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NASA NTRS2014

Primitive Fine-Grained Matrix in the Unequilbrated Enstatite Chondrites

Enstatite chondrites (EC) have important implications for constraining conditions in the early solar system and for understanding the evolution of the Earth and other inner planets. They are among the most reduced solar system materials as reflected in their mineral compositions and assemblage. They are the only chondrites with oxygen as well as Cr, Ti, Ni and Zn stable isotope compositions similar to the earth and moon and most are completely dry, lacking any evidence of hydrous alteration; the only exception are EC clasts in the Kaidun breccia which have hydrous minerals. Thus, ECs likely formed within the snow line and are good candidates to be building blocks of the inner planets. Our goals are to provide a more detailed characterization the fine-grained matrix in E3 chondrites, understand its origin and relationship to chondrules, decipher the relationship between EH and EL chondrites and compare E3 matrix to matrices in C and O chondrites as well as other fine-grained solar system materials. Is E3 matrix the dust remaining from chondrule formation or a product of parent body processing or both?

Weisberg, M. K.↗
NASA NTRS2014

A Novel Hybrid Ultramicrotomy/FIB-SEM Technique: Preparation of Serial Electron-Transparent Thin Sections of a Hayabusa Grain

The Japanese space agency's (JAXA) Hayabusa mission returned the first particulate samples (typically <100micron) from the surface of an asteroid (25143 Itokawa). These precious samples provide important insights into early Solar System processes, but their sizes pose tremendous challenges to coordinated analysis using a variety of nano- and micro-beam techniques. The ability to glean maximal information from individual particles has become increasingly important and depends critically on sample preparation. We developed a hybrid technique combining traditional ultramicrotomy with focused ion beam (FIB) techniques, allowing for more thorough in situ investigations of grain surfaces and interiors. Using this method, we increase the number of FIB-prepared sections that can be recovered from a particle with dimensions on the order of tens of microns. These sections can be subsequently analyzed using a variety of analytical techniques. Particle RA-QD02-0211 is a approx. 40×40×20 micron particle from Itokawa containing olivine and Fe sulfides. It was embedded in low viscosity epoxy and partly sectioned to a depth of approx 10 micron; sections are placed on Cu grids with thin amorphous films for transmission electron microscope (TEM) analyses. With the sample surface partly exposed, the epoxy bullet is trimmed to a height of approx. 5mm to accommodate the allowable dimensions for FIB work (FEI Quanta 600 3D dual beam FIB-SEM). Using a diamond trim knife, the epoxy surrounding the grain is removed on 3 sides (to within a few microns of the grain); the depth of material removed extends well below the bottom of the particle. The sample is attached to an SEM pin mount, the epoxy coated with conductive paint, and the entire assembly coated with approx. 40nm of carbon to eliminate sample charging during FIB work. A protective carbon cap is placed according to the plan for the 15 FIB sections. The central 'spine' of the cap runs perpendicular to the front of the sample, and the 'ribs' protruding from either side run parallel. Each rib indicates the location of a planned FIB section, and the spine contains the final two planned sections. We use a cap with a 4 micron-wide spine and 2micron-wide ribs that have ≳3.5 micron of space between them (narrower cuts result in too much re-deposition of material inside the trenches). Using a 30kV, 3nA ion-beam we expose the front surface of the grain and commence milling trenches between sections. Rather than using the typical C-cut to prepare the sample for lift-out, an L-cut is used instead, leaving the sample connected by an interior tab. tab. Sections are lifted out, attached to TEM grids and thinned to electron transparency. TEM analyses show that our hybrid technique preserves both interior and edge features, including surface modifications from exposure to the space environment, such as damaged rims that form in response to solar wind implantation effects and adhering grains. In addition, the FIB sections provide larger areas that are free of fractures and chatter effects in comparison to the microtome thin sections, thus enabling more accurate measurements of solar flare particle track densities that are used to determine the surface exposure age of the particles.

