Evidence for a late chondritic veneer in the Earth's mantle from high-pressure partitioning of palladium and platinum

The high-pressure solubility in silicate liquids of moderately siderophile 'iron-loving' elements (such as nickel and cobalt) has been used to suggest that, in the early Earth, an equilibrium between core-forming metals and the silicate mantle was established at the bottom of a magma ocean. But observed concentrations of the highly siderophile elements--such as the platinum-group elements platinum, palladium, rhenium, iridium, ruthenium and osmium--in the Earth's upper mantle can be explained by such a model only if their metal-silicate partition coefficients at high pressure are orders of magnitude lower than those determined experimentally at one atmosphere (refs 3-8). Here we present an experimental determination of the solubility of palladium and platinum in silicate melts as a function of pressure to 16 GPa (corresponding to about 500 km depth in the Earth). We find that both the palladium and platinum metal-silicate partition coefficients, derived from solubility, do not decrease with pressure--that is, palladium and platinum retain a strong preference for the metal phase even at high pressures. Consequently the observed abundances of palladium and platinum in the upper mantle seem to be best explained by a 'late veneer' addition of chondritic material to the upper mantle following the cessation of core formation.     

Vapour undersaturation in primitive mid-ocean-ridge basalt and the volatile content of Earth's upper mantle

The analysis of volatiles in magmatic systems can be used to constrain the volatile content of the Earth's mantle and the influence that magmatic degassing has on the chemistry of the oceans and the atmosphere. But most volatile elements have very low solubilities in magmas at atmospheric pressure, and therefore virtually all erupted lavas are degassed and do not retain their primary volatile signatures. Here we report the undersaturated pre-eruptive volatile content for a suite of mid-ocean-ridge basalts from the Siqueiros intra-transform spreading centre. The undersaturation leads to correlations between volatiles and refractory trace elements that provide new constraints on volatile abundances and their behaviour in the upper mantle. Our data generate improved limits on the abundances of carbon dioxide, water, fluorine, sulphur and chlorine in the source of normal mid-ocean-ridge basalt. The incompatible behaviour of carbon dioxide, together with the CO(2)/Nb and CO(2)/Cl ratios, permit estimates of primitive carbon dioxide and chlorine to be made for degassed and chlorine-contaminated mid-ocean-ridge basalt magmas, and hence constrain degassing and contamination histories of mid-ocean ridges.     

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.     

40Ar retention in the terrestrial planets

The solid Earth is widely believed to have lost its original gases through a combination of early catastrophic release and regulated output over geologic time. In principle, the abundance of 40Ar in the atmosphere represents the time-integrated loss of gases from the interior, thought to occur through partial melting in the mantle followed by melt ascent to the surface and gas exsolution. Here we present data that reveal two major difficulties with this simple magmatic degassing scenario--argon seems to be compatible in the major phases of the terrestrial planets, and argon diffusion in these phases is slow at upper-mantle conditions. These results challenge the common belief that the upper mantle is nearly degassed of 40Ar, and they call into question the suitability of 40Ar as a monitor of planetary degassing. An alternative to magmatism is needed to release argon to the atmosphere, with one possibility being hydration of oceanic lithosphere consisting of relatively argon-rich olivine and orthopyroxene.     

Anisotropy of thermal diffusivity in the upper mantle.

Heat transfer in the mantle is a key process controlling the Earth's dynamics. Upper-mantle mineral phases, especially olivine, have been shown to display highly anisotropic thermal diffusivity at ambient conditions, and seismic anisotropy data show that preferred orientations of olivine induced by deformation are coherent at large scales (>50 km) in the upper mantle. Thus heat transport in the upper mantle should be anisotropic. But the thermal anisotropy of mantle minerals at high temperature and its relationship with deformation have not been well constrained. Here we present petrophysical modelling and laboratory measurements of thermal diffusivity in deformed mantle rocks between temperatures of 290 and 1,250 K that demonstrate that deformation may induce a significant anisotropy of thermal diffusivity in the uppermost mantle. We found that heat transport parallel to the flow direction is up to 30 per cent faster than that normal to the flow plane. Such a strain-induced thermal anisotropy implies that the upper-mantle temperature distribution, rheology and, consequently, its dynamics, will depend on deformation history. In oceans, resistive drag flow would result in lower vertical diffusivities in both the lithosphere and asthenosphere and hence in less effective heat transfer from the convective mantle. In continents, olivine orientations frozen in the lithosphere may induce anisotropic heating above mantle plumes, favouring the reactivation of pre-existing structures.     

