学条件下测得电导率有很大差异,但其指前因子和活化能之间存在良好的线性关系.基于矿物电导率补偿规律,形成了从矿物电导率计算元素扩散系数的新方法,其计算结果与实验扩散数据符合较好.利用钙钛矿的电导率补偿关系,结合电磁测深结果,亦能获得更合理的地球深内部电导率结构.     

Earth science: a wet mantle conductor?

The suggestion that the transition zone of Earth's mantle (410-670 km in depth) is enriched in water is of great possible significance to the geodynamics and geochemistry of Earth's interior, as well as for the role of the mantle in the global water cycle. Huang et al. compare the effect of water on electrical conductivities of transition-zone phases to electromagnetic and magnetotelluric soundings of the mantle beneath the North Pacific and conclude that the transition zone contains between 1,000 and 2,000 p.p.m. of water, which is considerably more than the 50-200 p.p.m. present in the upper mantle. This conclusion is predicated on the assumption that the transition zone is relatively oxidized, but in fact fairly reduced conditions are more likely. Here I show that if the transition zone is reduced, high conductivities can be explained without the requirement for large enrichments of water.     

Low-velocity zone atop the 410-km seismic discontinuity in the northwestern United States

The seismic discontinuity at 410 km depth in the Earth's mantle is generally attributed to the phase transition of (Mg,Fe)2SiO4 (refs 1, 2) from the olivine to wadsleyite structure. Variation in the depth of this discontinuity is often taken as a proxy for mantle temperature owing to its response to thermal perturbations. For example, a cold anomaly would elevate the 410-km discontinuity, because of its positive Clapeyron slope, whereas a warm anomaly would depress the discontinuity. But trade-offs between seismic wave-speed heterogeneity and discontinuity topography often inhibit detailed analysis of these discontinuities, and structure often appears very complicated. Here we simultaneously model seismic refracted waves and scattered waves from the 410-km discontinuity in the western United States to constrain structure in the region. We find a low-velocity zone, with a shear-wave velocity drop of 5%, on top of the 410-km discontinuity beneath the northwestern United States, extending from southwestern Oregon to the northern Basin and Range province. This low-velocity zone has a thickness that varies from 20 to 90 km with rapid lateral variations. Its spatial extent coincides with both an anomalous composition of overlying volcanism and seismic 'receiver-function' observations observed above the region. We interpret the low-velocity zone as a compositional anomaly, possibly due to a dense partial-melt layer, which may be linked to prior subduction of the Farallon plate and back-arc extension. The existence of such a layer could be indicative of high water content in the Earth's transition zone.     

Electromagnetic detection of a 410-km-deep melt layer in the southwestern United States

A deep-seated melt or fluid layer on top of the 410-km-deep seismic discontinuity in Earth's upper mantle, as proposed in the transition-zone 'water filter' hypothesis, may have significant bearing on mantle dynamics and chemical differentiation. The geophysical detection of such a layer has, however, proved difficult. Magnetotelluric and geomagnetic depth sounding are geophysical methods sensitive to mantle melt. Here we use these methods to search for a distinct structure near 410-km depth. We calculate one-dimensional forward models of the response of electrical conductivity depth profiles, based on mineral physics studies of the effect of incorporating hydrogen in upper-mantle and transition-zone minerals. These models indicate that a melt layer at 410-km depth is consistent with regional magnetotelluric and geomagnetic depth sounding data from the southwestern United States (Tucson). The 410-km-deep melt layer in this model has a conductance of 3.0 x 10(4) S and an estimated thickness of 5-30 km. This is the only regional data set that we have examined for which such a melt layer structure was found, consistent with regional seismic studies. We infer that the hypothesized transition-zone water filter occurs regionally, but that such a layer is unlikely to be a global feature.     

Multiple seismic discontinuities near the base of the transition zone in the Earth's mantle

The seismologically defined boundary between the transition zone in the Earth's mantle (410-660 km depth) and the underlying lower mantle is generally interpreted to result from the breakdown of the gamma-spinel phase of olivine to magnesium-perovskite and magnesiowustite. Laboratory measurements of these transformations of olivine have determined that the phase boundary has a negative Clapeyron slope and does indeed occur near pressures corresponding to the base of the transition zone. But a computational study has indicated that, because of the presence of garnet minerals, multiple seismic discontinuities might exist near a depth of 660 km (ref. 4), which would alter the simple negative correlation of changes in temperature with changes in the depth of the phase boundary. In particular, garnet minerals undergo exothermic transformations near this depth, acting to complicate the phase relations and possibly effecting mantle convection processes in some regions. Here we present seismic evidence that supports the existence of such multiple transitions near a depth of 660 km beneath southern California. The observations are consistent with having been generated by garnet transformations coupling with the dissociation of the gamma-spinel phase of olivine. Temperature anomalies calculated from the imaged discontinuity depths--using Clapeyron slopes determined for the various transformations--generally match those predicted from an independent P-wave velocity model of the region.     

