Conditions of core formation in the earth: Constraints from Nickel and Cobalt partitioning

The abundances of Ni and Co in the Earth’s mantle are depleted relative to chondrites due to terrestrial core formation. Recently, the observed mantle depletions of these elements have been explained by liquid metal-liquid silicate equilibrium during core formation in a high pressure, high temperature magma ocean on the early Earth. However, different magma ocean models, which would be expected to give consistent results, have proposed vastly different pressures (24 to 59 GPa), temperatures (2200 to >4000 K) and oxygen fugacities (−0.15 to −2.4 ΔIW) for the Earth’s magma ocean. In an attempt to resolve the contradictory results from different magma ocean models and determine the thermodynamic conditions appropriate for core formation in the Earth, experiments were conducted to better constrain the influences of temperature and C on the partitioning behaviors of Ni and Co. Results of experiments at 7 GPa with temperatures of 1923-2673 K show that the metal-silicate partition coefficients for both Ni and Co decrease with increasing temperature, with the effect being more significant for Ni. Little change in the partitioning behaviors of either Ni or Co with varying C-content of the metallic liquid was found. By combining the new temperature data with previous results from pressure and oxygen fugacity studies, we parameterized the partitioning behavior of Ni and Co and applied the parameterizations to core formation in a terrestrial magma ocean. Multiple combinations of pressure, temperature, and oxygen fugacity can explain the observed mantle depletions of Ni and Co, and all of the very different previously proposed magma ocean conditions are generally consistent with valid solutions. By using the FeO content of the Earth’s mantle as an additional constraint on the oxygen fugacity, magma ocean conditions of 30-60 GPa, > 2000 K, and −2.2 ΔIW are suggested. Similar systematic approaches and studies of other moderately siderophile elements could further constrain the magma ocean conditions on the early Earth.     

Oxygen fugacity dependence of Ni,Co, Mn,Cr, V,and Si partitioning between liquid metal and magnesiowüstite at 9–18 GPa and 2200°C

The oxidation states of Ni, Co, Mn, Cr, V and Si in magnesiowüstite have been determined in metal-oxide distribution experiments using a multi anvil apparatus at 9 and 18 GPa and 2200°C as a function of oxygen fugacity. Despite limitations to control oxygen fugacity by applying conventional buffering methods in high pressure experiments, a wide range of redox-conditions (3 log bar units) has been imposed to the metal-oxide partitioning experiments by varying the Si/O ratio of the starting material. The oxygen fugacity was calculated according to the Fe-FeO equilibrium between the run products. The ability to impose different oxygen fugacities by varying the starting material is confirmed by the large variation of element partitioning coefficients obtained at constant pressure and temperature. The calculated valences at both pressures investigated are divalent for Co, Mn, V and 4+ for Si. The results for Cr (∼2.5+) and Ni (∼1.5+) indicate non-ideal mixing of Ni and Cr in at least one of the product phases. Because the application of 1 bar activity coefficients for Ni and Cr in metal alloys does not change these valences, non-ideal mixing in magnesiowüstite or significantly larger non-ideal mixing properties of Ni and Cr in metal alloys at high pressure are likely to be responsible for the apparent valences. Omitting such non-ideal mixing properties when extrapolating high-pressure element partitioning data may be significant. The elements Cr, V and Mn become siderophile (D_M^met/ox > 1) at 9–18 GPa and 2200°C at oxygen fugacities below IW-2.7 to IW-3.7. Considering, in addition, the influence of temperature, the depletion of Cr, Mn and V in the Earth’s mantle may be due, at least partly, to siderophile behavior at high pressure and temperature.     

