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Microstructural Constraints on the Formation of Diamond in Ureilites, the Case from the Kenna Meteorite

The origin of diamonds in ureilitic meteorites, a major family of ultramafic achondrites, has long been debated, with various formation mechanisms inferred, including: 1) shock conversion of preexisting graphite due to a hypervelocity impact on the ureilite parent body; 2) vapor deposition during condensation of the solar nebula; or 3) static transformation in the mantle of a large planetesimal (>1000 km in diameter). The Kenna ureilite is a 10.9 kg stone that was found in Kansas in 1972 and is dominantly composed of olivine and pigeonite (68% and 22% modal abundance, respectively), together with minor metal and carbon-rich regions. Within the carbon-rich domains researchers have identified microdiamonds up to ~10 µm in size. Due to the proximity of the extremely hard microdiamonds with soft graphite and moderately hard silicates, achieving an appropriately flat surface for electron backscatter diffraction (EBSD) analysis has proved challenging. We have, therefore, employed a Hitachi ArBlade 5000 broad beam Ar ion milling system to prepare a sample with an adequate surface uniformity. The ion milling dramatically improved indexing of the EBSD patterns and facilitated high-resolution microstructural analysis of the carbon-rich domains. The carbon-bearing regions occur as tabular domains between polygonal olivine and pigeonite, and are composed of aggregates of micrometer-scale diamond with intermediate graphite, oxides and metal grains. Within the microdiamonds, {111} twins are abundant, many of which form ragged lamellae consistent with mechanical twinning. The microdiamond assemblages appear to pseudomorph tabular graphite habits, which together with the abundant deformation twins, supports a shock transformation mechanism for microdiamond formation within the Kenna meteorite. To compliment the EBSD microstructural analyses, coordinated laser Raman, focused ion beam/transmission electron microscopy imaging and diffraction data, and NanoSIMS N and C tomographic isotopic imaging will be collected. These data will provide further constraints on the formation of diamonds within ureilites.

Timmons M Erickson↗

Discovery of hydrated Clasts with Very High Abundance of Ferromagnesian 160-Rich Olivine: Inner or Outer Solar System origin?

Olivine is one of the major minerals in chondritic meteorites and occurs in all chondritic components, including amoeboid olivine aggregates (AOAs), forsterite-bearing Type B (FoB) Ca, Al-rich inclusions (CAIs), chondrules, and matrices. As a result, olivines could preserve chemical and isotopic characteristics of their formation environments. There are significant variations in oxygen isotopic compositions of chondritic olivine. Forsteritic olivine in AOAs and FoB-CAIs has solar-like 16O-rich compositions (D17O ~ -23±2‰); the former condensed from an 16O-rich gas of ~solar composition, whereas the latter crystallized from remelted condensates in an isotopic similar gaseous reservoir. Olivine phenocrysts in chondrules are significantly 16O-depleted compared to CAIs and AOAs: D17O ranges from ~ -7 to +3‰. Only rare relict olivines in chondrules have CAI/AOA-like 16O-rich compositions; these grains most likely represent fragments of CAIs and AOAs incompletely melted during chondrule formation. Olivine in matrices of weakly metamorphosed meteorites is extremely fine-grained (<100 nm) and has predominantly forsteritic composition. In metamorphosed chondrites, matrix olivines are coarse-grained (up to 10 μm) and enriched in FeO. Due to small grain sizes, oxygen isotopic compositions of matrix olivines are poorly known. Mapping of matrices of Vigarano and Kakangari using isotope microscopes (secondary ion mass-spectrometer (SIMS) plus SCAPS detector) revealed the presence of 16O-rich olivine grains. While most matrix olivines in Vigarano have 16O-poor compositions, nearly half of olivines measured in Kakangari matrix are16O-rich.Here, we present for the first time new lithologies largely composed of 16O-and Fe-rich olivine. We attempt to address the question of whether these 16O-richolivine grains were formed by condensation in the solar nebula or by a secondary process during the evolution of the parent body. Mineralogical characteristics of these unusual olivines, as well as in-situ measured oxygen-isotope compositions of different phases are reported in detail.

