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Comparison of the Organic Composition of Cometary Samples with Residues Formed from the UV Irradiation of Astrophysical Ice Analogs

The NASA Stardust mission successfully collected material from Comet 81P/Wild 2 [1], including authentic cometary grains [2]. X-ray absorption near-edge structure (XANES) spectroscopy analysis of these samples indicates the presence of oxygen-rich and nitrogen-rich organic materials, which contain a broad variety of functional groups (carbonyls, C=C bonds, aliphatic chains, amines, arnides, etc.) [3]. One component of these organics appears to contain very little aromatic carbon and bears some similarity to the organic residues produced by the irradiation of ices of interstellar/cometary composition, Stardust samples were also recently shown to contain glycine, the smallest biological amino acid [4]. Organic residues produced froth the UV irradiation of astrophysical ice analogs are already known to contain a large suite of organic molecules including amino acids [5-7], amphiphilic compounds (fatty acids) [8], and other complex species. This work presents a comparison between XANES spectra measured from organic residues formed in the laboratory with similar data of cometary samples collected by the Stardust mission

Milam, S. N.↗

Organic Matter in Extraterrestrial Water-Bearing Salt Crystals

Introduction: Direct samples of early Solar System fluids are present in two thermally-metamorphosed ordinary chondrite regolith breccias (Monahans (1998) [H5] and Zag [H3-6]), which were found to contain brine-bearing halite (NaCl) crystals that have been added to the regolith of an S-type asteroid following asteroidal metamorphism [1, 2]. The brine-bearing halite grains were proposed to be formed on an icy C-type asteroids (possibly Ceres), and transferred to an S-type asteroid via cryovolcanic event(s) [3]. A unique aspect of these halites is that they contain abundant organic rich solid inclusions hosted within the halites alongside the water inclusions. Methods: We analyzed in detail the compositions of the organic solids and the amino acid content of the halite crystals with two-step laser desorption/laser ionization mass spectrometry (L(sup 2) MS), Raman spectroscopy, X-ray absorption near edge structure (XANES), nanoscale secondary ion mass spectrometry (NanoSIMS), and ultra-performance liquid chromatography fluorescence detection and quadrupole time of flight hybrid mass spectrometry (UPLC-FD/QToF-MS). Results and Discussion: The L(sup 2) MS results show signatures of low-mass polyaromatic hydro-carbons (PAHs) indicated by sequences of peaks separated by 14 atomic mass units (amu) due to successive addition of methylene (CH2) groups to the PAH skeletons [4]. Raman spectra of the micron-sized solid inclusions of the halites indicate the presence of abundant and highly variable organic matter that include a mixture of short-chain aliphatic compounds and macromolecular carbon. C-XANES analysis identified C-rich areas with peaks at 285.0 eV (aromatic C=C) and 286.6 eV (vinyl-keto C=O). However, there is no 1s-sigma* exciton peak (291.7 eV) that is indicative of the development of graphene structure [5], which suggests the organics were synthesized cold. Na-noSIMS analyses show C-rich and N-rich areas that exhibit similar isotopic values with that of the IOM in the unweathered CR chondrites and less metamorphosed meteorites [6], and are moderately enriched in N-15 (delta N-15 = 106.1-164.5 per mille). The total amino acid distribution and abundance of the Zag matrix (approximately 1,940 parts per billion [ppb]) is comparable to other ordinary chondrites (60-3,330 ppb) [7, 8]. While the Zag matrix is gamma-ABA and EACA-deficient, the halite is shown to exhibit an opposite trend and is almost depleted in amino acids. The striking difference in the amino acid contents between the halite and matrix indicates their separate synthetic origins. Conclusion: Abundant, primitive, and highly-diverse N-15-rich organic compounds were detected in brine-water bearing halite crystals that were synthesized on a cryovolcanically-active asteroid. Our study suggests that the asteroidal parent body where the halite precipitated, potentially Ceres, is a host to abundance large variety organic precursors. Insoluble organic matter and amino acids can be synthesized from similar organic precusors under hydrous conditions [9].We envision that similar organic synthetic processes could have occurred on Ceres that synthesized organic solids as well as biologically relevant molecules.

