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All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Energy, volatile production, and climatic effects of the Chicxulub Cretaceous/Tertiary impact

A comprehensive analysis of volatiles in the Chicxulub impact strongly supports the hypothesis that impact-generated sulfate aerosols caused over a decade of global cooling, acid rain, and disruption of ocean circulation, which contributed to the mass extinction at the Cretaceous/Tertiary (K/T) boundary. The crater size, meteoritic content of the K/T boundary clay, and impact models indicate that the Chicxulub crater was formed by a short period comet or an asteroid impact that released 0.7-3.4 x 10(31) ergs of energy. Impact models and experiments combined with estimates of volatiles in the projectile and target rocks predict that over 200 gigatons (Gt) each of SO2 and water vapor, and over 500 Gt of CO2, were globally distributed in the stratosphere by the impact. Additional volatiles may have been produced on a global or regional scale that formed sulfate aerosols rapidly in cooler parts of the vapor plume, causing an early, intense pulse of sulfuric acid rain. Estimates of the conversion rate of stratospheric SO2 and water vapor to sulfate aerosol, based on volcanic production of sulfate aerosols, coupled with calculations of diffusion, coagulation, and sedimentation, demonstrate that the 200 Gt stratospheric SO2 and water vapor reservoir would produce sulfate aerosols for 12 years. These sulfate aerosols caused a second pulse of acid rain that was global. Radiative transfer modeling of the aerosol clouds demonstrates (1) that if the initial rapid pulse of sulfate aerosols was global, photosynthesis may have been shut down for 6 months and (2) that for the second prolonged aerosol cloud, solar transmission dropped 80% by the end of first year and remained 50% below normal for 9 years. As a result, global average surface temperatures probably dropped between 5 degrees and 31 degrees K, suggesting that global near-freezing conditions may have been reached. Impact-generated CO2 caused less than 1 degree K greenhouse warming and therefore was insignificant compare to the sulfate cooling. The magnitude of sulfate cooling depends largely upon the rate of ocean mixing as surface waters cool, sink, and are replaced by upwelling of deep ocean water. This upwelling apparently drastically altered ocean stratification and circulation, which may explain the global collapse of the delta 13C gradient between surface and deep ocean waters at the K/T boundary.

NASA Center JPL↗
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 NTRS1987

Natural abundances of carbon isotopes in acetate from a coastal marine sediment

Measurements of the natural abundances of carbon isotopes were made in acetate samples isolated from the anoxic marine sediment of Cape Lookout Bight, North Carolina. The typical value of the total acetate carbon isotope ratio (delta 13C) was -16.1 +/- 0.2 per mil. The methyl and carboxyl groups were determined to be -26.4 +/- 0.3 and -6.0 +/- 0.3 per mil, respectively, for one sample. The isotopic composition of the acetate is thought to have resulted from isotopic discriminations that occurred during the cycling of that molecule. Measurements of this type, which have not been made previously in the natural environment, may provide information about the dominant microbial pathways in anoxic sediments as well as the processes that influence the carbon isotopic composition of biogenic methane from many sources.

NASA Discipline Exobiology↗
NASA NTRS1986

Sources of carbon and sulfur nutrition for consumers in three meromictic lakes of New York State

The trophic importance of bacterioplankton as a source of carbon and sulfur nutrition for consumers in meromictic lakes was tested using stable carbon (delta 13C) and sulfur (delta 34S) isotopic measurements. Studies in three lakes near Syracuse, New York, showed that most consumers ultimately derive their C and S nutrition from a mixture of terrestrial detritus, phytoplankton, and littoral vegetation, rather than from bacterioplankton. Food webs in these meromictic lakes are thus similar to those in other lakes that lack dense populations of bacterioplankton.

