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At least 163 records · Page 9

Geochemical evidence bearing on the origin of aerobiosis, a speculative hypothesis

It is pointed out that the atmosphere and hydrosphere of the early Archean earth were essentially anoxic. The paleontological record shows that life existed in spite of the absence of oxygen. The present investigation is concerned with the presentation of a plausible sequence of events, linking features in the carbon isotopic record to the origin of oxygenic photosynthesis. The investigation takes into account that the record of carbon isotopic abundances in sedimentary organic matter displays marked variations about 2.8 Ga before the present. At least by 2.8 Ga before the present, if not before, something in the carbon cycle began to allow the incorporation in sediments of organic material extraordinarily depleted in C-13. Attention is given to a model for the development of C-13 depleted kerogens, conclusions regarding the late Archean carbon cycle, and the transition in the global ecosystem.

Hayes, J. M.↗

Predictive isotopic biogeochemistry: hydrocarbons from anoxic marine basins

Carbon isotopic compositions were determined for individual hydrocarbons in water column and sediment samples from the Cariaco Trench and Black Sea. In order to identify hydrocarbons derived from phytoplankton, the isotopic compositions expected for biomass of autotrophic organisms living in surface waters of both localities were calculated based on the concentrations of CO2(aq) and the isotopic compositions of dissolved inorganic carbon. These calculated values are compared to measured delta values for particulate organic carbon and for individual hydrocarbon compounds. Specifically, we find that lycopane is probably derived from phytoplankton and that diploptene is derived from the lipids of chemoautotrophs living above the oxic/anoxic boundary. Three acyclic isoprenoids that have been considered markers for methanogens, pentamethyleicosane and two hydrogenated squalenes, have different delta values and apparently do not derive from a common source. Based on the concentration profiles and isotopic compositions, the C31 and C33 n-alkanes and n-alkenes have a similar source, and both may have a planktonic origin. If so, previously assigned terrestrial origins of organic matter in some Black Sea sediments may be erroneous.

Non-NASA Center↗

Biogeochemical Protocols and Diagnostics for the CMIP6 Ocean Model Intercomparison Project (OMIP)

The Ocean Model Intercomparison Project (OMIP) focuses on the physics and biogeochemistry of the ocean component of Earth system models participating in the sixth phase of the Coupled Model Intercomparison Project (CMIP6). OMIP aims to provide standard protocols and diagnostics for ocean models, while offering a forum to promote their common assessment and improvement. It also offers to compare solutions of the same ocean models when forced with reanalysis data (OMIP simulations) vs. when integrated within fully coupled Earth system models (CMIP6). Here we detail simulation protocols and diagnostics for OMIP's biogeochemical and inert chemical tracers. These passive-tracer simulations will be coupled to ocean circulation models, initialized with observational data or output from a model spin-up, and forced by repeating the 1948-2009 surface fluxes of heat, fresh water, and momentum. These so-called OMIP-BGC simulations include three inert chemical tracers (CFC-11, CFC-12, SF [subscript] 6) and biogeochemical tracers (e.g., dissolved inorganic carbon, carbon isotopes, alkalinity, nutrients, and oxygen). Modelers will use their preferred prognostic BGC model but should follow common guidelines for gas exchange and carbonate chemistry. Simulations include both natural and total carbon tracers. The required forced simulation (omip1) will be initialized with gridded observational climatologies. An optional forced simulation (omip1-spunup) will be initialized instead with BGC fields from a long model spin-up, preferably for 2000 years or more, and forced by repeating the same 62-year meteorological forcing. That optional run will also include abiotic tracers of total dissolved inorganic carbon and radiocarbon, CTabio and 14CTabio, to assess deep-ocean ventilation and distinguish the role of physics vs. biology. These simulations will be forced by observed atmospheric histories of the three inert gases and CO2 as well as carbon isotope ratios of CO2. OMIP-BGC simulation protocols are founded on those from previous phases of the Ocean Carbon-Cycle Model Intercomparison Project. They have been merged and updated to reflect improvements concerning gas exchange, carbonate chemistry, and new data for initial conditions and atmospheric gas histories. Code is provided to facilitate their implementation.

