Density of hydrous silicate melt at the conditions of Earth's deep upper mantle

The chemical evolution of the Earth and the terrestrial planets is largely controlled by the density of silicate melts. If melt density is higher than that of the surrounding solid, incompatible elements dissolved in the melt will be sequestered in the deep mantle. Previous studies on dry (water-free) melts showed that the density of silicate melts can be higher than that of surrounding solids under deep mantle conditions. However, melts formed under deep mantle conditions are also likely to contain some water, which will reduce the melt density. Here we present data constraining the density of hydrous silicate melt at the conditions of approximately 410 km depth. We show that the water in the silicate melt is more compressible than the other components, and therefore the effect of water in reducing melt density is markedly diminished under high-pressure conditions. Our study indicates that there is a range of conditions under which a (hydrous) melt could be trapped at the 410-km boundary and hence incompatible elements could be sequestered in the deep mantle, although these conditions are sensitive to melt composition as well as the composition of the surrounding mantle.     

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.     

Spin crossover and iron-rich silicate melt in the Earth's deep mantle

A melt has greater volume than a silicate solid of the same composition. But this difference diminishes at high pressure, and the possibility that a melt sufficiently enriched in the heavy element iron might then become more dense than solids at the pressures in the interior of the Earth (and other terrestrial bodies) has long been a source of considerable speculation. The occurrence of such dense silicate melts in the Earth's lowermost mantle would carry important consequences for its physical and chemical evolution and could provide a unifying model for explaining a variety of observed features in the core-mantle boundary region. Recent theoretical calculations combined with estimates of iron partitioning between (Mg,Fe)SiO(3) perovskite and melt at shallower mantle conditions suggest that melt is more dense than solids at pressures in the Earth's deepest mantle, consistent with analysis of shockwave experiments. Here we extend measurements of iron partitioning over the entire mantle pressure range, and find a precipitous change at pressures greater than ～76?GPa, resulting in strong iron enrichment in melts. Additional X-ray emission spectroscopy measurements on (Mg(0.95)Fe(0.05))SiO(3) glass indicate a spin collapse around 70?GPa, suggesting that the observed change in iron partitioning could be explained by a spin crossover of iron (from high-spin to low-spin) in silicate melt. These results imply that (Mg,Fe)SiO(3) liquid becomes more dense than coexisting solid at ～1,800?km depth in the lower mantle. Soon after the Earth's formation, the heat dissipated by accretion and internal differentiation could have produced a dense melt layer up to ～1,000?km in thickness underneath the solid mantle. We also infer that (Mg,Fe)SiO(3) perovskite is on the liquidus at deep mantle conditions, and predict that fractional crystallization of dense magma would have evolved towards an iron-rich and silicon-poor composition, consistent with seismic inferences of structures in the core-mantle boundary region.     

Aluminium control of argon solubility in silicate melts under pressure

Understanding of the crystal chemistry of the Earth's deep mantle has evolved rapidly recently with the gradual acceptance of the importance of the effect of minor elements such as aluminium on the properties of major phases such as perovskite. In the early Earth, during its formation and segregation into rocky mantle and iron-rich core, it is likely that silicate liquids played a large part in the transport of volatiles to or from the deep interior. The importance of aluminium on solubility mechanisms at high pressure has so far received little attention, even though aluminium has long been recognized as exerting strong control on liquid structures at ambient conditions. Here we present constraints on the solubility of argon in aluminosilicate melt compositions up to 25 GPa and 3,000 K, using a laser-heated diamond-anvil cell. The argon contents reach a maximum that persists to pressures as high as 17 GPa (up to 500 km deep in an early magma ocean), well above that expected on the basis of Al-free melt experiments. A distinct drop in argon solubility observed over a narrow pressure range correlates well with the expected void loss in the melt structure predicted by recent molecular dynamics simulations. These results provide a process for noble gas sequestration in the mantle at various depths in a cooling magma ocean. The concept of shallow partial melting as a unique process for extracting noble gases from the early Earth, thereby defining the initial atmospheric abundance, may therefore be oversimplified.     

Dry mantle transition zone inferred from the conductivity of wadsleyite and ringwoodite

The Earth's mantle transition zone could potentially store a large amount of water, as the minerals wadsleyite and ringwoodite incorporate a significant amount of water in their crystal structure. The water content in the transition zone can be estimated from the electrical conductivities of hydrous wadsleyite and ringwoodite, although such estimates depend on accurate knowledge of the two conduction mechanisms in these minerals (small polaron and proton conductions), which early studies have failed to distinguish between. Here we report the electrical conductivity of these two minerals obtained by high-pressure multi-anvil experiments. We found that the small polaron conductions of these minerals are substantially lower than previously estimated. The contributions of proton conduction are small at temperatures corresponding to the mantle transition zone and the conductivity of wadsleyite is considerably lower than that of ringwoodite for both mechanisms. The dry model mantle shows considerable conductivity jumps associated with the olivine-wadsleyite, wadsleyite-ringwoodite and post-spinel transitions. Such a dry model explains well the currently available conductivity-depth profiles obtained from geoelectromagnetic studies. We therefore conclude that there is no need to introduce a significant amount of water in the mantle transition to satisfy electrical conductivity constraints.     