Chan, Q. H. S.↗

Biological Oxidation of Fe(II)-Bearing Smectite by Microaerophilic Iron Oxidizer Sideroxydans lithotrophicus Using Dual Mto and Cyc2 Iron Oxidation Pathways

Fe(II) clays are common across many environments, making them a potentially significant microbial substrate, yet clays are not well established as an electron donor. Therefore, we explored whether Fe(II)-smectite supports the growth of Sideroxydans lithotrophicus ES-1, a microaerophilic Fe(II)-oxidizing bacterium (FeOB), using synthesized trioctahedral Fe(II)-smectite and 2% oxygen. S. lithotrophicus grew substantially and can oxidize Fe(II)-smectite to a higher extent than abiotic oxidation, based on X-ray near-edge spectroscopy (XANES). Sequential extraction showed that edge-Fe(II) is oxidized before interior-Fe(II) in both biotic and abiotic experiments. The resulting Fe(III) remains in smectite, as secondary minerals were not detected in biotic and abiotic oxidation products by XANES and Mössbauer spectroscopy. To determine the genes involved, we compared S. lithotrophicus grown on smectite versus Fe(II)-citrate using reverse-transcription quantitative PCR and found that cyc2 genes were highly expressed on both substrates, while mtoA was upregulated on smectite. Proteomics confirmed that Mto proteins were only expressed on smectite, indicating that ES-1 uses the Mto pathway to access solid Fe(II). We integrate our results into a biochemical and mineralogical model of microbial smectite oxidation. This work increases the known substrates for FeOB growth and expands the mechanisms of Fe(II)-smectite alteration in the environment.

smectite↗

Moessbauer Spectroscopy of Mineral Separates from SNC Meteorites

Numerous workers have recently focused attention on the issue of the oxygen fugacity (f(sub O2)) of martian samples. Estimates of fO2 based on Fe-Ti oxides and D(sub Eu)/D(sub Gd) and D(sub Eu)/D(sub Sm) ratios suggest a range of fO2 values for SNC meteorites from IW+2.5 - IW+3.5 for Shergotty to IW- 2.0 - IW+0.2 for QUE94201. Fe(3+)/Fe(2+) is also a function of f(sub O2), and synchrotron micro-XANES values for olivine, pyroxene, and feldspar Fe(3+) have been reported. However, the relationship between the reported Fe(3+) values and the other methods for estimating f(sub O2) is not clear, and further measurements of Fe(3+)/Fe(2+) by a more conventional technique have been needed. Accordingly, in this project, new Mossbauer spectroscopy data on mineral separates handpicked from 10 SNC meteorites are reported.

Dyar, M. D.↗

Evidence for Terrestrial Organic Contamination of the Tagish Lake Meteorite

The Tagish Lake meteorite is a rare discovery in the meteorite world. Tentatively classified as an ungrouped type 2 carbonaceous chondrite, it is the first known CI2 meteorite [1, 2, 3]. Tagish Lake is the first meteorite to exhibit a reflectance spectrum showing the red color characteristic of the D- and P-type asteroids that populate the outer main-belt [2], although many interplanetary dust particles collected from the Earth s stratosphere exhibit a similar spectrum [4]. Several large pieces of the Tagish Lake meteorite were recovered on Jan. 18, 2000. We obtained two samples of the Tagish Lake meteorite, both collected on April 24, 2000, designated MG02 and MG03, from A. Hildebrand (Univ. of Calgary) and P. Brown (Univ. of Western Ontario). Smaller fragments collected in May 2000 were purchased from the The Meteorite Market (samples designated "MM"). We have reported preliminary results from infrared and X-ray Absorption Near-edge Structure (XANES) spectroscopy on the MM samples [5]. We report evidence to suggest that there was terrestrial contamination of the meteorite, even in fragments in contact with the lake ice for only a few months .

