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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Chemical and Thermal Analysis

Thermal decomposition activation energies have been determined using two methods of Thermogravimetric Analysis (TGA), with good correlation being obtained between the two techniques. Initial heating curves indicated a two-component system for Coflon (i.e. polymer plus placticizer) but a single component system for Tefzel. Two widely differing activation energies were for Coflon supported this view, 15 kcl/mol being associated with plasticizer, and 40 kcal/mol with polymer degradation. With Tefzel, values were 40-45 kcal/mol, the former perhaps being associated with a low molecular weight fraction. Appropriate acceleration factors have been determined. Thermomechanical Analysis (TMA) has shown considerable dimensional change during temperature cycles. For unaged pipe sections heating to 100 C and then holding the temperature resulted in a stable thickness increase of 2%, whereas the Coflon thickness decreased continuously, reaching -4% in 2.7 weeks. Previously strained tensile bars of Tefzel expanded on cooling during TMA. SEM performed on H2S-aged Coflon samples showed significant changes in both physical and chemical nature. The first may have resulted from explosive decompression after part of the aging process. Chemically extensive dehydrofluorination was indicated, and sulfur was present as a result of the aging. These observations indicate that chemical attack of PVDF can occur in some circumstances.

Bulluck, J. W.↗
NASA NTRS1997

High-Resolution Temperature-Dependent Photoabsorption Cross Section Measurements of S2, with Application to HST UV Spectra of SL9/Jupiter

The Hubble Space Telescope (HST) UV spectra of Jupiter after the collision of Comet SL9 show predominantly molecular features of S2, CS2, NH3, and H2S in the 1800-3200 A region. The HST observations were made under various phases of impact conditions which gave temperatures higher than 1000 K. It is thus clear that temperature-dependent laboratory cross section data are required in order to determine the molecular abundances in Jupiter's atmosphere after the impact of Comet Shoemaker-Levy 9. The required high-resolution temperature dependent S2 absorption cross sections have not been directly measured in the laboratory. To provide the required data for modelers our objective is to accurately measure the high-resolution (FWHM = 0.003 A) and medium resolution (FWHM - 0.08 A) temperature dependent S2 in the 2450-3200 A region. Using the experimental setup we have obtained absorbtion spectra of S2 under various temperature conditions.

Wu, C. Y. Robert↗
NASA NTRS1998

The Role of Grain Surface Reactions in the Chemistry of Star Forming Regions

The importance of reactions at the surfaces of dust grains has long been recognized to be one of the two main chemical processes that form molecules in cold, dark interstellar clouds where simple, saturated (fully-hydrogenated) molecules such as H2 water, methanol, H2CO, H2S, ammonia and CH4 are present in quantities far too high to be consistent with their extremely low gas phase formation rates. In cold dark regions of interstellar space, dust grains provide a substrate onto which gas-phase species can accrete and react. Grains provide a "third body" or a sink for the energy released in the exothermic reactions that form chemical bonds. In essence, the surfaces of dust grains open up alternative reaction pathways to form observed molecules whose abundances cannot be explained with gas-phase chemistry alone. This concept is taken one step further in this work: instead of merely acting as a substrate onto which radicals and molecules may physically adsorb, some grains may actively participate in the reaction itself, forming chemical bonds with the accreting species. Until recently, surface chemical reactions had not been thought to be important in warm circumstellar media because adspecies rapidly desorb from grains at very low temperatures; thus, the residence times of molecules and radicals on the surface of grains at all but the lowest temperatures are far too short to allow these reactions to occur. However, if the adspecies could adsorb more strongly, via a true chemical bond with surfaces of some dust grains, then grain surface reactions will play an important role in warm circumstellar regions as well. In this work, the surface-catalyzed reaction CO + 3 H2 yields CH4 + H2O is studied in the context that it may be very effective at converting the inorganic molecule CO into the simplest organic compound, methane. H2 and CO are the most abundant molecules in space, and the reaction converting them to methane, while kinetically inhibited in the gas phase under most astrophysical conditions, is catalyzed by iron, an abundant constituent of interstellar dust. At temperatures between 600 and 1000 K, which occur in the outflows from red giants and near luminous young stars, this reaction readily proceeds in the presence of an iron catalyst. Iron is one of the more abundant elements composing interstellar dust. Its abundance relative to hydrogen is almost that of silicon, and both of these heavy elements are primarily locked up in dust at all but the hottest regions of interstellar space.

Kress, M. E.↗
NASA NTRS1996

Endogenous Synthesis of Prebiotic Organic Molecules

The necessary condition for the synthesis of organic compounds on the primitive earth is the presence of reducing conditions. This means an atmosphere of CH4, CO, or CO2 + H2. The atmospheric nitrogen can be N2 with a trace of NH3, but NH4(+) is needed in the ocean at least for amino acid synthesis. Many attempts have been made to use CO2 + H2O atmospheres for prebiotic synthesis, but these give at best extremely low yields of organic compounds, except in the presence of H2. Even strong reducing agents such as FeS + H2S or the mineral assemblages of the submarine vents fail to give significant yields of organic compounds with CO2. There appears to be a high kinetic barrier to the non-biological reduction of CO2 at low temperatures using geological reducing agents. The most abundant source of energy for prebiotic synthesis is ultraviolet light followed by electric discharges, with electric discharges being more efficient, although it is not clear which was the important energy source. Photochemical process would also make significant contributions. In an atmosphere Of CO2, N2, and H2O with no H2, the production rates of HCN and H2CO would be very low, 0.001 or less than that of a relatively reducing atmosphere. The concentration of organic compounds under these non-reducing conditions would be so low that there is doubt whether the concentration mechanism would be adequate for further steps toward the origin of life. A number of workers have calculated the influx of comets and meteorites on the primitive earth as a source of organic compounds. We conclude that while some organic material was added to the earth from comets and meteorites the amount available from these sources at a given time was at best only a few percent of that from earth bases syntheses under reducing conditions.

Miller, Stanley L.↗
NASA NTRS1971

Improved Chromatographic Techniques for Sulfur Pollutants

This paper describes several improvements in instrumental techniques for the analysis of low ppb concentrations of sulfur gases using gas chromatography (G.C.). This work has focused on the analytical problem of ambient air monitoring of the two main sulfur gas pollutants, hydrogen sulfide and sulfur dioxide. The most significant technical improvement that will be reported here is the newly developed silica gel column for ppb concentrations of the light sulfur gases (COS, H2S, CS2, SO2, CH3SH). A simplified inlet system will be described which improves reliability of the GC system. The flame photometric detector is used as the means of selectively and sensitively detecting the low concentrations of sulfur gases. Improvements will be described which have yielded better performance than previously reported for this application of the detector. Also included in this paper will be a report of field monitoring using this improved GC system. Reliability and repeatability of performance at the low ppb concentrations of sulfur gases will be demonstrated.

Hartmann, C. H.↗
NASA NTRS1998

Contributions of Nimbus 7 TOMS Data to Volcanic Study and Hazard Mitigation

Nimbus TOMS data have led to advancements among many volcano-related scientific disciplines, from the initial ability to quantify SO2 clouds leading to derivations of eruptive S budgets and fluxes, to tracking of individual clouds, assessing global volcanism and atmospheric impacts. Some of the major aspects of TOMS-related research, listed below, will be reviewed and updated: (1) Measurement of volcanic SO2 clouds: Nimbus TOMS observed over 100 individual SO2 clouds during its mission lifetime; large explosive eruptions are now routinely and reliably measured by satellite. (2) Eruption processes: quantification of SO2 emissions have allowed assessments of eruption sulfur budgets, the evaluation of "excess" sulfur, and inferences of H2S emissions. (3) Detection of ash: TOMS data are now used to detect volcanic particulates in the atmosphere, providing complementary analyses to infrared methods of detection. Paired TOMS and AVHRR studies have provided invaluable information on volcanic cloud compositions and processes. (4) Cloud tracking and hazard mitigation: volcanic clouds can be considered gigantic tracers in the atmosphere, and studies of the fates of these clouds have led to new knowledge of their physical and chemical dispersion in the atmosphere for predictive models. (5) Global trends: the long term data set has provided researchers an unparalleled record of explosive volcanism, and forms a key component in assessing annual to decadal trends in global S emissions. (6) Atmospheric impacts: TOMS data have been linked to independent records of atmospheric change, in order to compare cause and effect processes following a massive injection of SO2 into the atmosphere. (7) Future TOMS instruments and applications: Nimbus TOMS has given way to new satellite platforms, with several wavelength and resolution modifications. New efforts to launch a geostationary TOMS could provide unprecedented observations of volcanic activity.

