Highly Siderophile Elements in Pallasites and Diogenites, Including the New Pallasite, CMS 04071

Pallasites are long thought to represent a metallic core-silicate mantle boundary, where the IIIAB irons are linked to the crystallization history of the metallic fraction, and the HED meteorites may be linked to the silicate fraction. However, measurement of trace elements in individual metallic and silicate phases is necessary in order to fully under-stand the petrogenetic history of pallasites, as well as any magmatic processes which may link pallasites to both IIIAB irons and HED meteorites. In order to achieve this objective, abundances of a suite of elements were measured, including the highly siderophile elements (HSEs), in kamacite, taenite, troilite, schreibersite, chromite and olivine for the pallasites Admire, Imilac, Springwater, CMS 04071. In the diogenites GRO 95555, LAP 91900, and MET 00436, metal, sulfide, spinel, pyroxene, and silica were individually measured

Partitioning of Pd Between Fe-S-C and Mantle Liquids at High Pressure and Temperature: Implications for Core Formation

One of the most elusive geochemical aspects of the early Earth has been explaining the near chondritic relative abundances of the highly siderophile elements (HSE; Au, Re and the platinum group elements) in Earth's primitive upper mantle (PUM). Perhaps they were delivered to the Earth after core formation, by late addition of carbonaceous chondrite material. However, the recognition that many moderately siderophile elements can be explained by high pressure and temperature (PT) metal-silicate equilibrium, leads to the question whether high PT equilibrium can also explain the HSE concentrations. Answers to this question have been slowed by experimental difficulties (nugget effect and very low solubilities). But two different perspectives have emerged from recent studies. One perspective is that D(M/S) for HSE at high PT are not low enough to explain terrestrial mantle depletions of these elements (for Pd and Pt). A second perspective is D(M/S) are reduced substantially at high PT and even low enough to explain terrestrial mantle depletions (for Au and Pt). Issues complicating interpretation of all experiments include use of MgO- and FeO-free silicate melts, and S-free and FeNi metal-free systems. In addition, conclusions for Pt rest on an interpretation that the tiny metallic nuggets plaguing many such experiments, were formed upon quench. There is not agreement on this issue, and the general question of HSE solubility at high PT remains unresolve

The Combined Strength of Thermodynamics and Comparative Planetology: Application of Activity Models to Core Formation in Terrestrial Bodies

Recent models for accretion of terrestrial bodies involve metal-silicate equilibrium as the metallic core formed during growth. Most elements considered are either refractory or well studied elements for which effects of pressure, temperature, oxygen fugacity, and metallic liquid composition are well known. There are a large number of elements that are both siderophile and volatile, whose fate in such models is unknown, largely due to a lack of data at comparable conditions and com-positions (FeNi core with light elements such as S, C, Si, and O). We have focused on Ge, In, As, Sb and determined the effect of Si and C on metal-silicate partitioning, and developed a thermo-dynamic model that allows application of these new data to a wide range of planetary bodies. New experiments: We have previously carried out experiments with FeSi metallic liquid at C-saturated conditions at 1600 and 1800 C [4]. In a new series of experiments we investigate the effect of Si in carbon-free systems at 1600 C for comparison. Experiments were carried out at 1 GPa in MgO capsules using the same basaltic starting composition as in previous studies. The MgO capsule reacts with the silicate melt to form more MgO-rich liquids that have 22-26 wt% MgO. Experimental met-als and silicates were analyzed using a combination of electron microprobe analysis and laser ablation ICP-MS. Results: The new results can be interpreted by considering Ge as an example, in the simple exchange equilibrium Fe + GeO = FeO + Ge, where the equilibrium constant Kd can be examined as a function of Si content of the metal. The slope of lnKd vs. (1-XSi) for this new series allows derivation of the epsilon interaction parameter for each of these four elements and Si (both C-saturated and C-free).All four elements have positive epsilon values, indicating that Si causes a decrease in the partition coefficients; values are 6.6, 6.5, 27.8 and 25.2 for In, Ge, As, and Sb, respectively, at 1 GPa and 1600 C. As an example of how large the effect of Si can be, these epsilon values correspond to activity coefficients (gamma) for As of 0.01 when XSi = 0, and up to gamma = 23 when XSi = 0.2. Combining these new results with previous determinations [5,6] of epsilon parameters for S and C for these elements allows us calculate activity of Ge, In, As, and Sb in Fe-Ni-Si-S-C-O metallic liquids. We apply this new model to sever-al terrestrial bodies such as Earth (Si-rich core), Mars (S-rich core), Moon (S-, C-, and Si-poor core), and Vesta, and examine the resulting core and mantle concentrations of these elements. Mantle concentrations of these four elements are well explained for Earth and Mars in models that call for mid-mantle equilibration between Si-bearing and S-bearing FeNi cores, respectively. Modeling results for the Moon and Vesta will also be presented

Experiments on Lunar Core Composition: Phase Equilibrium Analysis of A Multi-Element (Fe-Ni-S-C) System

