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.     

Effect of pressure, temperature, and oxygen fugacity on the metal-silicate partitioning of Te, Se, and S: Implications for earth differentiation

We have measured liquid Fe metal-liquid silicate partitioning (D_i) of tellurium, selenium, and sulfur over a range of pressure, temperature, and oxygen fugacity (1-19 GPa, 2023-2693 K, fO₂ −0.4 to −5.5 log units relative to the iron-wüstite buffer) to better assess the role of metallic melts in fractionating these elements during mantle melting and early Earth evolution. We find that metal-silicate partitioning of all three elements decreases with falling FeO activity in the silicate melt, and that the addition of 5-10 wt% S in the metal phase results in a 3-fold enhancement of both D_Te and D_Se. In general, Te, Se, and S all become more siderophile with increasing pressure, and less siderophile with increasing temperature, in agreement with previous work. In all sulfur-bearing experiments, D_Te is greater than D_Se or D_S, with the latter two being similar over a range of P and T. Parameterized results are used to estimate metal-silicate partitioning at the base of a magma ocean which deepens as accretion progresses, with the equilibration temperature fixed at the peridotite liquidus. We show that during accretion, Te behaves like a highly siderophile element, with expected core/mantle partitioning of >10⁵, in contrast to the observed core/mantle ratio of ∼100. Less extreme differences are observed for Se and S, which yielded core/mantle partitioning 100- to 10 times higher, respectively, than the observed value. Addition of ∼0.5 wt% of a meteorite component (H, EH or EL ordinary chondrite) is sufficient to raise mantle abundances to their current level and erase the original interelement fractionation of metal-silicate equilibrium.     

C- and S-rich molten alloy immiscibility and core formation of planetesimals

We present the results of melting experiments to 7.7 GPa and 2200 °C on a synthetic ‘chondrite-like’ composition suitable to model early planetesimal differentiation. Our principal observation is that two immiscible liquid alloys coexist to about 5.5 GPa in Fe-Ni-S-C-O compositional space, with one liquid alloy being enriched in S and the other enriched in C. The chemical distinctions between the two liquid alloys progressively weaken as pressure increases. This is related to the contraction of the miscibility gap with increasing pressure. With the moderately C- and S-depleted composition used in this study, we observed closure of the miscibility gap at about 5.5 GPa. Our results have implications for core formation on planetary bodies that have undergone extensive melting. Because of the characteristics of the immiscibility region, core formation and differentiation histories would have been largely dependent on the size of these bodies and their C and S contents. Our results indicate that relatively small bodies with elevated S and C contents would have likely experienced significant core stratification.     

Equation of state of iron–silicon alloys to megabar pressure

The stability and pressure–volume equation of state of iron–silicon alloys, Fe-8.7 wt% Si and Fe-17.8 wt% Si, have been investigated using diamond-anvil cell techniques up to 196 and 124 GPa, respectively. Angular–dispersive X-ray diffractions of iron–silicon alloys were measured at room temperature using monochromatic synchrotron radiation and an imaging plate (IP). A bcc–Fe-8.7 wt% Si transformed to hcp structure at around 1636 GPa. The high-pressure phase of Fe-8.7 wt% Si with hexagonal close-packed (hcp) structure was found to be stable up to 196 GPa and no phase transition of bcc–Fe-17.8 wt% Si was observed up to 124 GPa. The pressure–volume data were fitted to a third-order Birch–Murnaghan equation of state (BM EOS) with zero–pressure parameters: V₀=22.2(8) ų, K₀=198(9) GPa, and K₀=4.7(3) for hcp–Fe-8.7 wt% Si and V₀=179.41(45) ų, K₀=207(15) GPa and K₀=5.1(6) for Fe-17.8 wt% Si. The density and bulk sound velocity of hcp–Fe-8.7 wt% Si indicate that the inner core could contain 3–5 wt% Si.     

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.     