Evidence for high-pressure core-mantle differentiation from the metal-silicate partitioning of lithophile and weakly-siderophile elements

Liquid Fe metal-liquid silicate partition coefficients for the lithophile and weakly-siderophile elements Ta, Nb, V, Cr, Si, Mn, Ga, In and Zn have been measured in multianvil experiments performed from 2 to 24 GPa, 2023-2873 K and at oxygen fugacities of −1.3 to −4.2 log units relative to the iron-wüstite buffer. Compositional effects of light elements dissolved in the metal liquid (S, C) have been examined and experiments were performed in both graphite and MgO capsules, specifically to address the effect of C solubility in Fe-metal on siderophile element partitioning. The results were used to examine whether there is categorical evidence that a significant portion of metal-silicate equilibration occurred under very high pressures during core-mantle fractionation on Earth. Although the depletion of V from the mantle due to core formation is significantly greater than that of Nb, our results indicate that both elements have similar siderophile tendencies under reducing conditions at low pressures. With increasing pressure, however, Nb becomes less siderophile than V, implying that average metal-silicate equilibration pressures of at least 10-40 GPa are required to explain the Nb/V ratio of the mantle. Similarly the moderately-siderophile, volatile element ratios Ga/Mn and In/Zn are chondritic in the mantle but both volatility and core-mantle equilibration at low pressure would render these ratios strongly sub-chondritic. Our results indicate that pressures of metal-silicate partitioning exceeding 30-60 GPa would be required to render these element ratios chondritic in the mantle. These observations strongly indicate that metal-silicate equilibration must have occurred at high pressures, and therefore support core-formation models that involve deep magma oceans. Moreover, our results allow us to exclude models that envisage primarily low-pressure (<1 GPa) equilibration in relatively small planetary bodies. We also argue that the core cannot contain significant U as this would require metal-silicate equilibration at oxygen fugacities low enough for significant amounts of Ta to have also been extracted from the mantle. Likewise, as In is more siderophile than Pb but similarly volatile and also quite chalcophile it would have been difficult for Pb to enter the core without reversing the relative depletions of these elements in the mantle unless metal-silicate equilibration occurred at high pressures >20 GPa.     

The effect of Si on metal-silicate partitioning of siderophile elements and implications for the conditions of core formation

We have determined the liquid metal-liquid silicate partitioning of Ni, Co, Mo, W, V, Cr and Nb at 1.5 GPa/1923 K and 6 GPa/2123 K under conditions of constant silicate melt composition with variable amounts of Si in the Fe-rich metallic liquid. Partitioning of Ni, Co, Mo, W and V is sensitive to the Si content of the metal with, in all five cases, increasing Si tending to make the element more lithophile than for conditions where the metal is Si-free. In contrast, metal-silicate partitioning of Cr and Nb is, at constant silicate melt composition, insensitive to the Si content of the metal.The implications of our data are that if, as indicated by the Si isotopic composition of the silicate Earth ( [Georg et al., 2007] and [Fitoussi et al., 2009]), the core contains significant amounts of Si, the important siderophile elements Ni, Co, W and Mo were more lithophile during accretion and core formation than previously believed.We use our new data in conjunction with published metal-silicate partitioning results to develop a model of continuous accretion and core segregation taking explicit account of the partitioning of Si (this study) and O (from Ozawa et al., 2008) between metal and silicate and their effects on metal-silicate partitioning of siderophile elements. We find that the effect of Si on the siderophile characteristics of Ni, Co and W means that the pressures of core segregation estimated from these elements are ∼5 GPa lower than those derived from experiments in which the metal contained negligible Si (e.g., Wade and Wood, 2005). The core-mantle partitioning of Cr and Nb requires that most of Earth accretion took place under conditions which were much more reducing than those implied by the current FeO content of the mantle and that the oxidation took place late in the accretionary process. Paths of terrestrial accretion, oxidation state and partitioning which are consistent with the current mantle contents of Ni, Co, W, V, Cr and Nb lead to Si and O contents of the core of ∼4.3 wt.% and 0.15%, respectively.     

Systematics of metal-silicate partitioning for many siderophile elements applied to Earth’s core formation

