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Al, Ti, and Cr: Complex Zoning in Synthetic and Natural Nakhlite Pyroxenes

Nakhlites are olivine-bearing clinopyroxene cumulates. The cumulus pyroxenes have cores that are relatively homogeneous in Fe, Mg, and Ca, but show complex zoning of minor elements, especially Al, Ti, and Cr. Zoning patterns contain information about crystallization history parent magma compositions. But it has proven difficult to decipher this information and translate the zoning patterns into petrogenetic processes. This abstract reports results of high-precision Electron Probe MicroAnalysis (EPMA) analysis of synthetic nakhlite pyroxenes run at fO2 from IW to QFM. It compares these with concurrent analyses of natural nakhlite MIL03346 (MIL), and with standardprecision analyses of Y000593 (Y593) collected earlier. Results suggest that (1) different processes are responsible for the zoning of MIL and other more slowly-cooled nakhlites such as Y593, and (2) changes in oxidation conditions during MIL crystallization are not responsible for the unusual Cr zoning pattern

McKay, G.↗

Genesis of Augite-Bearing Ureilites: Evidence From LA-ICP-MS Analyses of Pyroxenes and Olivine

Ureilites are ultramafic achondrites composed primarily of coarse-grained low-Ca pyroxene and olivine with interstitial carbonaceous material, but a number of them contain augite [1]. Ureilites are considered to be restites after partial melting of a chondritic precursor, although at least some augite-bearing ureilites may be partially cumulate [1, 2]. In this scenario, the augite is a cumulus phase derived from a melt that infiltrated a restite composed of typical ureilite material (olivine+low-Ca pyroxene) [2]. To test this hypothesis, we examined the major and trace element compositions of silicate minerals in select augite-bearing ureilites with differing mg#. Polished thick sections of the augite-bearing ureilites ALH 84136 , EET 87511, EET 96293, LEW 88201, and META78008 and augite-free typical ureilite EET 90019 were examined by EPMA for major and minor elements and laser ablation ICP-MS (LA-ICP-MS) for trace elements, REE in particular. Although EET 87511 is reported to contain augite, the polished section that we obtained did not.

Herrin, J. S.↗

Ultrafast Phase Mapping of Thin-Sections from An Apollo 16 Drive Tube - a New Visualisation of Lunar Regolith

Polished thin-sections of samples extracted from Apollo drive tubes provide unique insights into the structure of the Moon's regolith at various landing sites. In particular, they allow the mineralogy and texture of the regolith to be studied as a function of depth. Much has been written about such thin-sections based on optical, SEM and EPMA studies, in terms of their essential petrographic features, but there has been little attempt to quantify these aspects from a spatial perspective. In this study, we report the findings of experimental analysis of two thin-sections (64002, 6019, depth range 5.0 - 8.0 cm & 64001, 6031, depth range 50.0 - 53.1 cm), from a single Apollo 16 drive tube using QEMSCAN . A key feature of the method is phase identification by ultrafast energy dispersive x-ray mapping on a pixel-by-pixel basis. By selecting pixel resolutions ranging from 1 - 5 microns, typically 8,500,000 individual measurement points can be collected on a thin-section. The results we present include false colour digital images of both thin-sections. From these images, information such as phase proportions (major, minor and trace phases), particle textures, packing densities, and particle geometries, has been quantified. Parameters such as porosity and average phase density, which are of geomechanical interest, can also be calculated automatically. This study is part of an on-going investigation into spatial variation of lunar regolith and NASA's ISRU Lunar Simulant Development Project.

