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NASA NTRS1974

Absorption cross sections of stratospheric molecules

Two classes of molecular species must be considered in a calculation of photochemical rates in the stratosphere. The first class consists of molecular oxygen and ozone, while the second class contains the remainder of the minor constituents. If accurate values of the transmitted fluxes are required at large optical depths, the cross sections for molecular oxygen and ozone must be known to within a few per cent at least. On the other hand, the photochemical rates for the minor species are given simply by the relevant cross sections. A review of published cross sections is presented, giving attention to molecular oxygen, ozone, nitric oxide, nitrogen dioxide, nitrous oxide, nitric acid, ammonia, water vapor, hydrogen peroxide, carbon monoxide, carbon dioxide, and sulfur dioxide.

Hudson, R. D.↗

NASA NTRS1998

Shock Modifications of Organic Compounds in Carbonaceous Chondrite Parent Bodies

Impacts among asteroidal objects would have altered or destroyed pre-existing organic matter in both targets and projectiles to a greater or lesser degree depending upon impact velocities. To begin filling a knowledge gap on the shock metamorphism of organic compounds, we are studying the effects of shock impacts on selected classes of organic compounds utilizing laboratory shock facilities. Our approach is to subject mixtures of organic compounds, embedded in the matrix of the Murchison meteorite, to simulated hypervelocity impacts by firing them into targets at various pressures. The mixtures are then analyzed to determine the amount of each compound that survives as well as to determine if new compounds are being synthesized. The initial compounds added to the matrix (with the exception of thiosulfate). The sulfonic acids were chosen in part because they are relatively abundant in Murchison, relatively stable, and because they and the phosphonic acids are the first well-characterized homologous series of organic sulfur and phosphorus compounds identified in an extraterrestrial material. Experimental procedures were more fully described in the original proposal. A 20 mm gun, with its barrel extending into a vacuum chamber (10(exp -2) torr), was used to launch the projectile containing the sample at approx. 1.6 km/sec (3,600 mi/hr) into the target material. Maximum pressure of impact depend on target/projectile materials. The target was sufficiently thin to assure minimum pressure decay over the total sample thickness.

Cooper, George W.↗

NASA NTRS1992

The effects of acid deposition on sulfate reduction and methane production in peatlands

Peatlands, as fens and bods, make up a large percentage of northern latitude terrestrial environments. They are organic rich and support an active community of anaerobic bacteria, such as methanogenic and sulfate-reducing bacteria. The end products of these microbial activities, methane and hydrogen sulfide, are important components in the global biogeochemical cycles of carbon and sulfur. Since these two bacterial groups compete for nutritional substrates, increases in sulfate deposition due to acid rain potentially can disrupt the balance between these processes leading to a decrease in methane production and emission. This is significant because methane is a potent greenhouse gas that effects the global heat balance. A section of Mire 239 in the Experimental Lakes Area, in Northwestern Ontario, was artificially acidified and rates of sulfate reduction and methane production were measured with depth. Preliminary results suggested that methane production was not affected immediately after acidification. However, concentrations of dissolved methane decreased and dissolved sulfide increased greatly after acidification and both took several days to recover. The exact mechanism for the decrease in methane was not determined. Analyses are under way which will be used to determine rates of sulfate reduction. These results will be available by Spring and will be discussed.

Murray, Georgia L.↗

NASA NTRS1987

Air Force electrochemical power research and technology program for space applications

An overview is presented of the existing Air Force electrochemical power, battery, and fuel cell programs for space application. Present thrusts are described along with anticipated technology availability dates. Critical problems to be solved before system applications occur are highlighted. Areas of needed performance improvement of batteries and fuel cells presently used are outlined including target dates for key demonstrations of advanced technology. Anticipated performance and current schedules for present technology programs are reviewed. Programs that support conventional military satellite power systems and special high power applications are reviewed. Battery types include bipolar lead-acid, nickel-cadmium, silver-zinc, nickel-hydrogen, sodium-sulfur, and some candidate advanced couples. Fuel cells for pulsed and transportation power applications are discussed as are some candidate advanced regenerative concepts.

