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NASA NTRS2007

Oxidation State of Nakhlites as inferred from Fe-Ti oxide Equilibria and Augite/Melt Europium Partitioning

Recent studies have shown that Martian magmas had wide range of oxygen fugacities (fO2) and that this variation is correlated with the variation of La/Yb ratio and isotopic characteristics of the Martian basalts, shergottite meteorites. The origin of this correlation must have important information about mantle sources and Martian evolution. In order to understand this correlation, it is necessary to know accurate value of oxidation state of other Martian meteorite groups. Nakhlites, cumulate clinopyroxenites, are another major group of Martian meteorites and have distinctly different trace element and isotopic characteristics from shergottites. Thus, estimates of oxidation state of nakhlites will give us important insight into the mantle source in general. Several workers have estimated oxidation state of nakhlites by using Fe-Ti oxide equilibrium. However, Fe-Ti oxides may not record the oxidation state of the parent melt of the nakhlite because it is a late-stage mineral. Furthermore, there is no comprehensive study which analyzed all nakhlite samples at the same time. Therefore, in this study (1) we reduced the uncertainty of the estimate using the same electron microprobe and the same standards under the same condition for Fe-Ti oxide in 6 nakhlites and (2) we also performed crystallization experiments to measure partition coefficients of Eu into pyroxene in the nakhlite system in order to estimate fO2 when the pyroxene core formed (i.e. Eu oxybarometer [e.g. 2,6]).

Makishima, J.↗
NASA NTRS2007

Diverse Metals and Sulfides in Polymict Ureilites EET 83309 and EET 87720

Ureilites are a group of carbon-bearing ultramafic achondrites. The majority of samples are monomict with major and trace element compositions consistent with a restitic origin after extensive loss of basaltic melts and significant loss of their metallic component during anatexis. Monomict ureilites are thought to represent largely intact samples of the ureilite parent body (UPB) mantle. Polymict ureilites, by contrast, are fragmental breccias consisting of welded lithic clasts and isolated mineral fragments thought to be regolith that assembled after major disruption fragmented large portions of the UPB mantle. In most polymict ureilites, the majority of clasts consist of material similar to monomict ureilites gardened from the UPB mantle but other materials, both endogenic and xenogenic to the UPB are also found in polymict ureilites, including clasts texturally and compositionally similar to known chondrite types as well as feldspathic melt rocks and clasts of Ca-Al-Ti-rich assemblages. In this study, we demonstrate that polymict ureilites also contain a variety of metal and sulfide compositions of diverse origins. They offer insight into the final equilibrium conditions of disrupted portions of the UPB mantle and the diversity of materials locally available for regolith formation, and provide evidence for only limited post-regolith formation thermal metamorphism.

Herrin, J. S.↗
NASA NTRS2007

Petrology and Geochemistry of New Ureilites and Ureilite Genesis

Ureilites are C-bearing, basalt-depleted olivine+pyroxene achondrites from a differentiated asteroid. The group is heterogeneous, exhibiting ranges in O isotopic composition, Fe/Mg, Fe/Mn, pyx/ol, siderophile and lithophile trace element content, and C content and isotopic composition [1]. Some of these characteristics are nebular in origin; others were strongly overprinted by asteroidal igneous processes. The consensus view is that most ureilites are melt-residues, but some are partial cumulates or have interacted with a melt [1,2]. An "unroofing" event occurred while the parent asteroid was hot that froze in mineral core com-positions and resulted in FeO reduction at olivine grain margins. We have studied several new ureilites, but will focus here on two anomalous stones; LAR 04315 and NWA 1241. LAR 04315 is texturally unusual. It contains olivine with angular subdomains, and low-Ca pyroxene riddled with wormy inclusions of metal+troilite, graphite, and possibly other phases, and irregular inclusions of high-Ca pyroxene. Reduction occurred along olivine grain margins and internal fractures, but not along subdomain boundaries. Although texturally odd, LAR 04351 is a typical ureilite in mineral and bulk composition. The olivine is Fo80.8 and falls on the ureilite Fe/Mn-Fe/Mg trend. Its olivine composition falls within the range of the majority of ureilites, and it is typical of these ureilites in bulk rock lithophile and siderophile element contents.