NASA Discipline Exobiology↗
NASA NTRS1995

Neoproterozoic variations in the C-isotopic composition of seawater: stratigraphic and biogeochemical implications

The recent proliferation of stratigraphic studies of delta 13C variation in carbonates and organic C in later Neoproterozoic and basal Cambrian successions (approximately 850-530 Ma) indicates a strong oscillating trend in the C-isotopic composition of surface seawater. Alone, this trend does not adequately characterize discrete intervals in Neoproterozoic time. However, integrated with the vectorial signals provided by fossils and Sr-isotopic variations, C isotope chemostratigraphy facilitates the interbasinal correlation of later Neoproterozoic successions. Results of these studies are evaluated in terms of four stratigraphic intervals: (1) the Precambrian/Cambrian boundary, (2) the post-Varanger terminal Proterozoic, (3) the late Cryogenian, and (4) the early Cryogenian. Where biostratigraphic or radiometric data constrain the age of Neoproterozoic sedimentary sequences, secular variations in C and Sr isotopes can provide a level of stratigraphic resolution exceeding that provided by fossils alone. Isotopic data place strong constraints on the chemical evolution of seawater, linking it to major tectonic and paleoclimatic events. They also provide a biogeochemical framework for the understanding of the initial radiation of macroscopic metazoans, which is associated stratigraphically, and perhaps causally, with a global increase in the burial of organic C and a concomitant rise of atmospheric O2.

NASA Discipline Exobiology↗
NASA NTRS1994

Acquisition and processing of data for isotope-ratio-monitoring mass spectrometry

Methods are described for continuous monitoring of signals required for precise analyses of 13C, 18O, and 15N in gas streams containing varying quantities of CO2 and N2. The quantitative resolution (i.e. maximum performance in the absence of random errors) of these methods is adequate for determination of isotope ratios with an uncertainty of one part in 10(5); the precision actually obtained is often better than one part in 10(4). This report describes data-processing operations including definition of beginning and ending points of chromatographic peaks and quantitation of background levels, allowance for effects of chromatographic separation of isotopically substituted species, integration of signals related to specific masses, correction for effects of mass discrimination, recognition of drifts in mass spectrometer performance, and calculation of isotopic delta values. Characteristics of a system allowing off-line revision of parameters used in data reduction are described and an algorithm for identification of background levels in complex chromatograms is outlined. Effects of imperfect chromatographic resolution are demonstrated and discussed and an approach to deconvolution of signals from coeluting substances described.

NASA Discipline Exobiology↗
NASA NTRS1994

Isotopic analyses of nitrogenous compounds from the Murchison meteorite: ammonia, amines, amino acids, and polar hydrocarbons

The combined volatile bases (ammonia, aliphatic amines, and possibly other bases), ammonia, amino acids, and polar hydrocarbons were prepared from the Murchison meteorite for isotopic analyses. The volatile bases were obtained by cryogenic transfer after acid-hydrolysis of a hot-water extract and analyzed by combined gas chromatography-mass spectrometry of pentafluoropropionyl derivatives. The aliphatic amines present in this preparation comprise a mixture that includes both primary and secondary isomers through C5 at a total concentration of > or = 100 nmoles g-1. As commonly observed for meteoritic organic compounds, almost all isomers through C5 are present, and the concentrations within homologous series decrease with increasing chain length. Ammonia was chromatographically separated from the other volatile bases and found at a concentration of 1.1-1.3 micromoles g-1 meteorite. The ammonia analyzed includes contributions from ammonium salts and the hydrolysis of extractable organic compounds, e.g., carboxamides. Stable isotope analyses showed the volatile bases to be substantially enriched in the heavier isotopes, relative to comparable terrestrial compounds delta D < or = +1221%; delta 13C = +22%; delta 15N = +93%). Ammonia, per se, was found to have a somewhat lower delta 15N value (+69%) than the total volatile bases; consequently, a higher delta 15N (>93%) can be inferred for the other bases, which include the amines. Solvent-extractable polar hydrocarbons obtained separately were found to be enriched in 15N (delta 15N = +104%). Total amino acids, prepared from a hydrolyzed hot-water extract by cation exchange chromatography, gave a delta 15N of +94%, a value in good agreement with that obtained previously. Nitrogen isotopic data are also given for amino acid fractions separated chromatographically. The delta 15N values of the Murchison soluble organic compounds analyzed to date fall within a rather narrow range (delta 15N = +94 +/- 8%), an observation consistent with their formation, or formation of their precursors, by interstellar chemistry.