Metal saturation in the upper mantle

The oxygen fugacity f(O2)of the Earth's mantle is one of the fundamental variables in mantle petrology. Through ferric-ferrous iron and carbon-hydrogen-oxygen equilibria, f(O2) influences the pressure-temperature positions of mantle solidi and compositions of small-degree mantle melts. Among other parameters, f(O2) affects the water storage capacity and rheology of the mantle. The uppermost mantle, as represented by samples and partial melts, is sufficiently oxidized to sustain volatiles, such as H2O and CO2, as well as carbonatitic melts, but it is not known whether the shallow mantle is representative of the entire upper mantle. Using high-pressure experiments, we show here that large parts of the asthenosphere are likely to be metal-saturated. We found that pyroxene and garnet synthesized at >7 GPa in equilibrium with metallic Fe can incorporate sufficient ferric iron that the mantle at >250 km depth is so reduced that an (Fe,Ni)-metal phase may be stable. Our results indicate that the oxidized nature of the upper mantle can no longer be regarded as being representative for the Earth's upper mantle as a whole and instead that oxidation is a shallow phenomenon restricted to an upper veneer only about 250 km in thickness.     

Kimberlite ascent by assimilation-fuelled buoyancy

Kimberlite magmas have the deepest origin of all terrestrial magmas and are exclusively associated with cratons. During ascent, they travel through about 150 kilometres of cratonic mantle lithosphere and entrain seemingly prohibitive loads (more than 25 per cent by volume) of mantle-derived xenoliths and xenocrysts (including diamond). Kimberlite magmas also reputedly have higher ascent rates than other xenolith-bearing magmas. Exsolution of dissolved volatiles (carbon dioxide and water) is thought to be essential to provide sufficient buoyancy for the rapid ascent of these dense, crystal-rich magmas. The cause and nature of such exsolution, however, remains elusive and is rarely specified. Here we use a series of high-temperature experiments to demonstrate a mechanism for the spontaneous, efficient and continuous production of this volatile phase. This mechanism requires parental melts of kimberlite to originate as carbonatite-like melts. In transit through the mantle lithosphere, these silica-undersaturated melts assimilate mantle minerals, especially orthopyroxene, driving the melt to more silicic compositions, and causing a marked drop in carbon dioxide solubility. The solubility drop manifests itself immediately in a continuous and vigorous exsolution of a fluid phase, thereby reducing magma density, increasing buoyancy, and driving the rapid and accelerating ascent of the increasingly kimberlitic magma. Our model provides an explanation for continuous ascent of magmas laden with high volumes of dense mantle cargo, an explanation for the chemical diversity of kimberlite, and a connection between kimberlites and cratons.     

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.     

Heterogeneous chemistry in the atmosphere of Mars

Hydrogen radicals are produced in the martian atmosphere by the photolysis of water vapour and subsequently initiate catalytic cycles that recycle carbon dioxide from its photolysis product carbon monoxide. These processes provide a qualitative explanation for the stability of the atmosphere of Mars, which contains 95 per cent carbon dioxide. Balancing carbon dioxide production and loss based on our current understanding of the gas-phase chemistry in the martian atmosphere has, however, proven to be difficult. Interactions between gaseous chemical species and ice cloud particles have been shown to be key factors in the loss of polar ozone observed in the Earth's stratosphere, and may significantly perturb the chemistry of the Earth's upper troposphere. Water-ice clouds are also commonly observed in the atmosphere of Mars and it has been suggested previously that heterogeneous chemistry could have an important impact on the composition of the martian atmosphere. Here we use a state-of-the-art general circulation model together with new observations of the martian ozone layer to show that model simulations that include chemical reactions occurring on ice clouds lead to much improved quantitative agreement with observed martian ozone levels in comparison with model simulations based on gas-phase chemistry alone. Ozone is readily destroyed by hydrogen radicals and is therefore a sensitive tracer of the chemistry that regulates the atmosphere of Mars. Our results suggest that heterogeneous chemistry on ice clouds plays an important role in controlling the stability and composition of the martian atmosphere.     

Pressure sensitivity of olivine slip systems and seismic anisotropy of Earth's upper mantle

The mineral olivine dominates the composition of the Earth's upper mantle and hence controls its mechanical behaviour and seismic anisotropy. Experiments at high temperature and moderate pressure, and extensive data on naturally deformed mantle rocks, have led to the conclusion that olivine at upper-mantle conditions deforms essentially by dislocation creep with dominant [100] slip. The resulting crystal preferred orientation has been used extensively to explain the strong seismic anisotropy observed down to 250 km depth. The rapid decrease of anisotropy below this depth has been interpreted as marking the transition from dislocation to diffusion creep in the upper mantle. But new high-pressure experiments suggest that dislocation creep also dominates in the lower part of the upper mantle, but with a different slip direction. Here we show that this high-pressure dislocation creep produces crystal preferred orientations resulting in extremely low seismic anisotropy, consistent with seismological observations below 250 km depth. These results raise new questions about the mechanical state of the lower part of the upper mantle and its coupling with layers both above and below.     

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.     

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.     

