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Danielson, L.

Publications and source records attributed to Danielson, L..

33 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS2012

Experimental Study of the Partitioning of Siderophile Elements in a Crystallizing Lunar Magma Ocean

The distributions of trace elements between the lunar interior and pristine crustal rocks were controlled by the composition of starting materials, lunar core formation, and crystallization of the lunar magma ocean (LMO) [1]. This study focuses on the partitioning of highly siderophile elements (HSE) including Re, Os, Ir, Ru, Pt, Rh, Pd and Au as well as the moderately siderophile elements Mo and W, and the lithophile elements of Hf and Sr. Our experiments also include Ga, which can be slightly siderophile, but is mostly considered to be chalcophile. Partitioning of these elements is not well known at the conditions of a crystallizing LMO. Previous studies of HSE partitioning in silicate systems have yielded highly variable results for differing oxygen fugacity (fO2) and pressure [2-4]. For example, under certain conditions Pt is compatible in clinopy-roxene [2] and Rh and Ru are compatible in olivine [3]. The silicate compositions used for these experiments were nominally basaltic. Ruthenium, Rh, and Pd are incompatible in plagioclase under these conditions[4]. However, this latter study was done at extremely oxidizing conditions and at atmospheric pressure, possibly limiting the applicability for consideration of conditions of a crystallizing LMO. In this study we address the effects of pressure and oxygen fugacity on the crystal/liquid partition coefficients of these trace elements. We are especially interested in the plagioclase/melt partition coefficients so that it may be possible to use reverse modeling to constrain the concentrations of these elements in the lunar mantle through their abundances in pristine crustal rocks.

Galenas, M.↗
NASA NTRS2011

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.

Righter, K.↗
NASA NTRS2011

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.

Righter, Kevin↗
NASA NTRS2010

High Pressure/Temperature Metal Silicate Partitioning of Tungsten

The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. <10 GPa, and in two cases at or near 20 GPa. According to those data, the stronger influences on the distribution coefficient of W are temperature, composition, and oxygen fugacity with a relatively slight influence in pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.

Shofner, G. A.↗
NASA NTRS2010

Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

King, C.↗
NASA NTRS2010

Metal/Silicate Partitioning at High Pressures and Temperatures

The behavior of siderophile elements during metal-silicate segregation, and their resulting distributions provide insight into core formation processes. Determination of partition coefficients allows the calculation of element distributions that can be compared to established values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Moderately siderophile elements, including W, are particularly useful in constraining core formation conditions because they are sensitive to variations in T, P, oxygen fugacity (fO2), and silicate composition. To constrain the effect of pressure on W metal/silicate partitioning, we performed experiments at high pressures and temperatures using a multi anvil press (MAP) at NASA Johnson Space Center and laser-heated diamond anvil cells (LHDAC) at the University of Maryland. Starting materials consisted of natural peridotite mixed with Fe and W metals. Pressure conditions in the MAP experiments ranged from 10 to 16 GPa at 2400 K. Pressures in the LHDAC experiments ranged from 26 to 58 GPa, and peak temperatures ranged up to 5000 K. LHDAC experimental run products were sectioned by focused ion beam (FIB) at NASA JSC. Run products were analyzed by electron microprobe using wavelength dispersive spectroscopy. Liquid metal/liquid silicate partition coefficients for W were calculated from element abundances determined by microprobe analyses, and corrected to a common fO2 condition of IW-2 assuming +4 valence for W. Within analytical uncertainties, W partitioning shows a flat trend with increasing pressure from 10 to 16 GPa. At higher pressures, W becomes more siderophile, with an increase in partition coefficient of approximately 0.5 log units.

