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NASA NTRS1998

Evidence for Microfossils in Ancient Rocks and Meteorites

The McKay et all. detection of chemical biomarkers and possible microfossils in an ancient meteorite from Mars (ALH84001) stimulated research in several areas of importance to the newly emerging field of Astrobiology. Their report resulted in a search for additional evidence of microfossils in ancient terrestrial rocks and meteorites. These studies of ancient rocks and meteorites were conducted independently (and later collaboratively) in the United States and Russia using the SEM, Environmental Scanning Electron Microscope (ESEM), and Field Emission Scanning Electron Microscope (FESEM). We have encountered in-situ in freshly broken carbonaceous chondrites a large number of complex microstructures that appear to be lithified microbial forms. The meteoritic microstructures have characteristics similar to the lithified remains of filamentous cyanobacteria and bacterial microfossils we have found in ancient phosphorites, ancient graphites and oil shales. Energy Dispersive Spectroscopy (EDS) and Link microprobe analysis shows the possible microfossils have a distribution of chemical elements characteristic of the meteorite rock matrix, although many exhibit a superimposed carbon enhancement. We have concluded that the mineralized bodies encountered embedded in the rock matrix of freshly fractured meteoritic surfaces can not be dismissed as recent surface contaminants. Many of the forms found in-situ in the Murchison, Efremovka, and Orgueil carbonaceous meteorites are strikingly similar to microfossils of coccoid bacteria, cyanobacteria and fungi such as we have found in the Cambrian phosphorites of Khubsugul, Mongolia and high carbon Phanerozoic and Precambrian rocks of the Siberian and Russian Platforms.

Hoover, Richard B.↗
NASA NTRS2001

Chemical Biomarkers and Microfossils in Carbonaceous Meteorites

Chemical, mineral and morphological biomarkers and microfossils are present in a wide variety of ancient rocks and meteorites. We discuss previous results and present images of microfossils of cyanobacteria, magnetotactic bacteria, and acritarchs detected in the Orgueil, Mighei, Nogoya, and Murchison carbonaceous meteorites.

Hoover, Richard B.↗
NASA NTRS2002

Isotopic Study of Silicon Carbide in Semarkona

We have measured Si and C isotopes for individual SiC grains from Semarkona. Our results are compared with those of previous studies on SiC from Murchison and Orgueil. Metamorphism and grain-size distribution can affect these comparisons. Additional information is contained in the original extended abstract.

Smith, Julie B.↗
NASA NTRS2003

Solar System Connections to the Organic Material In the ISM

The organic component of the interstellar medium (ISM) has relevance to the formation of the early solar nebula, since our solar system formed out of ISM material. Comparisons of near infrared spectra of the diffuse ISM dust with those of primitive solar system bodies (such as comets and meteorites) show a remarkable similarity, suggesting that perhaps some of the interstellar organic material made its way, unaltered, into our solar system. Tracing the interstellar organic material is necessary to understand how these materials may be important links in the development of prebiotic phenomena. Studies of the ISM reveal that the organic refractory component of the diffuse ISM is largely hydrocarbon in nature, possessing little N or O, with carbon distributed between the aromatic and aliphatic forms. There is a strong similarity in the near IR spectra of the diffuse ISM (the 3.4 micron hydrocarbon bands) and those seen in the Murchison and Orgueil meteorites, however, detailed comparisons at longer wavelengths reveal critical dissimilarities. Here we will present comparisons and discussion of relevant spectra. As we continue to explore, we will gain insight into the connection between planetesimals in the solar system and chemistry in the dusty space between the stars.

Pendleton, Yvonne J.↗
NASA NTRS2002

Amino acids in the Tagish Lake Meteorite

High-performance liquid chromatography (HPLC) based amino acid analysis of a Tagish Lake meteorite sample recovered 3 months after the meteorite fell to Earth have revealed that the amino acid composition of Tagish Lake is strikingly different from that of the CM and CI carbonaceous chondrites. We found that the Tagish Lake meteorite contains only trace levels of amino acids (total abundance = 880 ppb), which is much lower than the total abundance of amino acids in the CI Orgueil (4100 ppb) and the CM Murchison (16 900 ppb). Because most of the same amino acids found in the Tagish Lake meteorite are also present in the Tagish Lake ice melt water, we conclude that the amino acids detected in the meteorite are terrestrial contamination. We found that the exposure of a sample of Murchison to cold water lead to a substantial reduction over a period of several weeks in the amount of amino acids that are not strongly bound to the meteorite matrix. However, strongly bound amino acids that are extracted by direct HCl hydrolysis are not affected by the leaching process. Thus even if there had been leaching of amino acids from our Tagish Lake meteorite sample during its 3 month residence in Tagish Lake ice and melt water, a Murchison type abundance of endogenous amino acids in the meteorite would have still been readily detectable. The low amino acid content of Tagish Lake indicates that this meteorite originated fiom a different type of parent body than the CM and CI chondrites. The parent body was apparently devoid of the reagents such as aldehyldes/ketones, HCN and ammonia needed for the effective abiotic synthesis of amino acids. Based on reflectance spectral measurements, Tagish Lake has been associated with P- or D-type asteroids. If the Tagish Lake meteorite was indeed derived fiom these types of parent bodies, our understanding of these primitive asteroids needs to be reevaluated with respect to their potential inventory of biologically important organic compounds.