Wirick, S.↗

Workshop on Oxygen in the Terrestrial Planets

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe Oxidation State of Vanadium in Spinel-Melt Pairs; 44) Testing the Magma Ocean Hypothesis Using Metal-Silicate Partitioning of Te, Se and S; 45) Solubility of Oxygen in Liquid Iron at High Pressure and Consequences for the Early Differentiation of Earth and Mars Metallic Liquid Segregation in Planetesimals; 46) Oxygen Fugacity of Lunar Basalts and the Lunar Mantle. Range of fo2 and the Effectiveness of Oxybarometers; 47) Thermodynamic Study of Dissociation Processes of Molecular Oxygen in Vapor over Oxide Compounds; 48) Oxygen Profile of a Thermo-Haliophilic Community in the Badwater Salt Flat; 49) Oxygen Barometry Using Synchrotron MicroXANES of Vanadium; 50) Mass-Independent Isotopic Fractionation of Sulfur from Sulfides in the Huronian Supergroup, Canada; 51) Mass Independent Isotopes and Applications to Planetary Atmospheres; 52) Electrical Conductivity, Oxygen Fugacity, and Mantle Materials; 53) Crustal Evolution and Maturation on Earth: Oxygen Isotope Evidence; 54) The Oxygen Isotope Composition of the Moon: Implications for Planet Formation; 55) Oxygen Isotope Composition of Eucrites and Implications for the Formation of Crust on the HED Parent Body; and 56) The Role of Water in Determining the Oxygen Isotopic Composition of Planets.

Source record↗

Comparative Planetary Mineralogy: V/(Cr+Al) Systematics in Chromites as an Indicator of Relative Oxygen Fugacity

As our contribution to the new "Oxygen in the Solar System" initiative of the Lunar and Planetary Institute and the NASA Cosmochemistry Program, we have been developing oxygen barometers based largely on behavior of V which can occur in four valence states V2+, V3+, V4+, and V5+, and record at least 8 orders of magnitude of fO2. Our first efforts in measuring these valence proportions were by XANES techniques in basaltic glasses from Earth, Moon, and Mars. We now address the behavior of V valence states in chromite in basalts from Earth, Moon, and Mars. We have been looking for a "V in chromite oxybarometer" that works with data collected by the electron microprobe and thus is readily accessible to a large segment of the planetary materials community. This paper describes very early results that will be refined over the next two years.

Papike, J. J.↗

Synchrotron Characterization of Hydrogen and Ferric Iron in Martian Meteorites

The hydrogen budget of the Martian interior is distributed among several phases: melts, hydrous minerals, and nominally anhydrous minerals like olivine, pyroxene, and garnet. All these phases are vulnerable to loss of hydrogen during shock, excavation and transport via the mechanism of dehydrogenation, in which the charge on the H protons is left behind as polarons on Fe atoms. Thus, both H and F(3x) must be analyzed in order to reconstruct hydrogen and oxygen fugacities on Mars. To date, SIMS data have elucidated D/H and H contents of hydrous phases in SNC meteorites, but anhydrous martian minerals have not been systematically examined for trace hydrogen. Ferric iron has been quantified using XANES in many marital phases, but integrated studies of both Fe(3x) and H on the same spots are really needed to address the H budget. Here, we measure and profile H and Fe(3x) abundances in and across individual grains of glass and silicates in Martian meteorites. We use the new technology of synchrotron microFI'lR spectroscopy to measure the hydrogen contents of hydrous and nominally anhydrous minerals in martian meteorites on 30-100 microns thick, doubly polished thin sections on spots down to 3 x 3 microns. Synchrotron microXANES was used to analyze Fe(3x) on the same scale, and complementary SIMS D/H data will be collected where possible, though at a slightly larger scale. Development of this combination of techniques is critical because future sample return missions will generate only microscopic samples for study. Results have been used to quantitatively assess the distribution of hydrogen and ferric iron among phases in the martian interior, which will better constrain the geodynamic processes of the interior, as well as the overall hydrogen and water budgets on Mars.

