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NASA NTRS1992

Diterpanes, triterpanes, steranes, and aromatic hydrocarbons in natural bitumens and pyrolysates from different humic coals

Data are presented on the distribution of diterpanes, triterpanes, steranes, and aromatic hydrocarbons in the natural bitumens extracted from unheated coals identified as Rocky Mountain coal (RMC), Australian Gippsland Latrobe Eocene coal (GEC), Australian Gippsland Latrobe Cretaceous coal (GCC), and Texas Wilcox lignite (WL), as well as from pyrolysates obtained from heating of these coals. It was found that pentacyclic triterpanes are dominant in GEC, GCC, and WL, whereas diterpanes strongly predominate in the bitumen of RMC, indicating that resin is a more important constituent of RMC than of the other coals and that it releases the diterpenoids at an early stage of diagenesis. It was also found that the composition of diterpanes is different among these coals and that the distributions of sterane and triterpane in the natural bitumen of coals are very different from those of pyrolysates.

Lu, Shan-Tan↗

NASA NTRS1989

Cometary Evolution: Clues on Physical Properties from Chondritic Interplanetary Dust Particles

The degree of diversity or similarity detected in comets depends primarily on the lifetimes of the individual cometary nuclei at the time of analysis. It is inherent in our understanding of cometary orbital dynamics and the seminal model of comet origins by Oort that cometary evolution is the natural order of events in our Solar System. Thus, predictions of cometary behaviour in terms of bulk physical, mineralogical or chemical parameters should contain an appreciation of temporal variation(s). Previously, Rietmeijer and Mackinnon developed mineralogical bases for the chemical evolution of cometary nuclei primarily with regard to the predominantly silicate fraction of comet nuclei. We suggested that alteration of solids in cometary nuclei should be expected and that indications of likely reactants and products can be derived from judicious comparison with terrestrial diagenetic environments which include hydrocryogenic and low-temperature aqueous alterations. In a further development of this concept, Rietmeijer provides indirect evidence for the formation of sulfides and oxides in comet nuclei. Furthermore, Rietmeijer noted that timescales for hydrocryogenic and low-temperature reactions involving liquid water are probably adequate for relatively mature comets, e.g. P/comet Halley. In this paper, we will address the evolution of comet nuclei physical parameters such as solid particle grain size, porosity and density. In natural environments, chemical evolution (e.g. mineral reactions) is often accompanied by changes in physical properties. These concurrent changes are well-documented in the terrestrial geological literature, especially in studies of sediment diagenesis and we suggest that similar basic principles apply within the upper few meters of active comet nuclei. The database for prediction of comet nuclei physical parameters is, in principle, the same as used for the proposition of chemical evolution. We use detailed mineralogical studies of chondritic interplanetary dust particles (IDPS) as a guide to the likely constitution of mature comets traversing the inner Solar System. While there is, as yet, no direct proof that a specific sub-group or type of chondritic IDP is derived from a specific comet, it is clear that these particles are extraterrestrial in origin and that a certain portion of the interplanetary flux received by the Earth is cometary in origin. Two chondritic porous (CP) MPs, sample numbers W7010A2 and W7029Cl, from the Johnson Space Center Cosmic Dust Collection have been selected for this study of putative cometary physical parameters. This particular type of particle is considered a likely candidate for a cometary origin on the basis of mineralogy, bulk composition and morphology. While many IDPs have been subjected to intensive study over the past decade, we can develop a physical parameter model on only these two CP IDPs because few others have been studied in sufficient detail.

Rietmeijer, Frans J. M.↗

NASA NTRS1997

Cometary Evolution: Clues on Physical Properties from Chondritic Interplanetary Dust Particles