Superliquidus metal-silicate partitioning was investigated for a number of moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta) elements. To provide independent constrains on the effects of temperature, oxygen fugacity and silicate melt composition, isobaric (3 GPa) experiments were conducted in piston cylinder apparatus at temperature between 1600 and 2600 °C, relative oxygen fugacities of IW−1.5 to IW−3.5, and for silicate melt compositions ranging from basalt to peridotite. The effect of pressure was investigated through a combination of piston cylinder and multi-anvil isothermal experiments between 0.5 and 18 GPa at 1900 °C. Oxidation states of siderophile elements in the silicate melt as well as effect of carbon saturation on partitioning are also derived from these results. For some elements (e.g. Ga, Ge, W, V, Zn) the observed temperature dependence does not define trends parallel to those modeled using metal-metal oxide free energy data. We correct partitioning data for solute interactions in the metallic liquid and provide a parameterization utilized in extrapolating these results to the P-T-X conditions proposed by various core formation models. A single-stage core formation model reproduces the mantle abundances of several siderophile elements (Ni, Co, Cr, Mn, Mo, W, Zn) for core-mantle equilibration at pressures from 32 to 42 GPa along the solidus of a deep peridotitic magma ocean (∼3000 K for this pressure range) and oxygen fugacities relevant to the FeO content of the present-day mantle. However, these P-T-fO₂ conditions cannot produce the observed concentrations of Ga, Ge, V, Nb, As and P. For more reducing conditions, the P-T solution domain for single stage core formation occurs at subsolidus conditions and still cannot account for the abundances of Ge, Nb and P. Continuous core formation at the base of a magma ocean at P-T conditions constrained by the peridotite liquidus and fixed fO₂ yields concentrations matching observed values for Ni, Co, Cr, Zn, Mn and W but underestimates the core/mantle partitioning observed for other elements, notably V, which can be reconciled if accretion began under reducing conditions with progressive oxidation to fO₂ conditions consistent with the current concentration of FeO in the mantle as proposed by Wade and Wood (2005). However, neither oxygen fugacity path is capable of accounting for the depletions of Ga and Ge in the Earth’s mantle. To better understand core formation, we need further tests integrating the currently poorly-known effects of light elements and more complex conditions of accretion and differentiation such as giant impacts and incomplete equilibration.     

Metal-silicate partitioning and constraints on core composition and oxygen fugacity during Earth accretion

We present the results of new partitioning experiments between metal and silicate melts for a series of elements normally regarded as refractory lithophile and moderately siderophile and volatile. These include Si, Ti, Ni, Cr, Mn, Ga, Nb, Ta, Cu and Zn. Our new data obtained at 3.6 and 7.7 GPa and between 2123 and 2473 K are combined with literature data to parameterize the individual effects of oxygen fugacity, temperature, pressure and composition on partitioning. We find that Ni, Cu and Zn become less siderophile with increasing temperature. In contrast, Mn, Cr, Si, Ta, Nb, Ga and Ti become more siderophile with increasing temperature, with the highly charged cations (Nb, Ta, Si and Ti) being the most sensitive to variations of temperature. We also find that Ni, Cr, Nb, Ta and Ga become less siderophile with increasing pressure, while Mn becomes more siderophile with increasing pressure. Pressure effects on the partitioning of Si, Ti, Cu and Zn appear to be negligible, as are the effects of silicate melt composition on the partitioning of divalent cations. From the derived parameterization, we predict that the silicate Earth abundances of the elements mentioned above are best explained if core formation in a magma ocean took place under increasing conditions of oxygen fugacity, starting from moderately reduced conditions and finishing at the current mantle-core equilibrium value.     

Siderophile elements in Martian meteorites and implications for core formation in Mars

Noble metals, Mo, W, and 24 other elements were determined in six SNC meteorites of presumably Martian origin. Based on element correlations, representative siderophile element concentrations for the silicate mantle of Mars were inferred. From a comparison with experimentally determined metal/silicate partition coefficients of the moderately siderophile elements: Fe, Ni, Co, W, Mo, and Ga, it is concluded that equilibrium between core forming metal and silicates in Mars has occurred at high temperatures (around 2200°C) and low pressures (<1 GPa). This suggests that metal segregation occurred concurrently with rapid accretion of Mars, which is consistent with the inference from excess ¹⁸²W in Martian meteorites (Lee and Halliday, 1997). Concentrations of Ir, Os, Ru, Pt, and Au in the analyzed Martian meteorites, except ALH84001, are at a level of approximately 10⁻²–10⁻³ × CI. The comparatively high abundances of noble metals in Martian meteorites require the addition of chondritic material after core formation. The similarity in Au/La and Pt/Ca ratios between ALH84001 and the other Martian meteorites suggests crystallization of ALH84001 after complete accretion of Mars.     