Carbon↗

Use of Molecular Fossils for the Interpretation of Paleoenvironments on Early Earth: The Synthesis of Lipid Biomarkers by Methane-Oxidizing Bacteria

Over the course of Earth's history, the most important biological influence has come from the evolution of oxygenic photosynthesis and the development of an oxygen-rich biosphere. Although the availability of free oxygen had profound effects on subsequent biological and planetary evolution, clear paleobiological evidence of the timing of this transition is lacking. Recent technical advances in the microanalysis of organic matter has made it possible to detect residual molecules (biomarkers) in proterozoic (2.5 to 0.6 billion years) sedimentary rock characteristic of specific groups of microorganisms. When coupled with the carbon isotopic fractionations characteristic of biological systems and the new field of compound specific isotope analysis, biomarkers could prove to be a powerful tool for decoding ancient biochemistry from the geological record. We have been studying the carbon isotope fractionations associated with the synthesis of organic biomarker molecules in several types of methane-oxidizing bacteria that should have been key to carbon cycling in paleoenvironments after the evolution of oxygenic photosynthesis.

Jahnke, Linda L.↗

On the origin and evolution of isotopes of carbon, nitrogen, and oxygen

Calculations of CNO processing in stellar envelopes, based on theoretical nucleosynthesis rather than empirical abundances in evolving stars, are presented and used in two models for the chemical evolution of the solar neighborhood. Seven stable isotopes are considered: C-12, C-13, N-14, N-15, O-16, O-17, and O-18. The two models ('infall' and 'initial-burst') represent extremes of types consistent with general constraints and include theoretical estimates of other nucleosynthesis sites and yields for CNO isotopes. The results obtained are found to predict that all CNO isotopes are produced mainly by stars with lifetimes much less than the age of the Galaxy (even at the present time when low-mass stars have the greatest death rate), so that isotopic ratios evolve very slowly after the first few billion years. Consequences of these slow changes are that the isotopic ratios cannot be employed to test between alternative hypotheses and that galactic evolution does not seem to be able to account for the apparent difference between the C-13/C-12 ratio in the solar system and in molecular clouds. The predicted envelope processing is shown to lead to approximately the solar-system values for the C-13/C-12 and O-17/O-16 abundance ratios but to a N-14/C-12 ratio that is too small by at least a factor of 2.

Dearborn, D.↗

Carbon and Oxygen Isotope Measurements of Ordinary Chondrite (OC) Meteorites from Antarctica Indicate Distinct Carbonate Species Using a Stepped Acid Extraction Procedure

The purpose of this study is to characterize the stable isotope values of terrestrial, secondary carbonate minerals from five Ordinary Chondrite (OC) meteorites collected in Antarctica. These samples were identified and requested from NASA based upon their size, alteration history, and collection proximity to known Martian meteorites. They are also assumed to be carbonate-free before falling to Earth. This research addresses two questions involving Mars carbonates: 1) characterize terrestrial, secondary carbonate isotope values to apply to Martian meteorites for isolating in-situ carbonates, and 2) increase understanding of carbonates formed in cold and arid environments with Antarctica as an analog for Mars. Two samples from each meteorite, each approximately 0.5 grams, were crushed and dissolved in pure phosphoric acid for 3 sequential reactions: a) R times 0 for 1 hour at 30 degrees Centigrade (fine calcite extraction), b) R times 1 for 18 hours at 30 degrees Centigrade (course calcite extraction), and c) R times 2 for 3 hours at 150 degrees Centigrade (siderite and/or magnesite extraction). CO (sub 2) was distilled by freezing with liquid nitrogen from each sample tube, then separated from organics and sulfides with a TRACE GC using a Restek HayeSep Q 80/100 6 foot 2 millimeter stainless column, and then analyzed on a Thermo MAT 253 Isotope Ratio Mass Spectrometer (IRMS) in Dual Inlet mode. This system was built at NASA/JSC over the past 3 years and proof-tested with known carbonate standards to develop procedures, assess yield, and quantify expected error bands. Two distinct species of carbonates are found: 1) calcite, and 2) non-calcite carbonate (future testing will attempt to differentiate siderite from magnesite). Preliminary results indicate the terrestrial carbonates are formed at approximately sigma (sup 13) C equal to plus 5 per mille, which is consistent with atmospheric CO (sub 2) sigma (sup 13) C equal to minus 7 per mille and fractionation of plus12 per mille based upon polar temperature of -20 degrees Centigrade. The oxygen values fractionate sigma (sup 18) O equal to minus 10-20 per mille lighter between the R times 0 and R times 1 reactions at 30 degrees Centigrade. The carbonate oxygen isotope measurements are consistently heavier than expected with meteoric water and temperatures from Antarctica, perhaps due to secondary carbonate formation during curation in Houston, TX.

