Pressure-temperature cartography of Fe-S-Si immiscible system

Multi-anvil press experiments were performed using a single cell assembly containing six different compositions. This set-up allows a careful sampling of the miscibility gap for given P-T conditions. Shrinking of the miscibility gap in the Fe-S-Si system has been studied from 4 to 12 GPa up to 2200 K, demonstrating a stable immiscible zone up to 4 GPa and 2200 K and its closure at higher pressures. Presence of both S and Si in the Earth’s core is suggested by chondritic models. Therefore, its composition is inherited from processes at pressures higher than 4 GPa. This evolution of the Fe-S-Si miscibility gap is linked with the change in the local short-range order in Fe and Fe-S liquids. Our results indicate that core formation under reducing conditions would be affected by immiscibility for planetesimals up to size of the Moon. Furthermore, due to the difference in wetting properties between the two immiscible liquid phases, the S-rich metal phase would control the chemical exchange between liquid metals and silicates during early differentiation in planetesimals.     

High-pressure melting relations in Fe-C-S systems: Implications for formation, evolution, and structure of metallic cores in planetary bodies

We present new high-pressure temperature experiments on melting phase relations of Fe-C-S systems with applications to metallic core formation in planetary interiors. Experiments were performed on Fe-5 wt% C-5 wt% S and Fe-5 wt% C-15 wt% S at 2-6 GPa and 1050-2000 °C in MgO capsules and on Fe-13 wt% S, Fe-5 wt% S, and Fe-1.4 wt% S at 2 GPa and 1600 °C in graphite capsules. Our experiments show that: (a) At a given P-T, the solubility of carbon in iron-rich metallic melt decreases modestly with increasing sulfur content and at sufficiently high concentration, the interaction between carbon and sulfur can cause formation of two immiscible melts, one rich in Fe-carbide and the other rich in Fe-sulfide. (b) The mutual solubility of carbon and sulfur increases with increasing pressure and no super-liquidus immiscibility in Fe-rich compositions is likely expected at pressures greater than 5-6 GPa even for bulk compositions that are volatile-rich. (c) The liquidus temperature in the Fe-C-S ternary is significantly different compared to the binary liquidus in the Fe-C and Fe-S systems. At 6 GPa, the liquidus of Fe-5 wt% C-5 wt% S is 150-200 °C lower than the Fe-5 wt% S. (d) For Fe-C-S bulk compositions with modest concentration of carbon, the sole liquidus phase is iron carbide, Fe₃C at 2 GPa and Fe₇C₃ at 6 GPa and metallic iron crystallizes only with further cooling as sulfur is concentrated in the late crystallizing liquid. Our results suggest that for carbon and sulfur-rich core compositions, immiscibility induced core stratification can be expected for planets with core pressure less than ∼6 GPa. Thus planetary bodies in the outer solar system such as Ganymede, Europa, and Io with present day core-mantle boundary (CMB) pressures of ∼8, ∼5, and 7 GPa, respectively, if sufficiently volatile-rich, may either have a stratified core or may have experienced core stratification owing to liquid immiscibility at some stage of their accretion. A similar argument can be made for terrestrial planetary bodies such as Mercury and Earth’s Moon, but no such stratification is predicted for cores of terrestrial planets such as Earth, Venus, and Mars with the present day core pressure in the order ?136 GPa, ?100 GPa, and ?23 GPa. (e) Owing to different expected densities of Fe-rich (and carbon-bearing) and sulfur-rich metallic melts, their settling velocities are likely different; thus core formation in terrestrial planets may involve rain of more than one metallic melt through silicate magma ocean. (f) For small planetary bodies that have core pressures <6 GPa and have a molten core or outer core, settling of denser carbide-rich liquid or flotation of lighter, sulfide-rich melt may contribute to an early, short-lived geodynamo.     

The Fe-C system at 5 GPa and implications for Earth’s core

Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe₃C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe₃C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe₃C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe₃C. Fe₃C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe₃C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe₃C.     

Thermodynamics, structure, dynamics, and freezing of Mg2SiO4 liquid at high pressure

We perform first principles molecular dynamics simulations of Mg₂SiO₄ liquid and crystalline forsterite. On compression by a factor of two, we find that the Grüneisen parameter of the liquid increases linearly from 0.6 to 1.2. Comparison of liquid and forsterite equations of state reveals a temperature-dependent density crossover at pressures of ∼12-17 GPa. Along the melting curve, which we calculate by integration of the Clapeyron equation, the density crossover occurs within the forsterite stability field at P = 13 GPa and T = 2550 K. The melting curve obtained from the root mean-square atomic displacement in forsterite using the Lindemann law fails to match experimental or calculated melting curves. We attribute this failure to the liquid structure that differs significantly from that of forsterite, and which changes markedly upon compression, with increases in the degree of polymerization and coordination. The mean Si coordination increases from 4 in the uncompressed system to 6 upon twofold compression. The self-diffusion coefficients increase with temperature and decrease monotonically with pressure, and are well described by the Arrhenian relation. We compare our equation of state to the available highpressure shock wave data for forsterite and wadsleyite. Our theoretical liquid Hugoniot is consistent with partial melting along the forsterite Hugoniot at pressures 150-170 GPa, and complete melting at 170 GPa. The wadsleyite Hugoniot is likely sub-liquidus at the highest experimental pressure to date (200 GPa).     

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.     

Manganese partitioning during hydrous melting of peridotite

Manganese contents and the iron/manganese ratio of igneous rocks have been used as a method of probing the heterogeneity in the Earth’s mantle during melting of peridotite and pyroxenite lithologies. Most previous work has assumed that changes in these parameters require differences in either source lithology or composition based on experiments indicating that manganese is slightly incompatible during melting and that the iron/manganese ratio is fixed by the presence of olivine. However, the presence of volatiles in the mantle drives melting at lower temperatures and with different compositions than in volatile-free systems, and thus the partitioning of Fe and Mn may in fact vary. We have produced silicate liquids in equilibrium with a peridotite assemblage under hydrous conditions at 3 GPa that show that Mn can also be unexpectedly compatible in garnet at 1375 °C and that Mn partitioning between solids and liquids can be strongly affected by temperature and liquid composition. The compatibility of Mn in garnet provides a mechanism for large variations of Mn contents and the Fe/Mn ratio in silicate melts that solely involves melting of mantle peridotite with only small compositional changes. Correlations between Mn variations and other indices indicative of melting in the presence of garnet may provide a means of more completely understanding the role of garnet at high pressures in peridotite melting.     

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.     

Phase relations of carbonate-bearing eclogite assemblages from 2.5 to 5.5 GPa: implications for petrogenesis of carbonatites

We have experimentally investigated the phase and melting relations of garnet + clinopyroxene + carbonate assemblages at 2.5–5.5 GPa, to assess the feasibility of carbonated eclogite as a source for some crustally emplaced carbonatites. The solidus of our composition was at 1,125 °C at 2.5 GPa, 1,225 °C at 3.5 GPa and 1,310 °C at 5.0 GPa. Melts were sodic calcio-dolomitic carbonatites, and were markedly more calcic than the dolomitic melts produced by partial melting of carbonated peridotite. Na contents of the experimental carbonatites decreased with increasing pressure when compared at similar degrees of melting, and SiO₂ contents increased with degree of melting. Experiments on a second composition with enhanced Na₂O demonstrated its strong effect in lowering melting temperatures in carbonate eclogite. Natural carbonated eclogite bodies in the peridotitic upper mantle will have a range of solidus temperatures. In many cases, carbonate will be molten in the upper 250 km. Carbonate melt would segregate from its source eclogite at very low melt fractions and infiltrate surrounding peridotitic wall rock. This would result in metasomatic enrichment of the peridotitic wall rock, but its exact nature will depend on the relative P–T positions of the eclogite + CO₂ and peridotite + CO₂ solidii. As a result of these inevitable metasomatic interactions, it is considered unlikely that carbonatite melts derived from carbonated eclogite in the upper mantle could be emplaced into the crust unmodified. However, they may have a role in metasomatically enriching and carbonating parts of the upper mantle, producing sources suitable for subsequent production of silica undersaturated silicate liquids and carbonatites ultimately emplaced in the crust.Editorial responsibility: J. Hoefs     