I. Kerraouch↗

The Mineralogy of Circumstellar Silicates Preserved in Cometary Dust

Interplanetary dust particles (IDPs) contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula. Cometary IDPs have remained relatively unaltered since their accretion because of the lack of parent body thermal and aqueous alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these particles because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars. Five circumstellar grains have been identified including three amorphous silicate grains and two polycrystalline aggregates. All of these grains are between 0.2 and 0.5 micrometers in size. The isotopic compositions of all five presolar silicate grains fall within the range of presolar oxides and silicates, having large (17)O-enrichments and normal (18)O/(16)O ratios (Group 1 grains from AGB and RG stars). The amorphous silicates are chemically heterogeneous and contain nanophase FeNi metal and FeS grains in a Mg-silicate matrix. Two of the amorphous silicate grains are aggregates with subgrains showing variable Mg/Si ratios in chemical maps. The polycrystalline grains show annealed textures (equilibrium grains boundaries, uniform Mg/Fe ratios), and consist of 50-100 nm enstatite and pyrrhotite grains with lesser forsterite. One of the polycrystalline aggregates contains a subgrain of diopside. The polycrystalline aggregates form by subsolidus annealing of amorphous precursors. The bulk compositions of the five grains span a wide range in Mg/Si ratios from 0.4 to 1.2 (avg. 0.86). The average Fe/Si (0.40) and S/Si (0.21) ratios show a much narrower range of values and are approximately 50% of their solar abundances. The latter observation may indicate a decoupling of the silicate and sulfide components in grains that condense in stellar outflows. The amorphous silicate grains described here were not extensively affected by irradiation, sputtering, or thermal processing and may represent relatively pristine circumstellar grains. They are strong candidates for the "dirty silicates" in astronomical observations of circumstellar dust shells. The polycrystalline grains were originally amorphous silicate grains that were likely annealed in the early solar nebula but the processing was not sufficient to erase their anomalous oxygen isotopic compositions.

Keller, L. P.↗

Strong Sensitivity of the Isotopic Composition of Methane to the Plausible Range of Tropospheric Chlorine

The C-13 isotopic ratio of methane, δC-13 of CH4, provides additional constraints on the CH4 budget to complement the constraints from CH4 observations. The interpretation of δC-13 observations is complicated, however, by uncertainties in the methane sink. The reaction of CH4 with Cl is highly fractionating, increasing the relative abundance of 13CH4, but there is currently no consensus on the strength of the tropospheric Cl sink. Global model simulations of halogen chemistry differ strongly from one another in terms of both the magnitude of tropospheric Cl and its geographic distribution. This study explores the impact of the inter-model diversity in Cl fields on the simulated δC-13 of CH4. We use a set of GEOS global model simulations with different predicted Cl fields to test the sensitivity of the δC-13 of CH4 to the diversity of Cl output from chemical transport models. We find that δC-13 is highly sensitive to both the amount and geographic distribution of Cl. Simulations with Cl providing 0.28% or 0.66% of the total CH4 loss bracket the δC-13 observations for a fixed set of emissions. Thus, even when Cl provides only a small fraction of the total CH4 loss and has a small impact on total CH4, it provides a strong lever on δC-13. Consequently, it is possible to achieve a good representation of total CH4 using widely different Cl concentrations, but the partitioning of CH4 loss between the OH and Cl reactions leads to strong differences in isotopic composition depending on which model’s Cl field is used. Comparing multiple simulations, we find that altering the tropospheric Cl field leads to approximately a 0.5‰ increase in δ(13)CH4for each percent increase in how much CH4 is oxidized by Cl. The geographic distribution and seasonal cycle of Cl also impacts the hemispheric gradient and seasonal cycle of δC-13. The large effect of Cl on δC-13 compared to total CH4 broadens the range of CH4 source mixtures that can be reconciled with δC-13 observations. Stronger constraints on tropospheric Cl are necessary to improve estimates of CH4 sources from δC-13 observations.

Global model simulations of halogen chemistry↗

Chemical and isotopic constraints on the formation and crystallization of SA-1, a basaltic Allende plagioclase-olivine inclusion

Results are presented of a detailed petrologic, chemical, and Mg-isotope study of SA-1, a basaltic Allende plagioclase-olivine inclusion. The chemical and isotopic data were used to identify the signatures of nebular vs. planetary processes and to determine if SA-1 contains a component produced by planetary differentiation. It was found that the results of major-element and trace-element abundances in SA-1 are inconsistent with its formation as a mixture of nebular materials. It is suggested that SA-1 contains a chemically fractionated component produced by igneous differentiation.

Kennedy, Allen K.↗

Laser Time-of-Flight Mass Spectrometry for Space

A miniature reflection time-of-flight mass spectrometer for in situ planetary surface analysis is described. The laser ablation mass spectrometer (LAMS) measures the regolith's elemental and isotopic composition without high-voltage source extraction or sample preparation. The compact size (< 2 x 10(exp 3) cubic cm) and low mass (approximately 2 kg) of LAMS, due to its fully coaxial design and two-stage reflectron, fall within the strict resource limitations of landed science missions to solar system bodies. A short-pulse laser focused to a spot with a diameter approximately 30-50 micrometers is used to obtain microscopic surface samples. Assisted by a microimager, LAMS can interactively select and analyze a range of compositional regions (with lateral motion) and with repeated pulses can access unweathered, subsurface materials. The mass resolution is calibrated to distinguish isotopic peaks at unit masses, and detection limits are on resolved to a few ppm. The design and calibration method of a prototype LAMS device is described, which include the development of preliminary relative sensitivity coefficients for major element bulk abundance measurements.