Dyar, Melinda D.↗

High-Resolution Electron Energy-Loss Spectroscopy (HREELS) Using a Monochromated TEM/STEM

A 200 keV FEI TF20 XT monochromated (scanning) transmission electron microscope funded by NASA's SRLIDAP program is undergoing installation at Lawrence Livermore National Laboratory. Instrument specifications in STEM mode are Cs =1.0 mm, Cc =1.2 mm, image resolution =0.18 nm, and in TEM mode Cs =1.3 mm, Cc =1.3 mm, information limit =0.14 nm. Key features of the instrument are a voltage-stabilized high tension (HT) supply, a monochromator, a high-resolution electron energy-loss spectrometer/energy filter, a high-resolution annular darkfield detector, and a solid-state x-ray energy-dispersive spectrometer. The high-tension tank contains additional sections for 60Hz and high frequency filtering, resulting in an operating voltage of 200 kV plus or minus 0.005V, a greater than 10-fold improvement over earlier systems. The monochromator is a single Wien filter design. The energy filter is a Gatan model 866 Tridiem-ERS high resolution GIF spec d for less than or equal to 0.15 eV energy resolution with 29 pA of current in a 2 nm diameter probe. 0.13 eV has already been achieved during early installation. The x-ray detector (EDAX/Genesis 4000) has a take-off angle of 20 degrees, an active area of 30 square millimeters, and a solid angle of 0.3 steradians. The higher solid angle is possible because the objective pole-piece allows the detector to be positioned as close as 9.47 mm from the specimen. The voltage-stabilized HT supply, monochromator and GIF enable high-resolution electron energy-loss spectroscopy (HREELS) with energy resolution comparable to synchrotron XANES, but with approximately 100X better spatial resolution. The region between 0 and 100 eV is called the low-loss or valence electron energy-loss spectroscopy (VEELS) region where features due to collective plasma oscillations and single electron transitions of valence electrons are observed. Most of the low-loss VEELS features we are detecting are being observed for the first time in IDPs. A major focus of our research is to understand the origin and significance of these features and how they might be exploited to gain insight about IDPs and other meteoritic materials.

Sai, Z. R.↗

Sulfur and Iron Speciation in Gas-rich Impact-melt Glasses from Basaltic Shergottites Determined by Microxanes

Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Mossbauer studies on rocks at Meridian and Gusev, whereas MgSO4 is deduced from MgO - SO3 correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum and alunogen/ S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/ sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. To understand the implications of these observations for the formation of the Gas-rich Impact-melt (GRIM) glasses, we determined the oxidation state of Fe in the GRIM glasses using Fe K micro-XANES techniques.