Allen, Douglas↗

NASA NTRS2014

Satellite Monitoring Over the Canadian Oil Sands: Highlights from Aura OMI and TES

Satellite remote sensing provides a unique perspective for air quality monitoring in and around the Canadian Oil Sands as a result of its spatial and temporal coverage. Presented are Aura satellite observations of key pollutants including nitrogen dioxide (NO2), sulfur dioxide (SO2), carbon monoxide (CO), ammonia (NH3), methanol (CH3OH), and formic acid (HCOOH) over the Canadian Oil Sands. Some of the highlights include: (i) the evolution of NO2 and SO2 from the Ozone Monitoring Instrument (OMI), including comparisons with other nearby sources, (ii) two years of ammonia, carbon monoxide, methanol, and formic acid observations from 240 km North-South Tropospheric Emission Spectrometer (TES) transects through the oils sands, and (iii) preliminary insights into emissions derived from these observations.

NO2↗

NASA NTRS1978

Simultaneous treatment of SO2 containing stack gases and waste water

A process for simultaneously removing sulfur dioxide from stack gases and the like and purifying waste water such as derived from domestic sewage is described. A portion of the gas stream and a portion of the waste water, the latter containing dissolved iron and having an acidic pH, are contacted in a closed loop gas-liquid scrubbing zone to effect absorption of the sulfur dioxide into the waste water. A second portion of the gas stream and a second portion of the waste water are controlled in an open loop gas-liquid scrubbing zone. The second portion of the waste water contains a lesser amount of iron than the first portion of the waste water. Contacting in the openloop scrubbing zone is sufficient to acidify the waste water which is then treated to remove solids originally present.

Poradek, J. C.↗

NASA NTRS2011

Acid-Sulfate-Weathering Activity in Shergottite Sites on Mars Recorded in Grim Glasses

Based on mass spectrometric studies of sulfur species in Shergotty and EET79001, [1] and [2] showed that sulfates and sulfides occur in different proportions in shergottites. Sulfur speciation studies in gas-rich impact-melt (GRIM) glasses in EET79001 by the XANES method [3] showed that S K-XANES spectra in GRIM glasses from Lith A indicate that S is associated with Ca and Al presumably as sulfides/sulfates whereas the XANES spectra of amorphous sulfide globules in GRIM glasses from Lith B indicate that S is associated with Fe as FeS. In these amorphous iron sulfide globules, [4] found no Ni using FE-SEM and suggested that the globules resulting from immiscible sulfide melt may not be related to the igneous iron sulfides having approximately 1-3% Ni. Furthermore, in the amorphous iron sulfides from 507 GRIM glass, [5] determined delta(sup 34)S values ranging from +3.5%o to -3.1%o using Nano-SIMS. These values plot between the delta(sup 34)S value of +5.25%o determined in the sulfate fraction in Shergotty [6] at one extreme and the value of -1.7%o obtained for igneous sulfides in EET79001 and Shergotty [7] at the other. These results suggest that the amorphous Fe-S globules likely originated by shock reduction of secondary iron sulfate phases occurring in the regolith precursor materials during impact [7]. Sulfates in the regolith materials near the basaltic shergottite sites on Mars owe their origin to surficial acid-sulfate interactions. We examine the nature of these reactions by studying the composition of the end products in altered regolith materials. For the parent material composition, we use that of the host shergottite material in which the impact glasses are situated.

Rao, M. N.↗

NASA NTRS1992

Protein sequences and redox titrations indicate that the electron acceptors in reaction centers from heliobacteria are similar to Photosystem I

Photosynthetic reaction centers isolated from Heliobacillus mobilis exhibit a single major protein on SDS-PAGE of 47 000 Mr. Attempts to sequence the reaction center polypeptide indicated that the N-terminus is blocked. After enzymatic and chemical cleavage, four peptide fragments were sequenced from the Heliobacillus mobilis apoprotein. Only one of these sequences showed significant specific similarity to any of the protein and deduced protein sequences in the GenBank data base. This fragment is identical with 56% of the residues, including both cysteines, found in highly conserved region that is proposed to bind iron-sulfur center Fx in the Photosystem I reaction center peptide that is the psaB gene product. The similarity to the psaA gene product in this region is 48%. Redox titrations of laser-flash-induced photobleaching with millisecond decay kinetics on isolated reaction centers from Heliobacterium gestii indicate a midpoint potential of -414 mV with n = 2 titration behavior. In membranes, the behavior is intermediate between n = 1 and n = 2, and the apparent midpoint potential is -444 mV. This is compared to the behavior in Photosystem I, where the intermediate electron acceptor A1, thought to be a phylloquinone molecule, has been proposed to undergo a double reduction at low redox potentials in the presence of viologen redox mediators. These results strongly suggest that the acceptor side electron transfer system in reaction centers from heliobacteria is indeed analogous to that found in Photosystem I. The sequence similarities indicate that the divergence of the heliobacteria from the Photosystem I line occurred before the gene duplication and subsequent divergence that lead to the heterodimeric protein core of the Photosystem I reaction center.