Previous geochemical and geophysical experiments have proposed the presence of a small, metallic lunar core, but its composition is still being investigated. Knowledge of core composition can have a significant effect on understanding the thermal history of the Moon, the conditions surrounding the liquid-solid or liquid-liquid field, and siderophile element partitioning between mantle and core. However, experiments on complex bulk core compositions are very limited. One limitation comes from numerous studies that have only considered two or three element systems such as Fe-S or Fe-C, which do not supply a comprehensive understanding for complex systems such as Fe-Ni-S-Si-C. Recent geophysical data suggests the presence of up to 6% lighter elements. Reassessments of Apollo seismological analyses and samples have also shown the need to acquire more data for a broader range of pressures, temperatures, and compositions. This study considers a complex multi-element system (Fe-Ni-S-C) for a relevant pressure and temperature range to the Moon's core conditions

High Pressure and Temperature Core Formation as an Alternative to the "Late Veneer" Hypothesis

The highly siderophile elements (HSE; Re, Au and the Platinum Group Elements - Pd Pt, Rh, Ru, Ir, Os) are commonly utilized to constrain accretion processes in terrestrial differentiated bodies due to their affinity for FeNi metal [1]. These eight elements exhibit highly siderophile behavior, but nonetheless have highly diverse metal-silicate partition coefficients [2]. Therefore the near chondritic relative concentrations of HSEs in the terrestrial and lunar mantles, as well as some other bodies, are attributed to late accretion rather than core formation [1]. Evaluation of competing theories, such as high pressure metal-silicate partitioning or magma ocean hypotheses has been hindered by a lack of relevant partitioning data for this group of eight elements. In particular, systematic studies isolating the effect of one variable (e.g. temperature or melt compositions) are lacking. Here we undertake new experiments on all eight elements, using Fe metal and FeO-bearing silicate melts at fixed pressure, but variable temperatures. These experiments, as well as some additional planned experiments should allow partition coefficients to be more accurately calculated or estimated at the PT conditions and compositions at which core formation is thought to have occurred

Origin of Volatiles in Earth: Indigenous Versus Exogenous Sources Based on Highly Siderophile, Volatile Siderophile, and Light Volatile Elements

Origin of Earth's volatiles has traditionally been ascribed to late accretion of material after major differentiation events - chondrites, comets, ice or other exogenous sources. A competing theory is that the Earth accreted its volatiles as it was built, thus water and other building blocks were present early and during differentiation and core formation (indigenous). Here we discuss geochemical evidence from three groups of elements that suggests Earth's volatiles were acquired during accretion and did not require additional sources after differentiation

Iron Redox Systematics of Martian Magmas

Martian magmas are known to be FeO-rich and the dominant FeO-bearing mineral at many sites visited by the Mars Exploration rovers (MER) is magnetite [1]. Morris et al. [1] propose that the magnetite appears to be igneous in origin, rather than of secondary origin. However, magnetite is not typically found in experimental studies of martian magmatic rocks [2,3]. Magnetite stability in terrestrial magmas is well understood, as are the stability of FeO and Fe2O3 in terrestrial magmas [4,5]. In order to better understand the variation of FeO and Fe2O3, and the stability of magnetite (and other FeO-bearing phases) in martian magmas we have undertaken an experimental study with two emphases. First we document the stability of magnetite with temperature and fO2 in a shergottite bulk composition. Second, we determine the FeO and Fe2O3 contents of the same shergottite bulk composition at 1 bar and variable fO2 at 1250 C, and at variable pressure. These two goals will help define not only magnetite stability, but pyroxene-melt equilibria that are also dependent upon fO2

Partitioning of Phosphorus and Molybdenum between the Earth's Mantle and Core and the Conditions of Core Formation

There are several hypotheses on the specific processes that might have occurred during the formation of the Earth. One hypothesis that has been proposed is that early in the Earth's formation, there was a magma ocean present, and within this body, siderophile elements separated out of the silicate liquid to form the metal core. This study addresses this hypothesis. P and Mo are moderately siderophile elements that are present in both the mantle and the core. The concentrations of P and Mo in silicate vs. metal can be measured and in turn used to determine the temperatures, pressures, oxygen fugacity and melt composition required to achieve the same concentrations as observed in the mantle. The data here include eight experiments examining the partitioning of P and Mo between metallic liquid and silicate liquid. The purpose of the experiments has been to gain a greater understanding of core-mantle separation during the Earth formation process and examines temperature effect on P and Mo, which has not been systematically studied before

Iron redox systematics of martian magmas.

第2回極域科学シンポジウム/第34回南極隕石シンポジウム 11月18日（金） 国立国語研究所 2階講

V Xanes in Spinels as an Oxy-Barometer in Meteorites with Implications for Redox Variations in the Inner Solar System

The variation of oxygen fugacity within inner solar system materials spans a range of nearly 15 orders of magnitude. Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or con-strained such as FeTi oxides, olivine-opx-spinel, or some other oxy-barometer. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these achondrites is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in achondrite. Because the V pre-edge peak intensity and energy in chromites varies with fO2, and this has been calibrated over a large fO2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints