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Partitioning of Moderately Siderophile Elements Among Olivine, Silicate Melt, and Sulfide Melt: Constraints on Core Formation in the Earth and Mars

This study investigates the effects of Variations in the fugacities of oxygen and sulfur on the partitioning of first series transition metals (V, Cr, Mn, Fe, Co, Ni. and Cu) and W among coexisting sulfide melt, silicate melt, and olivine. Experiments were performed at 1 atm pressure, 1350 C, with the fugacities of oxygen and sulfur controlled by mixing CO2, CO, and SO2 gases. Starting compositions consisted of a CaO-MgO-Al2O3-SiO2-FeO-Na2O analog for a barred olivine chondrule from an ordinary chondrite and a synthetic komatiite. The f(sub O2)/f(sub S2), conditions ranged from log of f(sub O2) = -7.9 to - 10.6, with log of f(sub S2) values ranging from - 1.0 to -2.5. Our experimental results demonstrate that the f(sub O2)/f(sub S2) dependencies of sulfide melt/silicate melt partition coefficients for the first series transition metals arc proportional to their valence states. The f(sub O2)/f(sub S2) dependencies for the partitioning of Fe, Co, Ni, and Cu are weaker than predicted on the basis of their valence states. Variations in conditions have no significant effect on olivine/melt partitioning other than those resulting from f(sub O2)-induced changes in the valence state of a given element. The strong f(sub O2)/f(sub S2) dependence for the olivine/silicate melt partitioning of V is attributable to a change of valence state, from 4+ to 3+, with decreasing f(sub O2). Our experimentally determined partition coefficients are used to develop models for the segregation of sulfide and metal from the silicate portion of the early Earth and the Shergottite parent body (Mars). We find that the influence of S is not sufficient to explain the overabundance of siderophile and chalcophile elements that remained in the mantle of the Earth following core formation. Important constraints on core formation in Mars are provided by our experimental determination of the partitioning of Cu between silicate and sulfide melts. When combined with existing estimates for siderophile element abundances in the Martian mantle and a mass balance constraint from Fe, the experiments allow a determination of the mass of the Martian core (approx. 17 to 22 wt% of the planet) and its S content (approx.0.4 wt%). These modeling results indicate that Mars is depleted in S, and that its core is solid.

Gaetani, Glenn A.↗

Biological and Organic Chemical Decomposition of Silicates

The weathering of silicate rocks and minerals, an important concern of geologists and geochemists for many years, traditionally has been approached from strictly physical and chemical points of view. Biological effects were either unrecognized, ignored, or were mentioned in passing to account for such phenomena as the accumulation of organic matter in sediments or the generation of reducing environments. A major exception occurred in soil science where agricultural scientists, studying the factors important in the development of soils and their ability to nourish and sustain various crops, laid the foundation for much of what is known of the biological breakdown of silicate rocks and minerals. The advent of the space age accelerated the realization that many environmental problems and geo- chemical processes on Earth can only be understood in terms of ecosystems. This in turn, spurred renewed interest and activity among modem biologists, geologists and soil scientists attempting to unravel the intimate relations between biology and the weathering of silicate rocks and minerals of the earth surface.

Silverman, M. P.↗

Io's Volcanism: Thermo-Physical Models of Silicate Lava Compared with Observations of Thermal Emission

Analyses of thermal infrared outbursts from the jovian satellite Io indicate that at least some of these volcanic events are due to silicate lava. Analysis of the January 9, 1990 outburst indicates that this was an active eruption consisting of a large lava flow (with mass eruption rate of order 10(exp 5) cubic m/sec) and a sustained area at silicate liquidus temperatures. This is interpreted as a series of fire fountains along a rift zone. A possible alternative scenario is that of an overflowing lava lake with extensive fire fountaining. The January 9, 1990 event is unique as multispectral observations with respect to time were obtained. In this paper, a model is presented for the thermal energy lost by active and cooling silicate lava flows and lakes on Io. The model thermal emission is compared with Earth-based observations and Voyager IRIS data. The model (a) provides an explanation of the thermal anomalies on Io's surface; (b) provides constraints on flow behavior and extent and infers some flow parameters; and (c) determines flow geometry and change in flow size with time, and the temperature of each part of the flow or lava lake surface as a function of its age. Models of heat output from active lava flows or inactive but recently emplaced lava flows or overturning lava lakes alone are unable to reproduce the observations. If the January 9, 1990 event is the emplacement of a lava flow, the equivalent of 27 such events per year would yield a volume of material sufficient, if uniformly distributed, to resurface all of Io at a rate of 1 cm/year.