Kminek, G.↗
NASA NTRS2003

Approaches to Establishing the Chemical Structure of Extraterrestrial Organic Solids

The majority of extraterrestrial organic matter in carbonaceous chondrites resides in a chemically complex, insoluble and perhaps macromolecular phase. We have been applying a series of independent solid state NMR experiments that are designed to provide a self consistent chemical characterization of this complex material. To date we have thoroughly analyzed 8 organic residues from different meteorites, including a CR2 (EET92042), CIl(Orgueil), CM2 (Murchison), Tagish Lake, CM2 (AlH83100), CM2 (Cold Bokkefeld), CM2 (Mighei), CM3 (Y86720). In fig 1. (1)H to (13)C cross polarization NMR spectra of four of these are shown. Note that there exists an enormous range in chemistry exhibited in organic solid [evident by the breadth of the spectral features both in the aliphatic region (sp(sup 3)) and the aromatic region (sp(sup 2))]. There is also considerable differences in the carbon chemistry across the meteorite groups.

Cody, G. D.↗
NASA NTRS2003

Endemic Ru Isotopic Anomalies in Iron Meteorites and in Allende

Small variations for Mo isotopes have been observed recently in the Allende meteorite and in iron meteorites, mesosiderites, and pallasites, using ICPMS. Large effects for Mo have been reported for leaches of Orgueil and in SiC and graphite from Murchison. Variations for Mo in bulk Allende and in Murchison have also been presented by NTIMS. Effects in Ru isotopes can define further the preserved exotic r, s, and p contributions in this mass region, and possible effects in Ru-98 and Ru-99 from Tc-98 (4.2 Ma half-life) and Tc-99 (0.21 Ma half-life). Previous attempts at determination of Ru isotopes yielded no resolved effects. The present work represents a substantial improvement in precision over the earlier work. Chemical and mass spectrometric analytical techniques are presented to determine the Ru isotope compositions in terrestrial standards and in meteorites.

Chen, J. H.↗
NASA NTRS2003

Isotopic Composition of Silicon Carbide in the CO3 Chondrite Colony

Presolar grains have been identified in primitive members of all chondrite classes. The isotopic compositions of presolar grains provide probes of galactic evolution and nucleosynthesis in stars, while the abundances and characteristics of presolar grains contain a record of thermal processing in the solar system. Most of the detailed isotopic work has been done on SiC from Murchison and Orgueil, supplemented by a few studies of ordinary and enstatite chondrites. This work investigates SiC in the Colony CO3.O meteorite. SiC is present in Colony at a matrix-normalized abundance of approximately 3.7 ppm, much less than in CI chondrites and the matrixes of CM and primitive ordinary and enstatite chondrites. The abundances of SiC and other presolar grains in Colony seem to correlate with the chemical processing that produced CO3 chondrites. This implies that the known presolar grains experienced the same processing as the bulk CO3 material and assumes that the parent material was the same as that for other chondrites, including CI. That parent material is most plausibly the average material in the sun s parent molecular cloud. One test of this idea is to look for primary differences between SiC in Colony (and other meteorites) and that in CI and CM chondrites. True differences not related to thermal processing would falsify the assumption that all chondrite classes originated from the same reservoir of presolar dust.

Smith, J. B.↗
NASA NTRS2003

Manganese-Chromium Isotope Systematics of Ivuna, Kainsaz and Other Carbonaceous Chondrites

We have shown earlier that the bulk samples of carbonaceous chondrites [CC] reveal excesses in both Cr-53 (Cr-53*) and Cr-54 (Cr-54*) as compared to the terrestrial standard value. The Cr-53/52 ratios in bulk samples of Orgueil (CI), Murray (CM), Allende (CV), and the Bencubbin/CH-like meteorite Hammadah Al Hambra 237 (HH237) are correlated with the respective Mn/Cr ratios. In contrast to CC, HH237 is characterized by a deficit of Cr-53 (-0.15 +/- 0.10(epsilon)) at a low Mn/Cr ratio of 0.07. The HH237 data point, however, falls on the CC line. Here we report new Mn-53 - Cr-53 results for the CC Kainsaz (CO) and Ivuna (CI).