Brinckerhoff, W. B.↗

Coordinated Analysis of Phosphates in Samples From Asteroid (101955) Bennu

Asteroid (101955) Bennu is a B-type asteroid and a prime candidate for investigating the remnants of planet formation and enhancing our understanding of potential sources of crucial bio-essential elements for the early Earth. Remote observations of the surface of Bennu unveiled a terrain of boulders primarily composed of hydrated phyllosilicates, organic molecules, and carbonates. The hydrated nature of Bennu, the abundance of carbonates, and the presence of cm-scale carbonate veins provide clues to the nature of the building blocks of Bennu’s parent body and to its complex geological history. Here we present the first mineralogical, chemical, and isotopic results of analysis of phosphates in samples returned from Bennu by NASA’s OSIRIS-REx mission. We seek to test the hypothesis that heating of Bennu’s parent asteroid resulted in hydrothermal alteration in which melted ice reacted with the initial constituents.

J. J. Barnes↗

Chemical composition measurements of the atmosphere of Jupiter with the Galileo Probe mass spectrometer

The Galileo Probe entered the atmosphere of Jupiter on December 7, 1995. Measurements of the chemical and isotopic composition of the Jovian atmosphere were obtained by the mass spectrometer during the descent over the 0.5 to 21 bar pressure region over a time period of approximately 1 hour. The sampling was either of atmospheric gases directly introduced into the ion source of the mass spectrometer through capillary leaks or of gas, which had been chemically processed to enhance the sensitivity of the measurement to trace species or noble gases. The analysis of this data set continues to be refined based on supporting laboratory studies on an engineering unit. The mixing ratios of the major constituents of the atmosphere hydrogen and helium have been determined as well as mixing ratios or upper limits for several less abundant species including: methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. Analysis also suggests the presence of trace levels of other 3 and 4 carbon hydrocarbons, or carbon and nitrogen containing species, phosphine, hydrogen chloride, and of benzene. The data set also allows upper limits to be set for many species of interest which were not detected. Isotope ratios were measured for 3He/4He, D/H, 13C/12C, 20Ne/22Ne, 38Ar/36Ar and for isotopes of both Kr and Xe.

unmanned↗

Abundant ammonia and nitrogen-rich soluble organic matter in samples from asteroid (101955) Bennu

Organic matter in meteorites reveals clues about early Solar System chemistry and the origin of molecules important to life, but terrestrial exposure complicates interpretation. Samples returned from the B-type asteroid Bennu by the Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer mission enabled us to study pristine carbonaceous astromaterial without uncontrolled exposure to Earth’s biosphere. Here we show that Bennu samples are volatile rich, with more carbon, nitrogen and ammonia than samples from asteroid Ryugu and most meteorites. Nitrogen-15 isotopic enrichments indicate that ammonia and other N-containing soluble molecules formed in a cold molecular cloud or the outer protoplanetary disk. We detected amino acids (including 14 of the 20 used in terrestrial biology), amines, formaldehyde, carboxylic acids, polycyclic aromatic hydrocarbons and N-heterocycles (including all five nucleobases found in DNA and RNA), along with ~10,000 N-bearing chemical species. All chiral non-protein amino acids were racemic or nearly so, implying that terrestrial life’s left-handed chirality may not be due to bias in prebiotic molecules delivered by impacts. The relative abundances of amino acids and other soluble organics suggest formation and alteration by low-temperature reactions, possibly in NH 3 -rich fluids. Bennu’s parent asteroid developed in or accreted ices from a reservoir in the outer Solar System where ammonia ice was stable.