Nature of the chemical heterogeneity of the continental lithospheric mantle

The paper reports data on the chemical composition of mantle peridotite xenoliths from kimberlites and alkaline basalts that represent the continental lithospheric mantle (CLM) beneath Early Precambrian and Late Proterozoic-Cenozoic structures, respectively. In order to identify compositional trends during the melting of primitive material and propose the most reliable criteria for constraining the conditions of this process and its degree, we analyzed literature data on the melting of spinel and garnet peridotites within broad temperature and pressure ranges. It was determined that the degree of melting (F%) of pristine peridotite of composition close to that of the primitive mantle (PM) can be deduced from the Mg/Si and Al/Si ratios in the residue; an equation was proposed for evaluating F from the Mg/Si ratio. The Ca/Al ratio of residues at low (1–1.5 GPa) pressures and degrees of melting from 2–3 to 20–25% increases several times but decreases with increasing F at pressures higher than 3 GPa. The Na partition coefficient between melt and residue decreases at increasing pressure and approaches one at a pressure close to 20 GPa. Residues after low-degree melting are strongly depleted in Ti, Zr, Y, and Nb but are enriched in Cr. The application of these criteria to the composition of xenoliths brought to the surface from the mantle occurring beneath tectonic structures of various age led us to conclude that compositional heterogeneities of CLM (particularly the variations in the concentrations of major and certain siderophile elements) are controlled, first of all, by the melting of the mantle source material. These processes occurred under various thermodynamic conditions (T, P, and $ f_{O_2 } $ f_{O_2 } ) and differed in their intensity, and this predetermined the compositional diversity of the residual mantle material (its concentrations of Mg, Al, Si, Ca, Na, K, Ni, Co, V, and Cr). Our results are principally consistent with the hypothesis of the global magmatic ocean. It is thought that the early phases of its consolidation were variably controlled by the fractionation of minerals, for example, majorite. Moreover, heterogeneities in the distribution of siderophile elements could be partly predetermined by changes in the properties of these elements at ultrahigh temperatures and pressures. The processes of partial melting were the most intense during the early evolution of the mantle (perhaps, in the Early Precambrian), and hence, the mantle has different chemical composition beneath Archean cratons and Phanerozoic foldbelts.     

High-pressure Raman spectroscopic study of Mn2GeO4, Ca2GeO4, Ca2SiO4, and CaMgGeO4 olivines

We present a Raman spectroscopic study of the structural modifications of several olivines at high pressures and ambient temperature. At high pressures, the following modifications in the Raman spectra are observed: 1)?in Mn₂GeO₄, between 6.7 and 8.6?GPa the appearance of weak bands at 560 and 860?cm^?1; between 10.6 and 23?GPa, the progressive replacement of the olivine spectrum by the spectrum of a crystalline high pressure phase; upon decompression, the inverse sequence of transformations is observed with some hysteresis in the transformation pressures; this sequence may be interpreted as the progressive transformation of the olivine to a spinelloid where Ge tetrahedra are polymerized, and then to a partially inverse spinel; 2)?in Ca₂SiO₄, the olivine transforms to larnite between 1.9 and 2.1?GPa; larnite is observed up to the maximum pressure of 24?GPa and it can partially back-transform to olivine during decompression; 3)?in Ca₂GeO₄, the olivine transforms to a new structure between 6.8 and 8?GPa; the vibrational frequencies of the new phase suggest that the phase transition involves an increase of the Ca coordination number and that Ge tetrahedra are isolated; this high pressure phase is observed up to the maximum pressure of 11?GPa; during decompression, it transforms to a disordered phase below 5?GPa; 4)?in CaMgGeO₄, no significant modification of the olivine spectrum is observed up to 15?GPa; between 16 and 26?GPa, broadening of some peaks and the appearance of a weak broad feature at 700–900?cm^?1 suggests a progressive amorphization of the structure; near 27?GPa, amorphization is complete and an amorphous phase is quenched down to ambient pressure; this unique behaviour is interpreted as the result of the incompatibilities in the high pressure behaviour of the Ca and Mg sublattices in the olivine structure.     