The degree of diversity or similarity detected in comets depends primarily on the lifetimes of the individual cometary nuclei at the time of analysis. It is inherent in our understanding of cometary orbital dynamics and the seminal model of comet origins that cometary evolution is the natural order of events in our Solar System. Thus, predictions of cometary behaviour in terms of bulk physical, mineralogical or chemical parameters should contain an appreciation of temporal variation(s). Previously, Rietmeijer and Mackinnon [1987] developed mineralogical bases for the chemical evolution of cometary nuclei primarily with regard to the predominantly silicate fraction of comet nuclei. We suggested that alteration of solids in cometary nuclei should be expected and that indications of likely reactants and products can be derived from judicious comparison with terrestrial diagenetic environments which include hydrocryogenic and low-temperature aqueous alterations. In a further development of this concept, Rietmeijer [1988] provides indirect evidence for the formation of sulfides and oxides in comet nuclei. Furthermore, Rietmeijer [1988] noted that timescales for hydrocryogenic and low-temperature reactions involving liquid water are probably adequate for relatively mature comets, e.g. P/comet Halley. In this paper, we will address the evolution of comet nuclei physical parameters such as solid particle grain size, porosity and density. In natural environments, chemical evolution (e.g. mineral reactions) is often accompanied by changes in physical properties. These concurrent changes are well-documented in the terrestrial geological literature, especially in studies of sediment diagenesis and we suggest that similar basic principles apply within the upper few meters of active comet nuclei. The database for prediction of comet nuclei physical parameters is, in principle, the same as used for the proposition of chemical evolution. We use detailed mineralogical studies of chondritic interplanetary dust particles (IDPS) as a guide to the likely constitution of mature comets traversing the inner Solar System. While there is, as yet, no direct proof that a specific sub-group or type of chondritic IDP is derived from a specific comet, it is clear that these particles are extraterrestrial in origin and that a certain portion of the interplanetary flux received by the Earth is cometary in origin. Two chondritic porous (CP) IDPS, sample numbers W701OA2 and W7029CI, from the Johnson Space Center Cosmic Dust Collection have been selected for this study of putative cometary physical parameters. This particular type of particle is considered a likely candidate for a cometary origin on the basis of mineralogy, bulk composition and morphology. While many IDPs have been subjected to intensive study over the past decade, we can develop a physical parameter model on only these two CP IDPs because few others have been studied in sufficient detail.

Reitmeijer, Frans J. M.↗

NASA NTRS1998

Mineralization of Bacteria in Terrestrial Basaltic Rocks: Comparison With Possible Biogenic Features in Martian Meteorite Allan Hills 84001

The identification of biogenic features altered by diagenesis or mineralization is important in determining whether specific features in terrestrial rocks and in meteorites may have a biogenic origin. Unfortunately, few studies have addressed the formation of biogenic features in igneous rocks, which may be important to these phenomena, including the controversy over possible biogenic features in basaltic martian meteorite ALH84001. To explore the presence of biogenic features in igneous rocks, we examined microcosms growing in basaltic small-scale experimental growth chambers or microcosms. Microbial communities were harvested from aquifers of the Columbia River Basalt (CRB) group and grown in a microcosm containing unweathered basalt chips and groundwater (technique described in. These microcosms simulated natural growth conditions in the deep subsurface of the CRB, which should be a good terrestrial analog for any putative martian subsurface ecosystem that may have once included ALH84001. Here we present new size measurements and photomicrographs comparing the putative martian fossils to biogenic material in the CRB microcosms. The range of size and shapes of the biogenic features on the CRB microcosm chips overlaps with and is similar to those on ALH84001 chips. Although this present work does not provide evidence for the biogenicity of ALH84001 features, we believe that, based on criteria of size, shape, and general morphology, a biogenic interpretation for the ALH84001 features remains plausible.

Thomas-Keprta, K. L.↗

NASA NTRS1997

Constraints on the Nature and Distribution of Iridium Host Phases at the Cretaceous-Tertiary Boundary: Implications for Projectile Identity and dispersal on impact

