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NASA NTRS1985

Carbon monoxide isotope ratios in galactic centers and disks

For each of the six galaxies whose mm-wavelength emission of CO and C-13O were observed from both the center and the disk, and the ratio of integrated intensities P(CO)/P(C-13O) is noted to vary markedly from galactic center to galactic center, from galactic disk to galactic disk, and from point to point within a given galaxy. The observed integrated intensity ratios vary from 3 to 16, indicating that the use of a constant P(CO) to sigma(H2) conversion to derive H2 surface densities from extragalactic CO observations can produce major errors.

Rickard, L. J.↗
NASA NTRS1988

Strangelove ocean at era boundaries, terrestrial or extraterrestrial cause

Negative perturbations in carbon-isotope value of calcite in pelagic sediments were found at times of biotic crisis, marking horizons which are, or were proposed as era boundaries: Cretaceous/Tertiary (K/T), Permian/Triassic (P/T), and Precambrian/Cambrian (PreC/C). The anomaly was also found at several other mass-extinction horizons, such as terminal Ordovician, Frasnian-Famenian, etc. Studies of K/T boundary indicate that only the planktic fraction of the sediments has the negative isotope anomaly, whereas the benthic fraction has the same value across the boundary. This geochemical signal is thus considered a record of strangelove ocean, or an ocean where isotope fractionation of dissolved carbonate ions in surface waters (by biotic function of planktic organisms) has been significantly reduced because of the drastic reduction of the biomass in the oceans. The reduction of marine biomass at each of the era boundaries was related to chemical pollution of the oceans as a consequence of a catastrophic event; a pH decrease of 0.5 could inhibit the fertility of planktons. Studies of earthquakes, volcanic eruptions, and meteorite-impact occurrences have indicated a linearly inverse log/log relationship between the magnitude and frequency of events. The frequency of era boundaries in geologic history supports the postulate that the rare events causing those biotic crises were large bolide-impacts.

Hsue, Kenneth J.↗
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 NTRS1991

Isotopic analysis of cometary organic matter

Carbon isotope ratios have been measured for CN in the coma of Comet Halley and for several CHON particles emitted by Halley. Of these, only the CHON-particle data may be reasonably related to organic matter in the cometary nucleus, but the true range of (C-13)/(C-12) values in those particles is quite uncertain. The D/H ratio in H2O in the Halley coma resembles that in Titan/Uranus.

Kerridge, John F.↗
NASA NTRS1990

Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic sparites are most depleted in 13C. Carbonates in oxide-rich iron-formations are more depleted in 13C than those in siderite-rich iron-formation whereas the kerogens in oxide banded iron-formations (BIF) are more enriched. This implies that the siderite-rich iron-formations were not derived from oxide-rich iron-formation through reduction of ferric iron by organic matter. Organic matter oxidation by ferric iron did, however, decrease the abundance of kerogen in oxide-rich iron-formation and led to the formation of isotopically very light sparry carbonates. Siderite and calcmicrosparite both represent recrystallized primary micritic precipitates but differ in their 13C composition, with the siderites depleted in 13C by 4.6 per mil on average relative to calcmicrosparite. This means that the siderites were precipitated from water with dissolved inorganic carbon depleted in 13C by about 9 per mil relative to that from which the limestones precipitated. This implies an ocean system stratified with regard to total carbonate, with the deeper water, from which siderite-rich iron-formation formed, depleted in 13C. Iron-formations were deposited in areas of very low organic matter supply. Depletion of 13C may, therefore, derive not from degradation of organic matter but from hydrothermal activity, a conclusion which is supported by 18O composition of the carbonate minerals and trace element and rare earth element (REE) compositions of the iron-formations.