Mittlefehldt, David W.↗
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 NTRS2006

Derivation of Apollo 14 High-Al Basalts from Distinct Source Regions at Discrete Times: New Constraints

Apollo 14 basalts occur predominantly as clasts in breccias, but represent the oldest volcanic products that were returned from the Moon [1]. These basalts are relatively enriched in Al2O3 (11-16 wt%) compared to other mare basalts (7-11 wt%) and were originally classified into 5 compositional groups [2,3]. Neal et al. [4] proposed that a continuum of compositions existed. These were related through assimilation (of KREEP) and fractional crystallization (AFC). Age data, however, show that at least three volcanic episodes are recorded in the sample collection [1,5,6]. Recent work has demonstrated that there are three, possibly four groups of basalts in the Apollo 14 sample collection that were erupted from different source regions at different times [7]. This conclusion was based upon incompatible trace element (ITE) ratios of elements that should not be fractionated from one another during partial melting (Fig. 1). These groups are defined as Group A (Groups 4 & 5 of [3]), Group B (Groups 1 & 2 of [3]), and Group C (Group 3 of [3]). Basalt 14072 is distinct from Groups A-C.

Neal, C. R.↗
NASA NTRS2009

Northwest Africa 5298: A Basaltic Shergottite

NWA 5298 is a single 445 g meteorite found near Bir Gandouz, Morocco in March 2008 [1]. This rock has a brown exterior weathered surface instead of a fusion crust and the interior is composed of green mineral grains with interstitial dark patches containing small vesicles and shock melts [1]. This meteorite is classified as a basaltic shergottite [2]. A petrologic study of this Martian meteorite is being carried out with electron microprobe analysis and soon trace element analyses by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Oxygen fugacity is calculated from Fe-Ti oxides pairs in the sample. The data from this study constrains the petrogenesis of basaltic shergottites.

Hui, Hejiu↗
NASA NTRS2008

Compositional and Geochronological Constraints on the Lunar Cataclysm from Planetary Samples

Radiometric dating and compositional clustering of lunar impact-melt rocks form the backbone of the lunar cataclysm hypothesis. Precise age determinations of Apollo and Luna impact-melt rocks define the classic formulation of the cataclysm: a large number of samples 3.9 Ga old, a steep decline after 3.9 Ga, and few impact rocks older than ~4.0 Ga. Lunar meteorites more randomly sample the lunar surface, but impact-melt clasts in these rocks show the same apparent age cutoff at 4.0 Ga (though their ages extend approx.500 Myr later). Neither do impact-formed glass spherules and fragments, formed by impacts of all sizes throughout lunar history, predate 4.0 Ga. Geological associations between compositional groups of impact-melt rocks and specific impact basins imply that five large basins formed on the Moon within 200 Myr but a counter-argument postulates they are all products of the Imbrium basin-forming impact; it is not yet proven whether groups of impact melt that are resolvable from each other in age and in trace-element composition represent multiple impacts. The 3.9 Ga age peak and subsequent steep decline are not well mirrored in meteorite data. Radiometric ages in ordinary chondrites and HED meteorites peak around 3.9 Ga but ages older and younger than 3.9 Ga are common. Among Martian meteorites, there is a single impact-related age: ALH 84001 was shocked at 3.92 Ga. Differences in relative impact velocity, impact-melt production, and sampling rate could explain differences between the meteorite and lunar records. One way to anchor the early end of the lunar flux is to directly sample the impact-melt sheet of a large lunar basin distant from Imbrium, such as the South Pole-Aitken basin, where melt rocks probably still resides on the basin floor and could be directly sampled by a human or robotic mission.

Cohen, Barbara A.↗
NASA NTRS2009

Late Reduction Textures in Almahata Sitta Ureilite

The Almahata Sitta ureilite, derived from asteroid 2008 TC3, consists of many individual fragments recovered from the Nubian dessert strewn field [1]. Like most ureilites, it contains abundant carbon and exhibits examples of disequilibrium textures that record a late reduction event accompanied by rapid cooling (tens of degC/h) from high temperatures (1150-1300 C). Variations in Fe/Mg of silicate minerals are accompanied by variations in Fe/Mn, indicating loss of Fe into metal [2]. In coarser-grained fragments of Almahata Sitta, olivine exhibits irregular high mg# rims in contact with networks of interstitial metal 5- 20 microns in typical thickness. This is a common ureilite texture thought to be driven by the reaction of graphite to a CO gas phase and the concurrent reduction of FeO in olivine to Fe metal, with excess silica going primarily into pyroxene (2MgFeSiO4 + C approaches MgSiO4 + MgSiO3 + 2Fe + CO) [3, see also 4,5,6]. Other fragments of Almahata Sitta exhibit anomalous textures such as fine grain size, high porosity, and abundant graphite. Within these fragments pyroxene locally exhibits high-mg# rims in contact with metal and a discreet silica phase, suggesting that the reduction mechanism MgFeSi2O6 + C approaches MgSiO3 + Fe + SiO2 + CO. Metals in Almahata Sitta are particularly unaltered in comparison to ureilite finds. Variations in minor and trace element composition of this metal might partly result from localized dilution as iron is supplied by reduction of silicates.