NASA Discipline Number 52-30↗

NASA NTRS2003

Emissions of Trace Gases and Particles from Savanna Fires in Southern Africa

Airborne measurements made on initial smoke from 10 savanna fires in southern Africa provide quantitative data on emissions of 50 gaseous and particulate species, including carbon dioxide, carbon monoxide, sulfur dioxide, nitrogen oxides, methane, ammonia, dimethyl sulfide, nonmethane organic compounds, halocarbons, gaseous organic acids, aerosol ionic components, carbonaceous aerosols, and condensation nuclei (CN). Measurements of several of the gaseous species by gas chromatography and Fourier transform infrared spectroscopy are compared. Emission ratios and emission factors are given for eight species that have not been reported previously for biomass burning of savanna in southern Africa (namely, dimethyl sulfide, methyl nitrate, five hydrocarbons, and particles with diameters from 0.1 to 3 microns). The emission factor that we measured for ammonia is lower by a factor of 4, and the emission factors for formaldehyde, hydrogen cyanide, and CN are greater by factors of about 3, 20, and 3 - 15, respectively, than previously reported values. The new emission factors are used to estimate annual emissions of these species from savanna fires in Africa and worldwide.

Sinha, Parikhit↗

NASA NTRS1979

Sulfur and halogen chemistry of the stratosphere and of volcanic eruption plumes

The major eruption of Volcan de Fuego caused an enhancement of 1.6 x 10 to the 9 kg of SO4(-) in the stratosphere 6 months after the eruption. Measurable changes in nitric acid vapor and particulate chloride were not observed. Subsequent data suggests that HCl was not injected into the stratosphere. The first simultaneous measurement of halogen and sulfur content of gases and particles in explosive eruption plumes is reported. The average percents of elements in particles were sulfur, 2.5 + or - 2.1; chlorine, 18 + or - 12; and fluorine, 38 + or - 29. The average molecular ratio of HCl/SO2 and HCl/HF were 0.41 + or - 0.26 and 14 + or - 12 in the Guatemalan eruption plumes.

Lazrus, A. L.↗

NASA NTRS2014

Sulfur-Bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from approx.450 to 800 C during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2(approx. 3-22 micro-mol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (approx.41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (approx.1-5 nmol) and CS2(approx.0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

evolved gas analysis↗

NASA NTRS2014

Sulfur-bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from ~450 to 800degC during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2 (~3-22 μmol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (~41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (~1-5nmol) and CS2 (~0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

Gale Crater↗

NASA NTRS1984

Sulphur-rich volcanic eruptions and stratospheric aerosols

Data from direct measurements of stratospheric optical depth, Greenland ice-core acidity, and volcanological studies are compared, and it is shown that relatively small but sulfur-rich volcanic eruptions can have atmospheric effects equal to or even greater than much larger sulfur-poor eruptions. These small eruptions are probably the most frequent cause of increased stratospheric aerosols. The possible sources of the excess sulfur released in these eruptions are discussed.

Rampino, M. R.↗

NASA NTRS1992

Emissions of biogenic sulfur gases from northern bogs and fens

Sulfur gases are important components of the global cycle of S. They contribute to the acidity of precipitation and they influence global radiation balance and climate. The role of terrestrial sources of biogenic S and their effect on atmospheric chemistry remain as major unanswered questions in our understanding of the natural S cycle. The role of northern wetlands as sources and sinks of gaseous S by measuring rates of S gas exchange as a function of season, hydrologic conditions, and gradients in tropic status was investigated. Experiments were conducted in wetlands in New Hampshire, particularly a poor fen, and in Mire 239, a poor fen at the Experimental Lakes Area (ELA) in Ontario. Emissions were determined using Teflon enclosures, gas cryotrapping methods and gas chromatography (GC) with flame photometric detection. Dynamic (sweep flow) and static enclosures were employed which yielded similar results. Dissolved S gases and methane were determined by gas stripping followed by GC.