Among Cretaceous-Tertiary boundary sites worldwide, variations in the concentrations and ratios of elements commonly enriched in meteorites complicate traditional geochemical attempts at impactor identification. Yet they may provide constraints on the physical and chemical processes associated with large-body disruption and dispersal, as well as with diagenesis of projectile components. To this end, we continue our efforts to identify the mineral host-phases of projectile-derived elements, particularly for Ir, and to document their partitioning between crater deposits and ejecta resulting from the Chicxulub basin-forming impact. Building on earlier work, we used INAA to measure Ir concentrations in successively smaller splits of finely powdered impact melt breccia from the Chicxulub Crater in Mexico (sample Y6Nl9-R(b)), and K/T boundary fish clay from Stevns Klint, Denmark (sample FC-1, split from 40 kg of homogenized material intended as an analytical standard). Results for the Chicxulub sample show a heterogeneous Ir distribution and document that at least five discrete Ir-bearing host phases were isolated in subsequent splits, having Ir masses equivalent to pure Ir spheres from about 0.8 to about 3.5 mm in diameter. Three of these are within a sufficiently reduced mass of powder to warrant searching for them using backscattered electron microscopy. In contrast, successively smaller splits of the Stevns Klint fish clay show no statistically significant deviation from the reported value of 32 +/- 2 ng/g Ir, suggesting a uniform Ir host-phase distribution. For the smallest split obtained thus far (100 +/- 40 ng/g Ir), a pure Ir sphere of equivalent Ir mass would be <0.05 min in diameter. (n.b. Although homogenizing and sieving of FC-1 to <75 min obviously obscured variations in stratigraphic distribution, it is unlikely to have affected the size-frequency distribution of Ir host phases.) We previously identified micrometer-scale Ir host phases by electron microscopy in melt-rock samples from two widely separated drill holes at the Chicxulub Basin, including a replicate split of Y6-NI9-R. One is an aggregate of subhedral Ir metal grains enclosed in silicate, in which no other Pt group elements (PGE) were detected. A second particle with twice the mass as the first, concentrated predominantly in a single grain, is associated with minor concentrations of Os, Ru, and Pt, and with adhering particles of corundum and perovskite. A third Ir-rich particle, with a greater apparent Os concentration, was identified before being lost as a result of charging under the electron beam. In addition to demonstrating the preservation of projectile components within the Chicxulub Crater, analogous phase associations in Ca- and Al-rich inclusions (CAI) from C2 and C3 chondrites suggest to us that these melt-rock Ir host phases are relics from a carbonaceous chondrite K/T boundary impactor Although the obviously low Ru/Ir ratios of the Chicxulub Ir host phases are qualitatively consistent with suggested PGE fractionation with distance during condensation in an ejecta cloud, it seems difficult to explain the accumulation of the about 3 x 10(exp 11) Ir atoms required to form a about 10(exp -10) g nugget of pure Ir metal within a jet of vaporized projectile expanding at 1-4 km/s, or to effectively exclude or remove commonly alloyed PGE and siderophile elements by fractionation processes resulting from condensation, oxidation, sulfidization, exsolution, or autometamorphism during cooling of the melt. We do not dismiss the importance of these processes entirely; on the contrary, other geochemical and mineralogical aspects of the melt rocks require them, and condensation from the expanding ejecta cloud appears to best explain the primary Ir host-phase distribution in the fish clay, as well as the high Ir concentrations associated with spinel-bearing spheroids at the K/T boundary in the Pacific Ocean . If the "relict" hypothesis is correct, micronuggets of other PGEs and alloys, not detected by our INAA screening, should also occur in the melt rocks. Possibly, the discrete host phases with lesser Ir masses are such alloys with subordinate Ir, rather than simply smaller, predominantly Ir-bearing particles. A CAI source for the relics would be consistent with either a comet or an asteroid K/T impact at Chicxulub. (Additional information contained in the original.)

Schuraytz, B. C.↗

NASA NTRS1997

Cryptoblemes: A New Discovery with Major Economic Implications and Profound Changes to the Geologic Paradigm

Cryptoblemes are subtle impact shock signatures imprinted by cosmic debris on the crustal surfaces of lunar planetary bodes. These signatures constitute a complex cumulative overprinting of topographic, structural geophysical, and tectonic patterns that have a conspicuous radial centric multiringed symmetry. The geometry and distribution of cryptoblemes on Earth is comparable to the size and density of impact features on lunar planetary surfaces. Analysis of satellite imagery, sea-floor sonar, side-looking radar and aerial photographs of specific sites reveals new criteria for the identification and confirmation of impact-shock signatures. These criteria include joint and foliation patterns with asbestiform minerals, ribbon-quartz, spheroidal weathering, domal exfoliation, pencil shale, and shock spheres, which may originate from hydrocavitation of water-saturated sedimentary rocks. Cryptoblemes may also be associated with breccia pipes, sinkholes, buttes, mesas, and bogs, high-Rn anomalies, nodular concentrations, and earthquake epicenters. Major implications of cryptobleme identification include exploratory targeting of hydrocarbon and mineral deposits and the explanation of their origins. Analysis of known mineral deposits, structural traps and sedimentary basins show a direct correlation with cryptobleme patterns. Significant geologic paradigm shifts related to cryptoblemes include mountain building processes, structural orogenies, induced volcanism, earthquake origins, hydrocarbon diagenesis, formation mineral deposits, continental rifting, and plate movements, magnetic overprinting and local regional, and global geologic extinction and speciation patterns. Two figures provide a comparison between a multiring impact overprint in water and multiring cryptobleme in the U.S. basin range. (Additional information is contained in the original document).