NASA Discipline Number 52-30↗
NASA NTRS2017

Isotopic Composition of Carbonates in Antarctic Ordinary Chondrites and Miller Range Nakhlites: Insights into Martian Amazonian Aqueous Alteration

The martian surface contains features of ancient fluvial systems. Stable isotope analysis of carbonates that form in aqueous systems can reveal their formation conditions. The Nakhlite meteorites originally formed on Mars 1.3 Ga and were later exposed to aqueous fluids that left behind carbonate minerals [1], thus analysis of these carbonates can provide data to understand Amazonian climate conditions on Mars. Carbonates found in the Nakhlite meteorites contain a range of delta(sup 13)C values, which may be either martian carbonates or terrestrial contamination. To better under-stand terrestrial weathering products and martian carbonate formation processes, we conducted a set of carbonate isotope analyses on Antarctic meteorites focusing on Miller Range (MIL) Nakhlites as well as Ordinary Chondrites (OCs) (Figure 1)[1-11] [12]. OCs of petrology type H, L, and LL 3-6 were selected since they are not expected to contain preterrestrial carbonates, yet they have visible evaporite minerals on the fusion crust indicating terrestrial alteration. These cryogenically formed terrestrial carbonates may also provide an analog for cryogenic carbonate formation on Mars.

Evans, M. E.↗
NASA NTRS1994

Tectonic control of the crustal organic carbon reservoir during the Precambrian

Carbon isotopic trends indicate that the crustal reservoir of reduced, organic carbon increased during the Proterozoic, particularly during periods of widespread continental rifting and orogeny. No long-term trends are apparent in the concentration of organic carbon in shales, cherts and carbonates. The age distribution of 261 sample site localities sampled for well-preserved sedimentary rocks revealed a 500-700-Ma periodicity which coincided with tectonic cycles. It is assumed that the numbers of sites are a proxy for mass of sediments. A substantial increase in the number of sites in the late Archean correlates with the first appearance between 2.9 and 2.5 Ga of extensive continental platforms and their associated sedimentation. It is proposed that the size of the Proterozoic crustal organic carbon reservoir has been modulated by tectonic control of the volume of sediments deposited in environments favorable for the burial and preservation of organic matter. Stepwise increases in this reservoir would have caused the oxidation state of the Proterozoic environment to increase in a stepwise fashion.

NASA Center ARC↗
NASA NTRS1994

A molecular and isotopic study of the organic matter from the Paris Basin, France

Thirteen Liassic sedimentary rocks of increasing depth and three petroleums from the Paris Basin were studied for 13C/12C isotopic compositions and biological markers, including steranes, sterenes, methylphenanthrenes, methylanthracenes, and triaromatic steroids. The isotopic compositions of n-alkanes from mature sedimentary rocks and petroleums fall in a narrow range (2%), except for the deepest Hettangian rock and the Trias petroleum, for which the short-chain n-alkanes are enriched and depleted in 13C, respectively. Most of the molecular parameters increase over the 2000-2500 m depth range, reflecting the transformation of the organic matter at the onset of petroleum generation. In this zone, carbonate content and carbon isotopic composition of carbonates, as well as molecular parameters, are distinct for the Toarcian and Hettangian source rocks and suggest a migration of organic matter from these two formations. Two novel molecular parameters were defined for this task: one using methyltriaromatic steroids from organic extracts; the other using 1-methylphenanthrene and 2-methylanthracene from kerogen pyrolysates. The anomalous high maturity of the Dogger petroleum relative to the maturity-depth trend of the source rocks is used to estimate the minimal vertical distance of migration of the organic matter from the source rock to the reservoir.

Non-NASA Center↗
NASA NTRS2006

Isotope Variations in Terrestrial Carbonates and Thermal Springs as Biomarkers: Analogs for Martian Processes

Stable isotope measurements of carbonate minerals contained within ALH84001 [1] suggest that fluids were present at 3.9 Gy on Mars [2, 3, 4, 5]. Both oxygen and carbon isotopes provide independent means of deciphering paleoenvironmental conditions at the time of carbonate mineral precipitation. In terrestrial carbonate rocks oxygen isotopes not only indicate the paleotemperature of the precipitating fluid, but also provide clues to environmental conditions that affected the fluid chemistry. Carbon isotopes, on the other hand, can indicate the presence or absence of organic compounds during precipitation (i.e. biogenically vs. thermogenically-generated methane), thus serving as a potential biomarker. We have undertaken a study of micro scale stable isotope variations measured in some terrestrial carbonates and the influence of organic compounds associated with the formation of these carbonates. Preliminary results indicate that isotope variations occur within narrow and discrete intervals, providing clues to paleoenvironmental conditions that include both biological and non-biological activity. These results carry implications for deciphering Martian isotope data and therefore potential biological prospecting on the planet Mars. Recently, Fourier Transform Spectrometer observations have detected methane occurring in the Martian atmosphere [6] that could be attributed to a possible biogenic source. Indeed, Mars Express has detected the presence of methane in the Martian atmosphere [7], with evidence indicating that methane abundances are greatest above those basins with high water concentrations.