Botha, Pieter↗

Effect of Fluorine on Near-Liquidus Phase Equilibria of Basalts

Volatile species such as H2O, CO2, F, and Cl have significant impact in generation and differentiation of basaltic melts. Thus far experimental work has primarily focused on the effect of water and carbon dioxide on basalt crystallization, liquid-line of descent, and mantle melting [e.g., 1, 2] and the effects of halogens have received far less attention [3-4]. However, melts in the planetary interiors can have non-negligible chlorine and fluorine concentrations. Here, we explore the effects of fluorine on near-liquidus phase equilibria of basalt. We have conducted nominally anhydrous piston cylinder experiments using graphite capsules at 0.6 - 1.5 GPa on an Fe-rich model basalt composition. 1.75 wt% fluorine was added to the starting mix in the form of AgF2. Fluorine in the experimental glass was measured by SIMS and major elements of glass and minerals were analyzed by EPMA. Nominally volatile free experiments yield a liquidus temperature from 1330 C at 0.8GPa to 1400 at 1.6GPa and an olivine(Fo72)-pyroxene(En68)-liquid multiple saturation point at 1.25 GPa and 1375 C. The F-bearing experiments yield a liquiudus temperature from 1260 C at 0.6GPa to 1305 at 1.5GPa and an ol(Fo66)-pyx(En64)-MSP at 1 GPa and 1260 C. This shows that F depresses the basalt liquidus, extends the pyroxene stability field to lower pressure, and forces the liquidus phases to be more Fe-rich. KD(Fe-Mg/mineral-melt) calculated for both pyroxenes and olivines show an increase with increasing F content of the melt. Therefore, we infer that F complexes with Mg in the melt and thus increases the melt s silica activity, depressing the liquidus and changing the composition of the crystallizing minerals. Our study demonstrates that on a weight percent basis, the effect of fluorine is similar to the effect of H2O [1] and Cl [3] on freezing point depression of basalts. But on an atomic fraction basis, the effect of F on liquidus depression of basalts is xxxx compared to the effect of H. Future studies on kimberlitic and subduction zone magmas, which could have significant amount of fluorine, will need to consider the combined effects of F, Cl, and H on their stability and chemical evolution.

Filiberto, Justin↗

A CAI in the Ivuna CI1 Chondrite

We have recently discovered the first well-preserved calcium aluminum-rich inclusion (CAI) in a CI1 chondrite (Ivuna). Previously, all CI1 chondrites were thought to be devoid of preserved CAI and chondrules due to the near total aqueous alteration to which their parent body (bodies) have been subjected. The CAI is roughly spherical, but with a slight teardrop geometry and a maximum diameter of 170 microns (fig. 1). It lacks any Wark-Lovering Rim. Incipient aqueous alteration, and probably shock, have rendered large portions of the CAI poorly crystalline. It is extremely fine-grained, with only a few grains exceeding 10 microns. We have performed electron microprobe analyses (EPMA), FEG-SEM imaging and element mapping, as well as electron back-scattered diffraction (EBSD) and synchrotron X-ray diffraction (SXRD) in order to determine the fundamental characteristics of this apparently unique object.

Frank, David R.↗

Oxygen and Magnesium Isotopic Compositions of Asteroidal Materials Returned from Itokawa by the Hayabusa Mission

The Hayabusa spacecraft made two touchdowns on the surface of Asteroid 25143 Itokawa on November 20th and 26th, 2005. The Asteroid 25143 Itokawa is classified as an S-type asteroid and inferred to consist of materials similar to ordinary chondrites or primitive achondrites [1]. Near-infrared spectroscopy by the Hayabusa spacecraft proposed that the surface of this body has an olivine-rich mineral assemblage potentially similar to that of LL5 or LL6 chondrites with different degrees of space weathering [2]. The spacecraft made the reentry into the Earth s atmosphere on June 12th, 2010 and the sample capsule was successfully recovered in Australia on June 13th, 2010. Although the sample collection processes on the Itokawa surface had not been made by the designed operations, more than 1,500 grains were identified as rocky particles in the sample curation facility of JAXA, and most of them were judged to be of extraterrestrial origin, and definitely from Asteroid Itokawa on November 17th, 2010 [3]. Although their sizes are mostly less than 10 microns, some larger grains of about 100 microns or larger were also included. The mineral assembly is olivine, pyroxene, plagioclase, iron sulfide and iron metal. The mean mineral compositions are consistent with the results of near-infrared spectroscopy from Hayabusa spacecraft [2], but the variations suggest that the petrologic type may be smaller than the spectroscopic results. Several tens of grains of relatively large sizes among the 1,500 grains will be selected by the Hayabusa sample curation team for preliminary examination [4]. Each grain will be subjected to one set of preliminary examinations, i.e., micro-tomography, XRD, XRF, TEM, SEM, EPMA and SIMS in this sequence. The preliminary examination will start from the last week of January 2011. Therefore, samples for isotope analyses in this study will start from the last week of February 2011. By the time of the LPSC meeting we will have measured the oxygen and magnesium isotopic composition of several grains. We will present the first results from the isotope analyses that will have been performed.