The bulk composition of Mars

An accurate assessment of the bulk chemical composition of Mars is fundamental to understanding planetary accretion, differentiation, mantle evolution, the nature of the igneous parent rocks that were altered to produce sediments on Mars, and the initial concentrations of volatiles such as H, Cl and S, important constituents of the Martian surface. This paper reviews the three main approaches that have been used to estimate the bulk chemical composition of Mars: geochemical/cosmochemical, isotopic, and geophysical. The standard model is one developed by Wänke and Dreibus in a series of papers, which is based on compositions of Martian meteorites. Since their groundbreaking work, substantial amounts of data have become available to allow a reassessment of the composition of Mars from elemental data, including tests of the basic assumptions in the geochemical models. The results adjust some of the concentrations in the Wänke–Dreibus model, but in general confirm its accuracy. Bulk silicate Mars has roughly uniform depletion of moderately volatile elements such as K (0.6 × CI), and strong depletion of highly volatile elements (e.g., Tl). The highly volatile elements are within uncertainties uniformly depleted at about 0.06 CI abundances. The highly volatile chalcophile elements are likewise roughly uniformly depleted, but with more scatter, with normalized abundances of 0.03 CI. Bulk planetary H₂O is much higher than estimated previously: it appears to be slightly less than in Earth, but D/H is similar in Earth and Mars, indicating a common source of water-bearing material in the inner solar system. K/Th ranges from ∼3000 to ∼5000 among the terrestrial planets, a small range compared to CI chondrites (19,000). FeO varies throughout the inner solar system: ∼3 wt% in Mercury, 8 wt% in Earth and Venus, and 18 wt% in Mars. These differences can be produced by varying oxidation conditions, hence do not suggest the terrestrial planets were formed from fundamentally different materials. The broad chemical similarities among the terrestrial planets indicate substantial mixing throughout the inner solar system during planet formation, as suggested by dynamical models.     

Stable isotope and petrologic evidence for open-system degassing during the climactic and pre-climactic eruptions of Mt. Mazama, Crater Lake, Oregon

Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km³ of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43°N, long. 122°W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H₂O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing.Sulfur isotope analyses of climactic rhyodacitic whole rocks yield δ³⁴S values of 2.8-14.8‰ with corresponding matrix glass values of 2.4-13.2‰. δ³⁴S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8-5.2 wt% H₂O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4-5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in δ³⁴S from −0.4‰ to 5.8‰ and from −0.1‰ to 3.5‰, respectively. Initial δ³⁴S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0‰. Hydrogen isotope (δD) and total H₂O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values οf −103 to −53‰ and 0.23-1.74 wt%, respectively. Values of δD and wt% H₂O of obsidian decrease towards the top of the fall deposit. Samples with depleted δD, and mantle δ¹⁸O values, have elevated δ³⁴S values consistent with open-system degassing. These results imply that more mantle-derived sulfur is degassed to the Earth’s atmosphere/hydrosphere through convergent margin volcanism than previously attributed. Magmatic degassing can modify initial isotopic compositions of sulfur by >14‰ (to δ³⁴S values of 14‰ or more here) and hydrogen isotopic compositions by 90‰ (to δD values of −127‰ in this case).     

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.     

Metal-silicate partitioning of cesium: Implications for core formation

Here we present the first set of metal-silicate partitioning data for Cs, which we use to examine whether the primitive mantle depletion of Cs can be attributed to core segregation. Our experiments independently varied pressure from 5 to 15 GPa, temperature from 1900 to 2400 °C, metallic sulfur content from pure Fe to pure FeS, silicate melt polymerization, expressed as a ratio of non-bridging oxygens to tetrahedrally coordinated cations (nbo/t) from 1.26 to 3.1, and fO₂ from two to four log units below the iron-wüstite buffer. The most important controls on the partitioning behavior of alkalis were the metallic sulfur content, expressed as X_S, and the nbo/t of the silicate liquid. Normalization of X_S to 0.5 yielded the following expressions for D-values as a function of nbo/t: log D_Na = −2.0 + 0.44 × (nbo/t), log D_K = −2.4 + 0.67 × ( nbo/t), and log D_Cs = −3.2 + 1.17 × (nbo/t). Normalization of nbo/t to 2.7 resulted in the following equations for D-values as a function of S content: log D_Na = −4.1 + 6.4 × X_S, log D_K = −7.7 + 13.9 × X_S, and log D_Cs = −12.1 + 23.3 × X_S.There appears to be a negative pressure effect up to 15 GPa, but it should be noted that this trend was not present before normalization, and is based on only two measurements. There is a positive trend in cesium’s metal-silicate partition coefficient with increasing temperature. D_Cs exhibits the largest change and increased by a factor of three over 500 °C. The effect of oxygen fugacity has not been precisely determined but in general, lowering fO₂ by two log units resulted in a rise in all D-values of approximately an order of magnitude. In general, the sensitivity of partition coefficients to changing parameters increased with atomic number.The highest D-value for Cs observed in this study is 0.345, which was obtained at nbo/t of 2.7 and a metal phase of pure FeS. This metallic composition has far more S than has been suggested for any credible core-forming metal. We therefore conclude that the depletion of Cs in Earth’s mantle is either caused by radically different behavior of Cs at pressures higher than 15 GPa or is not related to core formation. Even so, we have shown that a planet with a sufficient S inventory may incorporate significant amounts of alkali elements into its core.     