Berger, Eve L.↗
NASA NTRS2014

Surviving High-temperature Components in CI Chondrites

The CI1 chondrites, while having the most solar-like compo-sition of any astromaterial available for laboratory analysis, have also been considerably altered by asteroidal processes including aqueous alteration. It is of fundamental importance to determine their pre-alteration mineralogy, so that the state of matter in the early Solar System can be better determined. In the course of a re-examination of the compositional range of olivine and low-Ca pyroxene in CI chondrites Orgueil, Ivuna and Alais [1] we found the first reported complete CAI, as already reported [2], with at-tached rock consisting mainly of olivine and low-Ca pyroxene. The range of residual olivine major element compositions we have determined in the CIs (Fig. 1) may now be directly com-pared with those of other astromaterials, including Wild 2 grains. The abundance of olivine and low-Ca pyroxene in CIs is higher than is generally appreciated, and in fact much higher than for some CMs [1]. We also noted numerous rounded objects varying in shape from spheres to oblate spheroids, and ranging up to 100μm in size (Fig. 2), which have been previously noted [3] but have not been well documented or appreciated. We characterized the mineralogy by transmission electron microscopy and found that they consist mainly of rather fine-grained, flaky single phase to intergrown serpentine and saponite. These two materials in fact dominate the bulk of the host CI1 chondrites. With the exception of sparse spinels, the rounded phyllosilicate objects are remarka-bly free of other minerals, suggesting that the precursor from which the phyllosilicates were derived was a homogeneous mate-rial. We suggest that these round phyllosilicates aggregates in CI1 chondrites were cryptocrystalline to glassy microchondrules. If so then CI chondrites cannot be considered chondrule-free. Small though they are, the abundance of these putative microchondrules is the same as that of chondrules in the Tagish Lake meteorite.

Zolensky, M.↗
NASA NTRS2014

Assessing the Origins of Aliphatic Amines in the Murchison Meteorite from their Compound-Specific Carbon Isotopic Ratios and Enantiomeric Composition

The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of L-enantiomeric excesses for alpha-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are chemically related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with delta C-13 values ranging from +21% to +129%, showing a decrease in C-13 with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an L-enantiomeric excess of 9.7; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential linkage to meteoritic amino acids.

prebiotic chemistry↗
NASA NTRS2015

Petrology and Cosmochemistry of a Suite of R Chondrites

Chondrites are among the most primitive surviving materials from the early solar system. They are divided into groups based on chemical types defined by mineralogy, bulk composition, and oxygen isotope compositions. Chondrites range in petrographic grade from type 1 to type 7. Type 3 chondrites are the most primitive and are little changed from the nebular solids accreted to form asteroids. They are composed of chondrules, fine-grained matrix, metal and sulfide, plus or minus Ca-Al-rich inclusions. With increasing aqueous alteration at low temperatures, members of some chondrite classes transformed from type 3 towards type 1. With increasing thermal metamorphism and low fluid content, members of other classes changed from type 3 towards type 7. Rumuruti (R) chondrites are a rare group (0.1% of falls) similar to ordinary chondrites in some properties but different in others. They are characterized by low chondrule/matrix modal abundance ratios, high oxidation state, small mean chondrule size, abundant sulfides and low metal contents. R chondrites vary in petrologic type from 3 to 6. They are important objects to study because some of them have undergone metamorphism at high temperatures in the presence of aqueous fluids. In contrast, CM and CI chondrites were heated to low temperatures in the presence of aqueous fluids leading to alteration; they contain low-T hydrous phases (phyllosilicates) and little or no remaining metal. Ordinary chondrites were heated to high temperatures in a low-fluid environment resulting in anhydrous metamorphic rocks. R6 chondrites are highly metamorphosed and some contain the high-T hydrous phases mica and amphibole. R chondrites are thus unique and give us an opportunity to examine whether there are compositional effects caused by high-T, highfluid metamorphism of nebular materials.

Torrano, Z. A.↗
NASA NTRS2015

Lithologies Making Up CM Carbonaceous Chondrites and Their Link to Space Exposure Ages

Chondrite parent bodies are among the first large bodies to have formed in the early Solar System, and have since remained almost chemically unchanged having not grown large enough or quickly enough to undergo differentiation. Their major nonvolatile elements bear a close resemblance to the solar photosphere. Previous work has concluded that CM chondrites fall into at least four distinct space exposure age groups (0.1 Ma, 0.2 Ma, 0.6 Ma and >2.0 Ma), but the meaning of these groupings is unclear. It is possible that these meteorites came from different parent bodies which broke up at different times, or instead came from the same parent body which underwent multiple break-up events, or a combination of these scenarios.