Siderophile geochemistry of ureilites: A record of early stages of planetesimal core formation

New bulk-compositional data, including trace siderophile elements such as Ir, Os, Au, and Ni, are presented for 25 ureilites. Without exception, ureilites have siderophile abundances too high to plausibly have formed as cumulates. Ureilites undoubtedly underwent a variety of “smelting,” by which C was oxidized to CO gas while olivine FeO was reduced to Fe-metal. However, pressure-buffered equilibrium smelting is not a plausible model for engendering the wide range (75-96 mol%) of mafic-silicate core mg among ureilites. The smelting reaction produces too much CO gas. Even supposing a disequilibrium process with the smelt-gas leaking out of the mantle, none of the ureilites, least of all the ureilite with the most “reduced” (highest) olivine-core mg (ALH84136), has the high Fe-metal abundance predicted by the smelted-cores model. In principle, the Fe-metal generated by smelting could have been subsequently lost, but siderophile data show that ureilites never underwent efficient depletion of Fe-metal. Ureilites display strong correlations among siderophile ratios such as Au/Ir, Ni/Ir, Co/Ir, As/Ir, Se/Ir, and Sb/Ir. Ureilite siderophile depletion patterns loosely resemble siderophile fractionations, presumably nebular in origin, among carbonaceous chondrites. However, Zn, for an element of moderate volatility, is anomalously high in ureilites. A tight correlation between Au and Ni extrapolates to the low-Ni/Au side of the compositional range of carbonaceous chondrites. From this mismatch, mild but nonetheless significant depletions of refractory siderophile elements such as Ir and Os, and moderate depletions of strongly siderophile, weakly chalcophile elements such as Ni and Au, we infer that the ureilite siderophile fractionations are largely the result of a non-nebular process, i.e., removal of S-rich metallic melt, possibly with minor entrainment of Fe-metal. Several lines of trace-element evidence indicate that melt porosity during ureilite anatexis was at least moderate. The ureilite pattern of very mild depletions of extremely siderophile elements, but much deeper depletions of moderately siderophile, chalcophile elements, suggests that asteroidal core formation probably occurs in two discrete stages. In general, separation of a considerable proportion (several wt%) of S-rich metallic melt probably occurs long before, and at a far lower temperature than, separation of the remaining S-poor Fe-metal. Apart from the Fe-metal itself, only extremely siderophile elements wait until the second stage to sequester mainly into the core.     

Chemical and physical studies of type 3 chondrites—VI: Siderophile elements in ordinary chondrites

The abundances of Fe, Ni, Co, Au, Ir, Ga, As and Mg have been determined by instrumental neutron activation analysis in 38 type 3 ordinary chondrites (10 of which may be paired) and 15 equilibrated chondrites. Classification of type 3 ordinary chondrites into the H, L and LL classes using oxygen isotopes and parameters which reflect oxidation state (Fa and Fs in the olivine and pyroxene and Co in kamacite) is difficult or impossible. Bulk compositional parameters, based on the equilibrated chondrites, have therefore been used to classify the type 3 chondrites. The distribution of the type 3 ordinary chondrites over the classes is very different from that of the equilibrated chondrites, the LL chondrites being more heavily represented. The type 3 ordinary chondrites contain 5 to 15 percent lower abundances of siderophile elements and a compilation of the present data and literature data indicates a small, systematic decrease in siderophile element concentration with decreasing petrologic type. The type 3 ordinary chondrites have, like the equilibrated ordinary chondrites, suffered a fractionation of their siderophile elements, but the loss of Ni in comparison with Au and Ir is greater for the type 3 chondrites. These siderophile element trends were established at the nebula phase of chondritic history and the co-variation with petrologic type implies onion-shell structures for the ordinary chondrite parent bodies. It is also clear that the relationship between the type 3 and the equilibrated ordinary chondrites involves more than simple, closed-system metamorphism.     