Demello, William Zamboni↗

NASA NTRS1992

Sulfur gas exchange in Sphagnum-dominated wetlands

Sulfur gases are important components of the global cycle of S. They contribute to the acidity of precipitation and they influence global radiation balance and climate. The role of terrestrial sources of biogenic S and their effect on atmospheric chemistry remain as major unanswered questions in our understanding of the natural S cycle. The role of northern wetlands as sources and sinks of gaseous S was investigated by measuring rates of S gas exchange as a function of season, hydrologic conditions, and gradients in trophic status. The effects of inorganic S input on the production and emission of gaseous S were also investigated. Experiments were conducted in wetlands in New Hampshire, particularly a poor fen, fens within the Experimental Lakes Area (ELA) in Ontario, Canada and in freshwater and marine tundra. Emissions were determined using Teflon enclosures, gas cryotrapping methods, and gas chromatography (GC) with flame photometric detection. Dynamic (sweep flow) and static enclosures were employed. Dissolved gases were determined by gas stripping followed by GC.

Hines, Mark E.↗

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 NTRS2015

Alternative-Fuel Effects on Contrails & Cruise Emissions (ACCESS-2) Flight Experiment

Although the emission performance of gas-turbine engines burning renewable aviation fuels have been thoroughly documented in recent ground-based studies, there is still great uncertainty regarding how the fuels effect aircraft exhaust composition and contrail formation at cruise altitudes. To fill this information gap, the NASA Aeronautics Research Mission Directorate sponsored the ACCESS flight series to make detailed measurements of trace gases, aerosols and ice particles in the near-field behind the NASA DC-8 aircraft as it burned either standard petroleum-based fuel of varying sulfur content or a 50:50 blend of standard fuel and a hydro-treated esters and fatty acid (HEFA) jet fuel produced from camelina plant oil. ACCESS 1, conducted in spring 2013 near Palmdale CA, focused on refining flight plans and sampling techniques and used the instrumented NASA Langley HU-25 aircraft to document DC-8 emissions and contrails on five separate flights of approx.2 hour duration. ACCESS 2, conducted from Palmdale in May 2014, engaged partners from the Deutsches Zentrum fuer Luft- und Raumfahrt (DLR) and National Research Council-Canada to provide additional scientific expertise and sampling aircraft (Falcon 20 and CT-133, respectively) with more extensive trace gas, particle, or air motion measurement capability. Eight, muliti-aircraft research flights of 2 to 4 hour duration were conducted to document the emissions and contrail properties of the DC-8 as it 1) burned low sulfur Jet A, high sulfur Jet A or low sulfur Jet A/HEFA blend, 2) flew at altitudes between 6 and 11 km, and 3) operated its engines at three different fuel flow rates. This presentation further describes the ACCESS flight experiments, examines fuel type and thrust setting impacts on engine emissions, and compares cruise-altitude observations with similar data acquired in ground tests.

Anderson, Bruce E.↗

NASA NTRS1995

A Model Simulation of Pinatubo Volcanic Aerosols in the Stratosphere

A one-dimensional, time-dependent model is used to study the chemical, microphysical, and radiative properties of volcanic aerosols produced by the Mount Pinatubo eruption on June 15, 1991. Our model treats gas-phase sulfur photochemistry, gas-to-particle conversion of sulfur, and the microphysics of sulfate aerosols and ash particles under stratospheric conditions. The dilution and diffusion of the volcanic eruption clouds are also accounted for in these conditions. Heteromolecular homogeneous and heterogeneous binary H2SO4/H2O nucleation, acid and water condensational growth, coagulation, and gravitational sedimentation are treated in detail in the model. Simulations suggested that after several weeks, the volcanic cloud was composed mainly of sulfuric acid/water droplets produced in situ from the SO2 emissions. The large amounts of SO2 (around 20 Mt) injected into the stratosphere by the Pinatubo eruption initiated homogeneous nucleation which generated a high concentration of small H2SO4/H2O droplets. These newly formed particles grew rapidly by condensation and coagulation in the first few months and then reach their stabilized sizes with effective radii in a range between 0.3 and 0.5 micron approximately one-half year after the eruption. The predicted volcanic cloud parameters reasonably agree with measurements in term of the vertical distribution and lifetime of the volcanic aerosols, their basic microphysical structures (e.g., size distribution, concentration, mass ratio, and surface area) and radiative properties. The persistent volcanic aerosols can produce significant anomalies in the radiation field, which have important climatic consequences. The large enhancement in aerosol surface area can result in measurable global stratospheric ozone depletion.

Zhao , Jing-xia↗