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Origin of Magnetite Crystals in Martian Meteorite ALH84001 Carbonate Disks

Martian meteorite ALH84001 preserves evidence of interaction with aqueous fluids while on Mars in the form of microscopic carbonate disks which are believed to have precipitated approx.3.9 Ga ago at beginning of the Noachian epoch. Intimately associated within and throughout these carbonate disks are nanocrystal magnetites (Fe3O4) with unusual chemical and physical properties, whose origins have become the source of considerable debate. One group of hypotheses argues that these Fe3O4 are the product of partial thermal decomposition of the host carbonate. Alternatively, the origins of Fe3O4 and carbonate may be unrelated; that is, from the perspective of the carbonate the magnetite is allochthonous. We have sought to resolve between these hypotheses through the detailed characterized of the compositional and structural relationships of the carbonate disks and associated magnetites with the orthopyroxene matrix in which they are embedded [1]. We focus this discussion on the composition of ALH84001 magnetites and then compare these observations with those from our thermal decomposition studies of sideritic carbonates under a range of plausible geological heating scenarios.

Thomas-Keprta, K.L.↗

Mapping the Iron Oxidation State in Martian Meteorites

Several types of Martian igneous meteorites have been identified: clinopyroxenites (nakhlites), basaltic shergottites, peridotitic shergottites, dunites (chassignites) and orthopyroxenites [1,2]. In order to constrain the heterogeneity of the Martian mantle and crust, and their evolution through time, numerous studies have been performed on the iron oxidation state of these meteorites [3,4,5,6,7,8,9]. The calculated fO2 values all lie within the FMQ-5 to FMQ+0.5 range (FMQ representing the Fayalite = Magnetite + Quartz buffer); however, discrepancies appear between the various studies, which are either attributed to the choice of the minerals/melts used, or to the precision of the analytical/calculation method. The redox record in volcanic samples is primarily related to the oxidation state in the mantle source(s). However, it is also influenced by several deep processes: melting, crystallization, magma mixing [10], assimilation and degassing [11]. In addition, the oxidation state in Martian meteorites is potentially affected by several surface processes: assimilation of sediment/ crust during lava flowing at Mars' surface, low temperature micro-crystallization [10], weathering at the surface of Mars and low temperature reequilibration, impact processes (i.e. high pressure phase transitions, mechanical mixing, shock degassing and melting), space weathering, and weathering on Earth (at atmospheric conditions different from Mars). Decoding the redox record of Martian meteorites, therefore, requires large-scale quantitative analysis methods, as well as a perfect understanding of oxidation processes.

Martin, A. M.↗

Report of the Workshop on Unmixing the SNCs: Chemical, Isotopic, and Petrologic Components of Martian Meteorites

Geochemical and petrologic studies of the Martian meteorites (nicknamed the SNCs) have proliferated in the past few years, from a wealth of new samples and the perfection of new analytical methods. An intriguing result from these studies is that the chemical and isotopic compositions of the Martian meteorites, all basalts or derived from basaltic magma, can be modeled as mixtures of a limited number of components. These mixing components were the focus of the workshop.

Treiman, Allan H.↗

Comparison of Synchrotron MicroXANES Determination of Fe(3+)/Sigma Fe with Moessbauer Values for Clean Mineral Separates of Pyroxene from Martian Meteorites

The oxidation state of Fe in Martian meteorites is a parameter of great interest and the ability to determine this value in micrometer scale samples is important. Intense, tunable x-ray sources at large synchrotron storage rings are being exploited to examine the Fe K-absorption edge with energy resolution of approx. 1-1.5eV in spots of 10x15 microns on thin sections of a wide variety of materials including several Martian meteorites. Synchrotron microXANES (SmX) spectroscopy is the technique that provides the most flexible capability for investigating Fe(3+)/Sigma Fe. Variation of Fe(3+)/Sigma Fe is manifested as a function of the energy of the pre-edge to the Fe absorption edge produced by the sample. SmX is at present the only technique that can be used with conventional polished thin sections. Data for a broad spectrum of minerals have been produced and indicate that SmX can be used with a large variety of samples types.