Davies, Ashely G.↗

Biological and Organic Chemical Decomposition of Silicates

The weathering of silicate rocks and minerals, an important concern of geologists and geochemists for many years, traditionally has been approached from strictly physical and chemical points of view. Biological effects were either unrecognized, ignored, or were mentioned in passing to account for such phenomena as the accumulation of organic matter in sediments or the generation of reducing environments. A major exception occurred in soil science where agricultural scientists, studying the factors important in the development of soils and their ability to nourish and sustain various crops, laid the foundation for much of what is known of the biological breakdown of silicate rocks and minerals. The advent of the space age accelerated the realization that many environmental problems and geochemical processes on Earth can only be understood in terms of ecosystems. This in turn, spurred renewed interest and activity among modem biologists, geologists and soil scientists attempting to unravel the intimate relations between biology and the weathering of silicate rocks and minerals of the earth's surface.

Sliverman, M. P.↗

Metal/Silicate Partitioning of P, Ga, and W at High Pressures and Temperatures: Dependence on Silicate Melt Composition

The distinctive pattern of element concentrations in the upper mantle provides essential evidence in our attempts to understand the accretion and differentiation of the Earth (e.g., Drake and Righter, 2002; Jones and Drake, 1986; Righter et al., 1997; Wanke 1981). Core formation is best investigated through use of metal/silicate partition coefficients for siderophile elements. The variables influencing partition coefficients are temperature, pressure, the major element compositions of the silicate and metal phases, and oxygen fugacity. Examples of studies investigating the effects of these variables on partitioning behavior are: composition of the metal phase by Capobianco et al. (1999) and Righter et al. (1997); silicate melt composition by Watson (1976), Walter and Thibault (1995), Hillgren et al. (1996), Jana and Walker (1997), and Jaeger and Drake (2000); and oxygen fugacity by Capobianco et al. (1999), and Walter and Thibault (1995). Here we address the relative influences of silicate melt composition, pressure and temperature.

Bailey, Edward↗

Formation of Metal and Silicate Globules in Gujba: A New Bencubbin-like Meteorite Fall

Gujba is a coarse-grained meteorite fall composed of 41 vol% large kamacite globules, 20 vol% large light-colored silicate globules with cryptocrystalline, barred pyroxene and barred olivine textures, 39 vol% dark-colored, silicate-rich matrix, and rare refractory inclusions. Gujba resembles Bencubbin and Weatherford in texture, oxygen-isotopic composition and in having high bulk delta N-15 values (approximately +685%0). The He-3 cosmic-ray exposure age of Gujba (26 +/- 7 Ma) is essentially identical to that of Bencubbin, suggesting that they were both reduced to meter-size fragments in the same parent-body collision. The Gujba metal globules exhibit metal-troilite quench textures and vary in their abundances of troilite and volatile siderophile elements. We suggest that the metal globules formed as liquid droplets either via condensation in an impact-generated vapor plume or by evaporation of preexisting metal particles in a plume. The lower the abundance of volatile elements in the metal globules, the higher the globule quench temperature. We infer that the large silicate globules also formed from completely molten droplets; their low volatile-element abundances indicate that they also formed at high temperatures, probably by processes analogous to those that formed the metal globules. The coarse-grained Bencubbin-Weatherford-Gujba meteorites may represent a depositional component from the vapor cloud enriched in coarse and dense particles. A second class of Bencubbin-like meteorites (represented by Hammadah a1 Hamra 237 and QUE 94411) may be a finer fraction derived from the same vapor cloud

Rubin, Alan E.↗

L-Edge Xanes Measurements of the Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses

Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted ~ 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies are inconsistent on whether W occurs as W(4+) or W(6+). It is assumed that W(4+) is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO2 is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO2 most relevant to core formation, around IW-2.

Danielson, L. R.↗

Molybdenum Valence in Basaltic Silicate Melts

The moderately siderophile element molybdenum has been used as an indicator in planetary differentiation processes, and is particularly relevant to core formation [for example, 1-6]. However, models that apply experimental data to an equilibrium differentiation scenario infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Partitioning behavior of molybdenum, a multivalent element with a transition near the J02 of interest for core formation (~IW-2) will be sensitive to changes in JO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo6+ can be either octahedrally or tetrahedrally coordinated. Here we present first XANES measurements of Mo valence in basaltic run products at a range of P, T, and JO2 and further quantify the valence transition of Mo.

Danielson, L. R.↗

Alkali Silicate Vehicle Forms Durable, Fireproof Paint

The problem: To develop a paint for use on satellites or space vehicles that exhibits high resistance to cracking, peeling, or flaking when subjected to a wide range of temperatures. Organic coatings will partially meet the required specifications but have the inherent disadvantage of combustibility. Alkali-silicate binders, used in some industrial coatings and adhesives, show evidence of forming a fireproof paint, but the problem of high surface-tension, a characteristic of alkali silicates, has not been resolved. The solution: Use of a suitable non-ionic wetting agent combined with a paint incorporating alkali silicate as the binder.