Evans, Michael E.↗

Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

NASA Program Exobiology↗

Carbon and its isotopes in mid-oceanic basaltic glasses

Sample surface carbon, mantle carbon dioxide in vesicles, and mantle carbon dissolved in glasses, are the three carbon components evident in the 11 mid-oceanic basalts presently analyzed. The total carbon content may be controlled by the depth of the shallowest ridge magma chamber, and carbon isotopic fractionation accompanies magma degassing. Using He-3 and carbon data for submarine hydrothermal fluids, the present day midoceanic ridge carbon flux is approximately estimated to be 1.0 x 10 to the 13th g C/yr, requiring 8 Gyr to accumulate the earth's present crustal carbon inventory.

Des Marais, D. J.↗

Climatic changes resulting from mass extinctions at the K-T boundary (and other bio-events)

The mass extinctions at the Cretaceous-Tertiary (K-T) boundary include about 90 percent of marine calcareous nannoplankton (coccoliths), and carbon-isotope data show that marine primary productivity was drastically reduced for about 500,000 years after the boundary event, the so-called Strangelove Ocean effect. One result of the elimination of most marine phytoplankton would have been a severe reduction in production of dimethyl sulfide (DMS), a biogenic gas that is believed to be the major precursor of cloud condensation nuclei (CCN) over the oceans. A drastic reduction in marine CCN should lead to a cloud canopy with significantly lower reflectivity, and hence cause a significant warming at the earth's surface. Calculations suggest that, all other things being held constant, a reduction in CCN of more than 80 percent (a reasonable value for the K-T extinctions) could have produced a rapid global warming of 6 C or more. Oxygen-isotope analyses of marine sediments, and other kinds of paleoclimatic data, have provided for a marked warming, and a general instability of climate coincident with the killoff of marine plankton at the K-T boundary. Similar reductions in phytoplankton abundance at other boundaries, as indicated by marked shifts in carbon-isotope curves, suggest that severe temperature changes may have accompanied other mass extinctions, and raises the intriguing possibility that the extinction events themselves could have contributed to the climatic instabilities at critical bio-events in the geologic record.

Rampino, Michael R.↗

Comparative Earth history and Late Permian mass extinction

The repeated association during the late Neoproterozoic Era of large carbon-isotopic excursions, continental glaciation, and stratigraphically anomalous carbonate precipitation provides a framework for interpreting the reprise of these conditions on the Late Permian Earth. A paleoceanographic model that was developed to explain these stratigraphically linked phenomena suggests that the overturn of anoxic deep oceans during the Late Permian introduced high concentrations of carbon dioxide into surficial environments. The predicted physiological and climatic consequences for marine and terrestrial organisms are in good accord with the observed timing and selectivity of Late Permian mass extinction.

