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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↗

NASA NTRS2004

Diels-Alder Trapping of Photochemically Generated o-Quinodimethane Intermediates: An Alternative Route to Photocured Polymer Film Development

Photolysis of o-methylphenyl ketones generates bis-o-quinodimethane intermediates that can be trapped in situ by dienophiles through Diels-Alder cycloadditions. This well-known photochemical process is applied to a series of six new photoreactive monomers containing bis-(o-methylphenyl ketone) functionalities combined with diacrylate and triacrylate ester monomers for the development of acrylic ester copolymer blends. Irradiation of cyclohexanone solutions of the bis-(o-methylphenyl ketone)s and acrylate esters produce thin polymer films. Solid state 13C NMR data indicated 47- 100% reaction of the bis-(o-methylphenyl ketone)s, depending on experimental conditions, to yield the desired products. DSC and TGA analyses were performed to determine the glass transition temperature, T,, and onset of decomposition, Td, of the resulting polymer films. A statistical Design of Experiments approach was used to obtain a systematic understanding of the effects of experimental variables on the extent of polymerization and the final polymer properties.

Tyson, Daniel S.↗

NASA NTRS2004

Soyuz 7 Return Samples: Assessment of Air Quality Aboard the International Space Station

The toxicological assessments of one grab sample canister (GSC), 6 dual sorbent tubes (DSTs), and 20 formaldehyde badges returned aboard Soyuz 7 are reported. Analytical methods have not changed from earlier reports. Surrogate standard recoveries from the GSC were 84-89%. The recoveries of the less volatile surrogates from the DSTs were 87 to 112%; however, 13C-acetone was only recovered at 53-59%. Formaldehyde recoveries from 2 lab controls were 87 and 95%; trip controls were not returned to ground.

James, John T.↗

NASA NTRS2007

Genesis Concentrator Target Particle Contamination Mapping and Material Identification

The majority of surface particles were found to be < 5 microns in diameter with increasing numbers close to the optical resolution limit of 0.3 microns. Acceleration grid EDS results show that the majority of materials appear to be from the SRC shell and SLA materials which include carbon-carbon fibers and Si-rich microspheres in a possible silicone binder. Other major debris material from the SRC included white paint, kapton, collector array fragments, and Al. Image analysis also revealed that SRC materials were also found mixed with the Utah mud and salt deposits. The EDS analysis of the acceleration grid showed that particles < 1 m where generally carbon based particles. Chemical cleaning techniques with Xylene and HF in an ultrasonic bath are currently being investigated for removal of small particles by the Genesis science team as well as ultra-pure water megasonic cleaning by the JSC team [4]. Removal of organic contamination from target materials is also being investigated by the science team with the use of UV-ozone cleaning devices at JSC and Open University [5]. In preparation for solar wind oxygen analyses at UCLA and Open University [1, 2], surface particle contamination on three Genesis concentrator targets was closely examined to evaluate cleaning strategies. Two silicon carbide (Genesis sample # 60001 and 60003) and one chemical vapor deposited (CVD) 13C concentrator target (60002) were imaged and mosaic mapped with optical microscopes. The resulting full target mosaic images and particle feature maps were subsequently compared with non-flight, but flight-like, concentrator targets and sample return capsule (SRC) materials. Contamination found on the flown concentrator acceleration grid was further examined using a scanning electron microscope (SEM). Energy dispersive X-ray spectroscopy (EDS) for particle identification was subsequently compared with the optical images from the flown targets. Figure 1 show that all three targets imaged in this report are fully intact and do not show any signs of material fractures. However, previous ellipsometry results and overview imaging of both flown SiC targets show a solar wind irradiation gradient from the center focal point to the outer edge [3]. In addition, due to the hard landing, each target has experienced varying degrees of impacts, scratches, and particle debris from the spacecraft and Utah impact site.

Calaway, Michael J.↗

NASA NTRS2008

NanoSIMS Sheds Light on the Origin and Significance of Early Archean Organic Microstructures from the Pilbara of Australia

NanoSIMS was used to characterize sub-micron scale morphology and elemental composition (C, N, S, Si, O) of organic microstructures in Early Archean (3 - 3.4 Ga) charts from the Pilbara of Western Australia. Three categories of structures were analyzed: small spheroids in clusters; spindle-shaped remains; and large spheroids. All are relatively poorly preserved and occur within the chert matrix of the samples. Carbonaceous material in a secondary hydrothermal vein also was analyzed, as an example of non-indigenous organic matter. Comparisons were made of NanoSIMS characteristics of the Archean samples and those from well-preserved, biogenic microfossils in the 0.8 Ga Bitter Springs Formation. The comparisons show that the Pilbara microstructures are generally distinct from material in the hydrothermal vein but similar in morphology and elemental composition to the Bitter Springs microfossils. In addition, the Pilbara structures exhibit a spatial relationship to silicon and oxygen that seemingly reflects silica nucleation on organic surfaces; this argues that the organic frameworks of the Archean structures were present in the sediment during crystallization of the silica matrix. The structures are thus interpreted as being indigenous to the enclosing sediment. While these results are suggestive of Early Archean biogenicity and are consistent with a growing body of data suggesting that life on Earth was well established by 3 to 3.4 Ga, work is continuing to determine the N/C and 13C ratios of individual forms, and this should provide additional insight into the derivation and significance of these ancient organic remains.

