Andrew J. Campbell

Siderophile element constraints on the formation of metal in the metal-rich chondrites Bencubbin, Weatherford, and Gujba

Laser ablation inductively coupled plasma mass spectrometry was used to measure abundances of P, Cr, Fe, Co, Ni, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, Sn, Sb, W, Re, Os, Ir, Pt, and Au in metal grains in the Bencubbin-like chondrites Bencubbin, Weatherford, and Gujba to determine the origin of large metal aggregates in bencubbinites. A strong volatility-controlled signature is observed among the metal grains. The refractory siderophiles Ru, Rh, Re, Os, Ir, and Pt are unfractionated from one another, and are present in approximately chondritic relative abundances. The less refractory elements Fe, Co, Ni, Pd, and Au are fractionated from the refractory siderophiles, with a chondritic Ni/Co ratio and a higher than chondritic Pd/Fe ratio. The moderately volatile siderophile elements Ga, Ge, As, Sn, and Sb are depleted in the metal, relative to chondritic abundances, by up to 3 orders of magnitude. The trace siderophile element data are inconsistent with the following proposed origins of Bencubbin-Weatherford-Gujba metal: (1) condensation from the canonical solar nebula, (2) oxidation of an initially chondritic metal composition, and (3) equilibration with a S-rich partial melt. A condensation model for metal-enriched (10 7 CI) gas is developed. Formation by condensation or evaporation in such a high-density, metal-enriched gas is consistent with the trace element measurements. The proposed model for generating such a gas is protoplanetary impact involving a metal-rich body. Copyright

Trace Element Microanalysis in Iron Meteorites by Laser Ablation ICPMS

A laser ablation microanalysis system has been developed that can analyze trace elements with a sensitivity in the ppb range, using a CETAC LSX-200 laser ablation system with a Finnigan Element. This capability has been applied to a set of iron meteorites to demonstrate the laser microprobes analytical capability for the determination of platinum group elements (PGEs) with a spatial resolution of ∼20 μm, comparable to that of dynamic secondary ion mass spectrometry (SIMS). The laser is shown to provide an accurate means of solid sampling for magnetic sector inductively coupled plasma mass spectrometry (ICPMS), allowing the determination of bulk metal composition, chemical zoning within the sample, and depth profiling. Recovery of the chemical zoning in taenite lamellae was achieved for Ru, Rh, and Pd, which was not previously possible using SIMS. The methods presented here show that magnetic sector ICPMS can be successfully coupled to a laser ablation system, providing the advantages of higher sensitivity of the sector instrument, low background count rates (<0.1 counts/s), and flat-topped spectral peaks, while minimizing tradeoff against the speed of data acquisition required to handle the transient signals from the laser ablation system.

Origin of zoned metal grains in the QUE94411 chondrite

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to measure distributions of the siderophile elements P, V. Cr, Fe, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir, and Pt in metal grains in the metal-rich chondrite QUE94411 with a spatial resolution of similar to 30 mum. The platinum group elements (PGEs), except Pd, exhibit radial zoning in these grains that mimics that previously observed in Ni and Co; the concentrations of these elements decreases from the cores to the rims of the grains. The PGE distributions support a condensation origin for the enhanced refractory element abundances in the zoned grains; the lack of zoning in Pd refutes an origin by a redox-controlled process, and none of the PGE-Ni relationships support an origin by fractional crystallization from a metallic melt. Several models of grain formation were explored, including equilibrium fractional condensation, which failed to yield the correct radial zoning. The zoning may be the product of a nonequilibrium fractional condensation process, in which the refractory siderophiles remained supersaturated in the cooling solar nebula, or of diffusion between refractory-enhanced Fe-Ni cores and other Fe-Ni metal that may have been deposited later from the solar nebula. Copyright (C) 2001 Elsevier Science Ltd.