Schutt, John B.↗

Microstructures of Rare Silicate Stardust from Nova and Supernovae

Most silicate stardust analyzed in the laboratory and observed around stellar environments derives from O-rich red giant and AGB stars [1,2]. Supernova (SN) silicates and oxides are comparatively rare, and fewer than 10 grains from no-va or binary star systems have been identified to date. Very little is known about dust formation in these stellar environments. Mineralogical studies of only three O-rich SN [3-5] and no nova grains have been performed. Here we report the microstructure and chemical makeup of two SN silicates and one nova grain.

Nguyen, A. N.↗

Coordinated STEM/FIB/NanoSIMS Analyses of Presolar Silicates in Comet Dust and Primitive Meteorites

Silicate grains were among the most abundant mineralogical building blocks of our Solar System. These grains were the detritus from earlier generations of stars that have been recycled in the early solar nebula. Rare sub-micrometer survivors of this processing have been identified in meteorites, micrometeorites and interplanetary dust particles (IDPs). These silicate grains are recognized as presolar in origin because of their extremely anomalous isotopic compositions that reflect nucleosynthetic processes in their stellar sources (evolved stars, novae and supernovae). We perform coordinated chemical, mineralogical and isotopic studies of these grains to determine their origins and histories. We examine the complex mineralogy and petrography of presolar silicates using imaging, diffraction and chemical data obtained from thin sections with the JSC JEOL 2500 field-emission STEM equipped with a Noran thin window energy dispersive x-ray (EDX) spectrometer and a Gatan Tridiem GIF. Quantitative element x-ray maps (spectrum images) are acquired by rastering a 4 nm incident probe whose dwell time is minimized to avoid beam damage and element diffusion during mapping. Successive image layers are acquired and combined in order to achieve approx 1% counting statistics for major elements. The IDP samples are prepared by ultramicrotomy of particles embedded in epoxy or elemental sulfur. After EDX mapping, the sections are subjected to C, N, and O isotopic imaging with the JSC NanoSIMS 50L ion microprobe. We prepare sections of some meteorite grains using the JSC FEI Quanta 3D focused ion beam (FIB) instrument. The specimen surface is protected from the FIB milling process by layers of electron beam-deposited C and Pt followed by an ion-deposited Pt layer. We also use the FIB to preferentially remove surrounding grains to reduce the background in subsequent NanoSIMS measurements. For mineralogical studies, we again employ the FIB instrument to deposit a protective cap over the grain of interest and then extract the grain and thin it to electron transparency for TEM analysis.

Keller, Lindsay↗

Metal-Silicate Partitioning of Tungsten from 10 to 50 GPa

Geochemical models of core formation are commonly based on core and mantle abundances of siderophile elements that partitioned between silicate and metal in a magma ocean in the early Earth. Tungsten is a moderately siderophile element that may provide constraints on the pressure, temperature, composition, and oxygen fugacity conditions, and on the timing of core formation in the Earth. Previous experimental studies suggest that pressure exerts little to no influence over W metal-silicate partitioning up to 24 GPa, and indicate that the stronger influences are temperature, composition, and oxygen fugacity. However, core formation models based in part on W, predict metal-silicate equilibration pressures outside the available experimental pressure range, requiring extrapolation of parameterized models. Therefore, higher pressure experimental data on W were needed to constrain this important parameter.

Shofner, G. A.↗

SOFIA Observations of SN 2010jl: Another Non-Detection of the 9.7 Micrometer Silicate Dust Feature

We present photometric observations from the Stratospheric Observatory for Infrared Astronomy (SOFIA) at 11.1 micrometers of the Type IIn supernova (SN IIn) 2010jl. The SN is undetected by SOFIA, but the upper limits obtained, combined with new and archival detections from Spitzer at 3.6 and 4.5 micrometers, allow us to characterize the composition of the dust present. Dust in other SN IIn has been shown in previous works to reside in a circumstellar shell of material ejected by the progenitor system in the few millennia prior to explosion. Our model fits show that the dust in the system shows no evidence for the strong, ubiquitous 9.7 micrometer feature from silicate dust, suggesting the presence of carbonaceous grains. The observations are best fit with 0.01−0.05 solar mass of carbonaceous dust radiating at a temperature of approximately 550−620 degrees Kelvin. The dust composition may reveal clues concerning the nature of the progenitor system, which remains ambiguous for this subclass. Most of the single star progenitor systems proposed for SNe IIn, such as luminous blue variables, red supergiants, yellow hypergiants, and B[e] stars, all clearly show silicate dust in their pre-SN outflows. However, this post-SN result is consistent with the small sample of SNe IIn with mid-infrared observations, none of which show signs of emission from silicate dust in their infrared spectra.