The composition of liquids coexisting with dense hydrous magnesium silicates at 11-13.5 GPa and the endpoints of the solidi in the MgO-SiO2-H2O system

High-pressure liquids in the MgO-SiO₂-H₂O (MSH) system have been investigated at 11 and 13.5 GPa and between 1000 and 1350 °C. A bulk composition more magnesian than the tie-line forsterite-H₂O was employed for the study. Rocking multi-anvil experiments were combined with a diamond trap set-up. After termination of the experiments, the liquid trapped in the diamond layer was analysed by laser ablation ICP-MS using the ‘freezing’ technique. At 11 GPa, liquids coexist with one or two of phase A, clinohumite, chondrodite, and forsterite. A marked discontinuity in the evolution of liquid compositions near 1100 °C is observed at 11 GPa. A step of ∼13 wt% H₂O and 13 wt% MgO is interpreted to result from overstepping the fluid-saturated solidus reaction mass balanced to 1.00(18) phase A + 1.07(4) fluid = 0.63(15) chondrodite + 1.44(2) melt. At 13.5 GPa liquids coexist with one or two of hydrous wadsleyite, clinohumite, superhydrous B, phase B, and forsterite. The discontinuity in liquid composition is no longer present, indicating that the second critical endpoint of the solidus has been overstepped. Thus, hydrous melts in the Mg-rich part of the MSH system (molar bulk Mg/Si > 2) are chemically distinct from aqueous fluids at pressure up to 11 GPa. Convergence of fluid and melt compositions along the solidus resulting in a supercritical liquid occurs between 11 and 13.5 GPa, at which pressure the entire MSH system becomes supercritical.     

Density measurements of liquid Fe–Si alloys at high pressure using the sink–float method

The compositional dependence on the density of liquid Fe alloys under high pressure is important for estimating the amount of light elements in the Earth’s outer core. Here, we report on the density of liquid Fe–Si at 4 GPa and 1,923 K measured using the sink–float method and our investigation on the effect of the Si content on the density of the liquid. Our experiments show that the density of liquid Fe–Si decreases from 7.43 to 2.71 g/cm³ non-linearly with increasing Si content (0–100 at%). The molar volume of liquid Fe–Si calculated from the measured density gradually decreases in the compositional range 0–50 at% Si, and increases in the range 50–100 at% Si. It should be noted that the estimated molar volume of the alloys shows a negative volume of mixing between Fe and Si. This behaviour is similar to Fe–S liquid (Nishida et al. in Phys Chem Miner 35:417–423, 2008). However, the excess molar volume of mixing for the liquid Fe–Si is smaller than that of liquid Fe–S. The light element contents in the outer core estimated previously may be an underestimation if we take into account the possible negative value of the excess mixing volume of iron–light element alloys in the outer core.     

Phase relations on the diopside-jadeite-hedenbergite join up to 24 GPa and stability of Na-bearing majoritic garnet