Shukolyukov, A.↗
NASA NTRS2003

Microfossils in CI and CO Carbonaceous Meteorites

Secondary and backscatter electron images and x-ray spectral data of selected CI (Alais, Orgueil, and Tagish Lake) and CO3 (Rainbow and Dar a1 Gani 749) carbonaceous meteorites have recently been obtained using Field Emission and Environmental Scanning Electron Microscopes These studies indicate the presence of a large assemblage of biomarkers and complex lithified and carbonized remains of bodies that we interpret as indigenous microfossils. We discuss the meteorites, provide images of many of the biogenic forms found embedded in the freshly fractured meteorite surfaces.

Hoover, Richard B.↗
NASA NTRS2004

Nitrogen and Carbon Isotopic Composition of Silicon Carbide in the CO3.0 Meteorite ALHA 77307, a NanoSIMS Study

Presolar grains have been identified in primitive members of all chondrite classes [1, 2]. The study of the isotopic compositions of presolar grains provides information on galactic evolution and nucleosynthesis in stars [3, 4], while the abundances and characteristics of presolar grains contain a record of thermal processing in the solar system [2, 5]. Much of the detailed work on presolar silicon carbide grains has focused on Murchison [e.g., 2] and Orgueil [4], but several other carbonaceous [6, 7], ordinary, and enstatite chondrites [8-11] have also been studied. This study investigates the isotopic composition of silicon carbide from the CO3.0 carbonaceous chondrites ALHA77307 and Colony. SiC is present in ALHA77307 at a matrix normalized abundance of ~8.8 ppm [5], which is approximately twice the abundance of Colony [5], but less than in CI chondrites and the matrices of CM and primitive ordinary and enstatite chondrites [3]. The abundances of SiC and other presolar grains in ALHA77307 seem to correlate with the degree of chemical processing that produced CO3 chondrites [2, 5]. This implies that the same nebular processing that produced the bulk composition of the CO3 chondrite class also modified the assemblage of known presolar grains [5]. To test whether all chondrite classes originated from the same reservoir of presolar dust it is necessary to look for primary differences, not related to thermal processing, between SiC in CO3 chondrites and other chondritic meteorites.

Smith, J. B.↗
NASA NTRS2004

Lunar and Planetary Science XXXV: Early Solar System Chronology

The following topics were presented in this report: Iron Isotopic Fractionation During Vacuum Evaporation of Molten W?stite and Solar Compositions; Mg Isotope Ratio Zonation in CAIs - New Constraints on CAI Evolution; Sm-Nd Systematics of Chondrites; AMS Measurement of Mg-24(He-3,p)Al-26 Cross Section, Implications for the Al-26 Production in the Early Solar System; On Early Solar System Chronology: Implications of an Initially Heterogeneous Distribution of Short-lived Radionuclides; Revisiting Extraterrestrial U Isotope Ratios; Helium-Shell Nucleosynthesis and Extinct Radioactivities; High Spatial Resolution Ion Microprobe Measurements Refine Chronology of Orgueil Carbonate Formation; and Calibration of the Galactic Cosmic Ray Flux.

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NASA NTRS2004

Lunar and Planetary Science XXXV: Big Dust, Little Dust, and Aerogel

The titles in this section include: 1) A First Look at Graphite Grains from Orgueil: Morphology, Carbon, Nitrogen and Neon Isotopic Compositions of Individual, Chemically Separated Grains; 2) Discovery of an In-Situ Presolar Silicate Grain with GEMS-Like Composition in the Bishumpur Matrix; 3) Revised Global Accretion Rates of Micrometeorites in the Last Glacial Period; 4) Isotopic Fractionation of Potassium in Stony Cosmic Spherules; 5) Crumbs from the Crust of Vesta: Achondritic Micrometeorites from the South Pole Water Well; 6) Preservation of Micrometeoroid Remains on Solar Cells Returned from Orbit; 7) High Input Rates of Micrometeoritic Sulfur, 'Smoke' Particles and Oligoelements on the Early Earth; 8) High Resolution Confocal Raman Imaging of an IDP; 9) A micro-Raman Survey of 10 IDPs and 6 Carbonaceous Chondrites; 10) Mid- and Far-Infrared Spectroscopy at the Advanced Light Source; 11) Hypervelocity Impact Energy Loss and Track Shape in Aerogels: Theory and Experiment; 12) Fiducial Marks for Location of Particles in Aerogel.