Krueger, Arlin J.↗
NASA NTRS1999

NASA GRC's High Pressure Burner Rig Facility and Materials Test Capabilities

The High Pressure Burner Rig (HPBR) at NASA Glenn Research Center is a high-velocity. pressurized combustion test rig used for high-temperature environmental durability studies of advanced materials and components. The facility burns jet fuel and air in controlled ratios, simulating combustion gas chemistries and temperatures that are realistic to those in gas turbine engines. In addition, the test section is capable of simulating the pressures and gas velocities representative of today's aircraft. The HPBR provides a relatively inexpensive. yet sophisticated means for researchers to study the high-temperature oxidation of advanced materials. The facility has the unique capability of operating under both fuel-lean and fuel-rich gas mixtures. using a fume incinerator to eliminate any harmful byproduct emissions (CO, H2S) of rich-burn operation. Test samples are easily accessible for ongoing inspection and documentation of weight change, thickness, cracking, and other metrics. Temperature measurement is available in the form of both thermocouples and optical pyrometery. and the facility is equipped with quartz windows for observation and video taping. Operating conditions include: (1) 1.0 kg/sec (2.0 lbm/sec) combustion and secondary cooling airflow capability: (2) Equivalence ratios of 0.5- 1.0 (lean) to 1.5-2.0 (rich), with typically 10% H2O vapor pressure: (3) Gas temperatures ranging 700-1650 C (1300-3000 F): (4) Test pressures ranging 4-12 atmospheres: (5) Gas flow velocities ranging 10-30 m/s (50-100) ft/sec.: and (6) Cyclic and steady-state exposure capabilities. The facility has historically been used to test coupon-size materials. including metals and ceramics. However complex-shaped components have also been tested including cylinders, airfoils, and film-cooled end walls. The facility has also been used to develop thin-film temperature measurement sensors.

Robinson, R. Craig↗
NASA NTRS2000

Volcanic Degassing of Hydrogen Compounds on Io

Thermodynamic calculations show that hydrogen, recently detected in Io's ionosphere by the Galileo spacecraft, can degas from high-temperature silicate magmas on Io in the form of H2O, H2S, HS, NaOH, H2, KOH, and HCl in order of decreasing abundance.

Zolotov, M. Yu.↗
NASA NTRS2001

Saturn Deep Atmospheric Entry Probes Delivered by INSIDE Jupiter Derivative Spacecraft

In situ probes are the most reliable means for sampling composition and conditions deep in giant planet atmospheres. Deep constituent abundances at the giant planets offer clues to conditions in the solar systems protoplanetary disk and variations with heliocentric distance. Currently in situ atmospheric data are available from only one giant planet, Jupiter, and probes that penetrate deeper than the Galileo probe are needed there to measure the deep abundances of such important species as H2O and H2S. Deep probes at Saturn would extend the sampled heliocentric range to Saturn, providing important constraints on the conditions and variability of the protoplanetary disk, and would provide significant new information about Saturn and its evolutionary processes. Such a probe mission could be implemented using a derivative of the INSIDE Jupiter mission's spacecraft as the Carrier/Relay Spacecraft (CRSC), with probes per JPL/Team X and other design studies. Additional information is contained in the original extended abstract.

Spilker, T. R.↗
NASA NTRS2001

Flyby Delivers Multiple Deep Jupiter Probes

In situ probes are the most reliable means for sampling composition and conditions deep in giant planet atmospheres. While exceeding its baseline mission, the Galileo probe entered a distinctly non-representative region of Jupiter (a 'hot spot') and apparently did not measure the full deep abundances of such important species as H2O and H2S, whose measured abundances were still increasing at the deepest datum. Multiple deep (approx. 100 bar) in situ probes minimize the hot spot risk, and address spatial variations and deep constituent abundances. Additional information is contained in the original extended abstract.