Phase relations on the diopside (Di)-hedenbergite (Hd)-jadeite (Jd) system modeling mineral associations of natural eclogites were studied for the compositions (mol %) Di₇₀Jd₃₀, Di₅₀Jd₅₀, Di₃₀Jd₇₀, Di₂₀Hd₈₀, and Di₄₀Hd₁₀Jd₅₀ using a toroidal anvil-with-hole (7 GPa) and a Kawai-type 6-8 multianvil apparatus (12-24 GPa). We established that Di, Hd, and Jd form complete series of solid solutions at 7 GPa, and melting temperatures of pure Di (1980 °C) and Jd (1870 °C) for that pressure were estimated experimentally. The melting temperature for the Di₅₀Jd₅₀ composition at 15.5 GPa is 2270 °C. The appearance of garnet is clearly dependent on initial clinopyroxene composition: at 1600 °C the first garnet crystals are observed at 13.5 GPa in the jadeite-rich part of the system (Di₃₀Jd₇₀), whereas diopside-rich starting material (Di₇₀Jd₃₀) produces garnet only above 17 GPa. The proportion of garnet increases rapidly above 18 GPa as pyroxene dissolves in the garnet structure and pyroxene-free garnetites are produced from diopside-rich starting materials. In all experiments, garnet coexists with stishovite (St). At a pressure above 18 GPa, pyroxene is completely replaced by an assemblage of majorite (Maj) + St + CaSiO₃-perovskite (Ca-Pv) in Ca-rich systems, whereas Maj is associated with almost pure Jd up to a pressure of 21.5 GPa. Above ∼22 GPa, Maj, and St are associated with NaAlSiO₄ with calcium ferrite structure (Cf). We established that an Hd component also spreads the range of pyroxene stability up to 20 GPa. In the Di₇₀Jd₃₀ system at 24 GPa an assemblage of Maj + Ca-Pv + MgSiO₃ with ilmenite structure (Mg-Il) was obtained. The experimentally established correlation between Na, Si, and Al contents in Maj and pressure in Grt(Maj)-pyroxene assemblages, may be the basis for a “majorite” geobarometer. The results of our experiments are applicable to the upper mantle and the transition zone of the Earth (400-670 km), and demonstrate a wide range of transformations from eclogite to perovskite-bearing garnetite. In addition, the mineral associations obtained from the experiments allowed us to simulate parageneses of inclusions in diamonds formed under the conditions of the transition zone and the lower mantle.     

Experimental constraints on ureilite petrogenesis

This experimental study explores the petrogenesis of ureilites by a partial melting/smelting process. Experiments have been performed over temperature (1150-1280 °C), pressure (5-12.5 MPa), and low oxygen fugacity (graphite-CO gas) conditions appropriate for a hypothetical ureilite parent body ∼200 km in size. Experimental and modeling results indicate that a partial melting/smelting model of ureilite petrogenesis can explain many of the unique characteristics displayed by this meteorite group. Compositional information preserved in the pigeonite-olivine ureilites was used to estimate the composition of melts in equilibrium with the ureilites. The results of 20 experiments saturated with olivine, pyroxene, metal, and liquid with appropriate ureilite compositions are used to calibrate the phase coefficients and pressure-temperature dependence of the smelting reaction. The calibrated coefficients are used to model the behavior of a hypothetical residue that is experiencing fractional smelting. The residue is initially olivine-rich and smelting progressively depletes the olivine content and enriches the pyroxene and metal contents of the residues. The modeled residue composition at 1260 °C best reproduces the trend of ureilite bulk compositions. The model results also indicate that as a ureilite residue undergoes isothermal decompression smelting over a range of temperatures, Ca/Al values and Cr₂O₃ contents are enriched at lower temperatures (below ∼1240 °C) and tend to decrease at higher temperatures. Therefore, fractional smelting can account for the high Ca/Al and Cr₂O₃ wt% values observed in ureilites. We propose that ureilites were generated from an olivine-rich, cpx-bearing residue. Smelting began when the residue was partially melted and contained liquid, olivine, and carbon. These residues experienced varying degrees of fractional smelting to produce the compositional variability observed within the pigeonite-bearing ureilites. Variations in mineral composition, modal proportions, and isotopic signatures are best described by heterogeneous accretion of the ureilite parent body followed by minimal and variable degrees of igneous processing.     

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 carbon on trace element partitioning behavior

Carbon has been proposed as a potential light element in planetary cores, included in models of planetary core formation, and found in meteoritic samples and minerals. To better understand the effect of C on the partitioning behavior of elements, solid/liquid partition coefficients (D = (solid metal)/(liquid metal)) were determined for 17 elements (As, Au, Co, Cr, Cu, Ga, Ge, Ir, Ni, Os, Pd, Pt, Re, Ru, Sb, Sn, and W) over a range of C contents in the Fe-Ni-C system at 1 atm. The partition coefficients for the majority of the elements increased as the C content of the liquid increased, an effect analogous to that of S for many of the elements. In contrast, three of the elements, Cr, Re, and W, were found to have anthracophile (C-loving) preferences, partitioning more strongly into the metallic liquid as the C content increased, resulting in decreases to their partition coefficients. For half of the elements examined, the prediction that partitioning in the Fe-Ni-S and Fe-Ni-C systems could be parameterized using a single set of variables was not supported. The effects of S and C on elemental partitioning behavior can be quite different; consequently, the presence of different non-metals can result in different fractionation patterns, and that uniqueness offers the opportunity to gain insight into the evolution of planetary bodies.     