Static compression of iron-silicon alloys: Implications for silicon in the Earth's core

lower the density of iron, but significantly changes its compressibility neither in the bcc phase, nor at high pressures in the hcp phase. Upon comparison with the Preliminary Reference Earth Model, the calculated equations of state (EOS) of hcp-Fe85Si15, using the Mie-Gruneisen EOS, indicate that an outer core containing about 8-10 wt.% Si and inner core containing about 4 wt.% Si in iron would satisfy the seismological constraints. Addition of silicon into iron increases the bulk sound velocity of iron, consistent with silicon being a light element in the Earths core. INDEX TERMS: 1015 Geochemistry: Composition of the core; 3919 Mineral Physics: Equations of state; 3924 Mineral Physics: High-pressure behavior; 3954 Mineral Physics: X ray, neutron, and electron spectroscopy and diffraction; KEYWORDS: high pressure, light elements, iron-silicon alloy, Earths core, X-ray diffraction, equation of state

Chemical evolution of metal in refractory inclusions in CV3 chondrites

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to measure distributions of the siderophile elements V, Fe, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in Fremdlinge with a spatial resolution of 15 to 25 m. A sulfide vein in a refractory inclusion in Allende (CV3-oxidized) is enriched in Rh, Ru, and Os with no detectable Pd, Re, Ir, or Pt, indicating that Rh, Ru, and Os were redistributed by sulfidation of the inclusion, causing fractionation of Re/Os and other siderophile element ratios in Allende CAIs. Fremdlinge in compact Type-A inclusions from Efremovka (CV3-reduced) exhibit subsolidus exsolution into kamacite and taenite and minimal secondary formation of V-magnetite and schreibersite. Siderophile element partitioning between taenite and kamacite is similar to that observed previously in iron meteorites, while preferential incorporation of the light PGEs (Ru, Rh, Pd) relative to Re, Os, Ir, and Pt by schreibersite was observed. Fremdling EM2 (CAI Ef2) has an outer rim of P-free metal that preserves the PGE signature of schreibersite, indicating that EM2 originally had a phosphide rim and lost P to the surrounding inclusion during secondary processing. Most Fremdlinge have chondrite-normalized refractory PGE patterns that are unfractionated, with PGE abundances derived from a small range of condensation temperatures, 1480 to 1468 K at Ptot 10 3 bar. Some Fremdlinge from the same CAI exhibit sloping PGE abundance patterns and Re/Os ratios up to 2 CI that likely represent mixing of grains that condensed at various temperatures. Copyright

The Genesis solar-wind collector materials

Genesis (NASA Discovery Mission #5) is a sample return mission. Collectors comprised of ultra-high purity materials will be exposed to the solar wind and then returned to Earth for laboratory analysis. There is a suite of fifteen types of ultra-pure materials distributed among several locations. Most of the materials are mounted on deployable panels (‘collector arrays’), with some as targets in the focal spot of an electrostatic mirror (the ‘concentrator’). Other materials are strategically placed on the spacecraft as additional targets of opportunity to maximize the area for solar-wind collection.Most of the collection area consists of hexagonal collectors in the arrays; approximately half are silicon, the rest are for solar-wind components not retained and/or not easily measured in silicon. There are a variety of materials both in collector arrays and elsewhere targeted for the analyses of specific solar-wind components.Engineering and science factors drove the selection process. Engineering required testing of physical properties such as the ability to withstand shaking on launch and thermal cycling during deployment. Science constraints included bulk purity, surface and interface cleanliness, retentiveness with respect to individual solar-wind components, and availability.A detailed report of material parameters planned as a resource for choosing materials for study will be published on a Genesis website, and will be updated as additional information is obtained. Some material is already linked to the Genesis plasma data website (genesis.lanl.gov). Genesis should provide a reservoir of materials for allocation to the scientific community throughout the 21st Century.