Spilker, T. R.↗
NASA NTRS1994

Fourfold Clusters of Rovibrational Energies in H2Te Studied With an Ab Initio Potential Energy Function

We report an ab initio investigation of the cluster effect (i.e., the formation of nearly degenerate, four member groups of rotation-vibration energy levels at higher J and K(sub a). values) in the H2Te molecule. The potential energy function has been calculated ab initio at a total of 334 molecular geometries by means of the CCSD(T) method where the (1s-4f) core electrons of Te were described by an effective core potential. The values of the potential energy function obtained cover the region up to around 10,000/cm above the equilibrium energy. On the basis of the ab initio potential, the rotation-vibration energy spectra of H2Te-130 and its deuterated isotopomers have been calculated with the MORBID (Morse Oscillator Rigid Bender Internal Dynamics) Hamiltonian and computer program. In particular, we have calculated the rotational energy manifolds for J less than or = 40 in the vibrational ground state, the upsilon(sub 2) state, the "first triad" (the upsilon(sub l)/upsilon(sub 3)/2upsilon(sub 2) interacting vibrational states), and the "second triad" (the upsilon(sub 1) + upsilon(sub 2/upsilon(sub 2) + upsilon(sub 3)/3upsilon(sub 2) states) of H2Te-130. We find that the cluster formation in H2Te is very similar to those of of H2Se and H2S, which we have studied previously. However, contrary to semiclassical predictions, we do not determine any significant displacement of the clusters towards lower J values relative to H2Se. Hence the experimental observation of the cluster states in H2Te will be at least as difficult as in H2Se.

Jensen, Per↗
NASA NTRS2000

Thermodynamics of Aqueous Organic Sulfur Compounds: A Key to the Organic Geochemistry of Hydrothermal Systems?

Hydrothermal environments are locations of varied geochemistry due to the disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Observations of the organic geochemistry of hydrothermal vent sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols. thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments as well as in a variety of biological processes and other abiotic reactions (Wachtershauser, 1990, OLEB 20, 173; Heinen and Lauwers, 1996, OLEB 26, 13 1, Huber and Wachtershauser, 1997, Science 276, 245; Russell et al., 1998, in Thermophiles: The keys to molecular evolution and the origin of life?). The reduction of CO2 to thiols, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power (see Schoonen et al., 1999, OLEB 29, 5). In addition, the enzyme involved in final stage of methanogenesis, coenzyme-M, is itself a thiol. Thus, organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life at high temperatures. Understanding the biochemical processes of microorganisms that can live to temperatures at least as high as 113 C (Blochl et al., 1996, Extremophiles 1, 14) requires knowledge of the properties of the chemical reactions involved. In order to assess the role of aqueous organic sulfur compounds in hydrothermal organic geochemistry, we have been attempting to determine their thermodynamic properties. We have culled the literature to obtain the properties of organic sulfur compounds. We are able to calculate a number of essential properties, such as free energies of formation, from solubility data available in the literature together with standard properties of organic sulfur gases. However, a number of the properties for aqueous organic sulfur compounds have not been experimentally determined. Furthermore, most of thermodynamic data that are available are for 25 C and 1 bar. In order to determine reaction properties to temperatures and pressures appropriate to the hydrothermal conditions in which thermophilic organisms actually live, we use equations of state developed by Helgeson and co-workers (Helgeson et al., 1981, AJS 281, 1249). A key piece of information needed to go up in temperature is the partial molal heat capacity, which is one of the properties for which experimental data are unavailable for nearly all organic sulfur compounds. We have used correlation methods to determine the partial molal heat capacities and volumes of many organic solutes. These estimates allow us to asses the role of organic sulfur compounds during the reduction of carbon in hydrothermal settings. We will present these data, along with examples of the thermodynamic properties of reactions involving aqueous organic sulfur compounds.