The Composition of Near-solidus Partial Melts of Fertile Peridotite at 1 and 1{middle dot}5 GPa: Implications for the Petrogenesis of MORB

We have determined the near-solidus melt compositions for peridotiteMM-3, a suitable composition for the production of mid-oceanridge basalt (MORB) by decompression partial melting, at 1 and1·5 GPa. At 1 GPa the MM-3 composition has a subsolidusplagioclase-bearing spinel lherzolite assemblage, and a solidusat 1270°C. At only 5°C above the solidus, 4% meltis present as a result of almost complete melting of plagioclase.This melting behaviour in plagioclase lherzolite is predictedfrom simple systems and previous experimental work. The persistenceof plagioclase to > 0·8 GPa is strongly dependenton bulk-rock CaO/Na₂O and normative plagioclase content in theperidotite. At 1·5 GPa the MM-3 composition has a subsolidusspinel lherzolite assemblage, and a solidus at 1350°C.We have determined a near-solidus melt composition at 2% meltingwithin 10°C of the solidus. Near-solidus melts at both 1and 1·5 GPa are nepheline normative, and have low normativediopside contents; also they have the highest TiO₂, Al₂O₃ andNa₂O, and the lowest FeO and Cr₂O₃ contents compared with higherdegree partial melts. Comparison of these near-solidus meltswith primitive MORB glasses, which lie in the olivine-only fieldof crystallization at low pressure, indicate that petrogeneticmodels involving aggregation of near-fractional melts formedduring melting at pressures of 1·5 GPa or less are unlikelyto be correct. In this study we use an experimental approachthat utilizes sintered oxide mix starting materials and peridotitereaction experiments. We also examine some recent studies usingan alternative approach of melt migration into, and entrapmentwithin ‘melt traps’ (olivine, diamond, vitreouscarbon) and discuss optimal procedures for this method. KEY WORDS: experimental petrology; mantle melting; near-solidus; fertile peridotite; MORB     

The Fe-rich liquidus in the Fe-FeS system from 1 bar to 10 GPa

The composition and evolution of a metallic planetary core is determined by the behavior with pressure of the eutectic and the liquidus on the Fe-rich side of the Fe-FeS eutectic. New experiments at 6 GPa presented here, along with existing experimental data, inform a thermodynamic model for this liquidus from 1 bar to at least 10 GPa. Fe-FeS has a eutectic that becomes more Fe-rich but remains constant in T up to 6 GPa. The 1 bar, 3 GPa, and 6 GPa liquidi all cross at a pivot point at 1640 ± 5 K and FeS_37 ± 0.5. This liquid/crystalline metal equilibrium is T-x-fixed and pressure independent through 6 GPa. Models of the 1 bar through 10 GPa experimental liquidi show that with increasing P there is an increase in the T separation between the liquidus and the crest of the metastable two-liquid solvus. The solvus crest decreases in T with increasing P. The model accurately reproduces all the experimental liquidi from 1 bar to 10 GPa, as well as reproducing the 0-6 GPa pivot point. The 14 GPa experimental liquidus ( [Chen et al., 2008a] and Chen et al., 2008b) deviates sharply from the lower pressure trends indicating that the 0-10 GPa model no longer applies to this 14 GPa data.     