Windolph, J., Jr.↗

NASA NTRS1994

Microbial Fossilization in Mineralizing Environments: Relevance for Mars "EXOPALEONTOLOGY"

The goals of post-Viking exobiology include the search for a Martian fossil record. How can we optimize future exploration efforts to search for fossils on Mars? The Precambrian fossil record indicates that key factors for the long-term preservation of microbial fossils include: 1) the rapid entombment and/or replacement of organisms and organic matter by fine-grained, stable mineral phases (e.g. silica, phosphate, and to a lesser extent, carbonate), 2) low-permeability host sediments (maintaining a closed chemical system during early diagenesis), and 3) shallow burial (maintaining post-depositional temperatures and pressures within the stability range for complex organic molecules). Modem terrestrial environments where early mineralization commonly occurs in association with microbial organisms include: subaerial thermal springs and shallow hydrothermal systems, sub-lacustrine springs and evaporites of alkaline lakes, and subsoil environments where hardpans (e.g. calcretes, silcretes) and duricrusts form. Studies of microbial fossilization in such environments provide important insights preservation patterns in Precambrian rocks, while also playing a role in the development of strategies for Mars exopaleontology. The refinement of site priorities for Mars exopaleontology is expected to benefit greatly from high resolution imaging and altimetry acquired during upcoming orbital missions, and especially infrared and gamma ray spectral data needed for determining surface composition. In anticipation of future orbital missions, constraints for identifying high priority mineral deposits on Mars are being developed through analog remote sensing studies of key mineralizing environments on Earth.

Farmer, Jack D.↗

NASA NTRS1994

Diagenetic Microcrystalline Opal Varieties from the Monterey Formation, CA: HRTEM Study of Structures and Phase Transformation Mechanisms

Microcrystalline opal varieties form as intermediary precipitates during the diagenetic transformation of biogenically precipitated non-crystalline opal (opal-A) to microquartz. With regard to the Monterey Formation of California, X-ray powder diffraction studies have shown that a decrease in the primary d-spacing of opal-CT toward that of cristobalite occurs with increasing diagenesis. The initial timing of opal-CT/quartz formation and the value of the primary opal-CT d-spacing, are influenced by the sediment. lithology. Transmission electron microscopy methods (CTEM/HRTEM) were used to investigate the structure of the diagenetic phases and establish transformation mechanisms between the varieties of microcrystalline opals in charts and porcelanites from the Monterey Formation. HRTEM images revealed that the most common fibrous varieties of microcrystalline opals contain varying amounts of structural disorder. Finite lamellar units of cristobalite-and tridymite-type. layer sequences were found to be randomly stacked in a direction perpendicular to the fiber axis. Disordered and ordered fibers were found to have coprecipitated within the same radial fiber bundles that formed within the matrix of the Most siliceous samples. HRTEM images, which reveal that the fibers within radial and lepispheric fiber bundles branch non-crystallographically, support an earlier proposal that microspheres in chert grow via a spherulitic growth mechanism. A less common variety of opal-CT was found to be characterized by non-parallel (low-angle) stacking sequences that often contain twinned lamellae. Tabular-shaped crystals of orthorhombic tridymite (PO-2) were also identified in the porcelanite samples. A shift in the primary d-spacing of opal-CT has been interpreted as an indication of solid-state ordering g toward a predominantly cristobalite structure, (opal-C). Domains of opal-C were identified as topotactically-oriented overgrowths on discrete Sections of opal-CT fibers and as lamellar domains within relict opal-CT fibers. These findings indicate that the type of transformation mechanism depends upon the primary structural characteristics of the authigenic opaline. varieties that are in turn influenced by the sediment lithology.