SOFIA Observations of SN 2010jl↗

Differentiation of Asteroid 4 Vesta: Core Formation by Iron Rain in a Silicate Magma Ocean

Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA's Dawn spacecraft while orbiting asteroid 4 Vesta, suggest that Vesta resembles H chondrites in bulk chemical composition, possible with about 25 percent of a CM-chondrite like composition added in. For this model, the core is 15 percent by mass (or 8 percent by volume) of the asteroid, with a composition of 73.7 percent by weight Fe, 16.0 percent by weight S, and 10.3 percent by weight Ni. The abundances of moderately siderophile elements (Ni, Co, Mo, W, and P) in eucrites require that essentially all of the metallic phase in Vesta segregated to form a core prior to eucrite solidification. The combination of the melting phase relationships for the silicate and metal phases, together with the moderately siderophile element concentrations together require that complete melting of the metal phase occurred (temperature is greater than1350 degrees Centigrade), along with substantial (greater than 40 percent) melting of the silicate material. Thus, core formation on Vesta occurs as iron rain sinking through a silicate magma ocean.

Kiefer, Walter S.↗

Anionic Pt in Silicate Melts at Low Oxygen Fugacity: Speciation, Partitioning and Implications for Core Formation Processes on Asteroids

Most siderophile element concentrations in planetary mantles can be explained by metal/ silicate equilibration at high temperature and pressure during core formation. Highly siderophile elements (HSE = Au, Re, and the Pt-group elements), however, usually have higher mantle abundances than predicted by partitioning models, suggesting that their concentrations have been set by late accretion of material that did not equilibrate with the core. The partitioning of HSE at the low oxygen fugacities relevant for core formation is however poorly constrained due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variables like temperature, pressure, and oxygen fugacity. To better understand the relative roles of metal/silicate partitioning and late accretion, we performed a self-consistent set of experiments that parameterizes the influence of oxygen fugacity, temperature and melt composition on the partitioning of Pt, one of the HSE, between metal and silicate melts. The major outcome of this project is the fact that Pt dissolves in an anionic form in silicate melts, causing a dependence of partitioning on oxygen fugacity opposite to that reported in previous studies.

Medard, E.↗

Microstructural Study of an 18-O-Poor Presolar Silicate Grain from The Meteorite Hills 00426 Cr2 Chondrite

The majority of presolar silicate and oxide grains derive from low-mass red giant and asymptotic giant branch (AGB) stars of approximately solar metallicity (Z). A small subclass of presolar O-rich grains (less than 7%) is thought to originate from stars having lower-than-solar Z. These "Group 3" [1] grains have depletions in 18O and 17O that typically fall along or above the Galactic chemical evolution (GCE) line. Other Group 3 grains show greater 17O than 18O depletions and most likely have supernova (SN) origins. Owing to their rarity, only two Group 3 silicates have been mineralogically examined in detail [2, 3]. Here we present a mineralogical study of a Group 3 presolar silicate to explore its formation conditions and interstellar history.

Nguyen, A. N.↗

Climates of Warm Earth-like Planets. II. Rotational "Goldilocks" Zones for Fractional Habitability and Silicate Weathering

Planetary rotation rate has a significant effect on atmospheric circulation, where the strength of the Coriolis effect in part determines the efficiency of latitudinal heat transport, altering cloud distributions, surface temperatures, and precipitation patterns. In this study, we use the ROCKE-3D dynamic ocean general circulation model to study the effects of slow rotations and increased insolations on the "fractional habitability" and silicate weathering rate of an Earth-like world. Defining the fractional habitability f(sub h) to be the percentage of a planet's surface that falls in the 0 ≤ T ≤ 100 °C temperature regime, we find a moderate increase in f(sub h) with a 10% and 20% increase in insolation and a possible maximum in f(sub h) at sidereal day lengths between 8 and 32 times that of the modern Earth. By tracking precipitation and runoff, we further determine that there is a rotational regime centered on a 4 day period in which the silicate weathering rate is maximized and is particularly strongly peaked at higher overall insolations. Because of weathering's integral role in the long-term carbonate–silicate cycle, we suggest that climate stability may be strongly affected by the anticipated rotational evolution of temperate terrestrial-type worlds and should be considered a major factor in their study. In light of our results, we argue that planetary rotation period is an important factor to consider when determining the habitability of terrestrial worlds.

Atmospheric effects↗