Gregory, Timothy↗
NASA NTRS2015

Lithologies Making Up CM Carbonaceous Chondrites and Their Link to Space Exposure Ages

Chondrite parent bodies are among the first large bodies to have formed in the early Solar System, and have since remained almost chemically unchanged having not grown large enough or quickly enough to undergo differentiation. Their major nonvolatile elements bear a close resemblance to the solar photosphere. Previous work has concluded that CM chondrites fall into at least four distinct space exposure age groups (0.1 megaannus, 0.2 megaannus, 0.6 megaannus and 2.0 megaannus), but the meaning of these groupings is unclear. It is possible that these meteorites came from different parent bodies which broke up at different times, or instead came from the same parent body which underwent multiple break-up events, or a combination of these scenarios.

Gregory, Timothy↗
NASA NTRS2015

Na, K-Rich Rim Around a Chondrule in Unequilibrated Ordinary Chondrite Lew 86018 (L3.1)

Ordinary chondrites represent the most abundant early Solar system extra-terrestrial (approximately 85% abundance) material available for laboratory studies and expectedly record the most extensive range of alterations effects from unmetamorphosed chondritic material to the highest temperatures of thermal metamorphism. The least metamorphosed chondrites belonging to petrologic type 3, the so called unequili-brated ordinary chondrites (UOCs), provide insights into alteration that happened during the primeval, ear-liest stage of Solar system formation. The higher grade petrologic types 4-6 ordinary chondrites on the other hand document up to near textural equilibrium (in type 6) extensive thermal metamorphism consisting of minerals and phases providing evidence of equilibration of heterogeneous mineral composition, solid-state recrystallization. Despite being the most abundant, the effect of alteration is less explicitly understood in ordinary chondrites (even less in UOCs) compared to other groups (e.g. CV, CO, CR). Additionally, the relationship between metasomatism (also referred as aqueous alteration or fluid-assisted metamorphism) and metamorphism (primarily thermal driven) has not been studied and alterations in the ordinary chondrites have been considered to have occurred in absence of fluids in general. Despite this conventional view, UOCs of lowest grades (3.0-3.2) show some evidence of low temperature (approximately 200 C), fluid assisted metamorphism in the form of the presence of phyllosilicates, ferroan olivine, and magnetites in their matrices and occasionally in chondrules. Here, we present petrographic and mineralogical studies of UOC, Lewis Hills (LEW) 86018 to further our understanding of the extent and relative importance of metasomatism and/or metamorphism in UOCs.

Mishra, R. K.↗
NASA NTRS2015

Evidence of Metasomatism in the Lowest Petrographic Types Inferred from A Na(-), K, Rich Rim Around A LEW 86018 (L3.1) Chondrule

Ordinary chondrites (OCs) represent the most abundant extraterrestrial materials and also record the widest range of alteration of primary, pristine minerals of early Solar system material available for study. Relatively few investigations, however, address: (1) the role of fluid alteration, and (2) the relationship between thermal metamorphism and metasomatism in OCs, issues that have been extensively studied in many other meteorite groups e.g., CV, CO, CR, and enstatite chondrites. Detailed elemental abundances profiles across individual chondrules, and mineralogical studies of Lewis Hills (LEW) 86018 (L3.1), an unequilibrated ordinary chondrite (UOC) of low petrographic type of 3.1 returned from Antarctica, provide evidence of extensive alteration of primary minerals. Some chondrules have Na(-), K(-), rich rims surrounded by nepheline, albite, and sodalite-like Na(-), Cl(-), Al-rich secondary minerals in the near vicinity within the matrices. Although, limited evidences of low temperature (approximately 250 C) fluid-assisted alteration of primary minerals to phyllosilicates, ferroanolivine, magnetite, and scapolite have been reported in the lowest grades (less than 3.2) Semarkona (LL3.00) and Bishunpur (LL3.10), alkali-rich secondary mineralization has previously only been seen in higher grade greater than 3.4 UOCs. This preliminary result suggests highly localized metamorphism in UOCs and widens the range of alteration in UOCs and complicates classification of petrographic type and extent of thermal metamorphism or metasomatism. The work in progress will document the micro-textures, geochemistry (Ba, Ca, REE), and isotopic composition (oxygen, Al(-)- 26 Mg-26) of mineral phases in chondrules and adjoining objects to help us understand the formation scenario and delineate possible modes of metamorphism in UOCs.