Non-NASA Center↗

Chemical abundance of comets

Observations of NH2, (OI) and molecular ion spectra in comets represent virtually all of the volatile fraction of a comet nucleus. Their study leads to the N2, NH3, H2O, CO2, CO content of the nucleus, and thus to important constraints on models of comet formation and chemical processing in the primitive solar nebula. The observations of Comet Halley provide the opportunity for the first comprehensive determination of the abundances in a comet nucleus. The carbon isotope abundance ratio 12 C/13 C = 65 plus or minus 8 has been determined for Comet Halley from resolved rotational line structure in the CN B-X (0,0) band. The ratio is approximately 30 pct lower than the solar system value, 89, indicating either an enhancement of 13CN or a depletion of 12CN in the comet. Scenarios consistent with the observed carbon isotope ratio are: (1) formation of the comet at the periphery of the solar nebula in a fractionation-enriched 13CN region, or hidden from 12CN enrichment sources, and (2) capture of an interestellar comet. Long-slit charge coupled device (CCD) spectra obtained at the time of the spacecraft encounter of Comet Halley have also been analyzed. Scale lengths, production rates and column densities of CH, CN, C2 and NH2 were determined.

Wyckoff, Susan↗

Identification of Methanotrophic Lipid Biomarkers in Cold-Seep Mussel Gills: Chemical and Isotopic Analysis

A lipid analysis of the tissues of a cold-seep mytilid mussel collected from the Louisiana slope of the Gulf of Mexico was used in conjunction with a compound-specific isotope analysis to demonstrate the presence of methanotrophic symbionts in the mussel gill tissue and to demonstrate the host's dependence on bacterially synthesized metabolic intermediates. The gill tissue contained large amounts of group-specific methanotrophic biomarkers, bacteriohopanoids, 4-methylsterols, lipopolysaccharide-associated hydroxy fatty acids, and type I-specific 16:1 fatty acid isomers with bond positions at delta-8, delta-10, and delta-ll. Only small amounts of these compounds were detected in the mantle or other tissues of the host animal. A variety of cholesterol and 4-methylsterol isomers were identified as both free and steryl esters, and the sterol double bond positions suggested that the major bacterially derived gill sterol(11.0% 4(alpha)-methyl-cholesta-8(14), 24-dien-3(beta)-ol) was converted to host cholesterol (64.2% of the gill sterol was cholest-5-en-3(beta)-ol). The stable carbon isotope values for gill and mantle preparations were, respectively, -59.0 and -60.4 per thousand for total tissue, -60.6 and -62.4 per thousand for total lipids, -60.2 and -63.9 per thousand for phospholipid fatty acids, and -71.8 and -73.8 per thousand for sterols. These stable carbon isotope values revealed that the relative fractionation pattern was similar to the patterns obtained in pure culture experiments with methanotrophic bacteria further supporting the conversion of the bacterial methyl-sterol pool.

Jahnke, Linda L.↗

Organic Chemistry of Carbonaceous Meteorites

Chiral and carbon-isotopic analyses of isovaline have been carried out on numerous samples of the Murchison and one sample of the Murray carbonaceous chondrite. The isovaline was found to be heterogeneous with regard to enantiomeric excess (ee) both between samples and within a single Murchison sample. L-Excesses ranging from 0 to 15% were observed. The isovaline delta(sup 13) C was found to be about +18%. No evidence was obtained suggesting terrestrial contamination in the more abundant L-enantiomer. A correlation was observed between isovaline (also alpha - aminoisobutyric acid) concentration and PCP content of five CM chondrites. It is suggested that isovaline, along with other meteoritic a-methyl amino acids with ee, are of presolar origin. The possible formation of ee in extraterrestrial amino acids by exposure to circularly polarized light or by magnetochiral photochemistry is discussed. Key words: Murchison meteorite, Murray meteorite, amino acids, isovaline, chirality, carbon isotopes, PCP.