Delaney, J. S.↗

Petrogenesis of Igneous-Textured Clasts in Martian Meteorite Northwest Africa 7034

The martian meteorite Northwest Africa 7034 (and pairings) is a breccia that samples a variety of materials from the martian crust. Several previous studies have identified multiple types of igneous-textured clasts within the breccia [1-3], and these clasts have the potential to provide insight into the igneous evolution of Mars. One challenge presented by studying these small rock fragments is the lack of field context for this breccia (i.e., where on Mars it formed), so we do not know how many sources these small rock fragments are derived from or the exact formation his-tory of these sources (i.e., are the sources mantle de-rived melt or melts contaminated by a meteorite impactor on Mars). Our goal in this study is to examine specific igneous-textured clast groups to determine if they are petrogenetically related (i.e., from the same igneous source) and determine more information about their formation history, then use them to derive new insights about the igneous history of Mars. We will focus on the basalt clasts, FTP clasts (named due to their high concentration of iron, titanium, and phosphorous), and mineral fragments described by [1] (Fig. 1). We will examine these materials for evidence of impactor contamination (as proposed for some materials by [2]) or mantle melt derivation. We will also test the petrogenetic models proposed in [1], which are igneous processes that could have occurred regardless of where the melt parental to the clasts was formed. These models include 1) derivation of the FTP clasts from a basalt clast melt through silicate liquid immiscibility (SLI), 2) derivation of the FTP clasts from a basalt clast melt through fractional crystallization, and 3) a lack of petrogenetic relationship between these clast groups. The relationship between the clast groups and the mineral fragments will also be explored.

Santos, A. R.↗

Curation of US Martian Meteorites Collected in Antarctica

To date the ANSMET field team has collected five martian meteorites (see below) in Antarctica and returned them for curation at the Johnson Space Center (JSC) Meteorite Processing Laboratory (MPL). ne meteorites were collected with the clean procedures used by ANSMET in collecting all meteorites: They were handled with JSC-cleaned tools, packaged in clean bags, and shipped frozen to JSC. The five martian meteorites vary significantly in size (12-7942 g) and rock type (basalts, lherzolites, and orthopyroxenite). Detailed descriptions are provided in the Mars Meteorite compendium, which describes classification, curation and research results. A table gives the names, classifications and original and curatorial masses of the martian meteorites. The MPL and measures for contamination control are described.

Lindstrom, M.↗

Alteration of Sedimentary Clasts in Martian Meteorite Northwest Africa 7034

The martian meteorite Northwest Africa (NWA) 7034 and pairings represent the first brecciated hand sample available for study from the martian surface [1]. Detailed investigations of NWA 7034 have revealed substantial lithologic diversity among the clasts [2-3], making NWA 7034 a polymict breccia. NWA 7034 consists of igneous clasts, impact-melt clasts, and "sedimentary" clasts represented by prior generations of brecciated material. In the present study we conduct a detailed textural and geochemical analysis of the sedimentary clasts.

McCubbin, F. M.↗

Morphological Evidence for an Exclusively Inorganic Origin for Magnetite in Martian Meteorite ALH84001

The origin of magnetite crystals in Martian Meteorite ALH84001 is the focus of a debate about the possibility of past (and present) life on Mars. McKay et al. originally suggested that some of the magnetite crystals associated with carbonate globules in Martian Meteorite ALH84001 are biogenic in ori-gin, because they are single magnetic domain, free of crystalline defects, chemically pure, and coexist with other metastable phases in apparent disequilibrium. Thomas-Keprta et al. reported that a subpopulation of magnetite crystals (approx. 25%) associated with carbonate globules in ALH84001 and magnetite crystals produced by magnetotactic bacterial strain MV-1 have similar morphologies with crystal elongation along the [111] crystallographic axis that they describe as "truncated hexa-octahedral" ([111-THO]) magnetite. Along with several other properties, the [111]-THO morphology has been proposed to constitute a biomarker (i.e., formed only in biogenic processes), so that the presence of [111]-THO magnetite in ALH84001 may be evidence for past life on Mars.

Golden, D. C.↗

Sm-Nd and Rb-Sr Isotopic Systematics of a Heavily Shocked Martian Meteorite Tissint and Petrogenesis of Depleted Shergottites

Tissint is a very fresh Martian meteorite that fell near the town of Tissint in Morocco on July 18, 2011. It contains abundant olivine megacrysts (~23%) in a fine-grained matrix of pyroxene (~55%), maskelynitized plagioclase (~15%), opaques (~4%) and melt pockets (~3%) and is petrographically similar to lithologies A and C of picritic shergottite EETA 79001 [1,2]. The presence of 2 types of shock-induced glasses and all 7 high-pressure mineral phases that were ever found in melt pockets of Martian meteorites suggests it underwent an intensive shock metamorphism of ~25 GPa and ~2000 C localized in melt pockets [2]. Mineral textures suggest that olivines, pyroxenes and plagioclases probably did not experience such hightemperature. Earlier determinations of its age yielded 596+/-23 Ma [3] and 616+/-67 Ma [4], respectively, for the Sm-Nd system and 583+/-86 Ma for the Lu-Hf system [4], in agreement with the 575+/-18 Ma age of the oldest olivine-phyric depleted shergottite Dho 019 [5]. However, the exposure ages of Tissint (~1 Ma [1, 6, 7]) and Dho 019 (~20 Ma [8]) are very different requiring two separate ejection events. These previously determined Sm-Nd and Lu-Hf ages are older than the Ar-Ar maskelynite plateau age of 524+/-15 Ma [9], reversing the pattern usually observed for Martian meteorites. In order to clarify these age issues and place models for Tissint's petrogenesis on a firm basis, we present new Rb-Sr and Sm- Nd isotopic results for Tissint, and discuss (a) the shock effects on them and the Ar-Ar chronometer, (b) correlation of the determined ages with those of other depleted shergottites, and (c) the petrogenesis of depleted shergottites. Since the meteorite is a recent fall, terrestrial contamination is expected to be minimal, but, the strong shock metamorphism might be expected to compromise the equilibrium of the isotopic systems.