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.     

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.     

Primary carbonatite melt from deeply subducted oceanic crust

Partial melting in the Earth's mantle plays an important part in generating the geochemical and isotopic diversity observed in volcanic rocks at the surface. Identifying the composition of these primary melts in the mantle is crucial for establishing links between mantle geochemical 'reservoirs' and fundamental geodynamic processes. Mineral inclusions in natural diamonds have provided a unique window into such deep mantle processes. Here we provide experimental and geochemical evidence that silicate mineral inclusions in diamonds from Juina, Brazil, crystallized from primary and evolved carbonatite melts in the mantle transition zone and deep upper mantle. The incompatible trace element abundances calculated for a melt coexisting with a calcium-titanium-silicate perovskite inclusion indicate deep melting of carbonated oceanic crust, probably at transition-zone depths. Further to perovskite, calcic-majorite garnet inclusions record crystallization in the deep upper mantle from an evolved melt that closely resembles estimates of primitive carbonatite on the basis of volcanic rocks. Small-degree melts of subducted crust can be viewed as agents of chemical mass-transfer in the upper mantle and transition zone, leaving a chemical imprint of ocean crust that can possibly endure for billions of years.     

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.     

Breaking of Henry's law for noble gas and CO2 solubility in silicate melt under pressure

Degassing of the Earth is still poorly understood, as is the large scatter in He/Ar ratios observed in mid-ocean ridge basalts. A possible explanation for such observations is that vesiculation occurs at great depths with noble-gas solubilities different from those measured at 1 bar (ref. 1). Here we develop a hard-sphere model for noble-gas solubility and find that, owing to melt compaction, solubility may decrease by several orders of magnitude when pressure increases, an effect subtly overbalanced by the compression of the fluid phase. Our results satisfactorily explain recent experimental data on argon solubility in silicate melts, where argon concentration increases almost linearly with pressure, then levels off at pressures of 50-100 kbar (refs 2-5). We also model vesiculation during magma ascent at ridges and find that noble-gas partitioning between melt and CO2 vesicles at depth differs significantly from that at low pressure. Starting at 10 kbar (approximately 35 km depth), several stages of vesiculation occur followed by vesicle loss, which explains the broad variability of He-Ar concentration data in mid-ocean ridge basalts. 'Popping rocks', exceptional samples with high vesicularity, may represent fully vesiculated ridge magma, whereas common samples would simply have lost such vesicles.     

Iron-silica interaction at extreme conditions and the electrically conducting layer at the base of Earth's mantle

The boundary between the Earth's metallic core and its silicate mantle is characterized by strong lateral heterogeneity and sharp changes in density, seismic wave velocities, electrical conductivity and chemical composition. To investigate the composition and properties of the lowermost mantle, an understanding of the chemical reactions that take place between liquid iron and the complex Mg-Fe-Si-Al-oxides of the Earth's lower mantle is first required. Here we present a study of the interaction between iron and silica (SiO2) in electrically and laser-heated diamond anvil cells. In a multianvil apparatus at pressures up to 140 GPa and temperatures over 3,800 K we simulate conditions down to the core-mantle boundary. At high temperature and pressures below 40 GPa, iron and silica react to form iron oxide and an iron-silicon alloy, with up to 5 wt% silicon. At pressures of 85-140 GPa, however, iron and SiO2 do not react and iron-silicon alloys dissociate into almost pure iron and a CsCl-structured (B2) FeSi compound. Our experiments suggest that a metallic silicon-rich B2 phase, produced at the core-mantle boundary (owing to reactions between iron and silicate), could accumulate at the boundary between the mantle and core and explain the anomalously high electrical conductivity of this region.     

Trace-element of Tuoyun clinopyroxene: Implication for the deep processes of lithospheric mantle beneath the southwest Tianshan, West China

Based on the LAM-ICPMS analytic results on the trace elements of clinopyroxenes in peridotitic xenoliths occurring in early-Cretaceous basalts from western Xinjiang, the properties and the deep processes, including partial melting and mantle metasomatism, of the subcontinental lithospheric mantle beneath the Tuoyun Basin are analyzed. In the northern edge of the Tarim Basin (southwest Tianshan), the Mesozoic subcontinental lithosphere which has experienced the effect of partial melting (<10%) and intricate mantle metasomatism is characterized by Phanerozoic ‘ocean-type’ mantle. The superposed influence of SiO₂-unsaturated silicate melt and carbonate melt probably results in the metasomatic medium which resembles the hydrous silicated carbonate melt in some aspects. By comparing Tuoyun mantle with Cenozoic main mantle beneath eastern China, the properties are similar, while the former shows finer grain and higher diopside content of the peridotites and more conspicuous modal metasomatism.     

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.     

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%.     

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.     

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.     