Mishra, Ritesh Kumar↗
NASA NTRS2016

Organic Analysis in the Miller Range 090657 CR2 Chondrite: Part 2 Amino Acid Analyses

Primitive carbonaceous chondrites contain a wide variety of organic material, ranging from soluble discrete molecules to insoluble, unstructured kerogen-like components, as well as structured nano-globules of macromolecular carbon. The relationship between the soluble organic molecules, macromolecular organic material, and host minerals are poorly understood. Due to the differences in extractability of soluble and insoluble organic materials, the analysis methods for each differ and are often performed independently. The combination of soluble and insoluble analyses, when performed concurrently, can provide a wider understanding of spatial distribution, and elemental, structural and isotopic composition of organic material in primitive meteorites. Using macroscale extraction and analysis techniques in combination with in situ microscale observation, we have been studying both insoluble and soluble organic material in the primitive CR2 chondrite Miller Range (MIL) 090657. In accompanying abstracts (Cao et al. and Messenger et al.) we discuss insoluble organic material in the samples. By performing the consortium studies, we aim to improve our understanding of the relationship between the meteorite minerals and the soluble and insoluble organic phases and to delineate which species formed within the meteorite and those that formed in nebular or presolar environments. In this abstract, we present the results of amino acid analyses of MIL 090657 by ultra performance liquid chromatography with fluorescence detection and quadrupole-time of flight mass spectrometry. Amino acids are of interest because they are essential to life on Earth, and because they are present in sufficient structural, enantiomeric and isotopic diversity to allow insights into early solar system chemical processes. Furthermore, these are among the most isotopically anomalous species, yet at least some fraction are thought to have formed by aqueously-mediated processes during parent body alteration.

Burton, A. S.↗
NASA NTRS2016

The Foreign Clast Populations of Anomalous Polymict Urelite Almahata Sitta (Asteroid 2008 TC(sub3) and Typical Polymict Ureilites: Implications for Asteroid-Meteorite Connections

Almahata Sitta (AhS) is the first meteorite to originate from an asteroid (2008 TC3) that had been studied in space before it hit Earth [1,2]. It is also unique because the fallen fragments comprise a variety of types: approximately 69% ureilites (achondrites) and 31% chondrites [3]. Two models have been proposed for the origin 2008 TC3: 1) an accretionary model [3,4]; or 2) a regolith model [5,6]. Typical polymict ureilites are interpreted to represent regolith, and contain a few % foreign clasts [7,8]. The most common are dark (CC matrix-like) clasts similar to those in many meteoritic breccias [9]. A variety of other chondrites, as well as achondrites (angrites), have also been reported [7,9,10]. We have been working to determine the full diversity of these clasts [10-13] for comparison with AhS. We discuss implications for mixing of materials in the early solar system and the origin of 2008 TC3.

Goodrich, C. A.↗
NASA NTRS2016

Ceres Revealed in a Grain of Salt

Introduction: Zag and Monahans (1998) are H chondrite regolith breccias containing 4.5 giga-year-old halite crystals which contain abundant inclusions of aqueous fluids, solids and organics. These all originated on a cryo-volcanically-active C class asteroid, probably 1 Ceres; the halite was transported to the regolith of the H chondrite parent asteroid, potentially 6 Hebe. Detailed analysis of these solids will thus potentially reveal the mineralogy of Ceres. Mineralogy of solids in the Monahans Halite Solid grains are present in the halites, which were entrained within the mother brines during eruption, including material from the interior and surface of the erupting body. The solids include abundant, widely variable organics that could not have been significantly heated (which would have resulted in the loss of fluids from the halite). Our analyses by Raman microprobe, SEM/EDX, synchrotron X-ray diffraction, UPLC-FD/QToF-MS, C-XANES and TEM reveal that these trapped grains include macromolecular carbon (MMC) similar in structure to CV3 chondrite matrix carbon, aliphatic carbon compounds, olivine (Fo99-59), high- and low-Ca pyroxene, feldspars, phyllosilicates, magnetite, sulfides, metal, lepidocrocite, carbonates, diamond, apatite and zeolites. Conclusions: The halite in Monahans and Zag derive from a water and carbon-rich object that was cryo-volcanically active in the early solar system, probably Ceres. The Dawn spacecraft found that Ceres includes C chondrite materials. Our samples include both protolith and aqueously-altered samples of the body, permitting understanding of alteration conditions. Whatever the halite parent body, it was rich in a wide variety of organics and warm, liquid water at the solar system's dawn.