Sutton, S. R.↗

Sulfur Speciation in the Martian Regolith Component in Shergottite Glasses

We have shown that Gas-Rich Impact-Melt (GRIM) glasses in Shergotty, Zagami, and EET79001 (Lith A and Lith B) contain Martian regolith components that were molten during impact and quenched into glasses in voids of host rock materials based on neutron-capture isotopes, i.e., Sm-150 excesses and Sm-149 deficits in Sm, and Kr-80 excesses produced from Br [1, 2]. These GRIM glasses are rich in S-bearing secondary minerals [3.4]. Evidence for the occurrence of CaSO4 and S-rich aluminosilicates in these glasses is provided by CaO-SO3 and Al2O3-SO3 correlations, which are consistent with the finding of gypsum laths protruding from the molten glass in EET79001 (Lith A) [5]. However, in the case of GRIM glasses from EET79001 (Lith B), Shergotty and Zagami, we find a different set of secondary minerals that show a FeO-SO3 correlation (but no MgOSO3 correlation), instead of CaO-SO3 and Al2O3-SO3 correlations observed in Lith A. These results might indicate different fluidrock interactions near the shergottite source region on Mars. The speciation of sulfur in these salt assemblages was earlier studied by us using XANES techniques [6], where we found that Lith B predominantly contains Fe-sulfide globules (with some sulfate). On the other hand, Lith A showed predominantly Casulfite/ sulfate with some FeS. Furthermore, we found Fe to be present as Fe2+ indicating little oxidation, if any, in these glasses. To examine the sulfide-sulfate association in these glasses, we studied their Fe/Ni ratios with a view to find diagnostic clues for the source fluid. The Fe-sulfide mineral (Fe(0.93)Ni(0.3)S) in EET79001, Lith A is pyrrhotite [7, 8]. It yields an Fe/Ni ratio of 31. In Shergotty, pyrrhotite occurs with a molar ratio of Fe:S of 0.94 and a Ni abundance of 0.12% yielding a Fe/Ni ratio of approx.500 [8]. In this study, we determined a NiO content of approx.0.1% and FeO/NiO ratio of approx.420 in S-rich globules in #507 (EET79001, Lith B) sample using FE-SEM. In the same sample (bulk), using EMPA, we determined a FeO/NiO ratio of approx.700 (raster mode). Using similar techniques, we determined a NiO content of approx.0.015% and a FeO/NiO ratio of approx.800 in #506 (EET79001, Lith A). Moreover, a NiO content of approx.150 ppm and 6.1% FeO were found in Lith A GRIM glasses using neutron activation analysis [9] yielding a FeO/NiO ratio of approx.420. The FeO/NiO ratios in secondary mineral phases in S-rich pockets of EET79001 (Lith A/B) and Shergotty are high (approx.400) compared to the FeO/NiO ratio of 31 in Lith A pyrrhotite. These results suggest similar kind of fluids interacted with different rock materials to yield the observed variations in GRIM glasses in EET79001 Lith A and B.

Rao, M. N.↗

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.↗

Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re-dox issue because it has multiple valence states and is a well-studied element. Ferrous-dominated iron valences determined by microXANES on the Lith A and Lith B glasses provide little redox sensitivity. Vanadium valence measurements for impact glass in Lith C at three different locations yielded valence values of 3.1, 3.2 and 3.4 with inferred fO2 values of IW-0.7, IW-0.1 and IW+0.7, respectively. This range of oxygen-fugacity values is understandable because the glasses are shock-molten impact glasses which are heterogeneous in nature. Oxygen fugacity values obtained from the analysis of Fe-Ti oxides and Eu partitioning in pyroxenes from EET79001 Lith A and Lith B (host lithologies) were in the range of IW+0.3 to IW+1.9 suggesting that V in the Lith C impact glass was reduced in the impact process. Here, we examine whether the 506 from Lith A and 507 from Lith B GRIM glasses yield similar or different fO2 values from those of Lith C using the vanadium K-edge microXANES technique.

Sutton, S. R.↗

Molybdenum Valence in Basaltic Silicate Melts: Effects of Temperature and Pressure

The metal-silicate partitioning behavior of molybdenum has been used as a test for equilibrium core formation hypotheses [for example, 1-6]. However, current models that apply experimental data to equilibrium core-mantle differentiation infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Molybdenum, a multi-valent element with a valence transition near the fO2 of interest for core formation (approx.IW-2) will be sensitive to changes in fO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo(6+) can be either octahedrally or tetrahedrally coordinated. Here we present X-ray absorption near edge structure (XANES) measurements of Mo valence in basaltic run products at a range of P, T, and fO2 and further quantify the valence transition of Mo.