Cady, Sherry L.↗

NASA NTRS2001

Benthic Marine Cyanobacterial Mat Ecosystems: Biogeochemistry and Biomarkers

Cyanobacterial mats are complete ecosystems that can include processes of primary production, diagenesis and lithification. Light sustains oxygenic photosynthesis, which in turn provides energy, organic matter and oxygen to the community. Due to both absorption and scattering phenomena, incident light is transformed with depth in the mat, both in intensity and spectral composition. Mobile photo synthesizers optimize their position with respect to this light gradient. When photosynthesis ceases at night, the upper layers of the mat become reduced and sulfidic. Counteracting gradients of oxygen and sulfide combine to provide daily-contrasting environments separated on a scale of a few mm. The functional complexity of mats, coupled with the highly proximal and ordered spatial arrangement of biota, offers the potential for a staggering number of interactions. At a minimum, the products of each functional group of microorganisms affect the other groups both positively and negatively. For example, cyanobacteria generate organic matter (potential substrates) but also oxygen (a toxin for many anaerobes). Anaerobic activity recycles nutrients to the photosynthesizers but also generates potentially toxic sulfide. The combination of benefits and hazards of light, oxygen and sulfide promotes the allocation of the various essential mat processes between light and dark periods, and to various depths in the mat. Observations of mats have produced numerous surprises. For example, obligately anaerobic processes can occur in the presence of abundant oxygen, highly reduced gases are produced in the presence of abundant sulfate, meiofauna thrive at high sulfide concentrations, and the mats' constituent populations respond to environmental changes in complex ways. While photosynthetic bacteria dominate the biomass and productivity of the mat, nonphotosynthetic, anaerobic processes constitute the ultimate biological filter on the ecosystem's emergent biosignatures, including those sedimentary textures, organic compounds, and minerals that enter the fossil record. The ability of cyanobacterial mats to channel abundant solar energy into the creation and maintenance of complex structures and processes has created a multitude of consequences, both for sedimentation and for the early evolution of our biosphere.

DesMarais, David J.↗

NASA NTRS1997

Fossilization of Coniform (Phormidium) Stromatolites In Siliceous Thermal Springs, Yellowstone National Park

We have studied fossilization processes in well-developed cyanobacterial mats present in mid-terrace ponds of silica-precipitating thermal springs of Yellowstone National Park. These mats occur over temperatures of approx.35-60 C and are dominated by species of Phormidium. Within Bonded systems two end member environments have been distinguished based temperature, depth, and the stability of spring inflows, each differing substantially in the style of stromatolite morphogenesis and fossilization. Type 1 systems include shallow, ephemeral ponds where water flow and temperature fluctuates widely on a seasonal basis; mats typically secrete rapidly up to the air-water interface, forming exposed islands. Silicification occurs primarily by the wicking of water onto the surface of exposed mats, leading to the evaporative concentration of silica near the surface. pH microelectronic measurements in partially-exposed columns show strong gradients in pH with values exceeding 10.5 in the upper am of silicifying mats, decreasing to <9.0 a few mm below the surface. High oxygen concentrations lead to the rapid oxidation of most organic materials. In Type I systems, the tops of coniform and columnar stromatolites become silicified first, followed by the bases. This typically leads to extensive fragmentation during the initial stages of burial. Case 2 systems include deeper ponds where the water flow, temperature and depth are seasonally more stable, and where mats develop larger-scale tufts and columns. Alkalinity in permanently submerged mats increases into tuft interiors from approx.9.0 near the surface to >10.0 at depth. Moderate silicification is apparent throughout mat frameworks, although there is frequently a densely silicified core near the base. In Type 2 systems, preservation of the coniform and columnar architecture of stromatoilites is much more robust. Sub-fossil examples suggest minimal fragmentation prior to burial. Comparative rapid analysis of the phone zones of submerged and exposed (silicifying) mats demonstrated the recovery of comparable levels of esterified fatty acids in both types of mats. Membrane lipids apparently remain intact during the early stages of silicification, although their fate during early diagenesis is still being evaluated.

Farmer, Jack↗

NASA NTRS2003

The Disposition of Pt, Pd, Ir, Os, and Ru in Marine Sediments and the K/T Boundary