Schulte, Mitchell↗
NASA NTRS2001

The Biogeochemistry of Sulfur in Hydrothermal Systems

The incorporation of sulfur into many biomolecules likely dates back to the development of the earliest metabolic strategies. Sulfur is common in enzymes and co-enzymes and is an indispensable structural component in many peptides and proteins. Early metabolism may have been heavily influenced by the abundance of sulfide minerals in hydrothermal systems. The incorporation of sulfur into many biomolecules likely dates back to the development of the earliest metabolic strategies. Sulfur is common in enzymes and co-enzymes and is an indispensable structural component in many peptides and proteins. Early metabolism may have been heavily influenced by the abundance of sulfide minerals in hydrothermal systems. Understanding how sulfur became prevalent in biochemical processes and many biomolecules requires knowledge of the reaction properties of sulfur-bearing compounds. We have previously estimated thermodynamic data for thiols, the simplest organic sulfur compounds, at elevated temperatures and pressures. If life began in hydrothermal environments, it is especially important to understand reactions at elevated temperatures among sulfur-bearing compounds and other organic molecules essential for the origin and persistence of life. Here we examine reactions that may have formed amino acids with thiols as reaction intermediates in hypothetical early Earth hydrothermal environments. (There are two amino acids, cysteine and methionine, that contain sulfur.) Our calculations suggest that significant amounts of some amino acids were produced in early Earth hydrothermal fluids, given reasonable concentrations H2, NH3, H2S and CO. For example, preliminary results indicate that glycine activities as high as 1 mmol can be reached in these systems at 100 C. Alanine formation from propanethiol is also a favorable reaction. On the other hand, the calculated equilibrium log activities of cysteine and serine from propanethiol are -21 and -19, respectively, at 100 C. These results indicate that while amino acid formation with thiols as intermediates is favored in some cases, other mechanisms may have been necessary to produce significant amounts of other amino acids. Coupled with our previous results for thiols, these studies imply that sulfur may have been easily incorporated into the organic geochemistry of early Earth hydrothermal systems, leading to its widespread use in biomolecules. Formation of more complex biomolecules in hydrothermal systems may have required sulfur-bearing organic compounds as reaction intermediates.

Schulte, Mitchell↗
NASA NTRS2001

Annealing of Solar Cells and Other Thin Film Devices

Annealing is a key step in most semiconductor fabrication processes, especially for thin films where annealing enhances performance by healing defects and increasing grain sizes. We have employed a new annealing oven for the annealing of CdTe-based solar cells and have been using this system in an attempt to grow US on top of CdTe by annealing in the presence of H2S gas. Preliminary results of this process on CdTe solar cells and other thin-film devices will be presented.

Escobar, Hector↗
NASA NTRS2001

Landform Degradation and Slope Processes on Io: The Galileo View

The Galileo mission has revealed remarkable evidence of mass movement and landform degradation on Io. We recognize four major slope types observed on a number of intermediate resolution (250 m/pixel) images and several additional textures on very high resolution (10 m/pixel) images. Slopes and scarps on Io often show evidence of erosion, seen in the simplest form as alcove-carving slumps and slides at all scales. Many of the mass movement deposits on Io are probably mostly the consequence of block release and brittle slope failure. Sputtering plays no significant role. Sapping as envisioned by McCauley et al. remains viable. We speculate that alcove-lined canyons seen in one observation and lobed deposits seen along the bases of scarps in several locations may reflect the plastic deformation and 'glacial' flow of interstitial volatiles (e.g., SO2) heated by locally high geothermal energy to mobilize the volatile. The appearance of some slopes and near-slope surface textures seen in very high resolution images is consistent with erosion from sublimation-degradation. However, a suitable volatile (e.g., H2S) that can sublimate fast enough to alter Io's youthful surface has not been identified. Disaggregation from chemical decomposition of solid S2O and other polysulfur oxides may conceivably operate on Io. This mechanism could degrade landforms in a manner that resembles degradation from sublimation, and at a rate that can compete with resurfacing.