Herrin, J. S.↗
NASA NTRS2010

FIB-NanoSIMS-TEM Coordinated Study of a Wark-Lovering Rim in a Vigarano Type A CAI

Wark-Lovering (WL) rims are thin multi layered mineral sequences that surround most Ca, Al-rich inclusions (CAIs). Unaltered WL rims are composed of the same primary high temperature minerals as CAIs, such as melilite, spinel, pyroxene, hibonite, perovskite, anorthite and olivine. It is still unclear whether the rim minerals represent a different generation formed by a separate event from their associated CAIs or are a byproduct of CAI formation. Several models have been proposed for the origins of WL rims including condensation, flashheating, reaction of a CAI with a Mg-Si-rich reservoir (nebular gas or solid); on the basis of mineralogy, abundances of trace elements, O and Mg isotopic studies. Detailed mineralogical characterizations of WL rims at micrometer to nanometer scales have been obtained by TEM observations, but so far no coordinated isotopic - mineralogical studies have been performed. Thus, we have applied an O isotopic imaging technique by NanoSIMS 50L to investigate heterogeneous distributions of O isotopic ratios in minerals within a cross section of a WL rim prepared using a focused ion beam (FIB) instrument. After the isotopic measurements, we determine the detailed mineralogy and microstructure of the same WL FIB section to gain insight into its petrogenesis. Here we present preliminary results from O isotopic and elemental maps by NanoSIMS and mineralogical analysis by FE-SEM of a FIB section of a WL rim in the Vigarano reduced CV3 chondrite.

Cai, A.↗
NASA NTRS2010

Concentrations and Origins of Atmospheric Lead and Other Trace Species at a Rural Site in Northern China

In this study we analyze the ambient levels of lead and other trace species in the bulk aerosol samples from a rural site approx.70 km ESE of Beijing in spring 2005. Lead (0.28+/-0.24 micro-g/cu m, average +/- standard deviation), along with several pollution \related trace elements, was enriched by over 100 fold relative to the Earth's crust. The ambient lead levels showing large synoptic variations were well-correlated with other anthropogenic pollutants (e.g., CO and SO2). The Unmix receptor model resolved four factors in the aerosol composition data: a biomass burning source, an industrial and coal combustion source, a secondary aerosol source, and a dust source. The first three sources were strongest in weak southerly winds ahead of cold fronts, while the dust source peaked in strong northerly winds behind cold fronts. The second source, primarily representing emissions from industrial processes and relatively small \scale coal burning such as in home and institutional heating, was identified as the main source of ambient lead in this study. Mobile sources might also contribute to this factor, but there was no distinct evidence of emissions due to combustion of leaded gasoline, despite a correlation between lead and CO. Potential source contribution function, calculated from backward trajectories and aerosol composition, further reveals that lead observed in this study was predominantly from the populated and industrialized areas to the south and SW of Xianghe, rather than Beijing to the west. Our results and several recent studies show that the lead levels in suburban areas near big cities in China, although generally lower than those in industrial districts and urban areas, are substantial (near or above 0.15 micro-g/cu m). More extensive studies on airborne lead and its emission sources in China are called for.

Li, Can↗
NASA NTRS2012

Formation and Processing of Amorphous Silicates in Primitive Carbonaceous Chondrites and Cometary Dust

Chondritic-porous interplanetary dust particles (CP IDPs) exhibit strongly heterogeneous and unequilibrated mineralogy at sub-micron scales, are enriched in carbon, nitrogen and volatile trace elements, and contain abundant presolar materials [1-4]. These observations suggest that CP IDPs have largely escaped the thermal processing and water-rock interactions that have severely modified or destroyed the original mineralogy of primitive meteorites. CP IDPs are believed to represent direct samples of the building blocks of the Solar System - a complex mixture of nebular and presolar materials largely unperturbed by secondary processing. The chemical and isotopic properties of CP IDPs and their atmospheric entry velocities are also consistent with cometary origins. GEMS (glass with embedded metal and sulfides) grains are a major silicate component of CP IDPs. GEMS grains are < 0.5 microns in diameter objects that consist of numerous 10 to 50 nm-sized Fe-Ni metal and Fe-Ni sulfide grains dispersed in a Mg-Si-Al-Fe amorphous silicate matrix [2, 5]. Based on their chemistry and isotopic compositions, most GEMS appear to be non-equilibrium condensates from the early solar nebula [2]. If GEMS grains are a common nebular product, then they should also be abundant in the matrices of the most physically primitive chondritic meteorites. Although amorphous silicates are common in the most primitive meteorites [6-9], their relationship to GEMS grains and the extent to which their compositions and microstructure have been affected by parent body processing (oxidation and aqueous alteration) is poorly constrained. Here we compare and contrast the chemical, microstructural and isotopic properties of amorphous silicates in primitive carbonaceous chondrites to GEMS grains in IDPs.