Measurement of temperature distributions across laser heated samples by multispectral imaging radiometry

Two-dimensional temperature mapping of laser heated diamond anvil cell samples is performed by processing a set of four simultaneous images of the sample, each obtained at a narrow spectral range in the visible to near infrared. The images are correlated spatially, and each set of four points is fitted to the Planck radiation function to determine the temperature and the emissivity of the sample, using the gray body approximation. The method is tested by measuring the melting point of Pt at 1 bar and measuring laser heated Fe at 20 GPa in the diamond anvil cell. The accuracy and precision are shown to compare well to standard spectroradiometry, and the effect of imaging resolution on the measured distribution is evaluated. The principal advantages of the method are (1) the temperature and emissivity of the sample are mapped in two dimensions; (2) chromatic aberrations are practically eliminated by independent focusing of each spectral band; and (3) all of the spectral images are obtained simultaneously, allowing temporal variations to be studied. This method of measuring temperature distributions can be generalized to other hot objects besides laser heated spots.

High-pressure melting of wüstite

Abstract Iron oxide (FeO) is an important component in the mineralogy of Earth’s lower mantle and possibly its core, so its phase diagram is essential to models of the planet’s interior. The melting curve of wüstite, Fe0.94O, was determined up to 77 GPa and 3100 K in a laser-heated diamond anvil cell. Melting transition temperatures were identified from discontinuities in the emissivity vs. temperature relationship within the laser-heated spot. The melting curve exhibits no obvious kinks that could be related to a subsolidus transition in wüstite, but there is evidence for a two-phase loop at pressures below 30 GPa. Comparison of these results to previous studies on Fe, Fe-O, and Fe-S confirms that the melting point depression in the Fe-O system remains significantly less, by a factor of 2 or more, than that in the Fe-S system up to pressures exceeding 80 GPa.

Equations of state in the Fe‐FeSi system at high pressures and temperatures

Earths core is an iron-rich alloy containing several weight percent of light element(s), possibly including silicon. Therefore, the high pressure-temperature equations of state of iron-silicon alloys can provide understanding of the properties of Earths core. We performed X-ray diffraction experiments using laser-heated diamond anvil cells to achieve simultaneous high pressures and temperatures, up to ~200 GPa for Fe–9 wt % Si alloy and ~145 GPa for stoichiometric FeSi. We determined equations of state of the D03, hcp + B2, and hcp phases of Fe–9Si, and the B20 and B2 phases of FeSi. We also calculated equations of state of Fe, Fe11Si, Fe5Si, Fe3Si, and FeSi using ab initio methods, finding that iron and silicon atoms have similar volumes at high pressures. By comparing our experimentally determined equations of state to the observed core density deficit, we find that the maximum amount of silicon in the outer core is ~11 wt %, while the maximum amount in the inner core is 6–8 wt %, for a purely Fe-Si-Ni core. Bulk sound speeds predicted from our equations of state also match those of the inner and outer core for similar ranges of compositions. We find a compositional contrast between the inner and outer core of 3.5–5.6 wt % silicon, depending on the seismological model used. Theoretical and experimental equations of state agree at high pressures. We find a good match to the observed density, density profile, and sound speed of the Earths core, suggesting that silicon is a viable candidate for the dominant light element.

Compression of MgS to 54 GPa

Abstract MgS (B1 or NaCl structure) was compressed in a diamond anvil cell at room temperature up to a pressure of 54 GPa. Diffraction experiments were performed using X-rays from both a rotating anode generator and synchrotron beam line. The B1 phase of MgS is stable to 54 GPa. A third order Birch-Murnaghan equation of state fitted to the data yields a bulk modulus of 78.9 ± 3.7 GPa with a pressure derivative of 3.71 ± 0.34. Universal equation of state parameters are virtually identical. The thermodynamic parameters obtained are consistent with most of the existing theoretical predictions. For comparison, a bulk modulus of 56.0 ± 1.4 GPa, with a pressure derivative of 5.3 ± 1.0, is calculated for CaS using previously published data. Finally, the pressure-volume data and elastic parameters of several alkali halides and alkaline-earth sulfides and oxides are used to evaluate the applicability of the Born model for these compounds.