Socki, Richard A.↗
NASA NTRS2014

A Novel Framework for Quantifying past Methane Recycling by Sphagnum-Methanotroph Symbiosis Using Carbon and Hydrogen Isotope Ratios of Leaf Wax Biomarkers

The concentration of atmospheric methane is strongly linked to variations in Earth's climate. Currently, we can directly reconstruct the total atmospheric concentration of methane, but not individual terms of the methane cycle. Northern wetlands, dominated by Sphagnum, are an important contributor of atmospheric methane, and we seek to understand the methane cycle in these systems. We present a novel method for quantifying the proportion of carbon Sphagnum assimilates from its methanotrophic symbionts using stable isotope ratios of leaf-wax biomarkers. Carbon isotope ratios of Sphagnum compounds are determined by two competing influences, water content and the isotope ratio of source carbon. We disentangled these effects using a combined hydrogen and carbon isotope approach. We constrained Sphagnum water content using the contrast between the hydrogen isotope ratios of Sphagnum and vascular plant biomarkers. We then used Sphagnum water content to calculate the carbon isotope ratio of Sphagnum's carbon pool. Using a mass balance equation, we calculated the proportion of recycled methane contributed to the Sphagnum carbon pool, 'PRM.' We quantified PRM in peat monoliths from three microhabitats in the Mer Bleue peatland complex. Modern studies have shown that water table depth and vegetation have strong influences on the peatland methane cycle on instrumental time scales. With this new approach, delta C-13 of Sphagnum compounds are now a useful tool for investigating the relationships among hydrology, vegetation, and methanotrophy in Sphagnum peatlands over the time scales of entire peatland sediment records, vital to our understanding of the global carbon cycle through the Late Glacial and Holocene.

air pollution↗
NASA NTRS1993

Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale

The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

NASA Discipline Exobiology↗
NASA NTRS1996

Evidence for Life on Earth before 3,800 Million Years Ago

It is unknown when life first appeared on Earth. The earliest known microfossils (approx. 3,500 Myr before present) are structurally complex, and if it is assumed that the associated organisms required a long time to develop this degree of complexity, then the existence of life much earlier than this can be argued. But the known examples of crustal rocks older than approx. 3,500 Myr have experienced intense metamorphism, which would have obliterated any fragile microfossils contained therein. It is therefore necessary to search for geochemical evidence of past biotic activity that has been preserved within minerals that are resistant to metamorphism. Here we report ion-microprobe measurements of the carbon-isotope composition of carbonaceous inclusions within grains of apatite (basic calcium phosphate) from the oldest known sediment sequences a approx. 3,800 Myr-old banded iron formation from the Isua supracrustal belt, West Greenland, and a similar formation from the nearby Akilia island that is possibly older than 3,850 Myr. The carbon in the carbonaceous inclusions is isotopically light, indicative of biological activity; no known abiotic process can explain the data. Unless some unknown abiotic process exists which is able both to create such isotopically light carbon and then selectively incorporate it into apatite grains, our results provide evidence for the emergence of life on Earth by at least 3,800 Myr before present.

Mojzsis, S. J.↗
NASA NTRS2000

Isotope Geochemistry of Possible Terrestrial Analogue for Martian Meteorite ALH84001