The origin and history of the metal and sulfide components of chondrules

Fourteen siderophile and other non-lithophile elements determined in 31 Semarkona (LL3.0) chondrules by neutron activation analysis are severely fractionated relative to lithophile elements. Their chondrule/whole-rock abundance ratios vary by factors of up to 1000; the mean ratio is ~0.2. Non-refractory siderophile abundance patterns in Ni-rich chondrules are smooth functions of volatility and in Ni-poor chondrules patterns are more irregular. Refractory siderophile elements are often fractionated from Ni; they covary, confirming the presence of a refractory metal component. The chalcophile element Se correlates with Br and siderophile elements. Zinc is uniformly low and uncorrelated with other elements.Most metal and sulfide in chondrules was probably present in the solar nebula before chondrule formation; most siderophile and chalcophile elements were in these materials. Some Fe was also in silicates, as were minor amounts of Ni, Co, Au, Ge and possibly Se. The amount of metal formed by reduction during chondrule melting was minor. The common metal component in chondrules is similar to, and may be the same as the common component involved in the metal/silicate fractionation of the ordinary chondrite groups.Chondrules are depleted in metal chiefly because they sampled metal-poor precursor assemblages. Metal segregation during the molten period and subsequent loss was a minor process that may be responsible for most surface craters on chondrules.     

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

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

The influence of sulfur on partitioning of siderophile elements

Sulfur is a potential light element in the liquid outer core of the Earth. Its presence in segregating metal may have had an influence in distribution of metal-loving (siderophile) elements during early accretion and core formation events in the Earth. The observed “excess” abundance of siderophile elements in the terrestrial mantle, relative to an abundance expected from simple core-mantle equilibrium at low temperature and pressure, may indicate a reduction in the iron-loving tendency of siderophile elements in the presence of sulfur in the metallic phase. The present experimental partitioning study between iron-carbon-sulfur-siderophile element bearing liquid metal and liquid silicate shows that for some siderophile elements this sulfur effect may be significant enough to even change their character to lithophile. Large and intricate variations in metal-silicate partition coefficients (D^met/sil) have been observed for many elements, e.g., Ni, Co, Ge, W, P, Au, and Re as a function of sulfur content. Moderately siderophile elements Ge, P, and W show the most significant response (sulfur-avoidance) by an enhanced segregation into the associated sulfur-deficient phases. Highly siderophile elements Ir, Pt, and Re show a different style of sulfur-avoidance (alloy-preference) by segregating as sulfur-poor, siderophile element-rich alloys. Both groups are chalcophobic. D^met/sil for Ni, Co, and Au moderately decreases with increasing sulfur-content in the liquid metal. D^met/sil for chalcophile element, Cr, in contrast, increases with sulfur. Irrespective of the sulfur-content, in the presence of a carbon-saturated liquid metal, P is always lithophile. The general nonmetal-avoidance tendency of siderophile elements (and acceptance of chalcophile elements) in the liquid metal, postulated by Jones and Malvin (1990) in the FeNiS(sulfur)M (siderophile) system is found to be present in the metal-silicate system as well. A sulfur-bearning liquid metal segregation can potentially reduce the metal-loving nature of many elements to explain the excess paradox. Sulfur-bearing core segregation, however, might require an efficient draining of exsolved immiscible sulfide liquids from the molten silicate, or an increasing siderophility of sulfur at high pressure to reduce the mantle sulfur content to the observed (<300 ppm) value. Moreover, the chondritic relative abundance pattern of many moderately or highly siderophile elements in the upper mantle is not explained by the presence of sulfur in the segregating metals. Core formation is more complex and intricate than equilibrium segregation.     

A Raman spectroscopic study of shock-wave densification of vitreous silica

The densification processes in SiO₂ glass induced by shock-wave compression up to 43.4 GPa are investigated by Raman spectroscopy. At first, densification increases with increasing shock pressure. A maximum densification of 11% is obtained for a shock pressure of 26.3 GPa. This densification is attributed to the reduction of the average Si−O−Si angle, which occurs first by the collapse of the largest ring cavities, then by further reduction of the average ring size. For higher shock pressures, a different structural modification is observed, resulting in decreasing densification with increasing shock pressure. Indeed, the recovered densification becomes very small, with values of 1.8 and 0.5% at 32 and 43.4 GPa, respectively. This is attributed to partial annealing of the samples due to high after shock residual temperatures. The study of the annealing process of the most densified glass by in situ high temperature Raman spectroscopy confirms that relaxation of the Si−O−Si angle starts at a lower temperature (about 800 K) than that of the siloxane rings (about 1000 K), thus explaining the high intensity of the siloxane defect bands in the samples schocked at compressions of 32 and 43.4 GPa. The large intensity of the siloxane bands in the nearly undensified samples shocked by compressions above 30 GPa may be explained by the relaxation during decompression of five- and six-fold coordinated silicon species formed at high pressure and high temperature during the shock event. Received: March 30, 1998 / Revised, accepted: August 21, 1998     