Zolensky, M. E.↗
NASA NTRS2017

Fine-Gained CAIs in Comet Samples: Moderate Refractory Character and Comparison to Small Refractory Inclusions in Chondrites

Examination of >200 comet Wild 2 particles collected by the Stardust (SD) mission shows that the CAI abundance of comet Wild 2's rocky material is near 1% and that nearly 50% of all bulbous tracks will contain at least one recognizable CAI fragment. A similar abundance to Wild 2 is found in a giant cluster IDP thought to be of cometary origin. The properties of these CAIs and their comparison with meteoritic CAIs provide important clues on the role of CAIs in the early Solar System (SS) and how they were transported to the edge of the solar nebula where Kuiper Belt comets formed. Previously, only two CAIs in comet Wild 2 had been identified and studied in detail. Here we present 2 new Wild 2 CAIs and 2 from a giant cluster cometary IDP, describe their mineralogical characteristics and show that they are most analogous to nodules in spinel-rich, fine-grained inclusions (FGIs) observed in CV3 and other chondrites. Additionally, we present new O isotope measurements from one CAI from comet Wild 2 and show that its oxygen isotopic composition is similar to some FGIs. This is only the second CAI from Wild 2 in which O isotopes have been measured.

Joswiak, D. J.↗
NASA NTRS2017

Distinct Chlorine Isotopic Reservoirs on Mars: Implications for Character, Extent and Relative Timing of Crustal Interaction with Mantle-Derived Magmas, Evolution of the Martian Atmosphere, and the Building Blocks of an Early Mars

The style, magnitude, timing, and mixing components involved in the interaction between mantle derived Martian magmas and Martian crust have long been a point of debate. Understanding this process is fundamental to deciphering the composition of the Martian crust and its interaction with the atmosphere, the compositional diversity and oxygen fugacity variations in the Martian mantle, the bulk composition of Mars and the materials from which it accreted, and the noble gas composition of Mars and the Sun. Recent studies of the chlorine isotopic composition of Martian meteorites imply that although the variation in delta (sup 37) Cl is limited (total range of approximately14 per mille), there appears to be distinct signatures for the Martian crust and mantle. However, there are potential issues with this interpretation. New Cl isotope data from the SAM (Sample Analysis at Mars) instrument on the Mars Science Lab indicate a very wide range of Cl isotopic compositions on the Martian surface. Recent measurements by [10] duplicated the results of [7,8], but placed them within the context of SAM surface data. In addition, Martian meteorite Chassigny contains trapped noble gases with isotopic ratios similar to solar abundance, and has long been considered a pristine, mantle derived sample. However, previous studies of apatite in Chassigny indicate that crustal fluids have interacted with regions interstitial to the cumulus olivine. The initial Cl isotope measurements of apatite in Chassigny suggest an addition of crustal component to this lithology, apparently contradicting the rare gas data. Here, we examine the Cl isotopic composition of multiple generations and textures of apatite in Chassigny to extricate the crustal and mantle components in this meteorite and to reveal the style and timing of the addition of crustal components to mantle-derived magmas. These data reveal distinct Martian Cl sources whose signatures have their origins linked to both the early Solar System and the evolving Martian atmosphere.