Keller, Lindsay P.↗
NASA NTRS2012

In Situ Analysis of Orthopyroxene in Diogenites Using Laser Ablation ICP-MS

Howardites, eucrites and diogenites (HED) form a suit of igneous achondrite meteorites that are thought to have formed on a single asteroidal body. While there have been many different models proposed for the formation of the HED parent asteroid they can be generalized into two end member models. One is the magma ocean model (e.g. [1]) in which the entire HED parent body was continuously fractionated from a planet wide magma ocean with diogenites representing the lower crust and eucrites being upper crustal rocks. The second model hypothesizes that diogenites and eucrites were formed as a series of intrusions and/or extrusions of partial melts of a primitive proto-Vesta [2]. We use in situ trace element analysis together with major and minor element analysis to try and distinguish between these different hypotheses for the evolution of the HED parent body.

Elk, Mattias↗
NASA NTRS2012

In Situ Chemical Characterization of Mineral Phases in Lunar Granulite Meteorite Northwest Africa 5744

Northwest Africa (NWA) 5744 meteorite is a granulitic and troctolitic lunar breccia which may represent nearly pristine lunar crust (Fig. 1). NWA 5744 is unusually magnesian compared to other lunar breccias, with bulk [Mg/(Mg+Fe)] ~ 0.79 [1, 2]. Inspection shows impactor content is likely to be very minor, with low Ni content and a lack of metal grains. Some terrestrial contamination is present, evidenced by calcite within cracks. NWA 5744 has notably low concentrations of incompatible trace elements (ITEs) [2]. The goal of this study is to attempt to classify this lunar granulite through analyses of in situ phases.

Kent, J. J.↗
NASA NTRS2012

Martian Igneous Geochemistry: The Nature of the Martian Mantle

Mafic igneous rocks probe the interiors of their parent objects, reflecting the compositions and mineralogies of their source regions, and the magmatic processes that engendered them. Incompatible trace element contents of mafic igneous rocks are widely used to constrain the petrologic evolution of planets. We focus on incompatible element ratios of martian meteorites to constrain the petrologic evolution of Mars in the context of magma ocean/cumulate overturn models [1]. Most martian meteorites contain some cumulus grains, but regardless, their incompatible element ratios are close to those of their parent magmas. Martian meteorites form two main petrologic/ age groupings; a 1.3 Ga group composed of clinopyroxenites (nakhlites) and dunites (chassignites), and a <1 Ga group composed of basalts and lherzolites (shergottites).

Mittlefehldt, D. W.↗
NASA NTRS2012

Observations and Models of the Lunar Sodium Exosphere 1988 - 1999

Sodium in the lunar exosphere is easily observed from the Earth's surface due to its strong resonance emission lines in the visible region of the spectrum. Although sodium is a trace element, it is easily ejected from the surface by a number of processes. The variation of this exospheric constituent both spatially and temporally can help to constrain these sources and the loss processes and their timescales. Due to a revival of interest in the Moon and its volatiles, observations of the lunar exosphere obtained at the McMath-Pierce solar telescope in 1998 and 1999 have recently been reduced and analyzed. In addition, observations of the lunar sodium exosphere obtained with the Mt. Lemmon Lunar Coronagraph on Mt. Lemmon, Arizona, have also been published. We combine these new data with data previously published and reanalyzed by Sarantos et al. This comprehensive data set will be modeled using both a simple Chamberlain exosphere model and a comprehensive Monte Carlo model.