Natural examples of olivine lattice preferred orientation patterns with a flow-normal a-axis maximum

Tectonic plate motion is thought to cause solid-state plastic flow within the underlying upper mantle and accordingly lead to the development of a lattice preferred orientation of the constituent olivine crystals. The mechanical anisotropy that results from such preferred orientation typically produces a direction of maximum seismic wave velocity parallel to the plate motion direction. This has been explained by the existence of an olivine preferred orientation with an 'a-axis' maximum parallel to the induced mantle flow direction. In subduction zones, however, the olivine a axes have been inferred to be arranged roughly perpendicular to plate motion, which has usually been ascribed to localized complex mantle flow patterns. Recent experimental work suggests an alternative explanation: under conditions of high water activity, a 'B-type' olivine preferred orientation may form, with the a-axis maximum perpendicular to the flow direction. Natural examples of such B-type preferred orientation are, however, almost entirely unknown. Here we document widespread B-type olivine preferred orientation patterns from a subduction-type metamorphic belt in southwest Japan and show that these patterns developed in the presence of water. Our discovery implies that mantle flow above subduction zones may be much simpler than has generally been thought.     

高温高压条件下甲烷和二氧化碳溶解度试验

根据不同温度和压力条件下测得的甲烷和二氧化碳两种气体在碳酸氢钠型水中的溶解度数据,对两种气体的溶解度与温度、压力及地层水矿化度之间的关系进行研究。结果表明:在地层水中的溶解机制不同,导致两种气体的溶解度值随温度、压力条件的变化具有不同的演变特征;综合前人低温(小于90℃)测试的溶解度数据,可将甲烷溶解度与温度之间的演变关系划分为缓慢递减(0~80℃)、快速递增(80~150℃)和缓慢递增(大于150℃)3个阶段;二氧化碳溶解度随温度的升高而逐渐降低,随压力升高而逐渐增大,其溶解与析离能力受压力影响更为明显;实际地层中,两种气体间溶解度的差异演变影响了天然气的空间分布。     

甘肃西部马鬃山超镁铁质杂岩岩石学地球化学信息及意义

马鬃山岩体在空间上分为有成因联系的两部分，主岩体为具有环状分异特征的辉长岩岩体，中心相为辉长岩，边缘相为闪长岩．主岩体东南子岩体为橄榄二辉岩岩体．赋存于其中的岩石学和地球化学信息暗示马鬃山杂岩体形成于活动大陆边缘张裂构造环境，为应力释放期的产物，岩浆来源于具有E—MORB性质的陆下岩石圈地幔与软流圈的边界。较大程度部分熔融产生的岩浆在上升途中同化了陆壳围岩。     

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%.     

An olivine-free mantle source of Hawaiian shield basalts

More than 50 per cent of the Earth's upper mantle consists of olivine and it is generally thought that mantle-derived melts are generated in equilibrium with this mineral. Here, however, we show that the unusually high nickel and silicon contents of most parental Hawaiian magmas are inconsistent with a deep olivine-bearing source, because this mineral together with pyroxene buffers both nickel and silicon at lower levels. This can be resolved if the olivine of the mantle peridotite is consumed by reaction with melts derived from recycled oceanic crust, to form a secondary pyroxenitic source. Our modelling shows that more than half of Hawaiian magmas formed during the past 1 Myr came from this source. In addition, we estimate that the proportion of recycled (oceanic) crust varies from 30 per cent near the plume centre to insignificant levels at the plume edge. These results are also consistent with volcano volumes, magma volume flux and seismological observations.     

Inhibition of carbonate synthesis in acidic oceans on early Mars

Several lines of evidence have recently reinforced the hypothesis that an ocean existed on early Mars. Carbonates are accordingly expected to have formed from oceanic sedimentation of carbon dioxide from the ancient martian atmosphere. But spectral imaging of the martian surface has revealed the presence of only a small amount of carbonate, widely distributed in the martian dust. Here we examine the feasibility of carbonate synthesis in ancient martian oceans using aqueous equilibrium calculations. We show that partial pressures of atmospheric carbon dioxide in the range 0.8-4 bar, in the presence of up to 13.5 mM sulphate and 0.8 mM iron in sea water, result in an acidic oceanic environment with a pH of less than 6.2. This precludes the formation of siderite, usually expected to be the first major carbonate mineral to precipitate. We conclude that extensive interaction between an atmosphere dominated by carbon dioxide and a lasting sulphate- and iron-enriched acidic ocean on early Mars is a plausible explanation for the observed absence of carbonates.     

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.     

Grain boundaries as reservoirs of incompatible elements in the Earth's mantle

The concentrations and locations of elements that strongly partition into the fluid phase in rocks provide essential constraints on geochemical and geodynamical processes in Earth's interior. A fundamental question remains, however, as to where these incompatible elements reside before formation of the fluid phase. Here we show that partitioning of calcium between the grain interiors and grain boundaries of olivine in natural and synthetic olivine-rich aggregates follows a thermodynamic model for equilibrium grain-boundary segregation. The model predicts that grain boundaries can be the primary storage sites for elements with large ionic radius--that is, incompatible elements in the Earth's mantle. This observation provides a mechanism for the selective extraction of these elements and gives a framework for interpreting geochemical signatures in mantle rocks.