Moore, Jeffrey M.↗
NASA NTRS2001

Thiols in Hydrothermal Solution: Standard Partial Molal Properties and Their Role in the Organic Geochemistry of Hydrothermal Environments

Modern seafloor hydrothermal systems are locations where great varieties of geochemistry occur due to the enormous disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Despite the incomplete understanding of the carbon budget in hydrothermal systems, the organic geochemistry of these sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols, thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments, as well as in a variety of biological processes and other abiotic reactions. The reduction of CO2 to thesis, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power. We have used recent advances in theoretical geochemistry to estimate the standard partial moral thermodynamic properties and parameters for the revised Helgeson-Kirkham-Flowers equation of state for aqueous straight-chain alkyl thesis. With these data and parameters we have evaluated the role that organic sulfur compounds may play as reaction intermediates during organic compound synthesis. We conclude that organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life in hydrothermal settings. These results may also explain the presence of sulfur in a number of biomolecules present in ancient thermophilic microorganisms.

Schulte, Mitchell D.↗
NASA NTRS2002

Hypersaline Microbial Mat Lipid Biomarkers

Lipid biomarkers and compound specific isotopic abundances are powerful tools for studies of contemporary microbial ecosystems. Knowledge of the relationship of biomarkers to microbial physiology and community structure creates important links for understanding the nature of early organisms and paleoenvironments. Our recent work has focused on the hypersaline microbial mats in evaporation ponds at Guerrero Negro, Baja California Sur, Mexico. Specific biomarkers for diatoms, cyanobacteria, archaea, green nonsulfur (GNS), sulfate reducing, sulfur oxidizing and methanotrophic bacteria have been identified. Analyses of the ester-bound fatty acids indicate a highly diverse microbial community, dominated by photosynthetic organisms at the surface. The delta C-13 of cyanobacterial biomarkers such as the monomethylalkanes and hopanoids are consistent with the delta C-13 measured for bulk mat (-10%o), while a GNS biomarker, wax esters (WXE), suggests a more depleted delta C-13 for GNS biomass (-16%o). This isotopic relationship is different than that observed in mats at Octopus Spring, Yellowstone National Park (YSNP) where GNS appear to grow photoheterotrophic ally. WXE abundance, while relatively low, is most pronounced in an anaerobic zone just below the cyanobacterial layer. The WXE isotope composition at GN suggests that these bacteria utilize photoautotrophy incorporating dissolved inorganic carbon (DIC) via the 3-hydroxypropionate pathway using H2S or H2.

Jahnke, Linda L.↗
NASA NTRS2002

Desulfonatronum paiuteum sp. nov.: A New Alkaliphilic, Sulfate-Reducing Bacterium, Isolated from Soda Mono Lake, California

A novel alkaliphilic, sulfate reducing bacterium strain MLF1(sup T) was isolated from sediments of soda Mono Lake, California. Gram-negative vibrion cells, motile by singular polar flagellum, with sizes 0.5 - 0.6x 1.2 - 2.0 micron occurred singly, in pairs or short spirilla. Growth was observed over the temperature range of +15 C to +48 C (optimum +37 C), NaCl concentration range is greater than 1 - 7 %, wt/vol (optimum 3 %, wt/vol) and pH range 7.8 - 10.5 (optimum pH 9.0 - 9.4). The novel isolate is strictly alkaliphilic, requires high carbonate concentration in medium, obligately anaerobic and catalase negative. As electron donors strain MLF1(sup T) uses hydrogen, formate, ethanol. Sulfate, sulfite, and thiosulfate (but not sulfur or nitrate) can be used as electron acceptors. The sole end product of growth on formate was H2S. Strain MLF1(sup T) is resistant to kanamycin and gentamycin, but sensitive to chloramphenicol and tetracycline. Na2MoO4 inhibits growth of strain MLF1(sup T). The sum of G+C in DNA is 63.1 mol% (by HPLC method). On the basis of physiological and molecular properties, the isolate was considered as novel species of genus Desulfonatronum; and the name Desulfonatronum paiuteum sp. nov., is proposed (type strain MLF1(sup T) = ATCC BAA-395(sup T) = DSMZ 14708(sup T).

Pikuta, Elena↗