We have studied the microdomain oxygen and carbon isotopic compositions by SIMS of complex carbonate rosettes from spinel therzolite xenoliths, hosted by nepheline basanite, from the island of Spitsbergen (Norway). The Quaternary volcanic rocks containing the xenoliths erupted into a high Arctic environment and through relatively thick continental crust containing carbonate rocks. We have attempted to constrain the sources of the carbonates in these rocks by combined O-18/O-16 and C-13/C-12 ratio measurements in 25 micron diameter spots of the carbonate and compare them to previous work based primarily on trace-element distributions. The origin of these carbonates can be interpreted in terms of either contamination by carbonate country rock during ascent of the xenoliths in the host basalt, or more probably by hydrothermal processes after emplacement. The isotopic composition of these carbonates from a combined delta.18O(sub SMOW) and delta.13C(sub PDB) standpoint precludes a primary origin of these minerals from the mantle. Here a description is given of the analysis procedure, standardization of the carbonates, major element compositions of the carbonates measured by electron microprobe, and their correlated C and O isotope compositions as measured by ion microprobe. Since these carbonate rosettes may represent a terrestrial analogue to the carbonate "globules" found in the martian meteorite ALH84001 interpretations for the origin of the features found in the Spitsbergen may be of interest in constraining the origin of these carbonate minerals on Mars.

Mojzsis, Stephen J.↗
NASA NTRS1984

Carbon and oxygen isotope fractionation in dense interstellar clouds

It is pointed out that isotope fractionation as a result of chemical reactions is due to the small zero-point energy differences between reactants and products of isotopically distinct species. Only at temperatures near absolute zero does this energy difference become significant. Favorable conditions for isotope fractionation on the considered basis exist in space within dense interstellar clouds. Temperatures of approximately 10 K may occur in these clouds. Under such conditions, ion-molecule reactions have the potential to distribute isotopes of hydrogen, carbon, oxygen unequally among the interstellar molecules. The present investigation makes use of a detailed model of the time-dependent chemistry of dense interstellar clouds to study cosmological isotope fractionation. Attention is given to fractionation chemistry and the calculation of rate parameters, the isotope fractionation results, and a comparison of theoretical results with observational data.

Langer, W. D.↗
NASA NTRS1992

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↗
NASA NTRS1974

Accumulation and isotopic evolution of carbon on the lunar surface

The processes of hydrogen stripping, agglutination and impact comminution, acting upon a regolith containing both indigenous and solar wind-implanted carbon, provide a quantitative explanation for the relationship between carbon abundance and isotopic composition observed for Apollo 16 soils.

Kerridge, J. F.↗
NASA NTRS2010

Reduced Martian Carbon: Evidence from Martian Meteorites

Identification of indigenous reduced carbon species on Mars has been a challenge since the first hypotheses about life on Mars were proposed. Ranging from the early astronomical measurements to analyses of samples from the Martian surface in the form of Martian meteorites. The first direct attempt to analyze the carbon species on the surface was in 1976 with the Viking GC-MS in-situ experiment which gave inconclusive results at two sites on Mars [1]. With the recognition in 1983 that samples of the Martian surface were already present on Earth in the form of Martian meteorites by Bogard and Johnson [2] new opportunities became available for direct study of Mars's samples in te rlraesbtrioalratories. Carbon isotopic compositional information suggested a reduced carbon component was present in the Martian meteorites [3-5]. Polycyclic aromatic hydrocarbons associated with carbonate globules in ALH84001 were later identified [6,7]. Jull et al [8] noted that an insoluble component was present within Nakhla and more than 75% of its C lacked any 14C, which is modern-day carbon contaminant. This carbon fraction was believed to be either indigenous (i..e. Martian) or ancient meteoritic carbon phase. Within the fractures of Nakhla and ALH84001, Fisk et al [9,10] identified reduced carbon-enriched areas. Gibson et al. [11] using a combination of NanoSIMS, Focused Electron microscopy, Laser Raman Spectroscopy and Stepped-Combustion Static Mass Spectrometry analyses the presence of possible indigenous reduced carbon components within the 1.3 Ga old Nakhla.

Gibson, Everett K.↗
NASA NTRS1995

Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with those of total organic carbon. A resistant aliphatic biomacromolecule produced by microalgae is, therefore, probably an important component of the kerogen. These variations reflect changes in the depositional environment and early diagenetic transformations. Changes in the concentrations of S-bound lipids induced by variations in conditions favourable for sulphurization were discriminated from those related to variations in primary producer assemblages. The water column of the lagoonal basin was stratified and photic zone anoxia occurred during the early and middle stages of marl deposition. During the last stage of the marl deposition the stratification collapsed due to a significant shallowing of the water column. Contributions from anaerobic photoautotrophs were apparently associated with variations in depth of the chemocline.

Non-NASA Center↗