79 ASTRONOMY AND ASTROPHYSICS↗

Abundant Ammonia and Nitrogen-Rich Soluble Organic Matter in Samples From Asteroid (101955) Bennu

Organic matter in meteorites reveals clues about early Solar System chemistry and the origin of molecules important to life, but terrestrial exposure complicates interpretation. Samples returned from the B-type asteroid Bennu by the Origins, Spectral Interpretation, Resource Identifcation, and Security–Regolith Explorer mission enabled us to study pristine carbonaceous astromaterial without uncontrolled exposure to Earth’s biosphere. Here we show that Bennu samples are volatile rich, with more carbon, nitrogen and ammonia than samples from asteroid Ryugu and most meteorites. Nitrogen-15 isotopic enrichments indicate that ammonia and other N-containing soluble molecules formed in a cold molecular cloud or the outer protoplanetary disk. We detected amino acids (including 14 of the 20 used in terrestrial biology), amines, formaldehyde, carboxylic acids, polycyclic aromatic hydrocarbons and N-heterocycles (including all fve nucleobases found in DNA and RNA), along with ~10,000 N-bearing chemical species. All chiral non-protein amino acids were racemic or nearly so, implying that terrestrial life’s left-handed chirality may not be due to bias in prebiotic molecules delivered by impacts. The relative abundances of amino acids and other soluble organics suggest formation and alteration by low-temperature reactions, possibly in NH3-rich fuids. Bennu’s parent asteroid developed in or accreted ices from a reservoir in the outer Solar System where ammonia ice was stable.

Daniel P Glavin↗

Recombination between 13 C and 2 H to Form Acetylide ( 13 C 2 2 H – ) Probes Nanoscale Interactions in Lipid Bilayers via Dynamic Secondary Ion Mass Spectrometry: Cholesterol and GM 1 Clustering

Although it is thought that there is lateral heterogeneity of lipid and protein components within biological membranes, probing this heterogeneity has proven challenging. The difficulty in such experiments is due to both the small length scale over which such heterogeneity can occur, and the significant perturbation resulting from fluorescent or spin labeling on the delicate interactions within bilayers. Atomic recombination during dynamic nanoscale secondary ion imaging mass spectrometry (NanoSIMS) is a non-perturbative method for examining nanoscale bilayer interactions. Atomic recombination is a variation on conventional NanoSIMS imaging, whereby an isotope on one molecule combines with a different isotope on another molecule during the ionization process, forming an isotopically enriched polyatomic ion in a distance-dependent manner. In this work, we show that the recombinant ion, 13 C 2 2 H – , is formed in high yield from 13 C- and 2 H-labeled lipids. The low natural abundance of triply labeled acetylide also makes it an ideal ion to probe GM 1 clusters in model membranes and the effects of cholesterol on lipid–lipid interactions. We find evidence supporting the cholesterol condensation effect as well as the presence of nanoscale GM 1 clusters in model membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interstellar Ice and Dust: The Feedstock of the Solar System

Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. There is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.

Allamandola, L. J.↗

Astronomical Problems and Laboratory Solutions

Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. there is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.

Allamandola, L. J.↗

Lunar and Planetary Surface Dynamics and Early History

This document, submitted as part of this proposal renewal represents the Final Report required by NASA for Grant NAGS-9442. It should be emphasized that, while this work statement in the original proposal outlined anticipated directions of our research, the specific activities we carried out during this period differed slightly from those proposed, capitalizing on new unexpected results and new advances in analytical capability. The thrust of all the work we completed were completely within the stated research goals of the proposal and significantly advanced our knowledge of planetary processes and our understanding of the early solar system. The following summary outlines our achievements in the different areas of research. These include: A) Early solar system processes and time scales using I-Xe chronometry; B) The Active Capture of Volatiles: A new mechanism for the capture of heavy noble gases, possible implications for phase Q and planetary heavy noble gases; C) Separation of Xe-L from Xe-H: Physically selective experiments; D) Abundances of Presolar grains; E) Studies of Neon and Helium from single interstellar SiC and graphite grains; F) Pre-compaction exposure of meteoritic grains and chondrules; G) Geochemically Measured Half-Lives: Double beta-decay of Te and Ba isotopes; H) Noble gases in stratospheric interplanetary dust particles; I) New Analytical Instrument.

Source record↗

Molecular and Dual-Isotopic Profiling of the Microbial Controls on Nitrogen Leaching in Agricultural Soils under Managed Aquifer Recharge