Non-NASA Center↗
NASA NTRS1990

Carbonate deposition during the late Proterozoic Era: an example from Spitsbergen

Carbonate sediments reflect the physico-chemical and biological circumstances of their formation; thus, features of limestones and dolomites may provide insights into both environmental and evolutionary change through geological time. The Upper Proterozoic (approx 800-700 Ma) Akademikerbreen Group, Spitsbergen, comprises 2000 m of carbonates, with only minor intercalations of quartz arenite and shale. Although Proterozoic carbonates are often seen as predominantly dolomitic, the Akademikerbreen Group is about 45 percent limestone. Stromatolites are conspicuous in outcrop but constitute only 25 percent of the total section. Micrites and coarser intraclastic carbonates derived mainly from micritric precursors comprise 60 percent of the group, while oolites make up the remaining 15 percent. Distinctive sedimentary features of the group include giant (up to 16 mm) ooids, very early diagenetic calcite nodules and cements, micrites containing subaqueous shrinkage cracks filled with equant microspar cement, and strong 13C enrichment in both carbonates and co-occurring organic matter. The principal features of Akademikerbreen carbonates are widely distributed in coeval successions. However, these rocks appear to differ from older limestones and dolomites in their relative abundance of grainstones and, perhaps, micrites, as well as their paucity of tufa-like laminates and columnar or coniform stromatolites that preserve petrographic evidence of in situ precipitation as a dominant means of carbonate accretion. Upper Proterozoic carbonates also differ from Paleozoic accumulations, but the transition is not abrupt. Most changes accompanying the Proterozoic/Phanerozoic transition can be interpreted in terms of the consequences rather than the causes of metazoan and metaphyte evolution, including the evolution of biomineralization. Carbonate sedimentology reinforces data from other sources which indicate the last 200 to 300 Ma of the Proterozoic Eon was a distinctive interval of Earth history.

NASA Discipline Number 52-30↗
NASA NTRS1990

Carbon-isotopic analysis of dissolved acetate

Heating of dried, acetate-containing solids together with oxalic acid dihydrate conveniently releases acetic acid for purification by gas chromatography. For determination of the carbon-isotopic composition of total acetate, the acetate-containing zone of the chromatographic effluent can be routed directly to a combustion furnace coupled to a vacuum system allowing recovery, purification, and packaging of CO2 for mass-spectrometric analysis. For analysis of methyl carbon, acetic acid can be cryogenically trapped from the chromatographic effluent, then transferred to a tube containing excess NaOH. The tube is evacuated, sealed, and heated to 500 degrees C to produce methane by pyrolysis of sodium acetate. Subsequent combustion of the methane allows determination of the 13C content at the methyl position in the parent acetate. With typical blanks, the standard deviation of single analyses is less than 0.4% for acetate samples larger than 5 micromoles. A full treatment of uncertainties is outlined.

Non-NASA Center↗
NASA NTRS1992

Fractionation of carbon isotopes by phytoplankton and estimates of ancient CO2 levels

Reports of the 13C content of marine particulate organic carbon are compiled and on the basis of GEOSECS data and temperatures, concentrations, and isotopic compositions of dissolved CO2 in the waters in which the related phytoplankton grew are estimated. In this way, the fractionation of carbon isotopes during photosynthetic fixation of CO2 is found to be significantly correlated with concentrations of dissolved CO2. Because ancient carbon isotopic fractionations have been determined from analyses of sedimentary porphyrins [Popp et al., 1989], the relationship between isotopic fractionation and concentrations of dissolved CO2 developed here can be employed to estimate concentrations of CO2 dissolved in ancient oceans and, in turn, partial pressures of CO2 in ancient atmospheres. The calculations take into account the temperature dependence of chemical and isotopic equilibria in the dissolved-inorganic-carbon system and of air-sea equilibria. Paleoenvironmental temperatures for each sample are estimated from reconstructions of paleogeography, latitudinal temperature gradients, and secular changes in low-latitude sea surface temperature. It is estimated that atmospheric partial pressures of CO2 were over 1000 micro atm 160 - 100 Ma ago, then declined to values near 300 micro atm during the next 100 Ma. Analysis of a high-resolution record of carbon isotopic fractionation at the Cenomanian-Turonian boundary suggests that the partial pressure of CO2 in the atmosphere was drawn down from values near 840 micro atm to values near 700 micro atm during the anoxic event.