Killen, Rosemary↗
NASA NTRS2013

Chemical Heterogeneity of a Large Cluster IDP: Clues to its Formation History Using X-ray Fluorescence Mapping and XANES Spectroscopy

Chondritic porous IDPs may be among the most primitive objects found in our solar system [1]. They consist of many micron to submicron minerals, glasses and carbonaceous matter [2,3,4,5,6,7] with > 10(exp 4) grains in a 10 micron cluster [8]. Speculation on the environment where these fine grained, porous IDPs formed varies with possible sources being presolar dusty plasma clouds, protostellar condensation, solar asteroids or comets [4,6,9]. Also, fine grained dust forms in our solar system today [10,11]. Isotopic anomalies in some particles in IDPs suggest an interstellar source[4,7,12]. IDPs contain relic particles left from the dusty plasma that existed before the protostellar disk formed and other grains in the IDPs formed later after the cold dense nebula cloud collapsed to form our protostar and other grains formed more recently. Fe and CR XANES spectroscopy is used here to investigate the oxygen environment in a large (>50 10 micron or larger sub-units) IDP. Conclusions: Analyzing large (>50 10 micron or larger sub-units) CP IDPs gives one a view on the environments where these fine dust grains formed which is different from that found by only analyzing the small, 10 micron IDPs. As with cluster IDP L2008#5 [3], L2009R2 cluster #13 appears to be an aggregate of grains that sample a diversity of solar and perhaps presolar environments. Sub-micron, grain by grain measurement of trace element contents and elemental oxidation states determined by XANES spectroscopy offers the possibility of understanding the environments in which these grains formed when compared to standard spectra. By comparing thermodynamic modeling of condensates with analytical data an understanding of transport mechanisms operating in the early solar system may be attained.

Wirick, S.↗
NASA NTRS2013

Testing the Origins of Basalt Fragments fro Apollo 16

Several 2-4 mm regolith fragments of basalt from the Apollo 16 site were recently described by [1]. These included a high-Ti vitrophyric basalts (60603,10-16) and one very-low-titanium (VLT) crystalline basalt (65703,9-13). As Apollo 16 was the only highlands sample return mission distant from the maria, identification of basaltic samples at the site indicates input from remote sites via impact processes [1]. However, distinguishing between impact melt and pristine basalt can be notoriously difficult and requires significant sample material [2-6]. The crystal stratigraphy method utilizes essentially non-destructive methods to make these distinctions [7,8]. Crystal stratigraphy combines quantitative petrography in the form of crystal size distributions (CSDs) coupled with mineral geochemistry to reveal the petrogenetic history of samples. The classic CSD plot of crystal size versus population density can reveal insights on growth/cooling rates, residence times, and magma history which in turn can be used to evaluate basaltic vs impact melt origin [7-9]. Electron microprobe (EMP) and laser ablation (LA)-ICP-MS analyses of mineral phases complement textural investigations. Trace element variations document subtle changes occurring during the formation of the samples, and are key in the interpretation and preservation of this rare lunar sample collection.

Donohue, P. H.↗
NASA NTRS2013

Investigating Titan's Atmospheric Chemistry at Low Temperature in Support of the NASA Cassini Mission

Titan's atmosphere, composed mainly of N2 and CH4, is the siege of a complex chemistry induced by solar UV radiation and electron bombardment from Saturn's magnetosphere. This organic chemistry occurs at temperatures lower than 200 K and leads to the production of heavy molecules and subsequently solid aerosols that form the orange haze surrounding Titan. The Titan Haze Simulation (THS) experiment has been developed on the COSMIC simulation chamber at NASA Ames in order to study the different steps of Titan's atmospheric chemistry at low temperature and to provide laboratory data in support for Cassini data analysis. The chemistry is simulated by plasma in the stream of a supersonic expansion. With this unique design, the gas mixture is adiabatically cooled to Titan-like temperature (approx. 150 K) before inducing the chemistry by plasma discharge. Different gas mixtures containing N2, CH4, and the first products of the N2,-CH4 chemistry (C2H2, C2H4, C6H6...) but also heavier molecules such as PAHs or nitrogen containing PAHs can be injected. Both the gas phase and solid phase products resulting from the plasma-induced chemistry can be monitored and analyzed. Here we present the results of recent gas phase and solid phase studies that highlight the chemical growth evolution when injecting heavier hydrocarbon trace elements in the initial N2-CH4 mixture. Due to the short residence time of the gas in the plasma discharge, only the first steps of the chemistry have time to occur in a N2-CH4 discharge. However by adding acetylene and benzene to the initial N2-CH4 mixture, we can study the intermediate steps of Titan's atmospheric chemistry as well as specific chemical pathways. These results show the uniqueness of the THS experiment to help understand the first and intermediate steps of Titan fs atmospheric chemistry as well as specific chemical pathways leading to Titan fs haze formation.

Sciamma-O'Brien, Ella↗