Silicon isotopes in meteorites and planetary core formation

The silicon (Si) isotope compositions of 42 meteorite and terrestrial samples have been determined using MC-ICPMS with the aim of resolving the current debate over their compositions and the implications for core formation. No systematic δ³⁰Si differences are resolved between chondrites (δ³⁰Si = −0.49 ± 0.15‰, 2σ_SD) and achondrites (δ³⁰Si = −0.47 ± 0.11‰, 2σ_SD), although enstatite chondrites are consistently lighter (δ³⁰Si = −0.63 ± 0.07‰, 2σ_SD) in comparison to other meteorite groups. The data reported here for meteorites and terrestrial samples display an average difference Δ³⁰Si_{BSE−meteorite∗} = 0.15 ± 0.10‰, which is consistent within uncertainty with previous studies. No effect from sample heterogeneity, preparation, chemistry or mass spectrometry can be identified as responsible for the reported differences between current datasets. The heavier composition of the bulk silicate Earth is consistent with previous conclusions that Si partitioned into the metal phase during metal-silicate equilibration at the time of core formation. Fixing the temperature of core formation to the peridotite liquidus and using an appropriate metal silicate fractionation factor (ε ∼0.89), the Δ³⁰Si_{BSE−meteorite∗} value from this study indicates that the Earth core contains at least 2.5 and possibly up to 16.8 wt% Si.     

Lunar rock-rain: Diverse silicate impact-vapor condensates in an Apollo-14 regolith breccia

Apollo 14 regolith breccia 14076, long known to be uniquely endowed with high-alumina, silica-poor (HASP) material of evaporation-residue origin, has been found to contain a diverse suite of complementary condensates, dubbed GASP (gas-associated spheroidal precipitates). GASP occurs in two forms: as glassy or extremely fine grained quenched-melt spheroids, mostly less than 5 μm across; and as quenched textured clasts up to 200 μm across. In two of the clasts, origin by aggregation of spheroidal GASP is confirmed by the presence of relict spheroids. GASP is distinctively depleted in the same refractory major oxides that are characteristically enriched in HASP: Al₂O₃ and CaO. Among the larger GASP spheroids, Al₂O₃ is seldom >1 wt%; among the clasts, excluding two instances of apparent contamination by Na- and K-rich substrate-derived melt, bulk Al₂O₃ averages 0.3 wt%. Depletion of Al₂O₃ and CaO is also manifested by pyroxene compositions in some clasts; e.g., in the largest clast, En₈₂Wo_0.45 with 0.07 wt% Al₂O₃. Although GASP bulk compositions are nearly pure SiO₂ + MgO + FeO, they are nonetheless highly diverse. Spheroid compositions range in mg from 7 to 84 mol%, and in FeO/SiO₂ (weight ratio) from 0.002 to 0.67. Bulk compositions and textures of many GASP spheroids suggest that liquid immiscibility occurred prior to quenching; implying that these materials were, some time after condensation, at temperatures of ∼1680 °C. Textural evidence for immiscibility includes lobate boundaries between silicic and mafic domains, and a general tendency for quenched mafic silicates to be concentrated into a few limited patches rather than evenly dispersed. The parent melt of the largest clast’s pyroxene is inferred to have formed as a partial melt within the parent aggregation of GASP matter, compositionally near the pyroxene + cristobalite + melt eutectic and thus at ∼1500 °C. A few GASP spheroids show possible signs of in-flight collision-coalescence, but aggregation of the much larger clasts probably took place in mushy puddles on the lunar surface. Little mixing took place between these GASP puddles and the related HASP, probably because GASP condensation did not commence until after an intermediate stage during which, while neither net evaporation nor net condensation took place, expansion of the vapor cloud carried the eventual GASP matter well apart from the HASP. Considering the characteristic length-scale of lunar regolith mixing, the concentration of both GASP and HASP into this single unique regolith sample (14076) is most consistent with a parent crater size (diameter) of 10-100 km. I speculate that the 14076 regolith may have been unusually situated, almost directly uprange from an unusually oblique large impact. Mercurian analogs of the 14076 impact condensates may have significant implications for remote sensing.     