Yurimoto, H↗

Three Dimensional Structures of Particles Recovered from the Asteroid Itokawa by the Hayabusa Mission and a Role of X-Ray Microtomography in the Preliminary Examination

Particles of regolith on S-type Asteroid 25143 Itokawa were successfully recovered by the Hayabusa mission of JAXA (Japan Aerospace Exploration Agency). Near-infrared spectral study of Itokawa s surface indicates that these particles are materials similar to LL5 or LL6 chondrites. High-resolution images of Itokawa's surface suggest that they may be breccias and some impact products. At least more than 1500 particles were identified as Itokawa origin at curation facility of JAXA. Preliminary analysis with SEM/EDX at the curation facility shows that they are roughly similar to LL chondrites. Although most of them are less than 10 micron in size, some larger particles of about 100 micron or larger were also identified. A part of the sample (probably several tens particles) will be selected by Hayabusa sample curation team, and sequential examination will start from January 2011 by Hayabusa Asteroidal Sample Preliminary Examination Team (HASPET). In mainstream of the analytical flow, each particle will be examined by microtomography, XRD and XRF first as nondestructive analyses, and then the particle will be cut by an ultra-microtome and examined by TEM, SEM, EPMA, SIMS, PEEM/XANES, and TOF-SIMS sequentially. Three-dimensional structures of Itokawa particles will be obtained by microtomography sub-team of HASPET. The results together with XRD and XRF will be used for design of later destructive analyses, such as determination of cutting direction and depth, to obtain as much information as possible from small particles. Scientific results and a role of the microtomography in the preliminary examination will be presented.

Tsuchiyama, A.↗

The Valence of Iron in CM Chondrite Serpentine as Measured by Synchrotron Xanes

Fe-bearing phyllosilicates are the dominant product of aqueous alteration in carbonaceous chondrites, and serpentine is the most abundant phyllosilicate in CM2 chondrites that are the most abundant carbonaceous chondrite. Browning et al. predicted that Fe(3+)/(sum of Fe) ratios of serpentine in CM chondrites should change with progressive alteration. They proposed that progressive CM alteration is best monitored by evaluating the progress of Si and Fe3+ substitutions that necessarily attend the transition from end-member cronstedtite to serpentine. Their proposed Mineralogic Alteration Index, 2-(Fe(3+)/(2-Si)), was intended to highlight and utilize the relevant ex-change information in the stoichiometric phyllosilicate formulas based upon the coupled substitution of 2(Fe(3+), Al) = Si + (Mg, Fe(2+)...) in serpentine. The value of this ratio increases as alteration proceeds. We always wanted to directly test Browning s pre-diction through actual measurements of the Fe3+ con-tent of serpentine at the micron scale appropriate to EPMA analyses (Zega et al. have measured it at much finer scale), and this test can now be made using Synchrotron Radiation X-ray Absorption Near-Edge Structure (SR-XANES). Thus, we have recently begun investigation with CMs that span a large portion of the range of observed aqueous alteration, and we first analyzed Murray, Nogoya, and ALH84029 by SR-XANES. However, we did not find clear correlation between Fe3+/(sum of Fe) ratios of serpentine and their alteration degrees. We thus analyzed serpentine in three more CMs and here report their Fe3+/(sum of Fe) ratios in comparison with our previous results.

Mikouchi, T.↗

Microscopic and Metallurgical Aspects of the Space Shuttle Columbia Accident Investigation and Reconstruction