The marine record of platinum group elements (PGEs) and Os isotopic compositions provides information on different inputs of PGEs into the oceans. Some studies based on a smaller subset of the PGEs suggest that the PGEs may suffer post-depositional mobility during diagenesis. In some K/T boundary clays, Kyte and others showed that the relative abundances of Pt, Pd, Ir, and Os can differ significantly from chondritic, which is the signature expected from fallout of the meteorite impact. In some K/T boundary sections, elevated Ir concentrations are observed as far as 1 meter from the cm-thick boundary clay containing the meteoritic ejecta. The purpose of this study was to characterize Pt, Pd, Ir, Os, and Ru abundances in zones including the K/T boundary. We determined PGE abundances of boundary clays at two hemipelagic sites (Stevns Klint, Denmark and Caravaca, Spain) in which previous studies by Kyte and others showed that the Ir anomaly is confined to within a few cm. We also analyzed two pelagic Pacific sites: a boundary clay from the north Pacific (Hole 465A) characterized by a 0.5 m thick Ir anomaly and a transect across the K/T boundary from the south Pacific (Hole 596) where the Ir anomaly spans 2 m. The Stevns Klint, Caravaca, and north Pacific sites are characterized by abundant marls and limestones in the section, whereas the south Pacific site is dominated by clays. Samples were spiked with isotopic tracers, mixed with a flux, S and Ni, and equilibrated by fusion. PGEs were extracted from the Ni and analyzed on a Finnigan Element ICP-MS. We find that the narrow Caravaca and Stevns Klint boundary clays have relative PGE abundance patterns indistinguishable from chondritic values. The two Pacific sites were found to have nearly identical PGE patterns but have ratios at the peak, which differ from chondritic values as found earlier by Evans et al. The Pacific sites were found to have nearly identical PGE patterns but are extremely depleted in OS (Os/Ir = 0.07-0.15) and slightly enriched in Pd and Pt relative to Ir.

Lee, Cin-Ty↗

NASA NTRS2003

A Search for Soot from Global Wildfires in Central Pacific Cretaceous-Tertiary Boundary and Other Extinction and Impact Horizon Sediments

Hypotheses of global wildfires following the Cretaceous-Tertiary (KT) boundary impact are supported by high concentrations of elemental carbon (3.6 mg cm-3) and soot (1.8 mg cm-2) in DSDP Site 465, which was located several thousand kilometers from potential continental sources at 65 Ma. Soot is not preserved at four other central Pacific KT localities, but this is attributed to loss during oxic diagenesis. We find no evidence for wildfires related to major impacts in the late Eocene or to Ir anomalies and extinctions in the late Cenomanian.

Wolbach, Wendy S.↗

NASA NTRS2003

A Case for Hydrothermal Gray Hematite in Aram Chaos

The Thermal Emission Spectrometer (TES) on Mars Global Surveyor has detected deposits of coarsegrained, gray crystalline hematite in Sinus Meridiani, Aram Chaos, and Vallis Marineris [1]. Detailed features in the hematite spectral signature of the Sinus Meridiani region show that the spectrum is consistent with emission dominated by crystal c-faces of hematite, implying that the hematite is specular [2]. Gray specular hematite (also known as specularite ) is a particular gray crystalline form that has intergrown, hexagonal plates with a silvery metallic luster. We believe that the key to the origin of specularite is that it requires crystallization at temperatures in excess of about 100 C. In reviewing the occurrence of gray hematite on Earth, we find no exceptions to this warm temperature requirement [3]. Thermal crystallization on Mars could occur (1) as diagenesis at a depth of a few kilometers of sediments originally formed in lowtemperature waters, or (2) as direct precipitation from hydrothermal solution. Aram Chaos has unique chaotic terrain that offers more clues to the formation of the hematite than the relatively featureless flat terrain (as seen from orbit) of Sinus Meridiani. Aram Chaos provides the opportunity to look at a combination of TES data, Mars Orbiter Camera images, and Mars Orbiter Laser Altimeter (MOLA) topography. This combination of data suggests that high concentrations of hematite were formed in planar strata and have since been exposed by erosion of an overlying light-toned, caprock. Lesser concentrations of hematite are found adjacent to these strata at lower elevations, which we interpret as perhaps a lag deposit. The topography and the collapsed nature of the chaotic terrain favor a hydrothermally charged aquifer as the original setting where the hematite formed. An alternative sedimentary origin requires post-depositional burial to a depth of ~3-5 km to induce thermally driven recrystallization of fine-grained iron oxides to coarse-grained hematite.