Shih, C.-Y.↗

What Were the Major Factors That Controlled Mineralogical Similarities and Differences of Basaltic, Lherzolitic and Clinopyroxentic Martian Meteorites Within Each Group

Twelve martian meteorites that have been re- covered so far are classified into five groups (basalt, lherzolite, clinopyroxenite, dunite, and orthopyroxenite) mainly from petrology and chemistry. Among them, the dunite and orthopyroxenite groups consist of only one meteorite each (dunite: Chassigny, orthopyroxenite: ALH 84001). The basalt group is the largest group and consists of four meteorites (Shergotty, Zagani, EETA 79001, and QUE 94201). The lherzolitic and clinopyroxenitic groups include three meteorites each (Lherzolite: ALH 77005, LEW 88516, and Y793605, clinopyroxenite: Nakhla, Governador Valadares, and Lafayette). These meteorites within each group are generally similar to the others, but none of them is paired with the others. In this abstract, we discuss the major factors that controlled mineralogical similarities and differences of basaltic, lherzolitic, and clinopyroxenitic meteorites within each group. This may help in understanding their petrogenesis and original locations on Mars in general.

Mikouchi, T.↗

Ar-Ar Dating of Martian Meteorite, Dhofar 378: An Early Shock Event?

Martian meteorite, Dhofar 378 (Dho378) is a basaltic shergottite from Oman, weighing 15 g, and possessing a black fusion crust. Chemical similarities between Dho378 and the Los Angeles 001 shergottite suggests that they might have derived from the same Mars locale. The plagioclase in other shergottites has been converted to maskelenite by shock, but Dho378 apparently experienced even more intense shock heating, estimated at 55-75 GPa. Dho378 feldspar (approximately 43 modal %) melted, partially flowed and vesiculated, and then partially recrystallized. Areas of feldspathic glass are appreciably enriched in K, whereas individual plagioclases show a range in the Or/An ratio of approximately 0.18-0.017. Radiometric dating of martian shergottites indicate variable formation times of ~160-475 Myr, whereas cosmic ray exposure (CRE) ages of shergottites indicate most were ejected from Mars within the past few Myr. Most determined Ar-39-Ar-40 ages of shergottites appear older than other radiometric ages because of the presence of large amounts of martian atmosphere or interior Ar-40. Among all types of meteorites and returned lunar rocks, the impact event that initiated the CRE age very rarely reset the Ar-Ar age. This is because a minimum time and temperature is required to facilitate Ar diffusion loss. It is generally assumed that the shock-texture characteristics in martian meteorites were produced by the impact events that ejected the rocks from Mars, although the time of these shock events (as opposed to CRE ages) are not directly dated. Here we report Ar-39-Ar-40 dating of Dho378 plagioclase. We suggest that the determined age dates the intense shock heating event this meteorite experienced, but that it was not the impact that initiated the CRE age.

Park, 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.↗

LU-HF Age of Martian Meteorite Larkman Nunatek 06319

Lu-Hf isotopic data were collected on mineral separates and bulk rock powders of LAR 06319, yielding an age of 197+/- 29 Ma. Sm-Nd isotopic data and in-situ LA-ICP-MS data from a thin section of LAR 06319 are currently being collected and will be presented at the 2009 LPSC. These new data for LAR 06319 extend the existing data set for the enriched shergottite group. Martian meteorites represent the only opportunity for ground truth investigation of the geochemistry of Mars [1]. At present, approximately 80 meteorites have been classified as Martian based on young ages and distinctive isotopic signatures [2]. LAR 06319 is a newly discovered (as part of the 2006 ANSMET field season) martian meteorite that represents an important opportunity to further our understanding of the geochemical and petrological constraints on the origin of Martian magmas. Martian meteorites are traditionally categorized into the shergottite, nakhlite, and chassignite groups. The shergottites are further classified into three distinct isotopic groups designated depleted, intermediate, and enriched [3,4] based on the isotope systematics and compositions of their source(s).