Survival times of anomalous melt inclusions from element diffusion in olivine and chromite

The chemical composition of basaltic magma erupted at the Earth's surface is the end product of a complex series of processes, beginning with partial melting and melt extraction from a mantle source and ending with fractional crystallization and crustal assimilation at lower pressures. It has been proposed that studying inclusions of melt trapped in early crystallizing phenocrysts such as Mg-rich olivine and chromite may help petrologists to see beyond the later-stage processes and back to the origin of the partial melts in the mantle. Melt inclusion suites often span a much greater compositional range than associated erupted lavas, and a significant minority of inclusions carry distinct compositions that have been claimed to sample melts from earlier stages of melt production, preserving separate contributions from mantle heterogeneities. This hypothesis is underpinned by the assumption that melt inclusions, once trapped, remain chemically isolated from the external magma for all elements except those that are compatible in the host minerals. Here we show that the fluxes of rare-earth elements through olivine and chromite by lattice diffusion are sufficiently rapid at magmatic temperatures to re-equilibrate completely the rare-earth-element patterns of trapped melt inclusions in times that are short compared to those estimated for the production and ascent of mantle-derived magma or for magma residence in the crust. Phenocryst-hosted melt inclusions with anomalous trace-element signatures must therefore form shortly before magma eruption and cooling. We conclude that the assumption of chemical isolation of incompatible elements in olivine- and chromite-hosted melt inclusions is not valid, and we call for re-evaluation of the popular interpretation that anomalous melt inclusions represent preserved samples of unmodified mantle melts.     

Low electrical resistivity associated with plunging of the Nazca flat slab beneath Argentina

Beneath much of the Andes, oceanic lithosphere descends eastward into the mantle at an angle of about 30 degrees (ref. 1). A partially molten region is thought to form in a wedge between this descending slab and the overlying continental lithosphere as volatiles given off by the slab lower the melting temperature of mantle material. This wedge is the ultimate source for magma erupted at the active volcanoes that characterize the Andean margin. But between 28 degrees and 33 degrees S the subducted Nazca plate appears to be anomalously buoyant, as it levels out at about 100 km depth and extends nearly horizontally under the continent. Above this 'flat slab', volcanic activity in the main Andean Cordillera terminated about 9 million years ago as the flattening slab presumably squeezed out the mantle wedge. But it is unknown where slab volatiles go once this happens, and why the flat slab finally rolls over to descend steeply into the mantle 600 km further eastward. Here we present results from a magnetotelluric profile in central Argentina, from which we infer enhanced electrical conductivity along the eastern side of the plunging slab, indicative of the presence of partial melt. This conductivity structure may imply that partial melting occurs to at least 250 km and perhaps to more than 400 km depth, or that melt is supplied from the 410 km discontinuity, consistent with the transition-zone 'water-filter' model of Bercovici and Karato.     

An interconnected network of core-forming melts produced by shear deformation

The formation mechanism of terrestrial planetary cores is still poorly understood, and has been the subject of numerous experimental studies. Several mechanisms have been proposed by which metal--mainly iron with some nickel--could have been extracted from a silicate mantle to form the core. Most recent models involve gravitational sinking of molten metal or metal sulphide through a partially or fully molten mantle that is often referred to as a 'magma ocean'. Alternative models invoke percolation of molten metal along an interconnected network (that is, porous flow) through a solid silicate matrix. But experimental studies performed at high pressures have shown that, under hydrostatic conditions, these melts do not form an interconnected network, leading to the widespread assumption that formation of metallic cores requires a magma ocean. In contrast, here we present experiments which demonstrate that shear deformation to large strains can interconnect a significant fraction of initially isolated pockets of metal and metal sulphide melts in a solid matrix of polycrystalline olivine. Therefore, in a dynamic (non-hydrostatic) environment, percolation remains a viable mechanism for the segregation and migration of core-forming melts in a solid silicate mantle.     

Evidence for mantle metasomatism by hydrous silicic melts derived from subducted oceanic crust

The low concentrations of niobium, tantalum and titanium observed in island-arc basalts are thought to result from modification of the sub-arc mantle by a metasomatic agent, deficient in these elements, that originates from within the subducted oceanic crust. Whether this agent is an hydrous fluid or a silica-rich melt has been discussed using mainly a trace-element approach and related to variable thermal regimes of subduction zones. Melting of basalt in the absence of fluid both requires high temperatures and yields melt compositions unlike those found in most modern or Mesozoic island arcs. Thus, metasomatism by fluids has been thought to be the most common situation. Here, however, we show that the melting of basalt under both H2O-added and low-temperature conditions can yield extremely alkali-rich silicic liquids, the alkali content of which increases with pressure. These liquids are deficient in titanium and in the elements niobium and tantalum and are virtually identical to glasses preserved in mantle xenoliths found in subduction zones and to veins found in exhumed metamorphic terranes of fossil convergent zones. We also found that the interaction between such liquids and mantle olivine produces modal mineralogies that are identical to those observed in metasomatized Alpine-type peridotites. We therefore suggest that mantle metasomatism by slab-derived melt is a more common process than previously thought.