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NASA NTRS2004

The Abundance and Isotopic Composition of Hg in Extraterrestrial Materials

During the past three year grant period we made excellent progress in our study of the abundances and isotopic compositions of Hg and other volatile trace elements in extraterrestrial materials. As part of my startup package I received funds to construct a state-of-the-art experimental facility to study gas-solid reaction kinetics. Much of our effort was spent developing the methodology to measure the abundance and isotopic composition of Hg at ultratrace levels in solid materials. In our first study, the abundance and isotopic composition of Hg was determined in bulk samples of the Murchison (CM) and Allende (CV) carbonaceous chondrites. We have continued our study of mercury in primitive meteorites and expanded the suite of meteorites to include other members of the CM and CV chondrite group as well as CI and CO chondrites. Samples of the CI chondrite Orgueil, the CM chondrites Murray, Nogoya, and Cold Bokkeveld, the CO chondrites Kainsaz, Omans, and Isna, and the CV chondrites Vigarano, Mokoia, and Grosnaja were tested. We have developed a thermal analysis ICP-MS technique and applied it to the study of a suite of thermally labile elements (Zn, As, Se, Cd, In, Sn, Sb, Te, Hg, Au, Tl, Pb, and Bi) in geologic materials as well.

Lauretta, D. S.↗
NASA NTRS2004

Fossil Signatures Using Elemental Abundance Distributions and Bayesian Probabilistic Classification

Elemental abundances (C6, N7, O8, Na11, Mg12, Al3, P15, S16, Cl17, K19, Ca20, Ti22, Mn25, Fe26, and Ni28) were obtained for a set of terrestrial fossils and the rock matrix surrounding them. Principal Component Analysis extracted five factors accounting for the 92.5% of the data variance, i.e. information content, of the elemental abundance data. Hierarchical Cluster Analysis provided unsupervised sample classification distinguishing fossil from matrix samples on the basis of either raw abundances or PCA input that agreed strongly with visual classification. A stochastic, non-linear Artificial Neural Network produced a Bayesian probability of correct sample classification. The results provide a quantitative probabilistic methodology for discriminating terrestrial fossils from the surrounding rock matrix using chemical information. To demonstrate the applicability of these techniques to the assessment of meteoritic samples or in situ extraterrestrial exploration, we present preliminary data on samples of the Orgueil meteorite. In both systems an elemental signature produces target classification decisions remarkably consistent with morphological classification by a human expert using only structural (visual) information. We discuss the possibility of implementing a complexity analysis metric capable of automating certain image analysis and pattern recognition abilities of the human eye using low magnification optical microscopy images and discuss the extension of this technique across multiple scales.

Hoover, Richard B.↗
NASA NTRS2005

Lunar and Planetary Science XXXVI, Part 10

The Problem of Incomplete Mixing of Interstellar Components in the Solar Nebula: Very High Precision Isotopic Measurements with Isoprobes P and T. Finally: Presolar Graphite Grains Identified in Orgueil. Basaltic Ring Structures as an Analog for Ring Features in Athabasca Valles, Mars. Experimental Studies of the Water Sorption Properties of Mars-Relevant Porous Minerals and Sulfates. Silicon Isotope Ratio Variations in CAI Evaporation Residues Measured by Laser Ablation Multicollector ICPMS. Crater Count Chronology and Timing of Ridged Plains Emplacement at Schiaparelli Basin, Mars. Martian Valley Networks and Associated Fluvial Features as Seen by the Mars Express High Resolution Stereo Camera (HRSC). Fast-Turnoff Transient Electromagnetic (TEM) Field Study at the Mars Analog Site of Rio Tinto, Spain. Time Domain Electromagnetics for Mapping Mineralized and Deep Groundwater in Mars Analog Environments. Mineralogical and Seismological Models of the Lunar Mantle. Photometric Observations of Soils and Rocks at the Mars Exploration Rover Landing Sites. Thermal Infrared Spectral Deconvolution of Experimentally Shocked Basaltic Rocks Using Experimentally Shocked Plagioclase Endmembers.