Experimental partitioning of uranium between liquid iron sulfide and liquid silicate: Implications for radioactivity in the Earth’s core

Measurable uranium (U) is found in metal sulfide liquids in equilibrium with molten silicate at conditions appropriate for a planetary magma ocean: 1-10 GPa, 1750-2100 °C, 0-28 wt% S, and fO₂ 2 log units below IW. However, the transfer of U from metal sulfide to silicate under our experimental conditions is so complete that insufficient U would remain so as to be of any importance to the core’s heat budget. U content in the sulfide phase increases strongly with S content but shows no significant variability with either pressure or temperature. Maximum is 0.001 while most values are considerably lower.     

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.     

High-pressure phase equilibria and element partitioning experiments on Apollo 15 green C picritic glass: Implications for the role of garnet in the deep lunar interior

We report results of nominally anhydrous near-liquidus experiments on a synthetic analog to very low-titanium Apollo 15 green C lunar picritic glass from ∼2 to 5 GPa. Apollo 15 green C glass (A15C) is saturated with garnet and pyroxene on the liquidus at ∼3 GPa. However, such an assemblage is unlikely to represent the lunar-mantle source region for this glass, and instead an olivine + orthopyroxene-dominated source is favored, in accord with earlier lower-pressure experiments on A15C. Near-liquidus garnet has a slight but significant majorite component at ∼5 GPa in this iron-rich bulk composition, as expected from our previous work in ordinary-chondritic bulk compositions. Ion microprobe measurements of partitioning of Sr, Ba, Sc, Nd, Sm, Dy, Yb, Y, Zr, Hf, and Th between garnet and coexisting melt in these experiments are the first garnet partition coefficients (D values) available that are directly relevant to lunar compositions. D values for these garnets differ significantly compared to D values for garnets grown in more magnesian, terrestrial bulk compositions, which until now are all that have been available in modeling the possible role of garnet in the lunar interior. For example, D values for heavy rare earth elements are lower than are those from terrestrial basaltic systems. These partitioning values are well-described by the lattice-strain partitioning model, but predictive relationships for garnet partitioning using that model fail to match the measured values, as was the case in our earlier work on chondritic compositions. Using our new D values in place of the “terrestrial” values in a variety of models of lunar petrogenesis, we suggest that garnet is unlikely to be present in the source regions for very titanium-poor lunar liquids despite its appearance on the liquidus of A15C.     

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.     

S-rich apatite-hosted glass inclusions in xenoliths from La Palma: constraints on the volatile partitioning in evolved alkaline magmas

The composition of S-rich apatite, of volatile-rich glass inclusions in apatite, and of interstitial glasses in alkaline xenoliths from the 1949 basanite eruption in La Palma has been investigated to constrain the partitioning of volatiles between apatite and alkali-rich melts. The xenoliths are interpreted as cumulates from alkaline La Palma magmas. Apatite contains up to 0.89 wt% SO₃ (3560 ppm S), 0.31 wt% Cl, and 0.66 wt% Ce₂O₃. Sulfur is incorporated in apatite via several independent exchange reactions involving (P⁵⁺, Ca²⁺) vs. (S⁶⁺, Si⁴⁺, Na⁺, and Ce³⁺). The concentration of halogens in phonolitic to trachytic glasses ranges from 0.15 to 0.44 wt% for Cl and from <0.07 to 0.65 wt% for F. The sulfur concentration in the glasses ranges from 0.06 to 0.23 wt% SO₃ (sulfate-saturated systems). The chlorine partition coefficients (D_Cl^{apatite/glass}) range from 0.4 to 1.3 (average D_Cl^{apatite/glass} = 0.8), in good agreement with the results of experimental data in mafic and rhyolitic system with low Cl concentrations. With increasing F in glass inclusions D_F^{apatite/glass} decreases from 35 to 3. However, most of our data display a high partition coefficient (~30) close to D_F^{apatite/glass} determined experimentally in felsic rock. D_S^{apatite/glass} decreases from 9.1 to 2.9 with increasing SO₃ in glass inclusions. The combination of natural and experimental data reveals that the S partition coefficient tends toward a value of 2 for high S content in the glass (>0.2 wt% SO₃). D_S^{apatite/glass} is only slightly dependent on the melt composition and can be expressed as: SO_{3 apatite} (wt%) = 0.157 * ln SO_{3 glass} (wt%) + 0.9834. The phonolitic compositions of glass inclusions in amphibole and haüyne are very similar to evolved melts erupted on La Palma. The lower sulfur content and the higher Cl content in the phonolitic melt compared to basaltic magmas erupted in La Palma suggest that during magma evolution the crystallization of haüyne and pyrrhotite probably buffered the sulfur content of the melt, whereas the evolution of Cl concentration reflects an incompatible behavior. Trachytic compositions similar to those of the (water-rich) glass inclusions analyzed in apatite and clinopyroxene are not found as erupted products. These compositions are interpreted to be formed by the reaction between water-rich phonolitic melt and peridotite wall-rock.     