Shafer, J. T.↗

Los Angeles: The Most Differentiated Basaltic Martian Meteorite

Los Angeles is a new martian meteorite that expands the compositional range of basaltic shergottites. Compared to Shergotty, Zagami, QUE94201, and EET79001-B, Los Angeles is more differentiated, with higher concentrations of incompatible elements (e.g., La) and a higher abundance of late-stage phases such as phosphates and K-rich feldspathic glass. The pyroxene crystallization trend starts at compositions more ferroan than in other martian basaits. Trace elements indicate a greater similarity to Shergotty and Zagami than to QUE94201 or EET79001-B, but the Mg/Fe ratio is low even compared to postulated parent melts of Shergotty and Zagami. Pyroxene in Los Angeles has 0.7-4-microns-thick exsolution lamellae, approx. 10 times thicker than those in Shergotty and Zaganii. Opaque oxide compositions suggest a low equilibration temperature at an oxygen fugacity near the fayafite-magnetitequartz buffer. Los Angeles cooled more slowly than Shergotty and Zagami. Slow cooling, coupled with the ferroan bulk composition, produced abundant fine-grained intergrowths of fayalite, hedenbergite, and silica, by the breakdown of pyroxferroite. Shock effects in Los Angeles include maskelynitized plagioclase, pyroxene with mosaic extinction, and rare fault zones. One such fault ruptured a previously decomposed zone of pyroxferroite. Although highly differentiated, the bulk composition of Los Angeles is not close to the low-Ca/Si composition or the globally wind-stirred soil of Mars.

Rubin, Alan E.↗

Scanning Electron Microscopy Investigation of a Sample Depth Profile Through the Martian Meteorite Nakhla

The ongoing scientific debate as to whether or not the Martian meteorite ALH84001 contained evidence of possible biogenic activities showed the need to establish consistent methods to ascertain the origin of such evidence. To distinguish between terrestrial organic material/microbial contaminants and possible indigenous microbiota within meteorites is therefore crucial. With this in mind a depth profile consisting of four samples from a new sample allocation of Martian meteorite Nakhla was investigated using scanning electron microscopy (SEM) and energy dispersive X-ray analysis. SEM imaging of freshly broken fractured chips revealed structures strongly recent terrestrial microorganisms, in some cases showing evidence of active growth. This conclusion was supported by EDX analysis, which showed the presence of carbon associated with these structures, we concluded that these structures represent recent terrestrial contaminants rather than structures indigenous to the meteorite. Page

Toporski, Jan↗

Pyroxenes in Martian meteorites as petrogenetic indicators

Pyroxenes in Martian meteorites are important recorders of petrogenetic processes. Understanding the details of pyroxene major and minor element compositional variations can provide important insights into those processes. A combination of careful petrographic analysis of natural samples and experimental crystallization studies can lead to better understanding of the processes that gave rise to these samples on Mars. In addition, experimentally determined major, minor and trace element partition coefficients are important for using natural pyroxenes to estimate the compositions of the melts from which they crystallized and the oxidation conditions that prevailed during crystallization. We will report on minor element (Al, Ti, Cr) zoning in nakhlite pyroxenes and in synthetic pyroxenes that we have grown for the purposes of determining pyroxene/melt partition coefficients for Sr and REE. The natural pyroxenes have patchy Al zoning that, by analogy with our experimental pyroxenes, we interpret as sector zoning. The irregular patchy nature of the zoning is probably the result of the vagaries of growth kinetics and local environment during crystal growth. More slowly cooled nakhlites have the most distinct bimodal zoning, with one mode having Al2O3 around 0.5-0.6 wt%, and the other around 0.9 %. Average Al content increases with increasing cooling rate. This feature is puzzling, since the cumulus pyroxenes were almost certainly present at the time of eruption. Al and Ti are strongly correlated, but Cr is completely decoupled from those elements. The synthetic pyroxenes are distinctly sector zoned in Al and Ti, and the sector-to-sector variation in Al within a single crystal has important effects on trace element partition coefficients. Trivalent REE are strongly correlated with Al, while divalent elements (Sr, Eu+2) show a significantly weaker correlation. For example, as the Al2O3 content varies from 0.3 to 0.6 wt % from one sector to another, D(Gd) increases by approx.80% while D(Sr) and D(Eu) only increase by 20-30% at oxygen fugacities near IW. The different Al dependency of D for trivalent REE vs. divalent Eu and Sr considerably complicates the calibration of the Eu oxybarometer.

McKay, Gordon↗