D C Catling↗

NASA NTRS2004

Aqueous Chemical Modeling of Sedimentation on Early Mars with Application to Surface-Atmosphere Evolution

This project was to investigate models for aqueous sedimentation on early Mars from fluid evaporation. Results focused on three specific areas: (1) First, a fluid evaporation model incorporating iron minerals was developed to compute the evaporation of a likely solution on early Mars derived from the weathering of mafic rock. (2) Second, the fluid evaporation model was applied to salts within Martian meteorites, specifically salts in the nakhlites and ALH84001. Evaporation models were found to be consistent with the mineralogy of salt assemblages-anhydrite, gypsum, Fe-Mg-Ca carbonates, halite, clays-- and the concentric chemical fractionation of Ca-to Mg-rich carbonate rosettes in ALH84001. We made progress in further developing our models of fluid concentration by contributing to updating the FREZCHEM model. (3) Third, theoretical investigation was done to determine the thermodynamics and kinetics involved in the formation of gray, crystalline hematite. This mineral, of probable ancient aqueous origin, has been observed in several areas on the surface of Mars by the Thermal Emission Spectrometer on Mars Global Surveyor. The "Opportunity" Mars Exploration Rover has also detected gray hematite at its landing site in Meridiani Planum. We investigated how gray hematite can be formed via atmospheric oxidation, aqueous precipitation and subsequent diagenesis, or hydrothermal processes. We also studied the geomorphology of the Aram Chaos hematite region using Mars Orbiter Camera (MOC) images.

Catling, David C.↗

NASA NTRS2004

Stable Isotope Composition of Carbonates Formed in Low-Temperature Terrestrial Environments as Martian Analogs

We examine the carbon and oxygen isotope composition of carbonate minerals that formed in two low-temperature terrestrial environments. Field locations were chosen to represent environments where microcrystalline carbonates (caliches) form. Samples include caliche crusts collected from the tsekel zone of N. Yucatan, Mexico, as well as carbonate mud from the edge of a near-by salt pan, representing both ancient and modern-precipitated carbonates. Additional field samples of surface-coating caliche were collected from two volcanic fields in Arizona. Preliminary results indicate that there is an overall depletion of 18O and 13C as a function of the extent of meteoric diagenesis. These data are used as terrestrial analogs to gauge whether carbonates that have been found within Martian meteorites could possibly have formed under these or similar conditions on Mars.

Socki, Richard A.↗

NASA NTRS2003

Insights into the Processing of Carbon by Early Microbial Ecosystems

Interactions between Earth and the biosphere that were crucial for early biological evolution also influenced substantially the processes that circulate C between its reservoirs in the atmosphere, ocean, crust and mantle. The C-13 C-12 values of crustal carbonates and organics have recorded changes both in biological discrimination and in the relative rates of burial of organics and carbonates. A full interpretation of these patterns needs further isotopic studies of microbial ecosystems and individual anaerobes. Thus we measured carbon isotope discrimination during autotrophic and heterotrophic growth of pure cultures of sulfate-reducing bacteria and archaea (SRB and SRA). Discrimination during CO2 assimilation is significantly larger than during heterotrophic growth on lactate or acetate. SRB grown lithoautotrophically consumed less than 3% of available CO2 and exhibited substantial discrimination, as follows: Desulfobacterium autotrophicum (alpha 1.0100 to 1.0123), Desulfobacter hydrogenophilus (alpha = 0.0138), and Desulfotomuculum acetoxidans (alpha = 1.0310). Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO2 resulted in biomass with delta C-13 composition intermediate to that of the substrates. We have recently extended these experiments to include the thermophilic SRA Archeoglobus spp. Ecological forces also influence isotopic discrimination. Accordingly, we quantified the flow of C and other constituents in modern marine cyanobacterial mats, whose ancestry extends back billions of years. Such ecosystem processes shaped the biosignatures that entered sediments and atmospheres. At Guerrero Negro, BCS, Mexico, we examined mats dominated by Microcoleus (subtidal) and Lyngbya (intertidal to supratidal) cyanobacteria. During 24 hour cycles, we observed the exchange of O2 and dissolved inorganic C (DIC) between mats and the overlying water. Microcoleus mats assimilated near-equal amounts of DIC during the day as they released at night, but Lyngbya mats typically showed net uptake of DIC over the diel cycle. Patterns of O2 daytime release and nighttime uptake mirrored these DIC trends in both mat types. Nighttime DIC effluxes from Microcoleus mats were equivalent in the presence versus absence of O2, whereas nighttime DIC effluxes from Lyngbya mats dropped markedly in the absence of O2. Thus aerobic diagenesis was more important in Lyngbya mats than in Microcoleus mats, perhaps because trapped O2 bubbles persist only in Lyngbya mats at night and thus sustain populations of aerbes. In both mat types, effluxes of H2, CH4 and short-chain fatty acids were much greater at night in the absence of 02, emphasizing the importance of fermentation. Differences observed between Microcoleus versus Lyngbya mats forecast differences in their microbial populations and in their patterns of gene expression.