Formation of IIAB iron meteorites

Group IIAB is the third largest group of iron meteorites and the second largest group that formed by fractional crystallization; many of these irons formed from the P-rich portion of a magma consisting of two-immiscible liquids. We report neutron-activation data for 78 IIAB irons. These confirm earlier studies showing that the group has the largest known range in Ir concentrations (a factor of 4000) and that slopes are steeply negative on plots of Ir vs. Au or As (or Ni). High negative slopes imply relatively high distribution coefficients for Ir, Au, and As (but, with rare exceptions, remaining less than unity for the latter). IIAB appears to have had the highest S contents of any magmatic group of iron meteorites, consistent with its high contents of other volatile siderophiles, particularly Ga and Ge. Large fractions of trapped melt were present in the IIAB irons with the highest Au and As and lowest Ir contents. As a result, when these irons crystallized, the D_Au and D_As values can, with moderate accuracy, be estimated to have been roughly 0.53 and 0.46, respectively. These low values imply that the initial nonmetal (S + P) content of the magma was much lower than 170 mg/g, as estimated in earlier studies; our estimate is 75 mg/g. Our results are consistent with an initial P/S ratio of 0.25, similar to the ratio estimated for other magmatic groups. There is little doubt that incompatible S-rich and P-rich metallic liquids were involved during the formation of group IIAB. After 20% crystallization of our assumed starting composition the two-liquid boundary is encountered (at 72 mg/g S and 18 mg/g P). Initially the volume of S-rich liquid is very small, but continued crystallization increased the volume of this phase and decreased its P/S ratio while increasing this ratio in the P-rich liquid. Most crystallization of the IIAB magma would have occurred in the lower, P-rich portion of the core. However, metal was still a liquidus phase at the top of the core and, because both the immiscible liquids would have convected, they may have approached equilibrium throughout the very limited crystallization of the magma recorded in group IIAB. All IIAB irons contain trapped melt, and this melt will have had very different compositions depending on whether the liquid is S-rich (at the outer solid/liquid interface) or P-rich (at the inner interface). The P/S ratio in the melt trapped in the Santa Luzia iron is about 0.6 g/g, consistent with our modeling of Ir-Au and Ir-As trends implying that Santa Luzia formed in the lower, P-rich portion of the core after about 48% crystallization of the magma. Because the liquids were in equilibrium, the point at which immiscibility first occurred is not recorded by a dramatic change in the trends on element-Au diagrams; the main compositional effect is recorded in the P/S ratio of the trapped melt. The high-Au (>0.8 μg/g) irons for which large sections are available all contain skeletal schreibersite implying a relatively high (>0.3 g/g) P/S ratio; none of these irons could have crystallized from the S-rich upper layer of the core.     

Melting of the Indarch meteorite (EH4 chondrite) at 1 GPa and variable oxygen fugacity: Implications for early planetary differentiation processes

In order to derive constraints on planetary differentiation processes, and ultimately the formation of the Earth, it is required to study a variety of meteoritic materials and to investigate their melting relations and elemental partitioning at variable pressures, temperatures, and oxygen fugacities (f_O2). This study reports the first high pressure (HP) and high temperature (HT) investigation of an enstatite chondrite (Indarch). Four series of experiments exploring various f_O2 conditions have been carried out at 1 GPa in a piston-cylinder apparatus using the EH4 chondrite Indarch. We show that temperature and redox conditions have important effects on the phase equilibria of the meteorite: the solidus and liquidus temperatures of the silicate portion increase with decreasing f_O2, and the stability fields of various phases are modified. Olivine and pyroxene are stable around 1.5 log f_O2 unit below the iron-wüstite buffer (IW−1.5), whereas quartz and pyroxene is the stable assemblage under the most reducing conditions, between IW−5.0 and IW−4.0, due to reduction of the silicate. While these changes are occurring in the silicate, the metal gains Si from the silicate, (Fe, Mg, Mn, Ca, Cr)-bearing sulfides are observed at f_O2 less than IW−4, and the partitioning of Ni and Mo are both affected by the presence of Si in Fe-S-C liquids. The f_O2 has also a significant effect on the liquid metal-liquid silicate partitioning behavior of Si and S, two possible light elements in planetary cores, and of the slightly siderophile elements Cr and Mn. With decreasing f_O2, S becomes increasingly lithophile, Si becomes increasingly siderophile, and Cr and Mn both become strongly siderophile and chalcophile. The partitioning behavior of these elements places new constraints on models of core segregation for the Earth and other differentiated bodies.     