双掺杂钙钛矿型复合氧化物La_(0.7)Sr_(0.3)Co_(1-x)M_xO_3的电性能研究

以开发新型激光器阴极材料和固体氧化物燃料电池阴极材料为目的 ,合成一系列钙钛矿型复合氧化物 La0 .7Sr0 .3 Co1- x Mx O3 ( M:过渡族金属元素 ) ,并对 Co位掺杂过渡族元素后样品的高温电阻率和热电动势进行研究 ,发现 Co位掺杂不同元素显著影响材料的电导率和导电类型 ,并对其相应的物理机制进行探讨 .     

固井水泥浆水化早期阶段水状态与电导率关系

油气井固井早期气窜现象常发生于固井水泥浆液固态转变阶段，准确掌握该阶段水泥浆的组织结构是探究固井早期气窜机理的关键。电导率方法是评价水泥浆水化进程及微观结构的有效方法之一。为此，利用电感式电导率仪研究了固井水泥浆沉降稳定性、水化速率对其电导率的影响；结合质量守恒定理和低场核磁共振技术，探究了水化早期阶段水泥浆中水状态与其电导率的关系。实验发现，在新配水泥浆中，孔溶液离子浓度和孔隙结构分布决定了水泥浆的初始电导率；随着水泥浆沉降稳定性的增加，水泥浆中孔结构分布更均匀，使其初始电导率由16.8 mS/cm增加至19.4 mS/cm；随水泥浆水化进程增加，水泥颗粒表面及孔隙中水化产物的形成改变了水泥浆的固相微观结构及孔隙结构，使分布于大孔隙中的自由水转变为小孔隙中的毛细水、凝胶水。实验结果表明，在水化早期阶段水泥浆的电导率与蒸发水、自由水含量呈线性关系。     

Stability of hydrous melt at the base of the Earth's upper mantle

Seismological observations have revealed the existence of low-velocity and high-attenuation zones above the discontinuity at 410 km depth, at the base of the Earth's upper mantle. It has been suggested that a small amount of melt could be responsible for such anomalies. The density of silicate melt under dry conditions has been measured at high pressure and found to be denser than the surrounding solid, thereby allowing the melt to remain at depth. But no experimental investigation of the density of hydrous melt has yet been carried out. Here we present data constraining the density of hydrous basaltic melt under pressure to examine the stability of melt above the 410-km discontinuity. We infer that hydrous magma formed by partial melting above the 410-km discontinuity may indeed be gravitationally stable, thereby supporting the idea that low-velocity or high-attentuation regions just above the mantle transition zone may result from the presence of melt.     

The distribution of water in the continental lithospheric mantle and its implications for the stability of continents

The lithospheric mantle is one of the key layers controlling the stability of continents. Even a small amount of water can influence many chemical and physical properties of rocks and minerals. Consequently, it is a pivotal task to study the distribution of water in the continental lithosphere. This paper presents a brief overview of the current state of knowledge about (1) the occurrence of water in the continental lithospheric mantle, (2) the spatial and temporal variations of the water content in the continental lithospheric mantle, and (3) the relationship between water content and continent stability. Additionally, suggestions for future research directions are briefly discussed.     

Faulting induced by precipitation of water at grain boundaries in hot subducting oceanic crust

Dehydration embrittlement has been proposed to explain both intermediate- and deep-focus earthquakes in subduction zones. Because such earthquakes primarily occur at shallow depths or within the core of the subducting plate, dehydration at relatively low temperatures has been emphasized. However, recent careful relocation of subduction-zone earthquakes shows that at depths of 100-250 km, earthquakes continue in the uppermost part of the slab (probably the former oceanic crust that has been converted to eclogite) where temperatures are higher. Here we show that at such pressures and temperatures, eclogite lacking hydrous phases but with significant hydroxyl incorporated as defects in pyroxene and garnet develops a faulting instability associated with precipitation of water at grain boundaries and the production of very small amounts of melt. This new faulting mechanism satisfactorily explains high-temperature earthquakes in subducting oceanic crust and could potentially be involved in much deeper earthquakes in connection with similar precipitation of water in the mantle transition zone (400-700 km depth). Of potential importance for all proposed high-pressure earthquake mechanisms is the very small amount of fluid required to trigger this instability.     