Pressure dependence of viscosity of rhyolitic melts

Viscosity of silicate melts is a critical property for understanding volcanic and igneous processes in the Earth. We investigate the pressure effect on the viscosity of rhyolitic melts using two methods: indirect viscosity inference from hydrous species reaction in melts using a piston cylinder at pressures up to 2.8 GPa and direct viscosity measurement by parallel-plate creep viscometer in an internally-heated pressure vessel at pressures up to 0.4 GPa. Comparison of viscosities of a rhyolitic melt with 0.8 wt% water at 0.4 GPa shows that both methods give consistent results. In the indirect method, viscosities of hydrous rhyolitic melts were inferred based on the kinetics of hydrous species reaction in the melt upon cooling (i.e., the equivalence of rheologically defined glass transition temperature and chemically defined apparent equilibrium temperature). The cooling experiments were carried out in a piston-cylinder apparatus using hydrous rhyolitic samples with 0.8-4 wt% water. Cooling rates of the kinetic experiments varied from 0.1 K/s to 100 K/s; hence the range of viscosity inferred from this method covers 3 orders of magnitude. The data from this method show that viscosity increases with increasing pressure from 1 GPa to 3 GPa for hydrous rhyolitic melts with water content ?0.8 wt% in the high viscosity range. We also measured viscosity of rhyolitic melt with 0.13 wt% water using the parallel-plate viscometer at pressures 0.2 and 0.4 GPa in an internally-heated pressure vessel. The data show that viscosity of rhyolitic melt with 0.13 wt% water decreases with increasing pressure. Combining our new data with literature data, we develop a viscosity model of rhyolitic melts as a function of temperature, pressure and water content.     

Origin of planetary cores: evidence from highly siderophile elements in martian meteorites

We present new bulk compositional data for 6 martian meteorites, including highly siderophile elements Ni, Re, Os, Ir and Au. These and literature data are utilized for comparison versus the siderophile systematics of igneous rocks from Earth, the Moon, and the HED asteroid. The siderophile composition of ALH84001 is clearly anomalous. Whether this reflects a more reducing environment on primordial Mars when this ancient rock first crystallized, or secondary alteration, is unclear. QUE94201 shows remarkable similarity with EET79001-B for siderophile as well as lithophile elements; both are extraordinarily depleted in the “noblest” siderophiles (Os and Ir), to roughly 0.00001 × CI chondrites. As in terrestrial igneous rocks, among martian rocks Ni, Os and Ir show strong correlations vs. MgO. In the case of MgO vs. Ni, the martian trend is displaced toward lower Ni by a large factor (5), but the Os and Ir trends are not significantly displaced from their terrestrial counterparts. For Mars, Re shows a rough correlation with MgO, indicating compatible behavior, in contrast to its mildly incompatible behavior on Earth. Among martian MgO-rich rocks, Au shows a weak anticorrelation vs. MgO, resembling the terrestrial distribution except for a displacement toward 2–3 times lower Au. The same elements (Ni, Re, Os, Ir and Au) show similar correlations with Cr substituted for MgO. Data for lunar and HED rocks generally show less clear-cut trends (relatively few MgO-rich samples are available). These trends are exploited to infer the compositions of the primitive Earth, Mars, Moon and HED mantles, by assuming that the trend intercepts the bulk MgO or Cr content of the primitive mantle at the approximate primitive mantle concentration of the siderophile element. Results for Earth show good agreement with earlier estimates. For Mars, the implied primitive mantle composition is remarkably similar to the Earth’s, except for 5 times lower Ni. The best constrained of the extremely siderophile elements, Os and Ir, are present in the martian mantle at 0.005 times CI, in comparison to 0.007 times CI in Earth’s mantle. This similarity constitutes a key constraint on the style of core-mantle differentiation in both Mars and Earth. Successful models should predict similarly high concentrations of noble siderophile elements in both the martian and terrestrial mantles (“high” compared to the lunar and HED mantles, and to models of simple partitioning at typical low-pressure magmatic temperatures), but only predict high Ni for the Earth’s mantle. Models that engender the noble siderophile excess in Earth’s mantle through a uniquely terrestrial process, such as a Moon-forming giant impact, have difficulty explaining the similarity of outcome (except for Ni) on Mars. The high Ni content of the terrestrial mantle is probably an effect traceable to Earth’s size. For the more highly siderophile elements like Os and Ir, the simplest model consistent with available constraints is the veneer hypothesis. Core-mantle differentiation was notably inefficient on the largest terrestrial planets, because during the final ∼ 1% of accretion these bodies acquired sufficient H₂O to oxidize most of the later-accreting Fe-metal, thus eliminating the carrier phase for segregation of siderophile elements into the core.     