Shearer, C. K.↗
NASA NTRS2017

BAOBAB (Big And Outrageously Bold Asteroid Belt) Project

One of the intriguing results of NASA's Dawn mission is the composition and structure of the Main Asteroid Belt's only known dwarf planet, Ceres [1]. It has a top layer of dehydrated clays and salts [2] and an icy-rocky mantle [3,4]. It is widely known that the asteroid belt failed to accrete as a planet by resonances between the Sun and Jupiter. About 20-30 asteroids >100 km diameter are probably differentiated protoplanets [5]. 1) how many more and which ones are fragments of protoplanets? 2) How many and which ones are primordial rubble piles left over from condensation of the solar nebula? 3) How would we go about gaining better and more complete characterization of the mass, interior structure and composition of the Main Belt asteroid population? 4) What is the relationship between asteroids and ocean worlds? Bulk parameters such as the mass, density, and porosity, are important to characterize the structure of any celestial body, and for asteroids in particular, they can shed light on the conditions in the early solar system. Asteroid density estimates exist but currently they are often based on assumed properties of taxonomic classes, or through astronomical survey data where interactions with asteroids are weak at best resulting in large measurement uncertainty. We only have direct density estimates from spacecraft encounters for a few asteroids at this time. Knowledge of the asteroids is significant not only to understand their role in solar system workings, but also to assess their potential as space resources, as impact hazards on Earth, or even as harboring life forms. And for the distant future, we want to know if the idea put forth in a contest sponsored by Physics Today, to surface the asteroids into highly reflecting, polished surfaces and use them as a massively segmented mirror for astrophysical exploration [6], is feasible.

Asteroid Belt↗
NASA NTRS2016

Isotopic Ratios of H, C, N, O, and S in Comets C2012 F6 (lemmon) and C2014 Q2 (lovejoy) * ** ***

The apparition of bright comets C/2012 F6 (Lemmon) and C/2014 Q2 (Lovejoy) in March-April 2013 and January 2015, combined with the improved observational capabilities of submillimeter facilities, offered an opportunity to carry out sensitive compositional and isotopic studies of the volatiles in their coma. We observed comet Lovejoy with the IRAM 30 meter telescope between 13 and 26 January 2015, and with the Odin submillimeter space observatory on 29 January - 3 February 2015. We detected 22 molecules and several isotopologues. The H2 O-16 and H2 O-18 production rates measured with Odin follow a periodic pattern with a period of 0.94 days and an amplitude of approximately 25 percent. The inferred isotope ratios in comet Lovejoy are O-16/O-18 = 499 +/- 24 and D/H equals 1.4 +/- 0.4 x 10(exp -4) in water, S-32/S-34 = equals 24.7 +/- 3.5 in CS, all compatible with terrestrial values. The ratio C-12/C-13 equals 109 +/- 14 in HCN is marginally higher than terrestrial and 14 N/ 15/N equals 145 +/- 12 in HCN is half the Earth ratio. Several upper limits for D/H or C-12/ C-13 in other molecules are reported. From our observation of HDO in comet C/2014 Q2 (Lovejoy), we report the first D/H ratio in an Oort Cloud comet that is not larger than the terrestrial value. On the other hand, the observation of the same HDO line in the other Oort-cloud comet, C/2012 F6 (Lemmon), suggests a D/H value four times higher. Given the previous measurements of D/H in cometary water, this illustrates that a diversity in the D/H ratio and in the chemical composition, is present even within the same dynamical group of comets, suggesting that current dynamical groups contain comets formed at very different places or times in the early solar system.

Biver, N.↗
NASA NTRS2017

A New Method of Absorption-Phase Nanotomography for 3D Observation of Mineral-Organic-Water Textiles and its Application to Pristine Carbonaceous Chondrites

Pristine carbonaceous chondrites contain fine-grained matrix, which is composed largely of amorphous silicates, sub-micron silicate and sulfide crystals, and organic materials. They are regarded as primitive dust in the early Solar System that have suffered minimal alteration in their parent bodies. The matrix generally has different lithologies; some of them are unaltered but some are more or less aqueously altered. Their textures have been examined in 2D usually by FE-SEM/EDS, TEM/EDS, nano-SIMS and micro-XRD. Observation of their complex fine textures, such as spatial relation between different lithologies in 3D, is important for understanding aggregation and alteration processes. Synchrotron radiation (SR)-based X-ray tomography reveals 3D structures nondestructively with high spatial resolution of approximately greater than 100 nm. We have developed a new technique using absorption contrasts called "dual-energy tomography" (DET) to obtain 3D distribution of minerals at SPring-8, SR facility in Japan, and applied successfully to Itokawa particles. Phase and absorption contrast images can be simultaneously obtained in 3D by using "scanning-imaging x-ray microscopy" (SIXM) at SPring-8, which can discriminate between void, water and organic materials. We applied this technique combined with FIB micro-sampling to carbonaceous chondrites to search for primitive liquid water. In this study, we combined the DET and SIXM to obtain three dimensional submicron-scale association between minerals, organic materials and water and applied this to pristine carbonaceous chondrites.

Tsuchiyama, A.↗
NASA NTRS2017

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.↗