Si in the core? New high-pressure and high-temperature experimental data

High-pressure high-temperature experiments have been carried out up to 25 GPa and 2200°C in a multianvil press on assemblages made of silicates and iron-silicon alloys. At 20 GPa, silicon is extracted from the metal phase, forming stishovite reaction rims around metal grains. The silicon content in metal has been measured by analytical electron microscopy and electron microprobe. In contrast with earlier experiments, the present data were obtained by using silicon-rich metal alloys as starting materials instead of studying incorporation of silicon in initially silicon-free metal. As in most of previous studies carried out below 25 GPa, the silicon content in liquid metal increases with increasing pressure and with decreasing oxygen fugacity. The oxygen fugacity in most experiments was calculated by using two independent buffers: iron/?stite (IW) and SiO₂/Si, allowing to link consistently the Fe contents in silicates, the Si contents in metal and the temperatures of the experiments. At oxygen fugacities 4 log units below IW, silicates are in equilibrium with Si-rich metallic alloys (up to 17 wt% of Si in metal at 20 GPa and 2200°C). Extrapolation to 2 log units below IW leads to less than 0.1 wt% Si in the metal phase. Presence of several wt% of silicon in the Earth’s core thus requires highly reduced initial materials that, if equilibrated at conditions relevant to small planets, should already contain significant amount of silicon dissolved in metal.     

The stability and major element partitioning of ilmenite and armalcolite during lunar cumulate mantle overturn

Ilmenite has played an important role in the petrogenesis of lunar high-Ti picritic magmas, and armalcolite is another high-Ti oxide that was first discovered on the moon. In this study, we examined the thermodynamic stability of ilmenite and armalcolite in the context of lunar cumulate mantle overturn. Two starting compositions were explored, an ilmenite-bearing dunite (olivine + ilmenite) and an ilmenite-bearing harzburgite (olivine + orthopyroxene + ilmenite). Experiments were conducted using a 19.05 mm piston-cylinder apparatus at temperatures of 1235-1475 °C and pressures of 1-2 GPa. In runs with the ilmenite-bearing dunite mixture, ilmenite is stable in the subsolidus assemblage at least up to 1450 °C and 2 GPa. In runs with the ilmenite-bearing harzburgite starting mixture, ilmenite is stable at pressures greater than 1.4 GPa, and armalcolite is stable at lower pressures. Solidi for both starting compositions were determined, and the phase boundary between ilmenite- and armalcolite-bearing harzburgite was shown to have little dependence on temperature. During lunar cumulate overturn, sinking ilmenite formed near the end of lunar magma ocean solidification transforms into armalcolite when in contact with harzburgite cumulates at depths of less than 280 km in the lunar mantle. Inefficient overturn could leave isolated, inhomogeneously distributed pockets of armalcolite-bearing harzburgite in the upper lunar mantle, underlain by an ilmenite-bearing lower lunar mantle. These high-Ti oxide-bearing harzburgitic pockets can serve as potential sources for the generation of high-Ti magmas through partial melting or through assimilation of high-Ti minerals during transport of low-Ti picritic magmas in the lunar mantle.FeO-MgO exchange between olivine and either ilmenite or armalcolite was also examined in this study. We found the FeO-MgO distribution coefficient to be effectively independent of temperature for the pressures, temperatures, and compositions explored, with an average value of 0.179 ± 0.008 for olivine/ilmenite and 0.319 ± 0.021 for olivine/armalcolite. Given the bulk composition of an overturned lunar cumulate mantle, our measured FeO-MgO distribution coefficients can be used to estimate the Mg# of coexisting minerals in armalcolite- or ilmenite-bearing harzburgite and dunite in the overturned lunar mantle. Finally, the transformation from ilmenite-bearing harzburgite to armalcolite-bearing harzburgite results in a density increase of up to 2%. Large armalcolite-bearing cumulate bodies in the upper lunar mantle may be detectable in future lunar geophysical experiments.