Nitrate (NO 3 – ) leaching is a serious health and ecological concern in global agroecosystems, particularly those under the application of agricultural-managed aquifer recharge (Ag-MAR); however, there is an absence of information on microbial controls affecting NO 3 – leaching outcomes. We combine natural dual isotopes of NO 3 – ( 15 N/ 14 N and 18 O/ 16 O) with metagenomics, quantitative polymerase chain reaction (PCR), and a threshold indicator taxa analysis (TITAN) to investigate the activities, taxon profiles, and environmental controls of soil microbiome associated with NO 3 – leaching at different depths from Californian vineyards under Ag-MAR application. The isotopic signatures demonstrated a significant priming effect (P < 0.01) of Ag-MAR on denitrification activities in the topsoil (0–10 cm), with a 12–25-fold increase of 15 N–NO 3 – and 18 O–NO 3 – after the first 24 h of flooding, followed by a sharp decrease in the enrichment of both isotopes with ~80% decline in denitrification activities thereafter. In contrast, deeper soils (60–100 cm) showed minimal or no denitrification activities over the course of Ag-MAR application, thus resulting in 10–20-fold of residual NO 3 – being leached. Metagenomic profiling and laboratory microcosm demonstrated that both nitrifying and denitrifying groups, responsible for controlling NO 3 – leaching, decreased in abundance and potential activity rates with soil depth. TITAN suggested that Nitrosocosmicus and Bradyrhizobium, as the major nitrifier and denitrifier, had the highest and lowest tipping points with regard to the NO 3 – changes (P < 0.05), respectively. Overall, our study provides new insight into specific depth limitations of microbial controls on soil NO 3 – leaching in agroecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

Initial SAM Calibration Gas Experiments on Mars: Quadrupole Mass Spectrometer Results and Implications

The Sample Analysis at Mars (SAM) instrument suite of the Mars Science Laboratory (MSL) Curiosity rover is equipped to analyze both martian atmospheric gases and volatiles released by pyrolysis of solid surface materials, with target measurements including chemical and isotopic composition (Mahaffy et al., 2012). To facilitate assessment of instrument performance and validation of results obtained on Mars, SAM houses a calibration cell containing CO2, Ar, N2, Xe, and several fluorinated hydrocarbon compounds (Franz et al., 2014; Mahaffy et al., 2012). This report describes the first two experiments utilizing this calibration cell on Mars and gives results from analysis of data acquired with the SAM Quadrupole Mass Spectrometer (QMS). These data support the accuracy of isotope ratios obtained with the QMS (Conrad et al., 2016; Mahaffy et al., 2013) and provide ground-truth for reassessment of analytical constants required for atmospheric measurements, which were reported in previous contributions (Franz et al., 2015, 2014). The most significant implication of the QMS data involves reinterpretation of pre-launch contamination previously believed to affect only CO abundance measurements (Franz et al., 2015) to affect N2 abundances, as well. The corresponding adjustment to the N2 calibration constant presented here brings the atmospheric volume mixing ratios for Ar and N2 retrieved by SAM into closer agreement with those reported by the Viking mission (Owen et al., 1977; Oyama and Berdahl, 1977).

Sample Analysis at Mars Investigation↗

Ion-beam analysis of meteoritic and lunar samples

Charged particle-induced nuclear reactions were used in the following problems: the determination of elemental abundances of boron and fluorine in carbonaceous chondritic meteorites; the identification of products of lunar vulcanism; and the study of solar wind-implanted atoms in lunar materials. The technique was seen as an important supplement to other methods of elemental and isotopic analysis. This was especially true for cases involving light elements at very low concentrations or where high resolution depth distribution information was needed in non-destructive analysis.

Tombrello, T. A.↗

An isotopic biogeochemical study of the Green River oil shale

Thirty-five different samples from three different sulfur cycles were examined in this stratigraphically oriented study of the Shell 22x-l well (U.S.G.S. C177 core) in the Piceance Basin, Colorado. Carbon isotopic compositions of constituents of Green River bitumens indicate mixing of three main components: products of primary photoautotrophs and their immediate consumers (delta approximately -30% vs PDB), products of methanotrophic bacteria (delta approximately -85%), and products of unknown bacteria (delta approximately -40%). For individual compounds synthesized by primary producers, delta-values ranged from -28 to -32%. 13C contents of individual primary products (beta-carotane, steranes, acyclic isoprenoids, tricyclic triterpenoids) were not closely correlated, suggesting diverse origins for these materials. 13C contents of numerous hopanoids were inversely related to sulfur abundance, indicating that they derived both from methanotrophs and from other bacteria, with abundances of methanotrophs depressed when sulfur was plentiful in the paleoenvironment. gamma-Cerane coeluted with 3 beta(CH3),17 alpha(H),21 beta(H)-hopane, but delta-values could be determined after deconvolution. gamma-Cerane (delta approximately -25%) probably derives from a eukaryotic heterotroph grazing on primary materials, the latter compound (delta approximately -90%) must derive from methanotrophic organisms. 13C contents of n-alkanes in bitumen differed markedly from those of paraffins generated pyrolytically. Isotopic and quantitative relationships suggest that alkanes released by pyrolysis derived from a resistant biopolymer of eukaryotic origin and that this was a dominant constituent of total organic carbon.

Non-NASA Center↗