Experiments on liquid immiscibility along tholeiitic liquid lines of descent

Crystallization experiments have been conducted on compositions along tholeiitic liquid lines of descent to define the compositional space for the development of silicate liquid immiscibility. Starting materials have 46–56 wt% SiO₂, 11.7–17.7 wt% FeO_tot, and Mg-number between 0.29 and 0.36. These melts fall on the basaltic trends relevant for Mull, Iceland, Snake River Plain lavas and for the Sept Iles layered intrusion, where large-scale liquid immiscibility has been recognized. At one atmosphere under anhydrous conditions, immiscibility develops below 1,000–1,020°C in all of these compositionally diverse lavas. Extreme iron enrichment is not necessary; immiscibility also develops during iron depletion and silica enrichment. Variations in melt composition control the development of silicate liquid immiscibility along the tholeiitic trend. Elevation of Na₂O + K₂O + P₂O₅ + TiO₂ promotes the development of two immiscible liquids. Increasing melt CaO and Al₂O₃ stabilizes a single-liquid field. New data and published phase equilibria show that anhydrous, low-pressure fractional crystallization is the most favorable condition for unmixing during differentiation. Pressure inhibits immiscibility because it expands the stability field of high-Ca clinopyroxene, which reduces the proportion of plagioclase in the crystallizing assemblage, thus enhancing early iron depletion. Magma mixing between primitive basalt and Fe–Ti–P-rich ferrobasalts can serve to elevate phosphorous and alkali contents and thereby promote unmixing. Water might decrease the temperature and size of the two-liquid field, potentially shifting the binodal (solvus) below the liquidus, leading the system to evolve as a single-melt phase.     

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.     

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.     

Phase relations in the carbon-saturated C–Mg–Fe–Si–O system and C and Si solubility in liquid Fe at high pressure and temperature: implications for planetary interiors

The phase and melting relations of the C-saturated C–Mg–Fe–Si–O system were investigated at high pressure and temperature to understand the role of carbon in the structure of the Earth, terrestrial planets, and carbon-enriched extraterrestrial planets. The phase relations were studied using two types of experiments at 4 GPa: analyses of recovered samples and in situ X-ray diffractions. Our experiments revealed that the composition of metallic iron melts changes from a C-rich composition with up to about 5 wt.% C under oxidizing conditions (ΔIW = ?1.7 to ?1.2, where ΔIW is the deviation of the oxygen fugacity (fO₂) from an iron-wüstite (IW) buffer) to a C-depleted composition with 21 wt.% Si under reducing conditions (ΔIW < ?3.3) at 4 GPa and 1,873 K. SiC grains also coexisted with the Fe–Si melt under the most reducing conditions. The solubility of C in liquid Fe increased with increasing fO₂, whereas the solubility of Si decreased with increasing fO₂. The carbon-bearing phases were graphite, Fe₃C, SiC, and Fe alloy melt (Fe–C or Fe–Si–C melts) under the redox conditions applied at 4 GPa, but carbonate was not observed under our experimental conditions. The phase relations observed in this study can be applicable to the Earth and other planets. In hypothetical reducing carbon planets (ΔIW < ?6.2), graphite/diamond and/or SiC exist in the mantle, whereas the core would be an Fe–Si alloy containing very small amount of C even in the carbon-enriched planets. The mutually exclusive nature of C and Si may be important also for considering the light elements of the Earth’s core.