Calculation of infrared and Raman vibration modes of magnesite at high pressure by density-functional perturbation theory and comparison with experiments

We predict the IR-TO, IR-LO and Raman modes (wave numbers and intensities) of magnesite (MgCO₃) up to 50 GPa, at T = 0 K, using the density-functional perturbation theory up to a third order perturbation, under the harmonic assumption. The predicted IR-TO and Raman mode wave numbers, the mode Grüneisen parameters and the Davydov splittings are systematically compared with experimental data for all modes up to the pressures of 10–30 GPa and for some modes up to 50 GPa. Existing experiments allow extending this comparison only to IR-LO wave numbers of the E _u (ν₃) asymmetric-stretch mode, confirming the odd experimental behavior of this mode at very high pressures. Predicted IR-TO, IR-LO and Raman intensities up to 50 GPa are just tabulated, but data are missing for their comparison with precise experiments. However, the generally good agreement observed between numerical results and experimental data, when their comparison is possible, suggests that first-principles methods are a major help to predict the entire spectrum up to very high pressures.     

Composition of aqueous fluid coexisting with mantle minerals at high pressure and its bearing on the differentiation of the Earth’s mantle

In order to understand the role of aqueous fluid on the differentiation of the mantle, the compositions of aqueous fluids coexisting with mantle minerals were investigated in the system MgO-SiO₂-H₂O at pressures of 3 to 10 GPa and temperatures of 1000 to 1500°C with an MA8-type multianvil apparatus. Phase boundaries between the stability fields of forsterite + aqueous fluid, forsterite + enstatite + aqueous fluid, and enstatite + aqueous fluid were determined by varying the bulk composition at constant temperature and pressure. The composition of aqueous fluid coexisting with forsterite and enstatite can be defined by the intersection of these two phase boundaries. The solubility of silicate components in aqueous fluid coexisting with forsterite and enstatite increases with increasing pressure up to 8 GPa, from about 30 wt% at 3 GPa to about 70 wt% at 8 GPa. It becomes almost constant above 8 GPa. The Mg/Si weight ratio of these aqueous fluids is much higher than at low pressure (0.2 at 1.5 GPa) and almost constant (1.2) at pressures between 3 and 8 GPa. At 10 GPa, it becomes about 1.4. Aqueous fluid migrating upward through the mantle can therefore dissolve large amounts of silicates, leaving modified Mg/Si ratios of residual materials. It is suggested that the chemical stratification of Mg/Si in the Earth may have been formed as a result of aqueous fluid migration.     

Study on the Electrical Conductivity of 0.025 mol NaCl Solution at 0.25–3.75 GPa and 20–370°C

The electrical conductance of 0.025 mol NaCl solution was measured at 0.25–3.75 GPa and 20–370°C As shown by the results, the conductance increases with temperature, and there is a liner relation between the reciprocal of temperature and the logarithm of the conductance but their slopes are different at different pressures. The relations between the conductance and pressure is rather complex and there are some discontinuities: in the range of 2.25–3.75 GPa, the conductance increases with the pressure; in the range of 1.25–2.0 GPa, the conductance is not related to the pressure; and at a pressure of 0.75 GPa, the conductance is higher than that at the pressures nearby. This reflects that the NaCl solution has rather different properties of electronic chemistry at various pressures, and probably is an important cause for the existence of the layers with high electrical conductance and low velocity in the Earth's crust and mantle.