NASA Discipline Exobiology↗
NASA NTRS1992

Diploptene: an indicator of terrigenous organic carbon in Washington coastal sediments

The pentacyclic triterpene 17 beta(H),21 beta(H)-hop-22(29)-ene (diploptene) occurs in sediments throughout the Columbia River drainage basin and off the southern coast of Washington state in concentrations comparable to long-chain plantwax n-alkanes. The same relationship is evident for diploptene and long-chain n-alkanes in soils from the Willamette Valley. Microorganisms indigenous to soils and soil erosion are indicated as the biological source and physical process, respectively, for diploptene in coastal sediments. Similarity between the stable carbon isotopic composition (delta 13CPDB) of diploptene isolated from soil in the Willamette Valley (-31.2 +/- 0.3%) and from sediments deposited throughout the Washington coastal environment (-31.2 +/- 0.5%) supports this argument. Values of delta for diploptene in river sediments are variable and 8-17% lighter, indicating that an additional biological source such as methane-oxidizing bacteria makes a significant contribution to the diploptene record in river sediments. Selective biodegradation resulting from a difference in the physicochemical association within eroded particles can explain the absence of the more-13C-depleted form of diploptene in Washington coastal sediments, but this mechanism remains unproven.

Non-NASA Center↗
NASA NTRS1992

Biostratigraphic and chemostratigraphic correlation of Neoproterozoic sedimentary successions: upper Tindir Group, northwestern Canada, as a test case

Recent advances in Proterozoic micropaleontology and sedimentary isotope geochemistry suggest that improved interbasinal correlation of Neoproterozoic (1000-540 Ma) successions is possible. Because widely varying interpretations of its age have been suggested and no reliable radiometric dates or paleomagnetic data are available, the upper Tindir Group of northwestern Canada provides an opportunity to test this hypothesis. The age of these strata is of paleontological importance because silicified carbonates near the top of the group contain disc-shaped-scale microfossils that may provide insights into the early evolution of biomineralization. A reinterpretation of upper Tindir microfossil assemblages suggests a late Riphean age. Although diagenesis and contact metamorphism have altered the isotopic compositions of some carbonates, least altered samples indicate that delta 13C of contemporaneous seawater was at least +4.7%, typical of Neoproterozoic, but not Cambrian, carbonates. Strontium isotopic compositions of the least altered samples yield values of approximately 0.7065, which can be uniquely correlated with late Riphean seawater. Together, micropaleontology and the isotopic tracers of C and Sr constrain the upper Tindir carbonates and their unique fossils to be late Riphean, likely between 620 and 780 Ma.

NASA Discipline Exobiology↗
NASA NTRS1989

Carbon isotope fractionation by thermophilic phototrophic sulfur bacteria: evidence for autotrophic growth in natural populations

Purple phototrophic bacteria of the genus Chromatium can grow as either photoautotrophs or photoheterotrophs. To determine the growth mode of the thermophilic Chromatium species, Chromatium tepidum, under in situ conditions, we have examined the carbon isotope fractionation patterns in laboratory cultures of this organism and in mats of C. tepidum which develop in sulfide thermal springs in Yellowstone National Park. Isotopic analysis (13C/12C) of total carbon, carotenoid pigments, and bacteriochlorophyll from photoautotrophically grown cultures of C. tepidum yielded 13C fractionation factors near -20%. Cells of C. tepidum grown on excess acetate, wherein synthesis of the Calvin cycle enzyme ribulose-1,5-bisphosphate carboxylase/oxygenase ribulose bisphosphate carboxylase) was greatly repressed, were isotopically heavier, fractionation factors of ca. -7% being observed. Fractionation factors determined by isotopic analyses of cells and pigment fractions of natural populations of C. tepidum growing in three different sulfide thermal springs in Yellowstone National Park were approximately -20%, indicating that this purple sulfur bacterium grows as a photoautotroph in nature.