The Space Shuttle Columbia was descending for a landing at the Kennedy Space Center (KSC) on February 1, 2003. Approximately 20 minutes prior to touchdown, the Columbia began disintegrating over the western United States; the majority of debris eventually impacted in eastern Texas and western Louisiana. A monumental effort eventually recovered approximately 84,000 pieces of debris, approximately 38% of the Orbiter's original dry weight. The debris was transported to KSC, where the items were catalogued and evaluated. Critical areas of interest, such as the left and right leading edge surfaces and the underside of the ship, were placed upon a grid to aid in the reconstruction. Items of interest included metallic structures, reinforced carbon-carbon composites, and ceramic heat insulation tiles. Many of the leading edge elements had re-solidified metallic deposits spattered on them. These deposits became known as slag and were one of the main focuses of the investigation. In order to help determine the sequence of events inside the left wing during the accident, the slag's composition, layering order, and directionality of deposition were studied. A myriad of analytical tests were performed in an attempt to ascertain the compositional and depositional characteristics of selected slag deposits, including the ordering of deposited layers within each individual slag deposit harvested. Initially, Scanning Electron Microscopy and Energy Dispersive X-Ray Spectroscopy (SEM/EDX) were performed to quickly characterize the overall composition of individual slag deposits: SEM utilizes a narrowlyfocused high-energy electron beam impinging upon a specimen. The incident beam excites and liberates lower energy secondary electrons, which are detected and analyzed, providing a visual representation of the sample's surface topography. EDX also relies on an incident electron beam, except an EDX unit measures X-ray energies generated by the impinging beam. Each element generates a unique X-ray signature; the EDX detector measures these discreet energies. EDX actually penetrates approximately 2 microns into the bulk of the sample. However, random examination of various portions of slag, coupled with the semiquantitative nature of the SEM/EDX analysis, did not yield convincingly pertinent data. Therefore, X-ray dot mapping was conducted, which provided more understandable data, both in terms of slag layering and composition. An X-ray dot map is generated by performing numerous EDX scans for individual elements, then compiling the scans in a visual representation. Eventually, specimens consisting of not only the slag, but of the adjacent RCC substrate as well were cross-sectioned. X-Ray dot mapping of the materialographicallymounted and -polished cross- sections provided a visual representation of both the layering sequence and compositional characteristics of the slag. Contemporaneously, Electron Spectroscopy for Chemical Analysis/X-Ray Photoelectron Spectroscopy (ESCA/XPS) and powdered X-Ray Diffraction (XRD) were performed to further characterize the deposits and to attempt to identify what, if any, compounds were present. The ESCA/XPS analysis allowed the analyst to "sputter" into the sample with an electron gun, aiding in the identification of the layering sequence. XPS uses photons, rather than electrons, which impinge upon the surface of the sample. XPS measures the electrons emitted from within the first 5 nm of the sample's surface. The XRD measures the scatter angles of incident X-rays; the angle and intensity of scatter depend upon the crystalline structure of the pulverized sample. XRD is considered a qualitative rather than quantitative technique. ESCA/XPS revealed that the final layer to deposit was predominantly carbonaceous. XRD was successful in identifying specific compounds, such as Al 2O3, Al and/or Al3 21SiO47, mullite (3(Al2)O3 -SiO2), and nickel-aluminides. Eventually, Electron MicroProbe Analysis (EMPA) was conducted on the marialographically-prepared cross- sections of selected slag deposits. Microprobe combines SEM and Wavelength Dispersive X-Ray Spectroscopy (WDS), and, like EDX, uses a narrowly-focused high-energy electron beam impinging upon a specimen to elicit, in the case of EPMA, characteristic X-rays with specific wavelengths. This quantitative, analytical tool proved the most useful in determining depositional layering and composition of the slag deposits. This information was utilized in verifying the location of the breach in the left leading edge of the wing of the Columbia.

McDaniels, Steven J.↗

The Role of Materials Degradation and Analysis in the Space Shuttle Columbia Accident Investigation

The efforts following the loss of the Space Shuttle Columbia included debris recovery, reconstruction, and analysis. The debris was subjected to myriad quantitative and semiquantitative chemical analysis techniques, ranging from examination via the scanning electron microscope (SEM) with energy dispersive spectrometer (EDS) to X-Ray diffraction (XRD) and electron probe micro-analysis (EPMA). The results from the work with the debris helped the investigators determine the location where a breach likely occurred in the leading edge of the left wing during lift off of the Orbiter from the Kennedy Space Center. Likewise, the information evidenced by the debris was also crucial in ascertaining the path of impinging plasma flow once it had breached the wing. After the Columbia Accident Investigation Board (CAIB) issued its findings, the major portion of the investigation was concluded. However, additional work remained to be done on many pieces of debris from portions of the Orbiter which were not directly related to the initial impact during ascent. This subsequent work was not only performed in the laboratory, but was also performed with portable equipment, including examination via portable X-Ray fluorescence (XRF) and Fourier transform infrared spectroscopy (FTIR). Likewise, acetate and silicon-rubber replicas of various fracture surfaces were obtained for later macroscopic and fractographic examination. This paper will detail the efforts and findings from the initial investigation, as well as present results obtained by the later examination and analysis of debris from the Orbiter including its windows, bulkhead structures, and other components which had not been examined during the primary investigation.