Danielson, L. R.↗

Relationship Between Iron Valence States of Serpentine in CM Chondrites and Their Aqueous Alteration Degrees

The 0.6-0.7 micron absorption band observed for C-type asteroids is caused by the presence of Fe(3+) in phyllosilicates . Because Fe-bearing phyllosilicates, especially serpentine, are the most dominant product of aqueous alteration in the most abundant carbonaceous chondrites, CM chondrites, it is important to understand the crystal chemistry of serpentine in CM chondrites to better understand spectral features of C-type asteroids. CM chondrites show variable degrees of aqueous alteration, which should be related to iron valences in serpentine. It is predicted that the Fe(3+)/Sum of (Fe) ratios of serpentine in CM chondrites decrease as alteration proceeds by Si and Fe(3+) substitutions from end-member cronstedtite to serpentine, which should be apparent in the absorption intensity of the 0.6-0.7 micron band from C-type asteroids. In fact, the JAXA Hayabusa 2 target (C-type asteroid: 1993 JU3) exhibits heterogeneous spectral features (0.7 micron absorption band disappears by rotation). From these points of view, we have analyzed iron valences of matrix serpentine in several CM chondrites which span the entire observed range of aqueous alteration using Synchrotron Radiation X-ray Absorption Near-Edge Structure (SR-XANES). In this abstract we discuss the relationship between obtained Fe(3+)/Sum of (Fe) ratios and alteration degrees by adding new data to our previous studies

Mikouchi, T.↗

Coordinated Analyses of Mineral-organic Matter Associations in Interplanetary Dust Particles

Little is known about the timing and processes involved in the incorporation of organic matter with inorganic materials in early Solar System bodies. Recently, X-ray absorption near-edge spectroscopy (XANES) studies showed carbon-rich rims surrounding individual mineral grains in anhydrous IDPs [1,2]. These carbonaceous rims are believed to have formed prior to parent body formation and likely served to bond mineral grains during accretion into larger aggregates. We are exploring the nature of these carbonaceous rims through coordinated analyses of their chemistry, mineralogy, spectroscopy and isotopic characteristics. Here we report our preliminary mineralogical observations.

Nakamura-Messenger, K.↗

Deducing Wild 2 Components with a Statistical Dataset of Olivine in Chondrite Matrix

Introduction: A preliminary exam of the Wild 2 olivine yielded a major element distribution that is strikingly similar to those for aqueously altered carbonaceous chondrites (CI, CM, and CR) [1], in which FeO-rich olivine is preferentially altered. With evidence lacking for large-scale alteration in Wild 2, the mechanism for this apparent selectivity is poorly understood. We use a statistical approach to explain this distribution in terms of relative contributions from different chondrite forming regions. Samples and Analyses: We have made a particular effort to obtain the best possible analyses of both major and minor elements in Wild 2 olivine and the 5-30 micrometer population in chondrite matrix. Previous studies of chondrite matrix either include larger isolated grains (not found in the Wild 2 collection) or lack minor element abundances. To overcome this gap in the existing data, we have now compiled greater than 10(exp 3) EPMA analyses of matrix olivine in CI, CM, CR, CH, Kakangari, C2-ungrouped, and the least equilibrated CO, CV, LL, and EH chondrites. Also, we are acquiring TEM/EDXS analyses of the Wild 2 olivine with 500s count times, to reduce relative errors of minor elements with respect to those otherwise available. Results: Using our Wild 2 analyses and those from [2], the revised major element distribution is more similar to anhydrous IDPs than previous results, which were based on more limited statistics (see figure below). However, a large frequency peak at Fa(sub 0-1) still persists. All but one of these grains has no detectable Cr, which is dissimilar to the Fa(sub 0-1) found in the CI and CM matrices. In fact, Fa(sub 0-1) with strongly depleted Cr content is a composition that appears to be unique to Kakangari and enstatite (highly reduced) chondrites. We also note the paucity of Fa(sub greater than 58), which would typically indicate crystallization in a more oxidizing environment [3]. We conclude that, relative to the bulk of anhydrous IDPs, Wild 2 may have received a larger contribution from the Kakangari and/or enstatite chondrite forming regions. Alternatively, Wild 2 may have undergone accretion in an anomalously reducing region, marked by nebular condensation of this atypical forsterite. In [4], a similar conclusion was reached with an Fe-XANES study. We will also use similar lines of reasoning, and our previous conclusions in [5], to constrain the relative contributions of silicates that appear to have been radially transported from different ordinary and carbonaceous chondrite forming regions to the Kuiper Belt. In addition, the widespread depletion of Cr in these FeO-rich (Fa(sub greater than 20)) fragments is consistent with mild thermal metamorphism in Wild 2.