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NASA NTRS2006

Probabilistic Classification Using Elemental Abundance Distributions and Lossless Image Compression in Apollo 17 Lunar Dust Samples from Mare Serenitatis

We have previously outlined a strategy for the detection of fossils [Storrie-Lombardi and Hoover, 2004] and extant microbial life [Storrie-Lombaudi and Hoover, 20051 during robotic missions to Mars using co-registered structural and chemical signatures. Data inputs included image lossless compression indices to estimate relative textural complexity and elemental abundance distributions. Two exploratory classification algorithms (principal component analysis and hierarchical cluster analysis) provide an initial tentative classification of all targets. Nonlinear stochastic neural networks are then trained to produce a Bayesian estimate of algorithm classification accuracy. The strategy previously has been successful in distinguishing regions of biotic and abiotic alteration of basalt glass from unaltered samples. [Storrie-Lombardi and Fisk, 2004; Storrie-Lombardi and Fisk, 2004] Such investigations of abiotic versus biotic alteration of terrestrial mineralogy on Earth are compromised by .the difficulty finding mineralogy completely unaffected by the ubiquitous presence of microbial life on the planet. The renewed interest in lunar exploration offers an opportunity to investigate geological materials that may exhibit signs of aqueous alteration, but are highly unlikely to contain contaminating biological weathering signatures. We here present an extension of our earlier data set to include lunar dust samples obtained during the Apollo 17 mission. Apollo 17 landed in the Taurus-Littrow Valley in Mare Serenitatis. Most of the rock samples from this region of the lunar highlands are basalts comprised primarily of plagioclase and pyroxene and selected examples of orange and black volcanic glass. SEM images and elemental abundances (C6, N7, O8, Na11, Mg12, Al13, Si14, P15, S16, Cll7, K19, Ca20, Fe26) for a series of targets in the lunar dust samples are compared to the extant cyanobacteria, fossil trilobites, Orgueil meteorite, and terrestrial basalt targets previously discussed. The data set provides a first step in producing a quantitative probabilistic methodology for geobiological analysis of returned lunar samples or in situ exploration.

Storrie-Lombardi, Michael C.↗
NASA NTRS2006

Comets, Asteroids, Meteorites, and the Origin of the Biosphere

During the past few decades, the delivery of water, organics, and prebiotic chemicals to the Biosphere of Earth during the Hadean (4.5-3.8 Ga) period of heavy bombardment by comets and asteroids has become more widely accepted. Comets are still largely regarded as frigid, pristine bodies of protosolar nebula material that are devoid of liquid water and therefore unsuitable for life. Complex organic compounds have been observed in comets and on the water-rich asteroid 1998 KY26 and near IR observations have indicated the presence of crystalline water ice and ammonia hydrate on the large Kuiper Belt object (50000) Quaoar that has resurfacing suggesting cryovolcanic outgassing. Spacecraft observations of the chemical compositions and characteristics of the nuclei of several comets (Halley, Borrelly, Wild 2, and Tempel 1) have shown that comets contain complex organic chemicals; that water is the predominant volatile; and that extremely high temperatures (approx. 350-400 K) can be reached on the surfae of the very black (albedo approx. 0.03) nuclei of comets when they approach the Sun. Impact craters and pinnacles observed on comet Wild 2 suggest a thick crust. Episodic outbursts and jets from the nuclei of several comets indicate that localized regimes of liquid water and water vapor can periodically exist beneath the comet crust. The Deep Impact mission found the temperature of the nucleus of comet Tempel 1 at 1.5 AU varied from a minimum of 280 plus or minus 8 K the 330K (57 C) on the sunlit side. In this paper it is argued that that pools and films of liquid water exist (within a wide range of temperatures) in cavities and voids just beneath the hot, black crust. The possibility of liquid water existing over a wide range of temperatures significantly enhances the possibility that comets might contain niches suitable for the growth of microbial communities and ecosystems. These regimes would be ideal for the growth of psychrophilic, mesophilic, and thermophilic photoautotrophs and chemolithotrophs such as the motile filamentous cyanobacteria (e.g., Calothrix, Oscillatoria, Phormidium, and Spirulina) that grow in geothermal springs and geysers of Earth at temperatures ranging fiom 320K to 345K and are also found growing in cold polar desert soils. The mineralized remains of morphotypes of all of these cyanobacteria have also been found in the Orgueil CI1 and the Murchison CN2 carbonaceous meteorites that may derive from cometary parent bodies. Observational results that support the hypothesis that liquid water can in active regions just beneath the surface of comets and that comets, carbonaceous meteorites, and asteroids may have played a significant role in the origin and evolution of the Biosphere and in the distribution of microbial life throughout the Solar System.

Hoover, Richard B.↗