McDanels, Steven J.↗

A Cabonaceous Chondrite Dominated Lithology from the HED Parent; PRA 04401

The paired howardite breccias Mt. Pratt (PRA) 04401 and PRA 04402 are notable for their high proportion of carbonaceous chondrite clasts [1]. They consist predominantly of coarse (0.1-7 mm) diogenite (orthopyroxene), eucrite (plagioclase + pyroxene), and carbonaceous chondrite clasts set in a finer grained matrix of these same materials. Coarse C-chondrite clasts up to 7 mm are composed mainly of fine-grained phyllosilicates with lesser sulfides and high-mg# anhydrous magnesian silicates. Most of these clasts appear to be texturally consistent with CM2 classification [1] and some contain relict chondrules. The clasts are angular and reaction or alteration textures are not apparent in the surrounding matrix. PRA 04401 contains about 70 modal% C-chondrite clasts while PRA 04402 contains about 7%. Although many howardites are known to contain abundant C-chondrite clasts [2,3,4], PRA 04401 is, to our knowledge, the most chondrite-rich howardite lithology identified to date. Low EPMA totals from CM2-type clasts in other howardites suggest that they frequently contain 10 wt% or more water [2], a figure consistent with their mineralogy. PRA 04401, therefore, demonstrates the potential for hydrous lithologies with greater than 5 wt% water to occur locally within the nominally anhydrous HED parent body. Since the origin of this water is xenogenic, it might therefore be concentrated in portions of the asteroid surface where it would be more readily observable by remote sensing techniques. We plan to further examine C-chondrite clasts in PRA 04401/2 with the intent of establishing firm chemical classification, estimating water content, and evaluating their relationship with the host breccia. To help place them in context of the HED parent, we will also compare these breccias with other howardites to evaluate which lithologies are likely to be more prevalent on the asteroid surface.

Herrin, Jason S.↗

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.↗

Origins and Distribution of Chondritic Olivine Inferred from Wild 2 and Chondrite Matrix

To date, only 180 particle impact tracks from Wild 2 have been extracted from the Stardust aerogel collector and even fewer have been thoroughly characterized. In order to provide a cohesive compositional dataset that can be compared to the meteorite record, we have made both major and minor element analyses (TEM/EDXS) of olivine and low-Ca pyroxene for 39 particles harvested from 26 tracks. However, the dearth of equivalent analyses for these phases in chondrite matrix hinders their comparison to the Wild 2 samples. To properly permit comparison of chondritic olivine and pyroxene to the Wild 2 samples, we have also provided a large, comprehensive EPMA dataset (greater than10(exp 3) analyses) of analogous grains (5-30 micrometers) isolated in L/LL3.0-4, CI, CM, CR, CH, CO, CV, Acfer 094, EH3, EL6, and Kakangari matrix

Frank, D. R.↗

Laboratory Instruments Available to Support Space Station Researchers at Marshall Space Flight Center

A number of research instruments are available at NASA's Marshall Space Flight Center (MSFC) to support ISS researchers and their investigations. These modern analytical tools yield valuable and sometimes new informative resulting from sample characterization. Instruments include modern scanning electron microscopes equipped with field emission guns providing analytical capabilities that include angstron-level image resolution of dry, wet and biological samples. These microscopes are also equipped with silicon drift X-ray detectors (SDD) for fast yet precise analytical mapping of phases, as well as electron back-scattered diffraction (EBSD) units to map grain orientations in crystalline alloys. Sample chambers admit large samples, provide variable pressures for wet samples, and quantitative analysis software to determine phase relations. Advances in solid-state electronics have also facilitated improvements for surface chemical analysis that are successfully employed to analyze metallic materials and alloys, ceramics, slags, and organic polymers. Another analytical capability at MSFC is a mganetic sector Secondary Ion Mass Spectroscopy (SIMS) that quantitatively determines and maps light elements such as hydrogen, lithium, and boron along with their isotopes, identifies and quantifies very low level impurities even at parts per billion (ppb) levels. Still other methods available at MSFC include X-ray photo-electron spectroscopy (XPS) that can determine oxidation states of elements as well as identify polymers and measure film thicknesses on coated materials, Scanning Auger electron spectroscopy (SAM) which combines surface sensitivity, spatial lateral resolution (approximately 20 nm), and depth profiling capabilities to describe elemental compositions in near surface regions and even the chemical state of analyzed atoms. Conventional Transmission Electron Microscope (TEM) for observing internal microstructures at very high magnifications and the Electron Probe Micro-analyzer (EPMA) for very precise microanalysis are available as needed by the researcher. Space Station researchers are invited to work with MSFC in analyzing their samples using these techniques.