DesMarais, D.↗

NASA NTRS1999

A Mossbauer investigation of iron-rich terrestrial hydrothermal vent systems: lessons for Mars exploration

Hydrothermal spring systems may well have been present on early Mars and could have served as a habitat for primitive life. The integrated instrument suite of the Athena Rover has, as a component on the robotic arm, a Mossbauer spectrometer. In the context of future Mars exploration we present results of Mossbauer analysis of a suite of samples from an iron-rich thermal spring in the Chocolate Pots area of Yellowstone National Park (YNP) and from Obsidian Pool (YNP) and Manitou Springs, Colorado. We have found that Mossbauer spectroscopy can discriminate among the iron-bearing minerals in our samples. Those near the vent and on the surface are identified as ferrihydrite, an amorphous ferric mineraloid. Subsurface samples, collected from cores, which are likely to have undergone inorganic and/or biologically mediated alteration (diagenesis), exhibit spectral signatures that include nontronite (a smectite clay), hematite (alpha-Fe2O3), small-particle/nanophase goethite (alpha-FeOOH), and siderite (FeCO3). We find for iron minerals that Mossbauer spectroscopy is at least as efficient in identification as X-ray diffraction. This observation is important from an exploration standpoint. As a planetary surface instrument, Mossbauer spectroscopy can yield high-quality spectral data without sample preparation (backscatter mode). We have also used field emission scanning electron microscopy (FESEM), in conjunction with energy-dispersive X ray (EDX) fluorescence spectroscopy, to characterize the microbiological component of surface sinters and the relation between the microbiological and the mineralogical framework. Evidence is presented that the minerals found in these deposits can have multi-billion-year residence times and thus may have survived their possible production in a putative early Martian hot spring up to the present day. Examples include the nanophase property and the Mossbauer signature for siderite, which has been identified in a 2.09-billion-year old hematite-rich chert stromatolite. Our research demonstrates that in situ Mossbauer spectroscopy can help determine whether hydrothermal mineral deposits exist on Mars, which is significant for exobiology because of the issue of whether that world ever had conditions conductive to the origin of life. As a useful tool for selection of samples suitable for transport to Earth, Mossbauer spectroscopy will not only serve geological interests but will also have potential for exopaleontology.

NASA Discipline Exobiology↗

NASA NTRS1989

Geochemical and isotopic evidence for paleoredox conditions during deposition of the Devonian-Mississippian New Albany Shale, southern Indiana

The upper part of the New Albany Shale is divided into three members. In ascending order, these are (1) the Morgan Trail Member, a laminated brownish-black shale; (2) the Camp Run Member, an interbedded brownish-black and greenish-gray shale; and (3) the Clegg Creek Member, also a laminated brownish-black shale. The Morgan Trail and Camp Run Members contain 5% to 6% total organic carbon (TOC) and 2% sulfide sulfur. Isotopic composition of sulfide in these members ranges from -5.0% to -20.0%. C/S plots indicate linear relationships between abundances of these elements, with a zero intercept characteristic of sediments deposited in a non-euxinic marine environment. Formation of diagenetic pyrite was carbon limited in these members. The Clegg Creek Member contains 10% to 15% TOC and 2% to 6% sulfide sulfur. Isotopic compositions of sulfide range from -5.0% to -40%. The most negative values occur in the uppermost Clegg Creek Member and are characteristic of syngenetic pyrite, formed within an anoxic water column. Abundances of carbon and sulfur are greater and uncorrelated in this member, consistent with deposition in as euxinic environment. In addition, DOP (degree of pyritization) values suggest that formation of pyrite was generally iron limited throughout Clegg Creek deposition, but sulfur isotopes indicate that syngenetic (water-column) pyrite becomes an important component in the sediment only in the upper part of the member. At the top of the Clegg Creek Member, a zone of phosphate nodules and trace-metal enrichment coincides with maximal TOC values. During euxinic deposition, phosphate and trace metals accumulated below the chemocline because of limited vertical circulation in the water column. Increased productivity would have resulted in an increased flux of particulate organic matter to the sediment, providing an effective sink for trace metals in the water column. Phosphate and trace metals released from organic matter during early diagenesis resulted in precipitation of metal-rich phosphate nodules.

NASA Discipline Exobiology↗