Frank, D. R.↗

Coordinated Microanalyses of Seven Particles of Probable Interstellar Origin from the Stardust Mission

Stardust, a NASA Discovery-class mission, was the first sample-return mission to return solid samples from beyond the Moon. Stardust was effectively two missions in one spacecraft: it returned the first materials from a known primitive solar system body, the Jupiter-family comet Wild 2; Stardust also returned a collector that was exposed to the contemporary interstellar dust stream for 200 days during the interplanetary cruise. Both collections present severe technical challenges in sample preparation and in analysis. By far the largest collection is the cometary one: approximately 300 micro g of material was returned from Wild 2, mostly consisting of approx. 1 ng particles embedded in aerogel or captured as residues in craters on aluminum foils. Because of their relatively large size, identification of the impacts of cometary particles in the collection media is straightforward. Reliable techniques have been developed for the extraction of these particles from aerogel. Coordinated analyses are also relatively straightforward, often beginning with synchrotron-based x-ray fluorescence (S-XRF), X-ray Absorption Near-Edge Spectoscopy (XANES) and x-ray diffraction (S-XRD) analyses of particles while still embedded in small extracted wedges of aerogel called ``keystones'', followed by ultramicrotomy and TEM, Scanning Transmission X-ray Microscopy (STXM) and ion microprobe analyses (e.g., Ogliore et al., 2010). Impacts in foils can be readily analyzed by SEM-EDX, and TEM analysis after FIB liftout sample preparation. In contrast, the interstellar dust collection is vastly more challenging. The sample size is approximately six orders of magnitude smaller in total mass. The largest particles are only a few pg in mass, of which there may be only approx.10 in the entire collection. The technical challenges, however, are matched by the scientific importance of the collection. We formed a consortium carry out the Stardust Interstellar Preliminary Examination (ISPE) to carry out an assessment of this collection, partly in order to characterize the collection in sufficient detail so that future investigators could make well-informed sample requests. The ISPE is the sixth PE on extraterrestrial collections carried out with NASA support. Some of the basic questions that we asked were: how many impacts are there in the collector, and what fraction of them have characteristics consistent with extraterrestrial materials? What is the elemental composition of the rock-forming elements? Is there crystalline material? Are there organics? Here we present coordinated microanalyses of particles captured in aerogel, using S-FTIR, S-XRF, STXM, S-XRD; and coordinated microanalyses of residues in aluminum foil, using SEMEDX, Auger spectroscopy, STEM, and ion microprobe. We discuss a novel approach that we employed for identification of tracks in aerogel, and new sample preparation techniques developed during the ISPE. We have identified seven particles - three in aerogel and four in foils - that are most consistent with an interstellar origin. The seven particles exhibit a large diversity in elemental composition. Dynamical evidence, supported supported by laboratory simulations of interstellar dust impacts in aerogel and foils, and numerical modeling of interstellar dust propagation in the heliosphere, suggests that at least some of the particles have high optical cross-section, perhaps due to an aggregate structure. However, the observations are most consistent with a variety of morphologies

Westphal, Andrew J.↗