Non-NASA Center↗
NASA NTRS2000

Sedimentology and geochemistry of a perennially ice-covered epishelf lake in Bunger Hills Oasis, East Antarctica

A process-oriented study was carried out in White Smoke lake, Bunger Hills, East Antarctica, a perennially ice-covered (1.8 to 2.8 m thick) epishelf (tidally-forced) lake. The lake water has a low conductivity and is relatively well mixed. Sediments are transferred from the adjacent glacier to the lake when glacier ice surrounding the sediment is sublimated at the surface and replaced by accumulating ice from below. The lake bottom at the west end of the lake is mostly rocky with a scant sediment cover. The east end contains a thick sediment profile. Grain size and delta 13C increase with sediment depth, indicating a more proximal glacier in the past. Sedimentary 210Pb and 137Cs signals are exceptionally strong, probably a result of the focusing effect of the large glacial catchment area. The post-bomb and pre-bomb radiocarbon reservoirs are c. 725 14C yr and c. 1950 14C yr, respectively. Radiocarbon dating indicates that the east end of the lake is >3 ka BP, while photographic evidence and the absence of sediment cover indicate that the west end has formed only over the last century. Our results indicate that the southern ice edge of Bunger Hills has been relatively stable with only minor fluctuations (on the scale of hundreds of metres) over the last 3000 years.

Non-NASA Center↗
NASA NTRS1999

Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions

Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

Non-NASA Center↗
NASA NTRS1999

Neocytolysis contributes to the anemia of renal disease

Neocytolysis is a recently described physiological process affecting the selective hemolysis of young red blood cells in circumstances of plethora. Erythropoietin (EPO) depression appears to initiate the process, providing the rationale to investigate its contributions to the anemia of renal disease. When EPO therapy was withheld, four of five stable hemodialysis patients showed chromium 51 (51Cr)-red cell survival patterns indicative of neocytolysis; red cell survival was short in the first 9 days, then normalized. Two of these four patients received oral 13C-glycine and 15N-glycine, and there was a suggestion of pathological isotope enrichment of stool porphyrins when EPO therapy was held, again supporting selective hemolysis of newly released red cells that take up the isotope (one patient had chronic hemolysis indicated by isotope studies of blood and stool). Thus, neocytolysis can contribute to the anemia of renal disease and explain some unresolved issues about such anemia. One implication is the prediction that intravenous bolus EPO therapy is metabolically and economically inefficient compared with lower doses administered more frequently subcutaneously.

Non-NASA Center↗
NASA NTRS1996

Lipid biomarkers for bacterial ecosystems: studies of cultured organisms, hydrothermal environments and ancient sediments

This paper forms part of our long-term goal of using molecular structure and carbon isotopic signals preserved as hydrocarbons in ancient sediments to improve understanding of the early evolution of Earth's surface environment. We are particularly concerned with biomarkers which are informative about aerobiosis. Here, we combine bacterial biochemistry with the organic geochemistry of contemporary and ancient hydrothermal ecosystems to construct models for the nature, behaviour and preservation potential of primitive microbial communities. We use a combined molecular and isotopic approach to characterize lipids produced by cultured bacteria and test a variety of culture conditions which affect their biosynthesis. This information is then compared with lipid mixtures isolated from contemporary hot springs and evaluated for the kinds of chemical change that would accompany burial and incorporation into the sedimentary record. In this study we have shown that growth temperature does not appear to alter isotopic fractionation within the lipid classes produced by a methanotropic bacterium. We also found that cultured cyanobacteria biosynthesize diagnostic methylalkanes and dimethylalkanes with the latter only made when growing under low pCO2. In an examination of a microbial mat sample from Octopus Spring, Yellowstone National Park (USA), we could readily identify chemical structures with 13C contents which were diagnostic for the phototrophic organisms such as cyanobacteria and Chloroflexus. We could not, however, find molecular evidence for operation of a methane cycle in the particular mat samples we studied.

NASA Discipline Exobiology↗
NASA NTRS1995

Hydroxycinnamic acid-derived polymers constitute the polyaromatic domain of suberin

Suberin is an abundant, complex, intractable, plant cell wall polymeric network that forms both protective and wound-healing layers. Its function is, therefore, critical to the survival of all vascular plants. Its chemical structure and biosynthesis are poorly defined, although it is known to consist of both aromatic and aliphatic domains. While the composition of the aliphatic component has been fairly well characterized, that of the phenolic component has not. Using a combination of specific carbon-13 labeling techniques, and in situ solid state 13C NMR spectroscopic analysis, we now provide the first direct evidence for the nature of the phenolic domain of suberin and report here that it is almost exclusively comprised of a covalently linked, hydroxycinnamic acid-derived polymeric matrix.

NASA Discipline Plant Biology↗