Panda, Binayak↗

In Situ Trace Element Analysis of an Allende Type B1 CAI: EK-459-5-1

Variations in refractory major and trace element composition of calcium, aluminum-rich inclusions (CAIs) provide constraints on physical and chemical conditions and processes in the earliest stages of the Solar System. Previous work indicates that CAIs have experienced complex histories involving, in many cases, multiple episodes of condensation, evaporation, and partial melting. We have analyzed major and trace element abundances in two core to rim transects of the melilite mantle as well as interior major phases of a Type B1 CAI (EK-459-5-1) from Allende by electron probe micro-analyzer (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to investigate the behavior of key trace elements with a primary focus on the REEs Tm and Yb.

Jeffcoat, C. R.↗

Microstructural and Compositional Relations of Granitoid Clasts in Lunar Breccias at the Micrometer to Sub-Micrometer Scale

Lunar granitoid lithologies have long been of interest for the information they provide on processes leading to silicic melt compositions on the Moon. The extraction of such melts over time affects the distribution and budget of incompatible materials (i.e., radiogenic heat producing elements and volatiles) of the lunar interior. We have recently shown that in addition to their high concentrations of incompatible lithophile elements, some granitoid clasts in lunar breccias have significant indigenous water contents in their alkali feldspars. This raises the importance of lunar granitoid materials in the expanding search for mineralogic/petrologic hosts of indigenous lunar water-related species. We are undertaking a detailed survey of the petrologic/mineralogical relations of granitoid clasts in lunar breccias to achieve a better understanding of the potential of these diverse assemblages as hosts for volatiles, and as candidates for additional isotope chronology studies. Our preliminary results reported here based on high-resolution field-emission SEM, EPMA and TEM studies uncover immense complexity in these materials at the micrometer to sub-micrometer scale that heretofore have not been fully documented.

Christoffersen, R.↗

Volatile Content of 4-Vesta: Evidence from Unequilibrated Eucrites

Eucrites are a class of basaltic meteorites that, along with the howardites and diogenites, likely derive from the asteroid 4-Vesta. This asteroid is depleted in moderately volatile elements relative to the Earth and carbonaceous chondrites. Extrapolation of this depletion trend predicts that bulk silicate 4-Vesta (BSV) contains at most 250-1000 μg/g H2O, which is approximately a factor of two lower than the H2O content of Earth. To obtain more accurate H2O and F estimates for BSV, we examined four unequilibrated antarctic meteorites, Yamato(Y)-793548, Y-82210, Y-75011, and Y-74450, by EPMA and SIMS. Pyroxenes contain MgO-rich cores and FeO-rich rims, consistent with primary magmatic zoning. Volatile concentrations generally follow patterns expected for growth zoning with lower values in the cores and higher in the rims. These features indicate that thermal metamorphism and other post-crystallization processes did not significantly perturb the volatile contents of these unequilibrated eucrite pyroxenes. We used these data to derive best estimates for the BSV H2O and F content based on experimentally determined pyroxene-melt partition coefficients and models for magma generation on Vesta. In addition, we measured D/H in the early crystallizing pyroxenes and late crystallzing apatites. We find that the D/H of pyroxene and apatite are within error of one another as well as previous measurements of apatite in equilibrated eucrites. These results imply that degassing was minimal or did not fractionate D/H. Degassing may have been limited if eucrites were shallowly emplaced sills or dykes, or the total H2O content of the magmas was too low for vapor saturation. An alternative mechanism for limited D/H fractionation is that degassing did occur, but the H2/H2O of the exsolved vapor was approximately 15:85, as predicted from experiments.

Sarafian, A. R.↗

Evolved-Lithology Clasts in Lunar Breccias: Relating Petrogenetic Diversity to Measured Water Content

Studies of the inventory and distribution of water in lunar rocks have recently begun to focus on alkali suite samples as possible water repositories, particularly the most highly evolved granitoid lithologies. Although H analyses of feldspars in these rocks have so far pointed to 'low' (less than 20 ppm) H2O contents, there is sufficient variability in the dataset (e.g., 2-20 ppm) to warrant consideration of the petrogenetic factors that may have caused some granitoid-to-intermediate rocks to be dryer or wetter than others. Given that all examples of these rocks occur as clasts in complex impact breccias, the role of impact and other factors in altering water contents established by primary igneous processes becomes a major factor. We are supporting our ongoing SIMS studies of water in evolved lunar lithologies with systematic SEM and EPMA observations. Here we report a synthesis of the observations as part of developing discriminating factors for reconstructing the thermal, crystallization and shock history of these samples as compared with their water contents.

Christoffersen, R.↗