Oehler, Dorothy Z.↗

NASA NTRS2009

Status of Reconstruction of Fragmented Diamond-on-Silicon Collector From Genesis Spacecraft Solar Wind Concentrator

In addition to passive solar wind collector surfaces, the Genesis Discovery Mission science canister had on board an electrostatic concave mirror for concentrating the solar wind ions, known as the concentrator . The 30-mm-radius collector focal point (the target) was comprised of 4 quadrants: two of single crystal SiC, one of polycrystalline 13C diamond and one of diamond-like-carbon (DLC) on a silicon substrate. [DLC-on-silicon is also sometimes referenced as Diamond-on-silicon, DOS.] Three of target quadrants survived the hard landing intact, but the DLC-on-silicon quadrant fractured into numerous pieces (Fig. 1). This abstract reports the status of identifying the DLC target fragments and reconstructing their original orientation.

Rodriquez, Melissa C.↗

NASA NTRS2009

A First Look at Carbon and Oxygen Stable Isotope Measurements of Martian Atmospheric C02 by the Phoenix Lander

Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars. The isotopic composition of the martian atmosphere has been measured using a number of different methods (Table 1), however a precise value (<1%) has yet to be achieved. Given the elevated 13C values measured in carbonates in martian meteorites it has been supposed that the martian atmosphere was enriched in delta(sup 13)C. This was supported by measurements of trapped CO2 gas in EETA 79001[2] which showed elevated delta(sup 13)C values (Table 1). More recently, Earth-based spectroscopic measurements of the martian atmosphere have measured the martian CO2 to be depleted in delta(sup 13)C relative to CO2 in the terrestrial atmosphere. The spectroscopic measurements performed by Krasnopolsky et al. were reported with approx.2% uncertainties which are much smaller than the Viking measurements, but still remain very large in comparison to the magnitude of carbon and oxygen isotope fractionations under martian surface conditions. The Thermal Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander included a magnetic sector mass spectrometer (EGA) which had the goal of measuring the isotopic composition of martian atmospheric CO2 to within 0.5%. The mass spectrometer is a miniature magnetic sector instrument intended to measure both the martian atmosphere as well as gases evolved from heating martian soils. Ions produced in the ion source are drawn out by a high voltage and focused by a magnetic field onto a set of collector slits. Four specific trajectories are selected to cover the mass ranges, 0.7 - 4, 7 - 35, 14 - 70, and 28 - 140 Da. Using four channels reduces the magnitude of the mass scan and provides simultaneous coverage of the mass ranges. Channel electron multiplier (CEM) detectors that operate in the pulse counting mode detect the ion beams.

Niles, P.B.↗

NASA NTRS2008

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect.

Reddy, V. Prakash↗

NASA NTRS2009

Ethane's 12C/13C Ratio in Titan: Implications for Methane Replenishment

As the .main destination of carbon in the destruction of methane in the atmosphere of Titan, ethane provides information about the carbon isotopic composition of the reservoir from which methane is replenished. If the amount of methane entering the atmosphere is presently equal to the amount converted to ethane, the 12C/13C ratio in ethane should be close to the ratio in the reservoir. We have measured the 12C/13C ratio in ethane both with Cassini CIRS(exp 1) and from the ground and find that it is very close to the telluric standard and outer planet values (89), consistent with a primordial origin for the methane reservoir. The lower 12C/13C ratio measured for methane by Huygens GCMS (82.3) can be explained if the conversion of CH4 to CH3 (and C2H6) favors 12C over 13C with a carbon kinetic isotope effect of 1.08. The time required for the atmospheric methane to reach equilibrium, i.e., for replenishment to equal destruction, is approximately 5 methane atmospheric lifetimes.

Jennings, Donald E.↗

NASA NTRS2010

Carbon and Oxygen Stable Isotope Measurements of Martian Atmospheric CO2 by the Phoenix Lander

Niles, Paul B.↗

NASA NTRS2010

STS 130 Return Samples: Assessment of Air Quality Aboard the Shuttle (STS-130) and International Space Station (20A)

The toxicological assessments of 3 grab sample canisters (GSCs) from the Shuttle are reported in Table 1. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates ( 13C-acetone, fluorobenzene, and chlorobenzene) from the 3 Shuttle GSCs averaged 96, 90, and 85 %, respectively. Based on the end-of-mission sample, the Shuttle atmosphere was acceptable for human respiration.

James, John T.↗

NASA NTRS2010

STS 132 Return Samples: Assessment of Air Quality Aboard the Shuttle (STS-132) and International Space Station (ULF4)

The toxicological assessments of 2 grab sample canisters (GSCs) from the Shuttle are reported. Analytical methods have not changed from earlier reports. The recoveries of the 3 surrogates (13C-acetone, fluorobenzene, and chlorobenzene) from the 2 Shuttle GSCs averaged 93, 85%, and 88%, respectively. Based on the end-of-mission sample, the Shuttle atmosphere was acceptable for human respiration. The toxicological assessment of 7 GSCs from the ISS is also shown. The recoveries of the 3 standards (as listed above) from the GSCs averaged 78, 96 and 90%, respectively. Recovery from formaldehyde control badges ranged from 90 to 112%.

James. John T.↗