大陆下地壳和岩石圈地幔中的水:基于捕虏体的红外光谱分析

根据对华北克拉通汉诺坝和女山两个捕虏体产地的麻粒岩和橄榄岩的FTIR实验测定,分析讨论了大陆深部岩石圈内水含量和分布上的一些显著特点.结果表明,大陆下地壳和岩石圈内矿物的水含量无论在横向还是垂向分布上都是明显不均一的,造成这些不均一性的机制可能复杂多样.     

Resistance to mantle flow inferred from the electromagnetic strike of the Australian upper mantle

Seismic anisotropy is thought to result from the strain-induced lattice-preferred orientation of mantle minerals, especially olivine, owing to shear waves propagating faster along the a-axis of olivine crystals than along the other axes. This anisotropy results in birefringence, or 'shear-wave splitting', which has been investigated in numerous studies. Although olivine is also anisotropic with respect to electrical conductivity (with the a-axis being most conductive), few studies of the electrical anisotropy of the upper mantle have been undertaken, and these have been limited to relatively shallow depths in the lithospheric upper mantle. Theoretical models of mantle flow have been used to infer that, for progressive simple shear imparted by the motion of an overriding tectonic plate, the a-axes of olivine crystals should align themselves parallel to the direction of plate motion. Here, however, we show that a significant discrepancy exists between the electromagnetic strike of the mantle below Australia and the direction of present-day absolute plate motion. We infer from this discrepancy that the a-axes of olivine crystals are not aligned with the direction of the present-day plate motion of Australia, indicating resistance to deformation of the mantle by plate motion.     

Hydrous olivine unable to account for conductivity anomaly at the top of the asthenosphere

The oceanic asthenosphere is observed to have high electrical conductivity, which is highly anisotropic in some locations. In the directions parallel and normal to the plate motion, the conductivity is of the order of 10(-1) and 10(-2) S m(-1), respectively, which cannot be explained by the conductivity of anhydrous olivine. But because hydrogen can be incorporated in olivine at mantle pressures, this observation has been attributed to olivine hydration, which might cause anisotropically high conductivity by proton migration. To examine this hypothesis, here we report the effect of water on electrical conductivity and its anisotropy for hydrogen-doped and undoped olivine at 500-1,500 K and 3 GPa. The hydrous olivine has much higher conductivity and lower activation energy than anhydrous olivine in the investigated temperature range. Nevertheless, extrapolation of the experimental results suggests that conductivity of hydrous olivine at the top of the asthenosphere should be nearly isotropic and only of the order of 10(-2) S m(-1). Our data indicate that the hydration of olivine cannot account for the geophysical observations, which instead may be explained by the presence of partial melt elongated in the direction of plate motion.     

Experimental measurement of the electrical conductivity of single crystal olivine at high temperature and high pressure under different oxygen fugacities

At 1.0?4.0 GPa and 1123?1473 K and under oxygen fugacity-controlled conditions (Ni+NiO, Fe+Fe₃O₄, Fe+FeO and Mo+MoO₂ buffers), a YJ-3000t Model six-anvil solid high-pressure apparatus and a Sarltron-1260 Impedance/Gain-Phase analyzer were employed to conduct an in situ measurement of the electrical conductivity of single crystal olivine. Experimental results showed that: (1) within the range of experimentally selected frequencies (10³?10⁶ Hz), the electrical conductivity of the sample is of great dependence on the frequency; (2) with the rise of temperature (T), the electrical conductivity (σ) will increase, and the Arrenhius linear relationship is established between lgσ and 1/T; (3) under the control of oxygen buffer Fe+Fe₃O₄, with the rise of pressure, the electrical conductivity tends to decrease whereas the activation enthalpy and independent-of-temperature preexponential factor tend to increase, with the activation energy and activation volume of the sample estimated at (1.25±0.08) eV and (0.105±0.025) cm³/mol, respectively; (4) under given pressure and temperature conditions, the electrical conductivity tends to increase whereas the activation energy tends to decrease with increasing oxygen fugacity; and (5) the mechanism of electrical conduction of small polarons can provide insight into the behavior of electrical conduction of olivine under high pressure and high temperature.