Cronin, John R.↗

Lipid Biomarkers for a Hypersaline Microbial Mat Community

The use of lipid biomarkers and their carbon isotopic compositions are valuable tools for establishing links to ancient microbial ecosystems. Various lipids associated with specific microbial groups can serve as biomarkers for establishing organism source and function in contemporary microbial ecosystems (membrane lipids), and by analogy, potential relevance to ancient organic-rich sedimentary rocks (geolipids). As witnessed by the stromatolite record, benthic microbial mats grew in shallow water lagoonal environments. Our recent work has focused on lipid biomarker analysis of a potential analogue for such ancient mats growing in a set of hypersaline evaporation ponds at Guerrero Negro, Baja California Sur, Mexico. The aerobic, surface layer of this mat (0 to 1 mm) contained a variety of ester-bound fatty acids (FA) representing a diverse bacterial population including cyanobacteria, sulphate reducers (SRB) and heterotrophs. Biomarkers for microeukaryotes detected in this layer included sterols, C-20 polyunsaturated FA and a highly branched isoprenoid, diagnostic for diatoms. Cyanobacteria were also indicated by the presence of a diagnostic set of mid-chain methylalkanes. C-28, to C-34 wax esters (WXE) present in relatively small amounts in the upper 3 mm of the mat are considered biomarkers for green non-sulphur bacteria. Ether-bound isoprenoids were also identified although in considerably lower abundance than ester-bound FA (approx. 1:l0). These complex ether lipids included archatol, hydroxyarchaeol and a C-40 tetraether, all in small amounts. After ether cleavage with boron tribromide, the major recovered isoprenyl was a C-30:1. This C(sub 30;1) yelded squalane after hydrogenation, a known geobiomarker for hypersaline environments in ancient oils and sediments. In this mat, it represents the dominant Archaeal population. The carbon isotopic composition of biomarker lipids were generally depleted relative to the bulk organic material (delta C-13 TOC -10%). Most depleted were the cyanobacterial methylalkanes at -27% with FA such as the SRB biomarker, 10- methyl C-I6, somewhat heavier at -16%, and WXE at -17%. The C-30:1 isoprenyl was most enriched with delta C-13 in the -7 to -11% range, much too heavy to represent the methanogen population responsible for mat methane values measured at -60%.

Jahnke, Linda↗

Carbon Tracers of Aqueous Processes: Isotopic Analysis of Cr Carbonate Grains With Implications for Bennu Samples

Carbonate grains in carbonaceous chondrites record aqueous alteration events on the asteroidal parent bodies, including evidence for episodic alteration, timing of alteration, and time and temperature evolution of volatiles. Spectral features in the 3.4 μm region at asteroid Bennu have been interpreted as coming from carbonate minerals. Coordinated analysis of carbonate grains will be a valuable tool for analysis of Bennu samples, and related analysis of analog materials provides important context for understanding aqueous alteration of carbonaceous asteroids more broadly. To that end, our team is analyzing carbonates in Bennu analog materials, using Raman spectroscopy to identify carbonates and assess the maturity of related organic materials, vacuum reflectance spectroscopy from the ultraviolet through thermal infrared range to constrain contributions from carbonates and organics, X-ray microtomography and electron probe microanalysis (EPMA) to assess the distribution of void space, transmission electron microscopy to characterize space weathering effects, and EPMA and secondary ion mass spectrometry (SIMS) to measure composition and isotopic ratios. Here, we describe in situ analysis of carbon and oxygen isotopes from carbonates in Grosvenor Mountains (GRO) 95577.

K E Miller↗

Theory of interstellar abundances of the isotopes of carbon, nitrogen and oxygen.

It is shown that CNO hydrogen burning in stars with a mass of 3 to 8 solar masses can account for both the likely abundances of C-13, N-14, and O-17 in the interstellar medium and the observed ratios C-12/C-13 O-16/O-17 in the atmospheres of evolved stars. A model which gives these abundances is shown to be consistent also with previously suggested mechanisms for the production of He-3, N-15, and O-18.

Wollman, E. R.↗