Shofner, G.↗
NASA NTRS2009

Solubility of Sulfur in Shergottitic Silicate Melts Up to 0.8 GPA: Implications for S Contents of Shergottites

Shergottites have high S contents (1300 to 4600 ppm; [1]), but it is unclear if they are sulfide saturated or under-saturated. This issue has fundamental implications for determining the long term S budget of the martian surface and atmosphere (from mantle degassing), as well as evolution of the highly siderophile elements (HSE) Au, Pd, Pt, Re, Rh, Ru, Ir, and Os, since concentrations of the latter are controlled by sulfide stability. Resolution of sulfide saturation depends upon temperature, pressure, oxygen fugacity (and FeO), and magma composition [2]. Expressions derived from experimental studies allow prediction of S contents, though so far they are not calibrated for shergottitic liquids [3-5]. We have carried out new experiments designed to test current S saturation models, and then show that existing calibrations are not suitable for high FeO and low Al2O3 compositions characteristic of shergottitic liquids. The new results show that existing models underpredict S contents of sulfide saturated shergottitic liquids by a factor of 2.

Righter, K.↗
NASA NTRS2009

Using Vanadium in Spinel as a Sensor of Oxygen Fugacity in Meteorites: Applications to Mars, Vesta, and Other Asteroids

Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or constrained such as FeTi oxides, olivine-opx-spinel, or some other oxybarometer [1]. 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 samples 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 natural meteorite samples. Because the V pre-edge peak intensity and energy in chromites varies with fO2 (Fig. 1) [2], and this has been calibrated over a large fO 2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints.

Righter, K.↗
NASA NTRS2008

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.

Acuff, K. M.↗
NASA NTRS2007

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 unresolved

Righter, K.↗
NASA NTRS2006

Oxygen Fugacity at High Pressure: Equations of State of Metal-Oxide Pairs

Oxygen fugacity (fO2) varies by orders of magnitude in nature, and can induce profound changes in the chemical state of a substance, and also in the chemical equilibrium of multicomponent systems. One prominent area in high pressure geochemistry, in which fO2 is widely recognized as a principal controlling factor, is that of metal-silicate partitioning of siderophile trace elements (e.g., [1]). Numerous experiments have shown that high pressures and temperatures can significantly affect metal/silicate partitioning of siderophile and moderately siderophile elements. Parameterization of these experimental results over P, T, X, and fO2 can allow the observed siderophile element composition of the mantle to be associated with particular thermodynamic conditions [2]. However, this is best done only if quantitative control exists over each thermodynamic variable relevant to the experiments. The fO2 values for many of these partitioning experiments were determined relative to a particular metal-oxide buffer (e.g., Fe-FeO (IW), Ni-NiO (NNO), Co-CoO, Re-ReO2 (RRO)), but the parameterization of all experimental results is weakened by the fact that the pressure-induced relative changes between these buffer systems are imprecisely known.

Campbell A. J.↗
NASA NTRS1987

Thermoelectric Properties of Lanthanum Sulfide

Report describes measurement of Seebeck coefficient, electrical resistivity, thermal conductivity, and Hall effect in gamma-phase lanthanum sulfide with composition of La3-x S4. Results of study, part of search for high-temperature thermoelectric energy-conversion materials, indicate this sulfide behaves like extrinsic semiconductor over temperature range of 300 to 1,400 K, with degenerate carrier concentration controlled by stoichiometric ratio of La to S.

Wood, C.↗
NASA NTRS1987

Effect of the microstructure on the thermoelectric properties of polycrystalline lanthanum chalcogenides

Small amounts of second phase materials can have important effects on the thermoelectric properties of polycrystalline gamma-La(3-x)X4 (X-S, Te; X in the range of 0 to 1/3). Microscopic examination by SEM of hot pressed La(3-x)Te4 samples has revealed from 1-5 vol. pct of La2O2Te, an amount which is not detected by X-ray powder diffraction measurements. This amount of La2O2Te resulting from oxygen contamination can reduce the concentration of electrons by as much as 10 to 75 percent below the electron concentration calculated for single phase La(3-x)Te4 in the composition range of greatest interest. Small amounts of second phase materials can also lower the lattice thermal conductivity by scattering low frequency phonons. These results indicate that microstructural effects should be considered when electrical and thermal properties of polycrystalline materials are analyzed.

Lockwood, A.↗