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At least 235 records · Page 13

Sources and geochemical evolution of cyanide and formaldehyde

The major source of cyanide has, in current paleoatmospheric models, been assumed to be the reaction of photodissociated thermospheric nitrogen with a limiting supply of stratospheric methane. Formaldehyde may be produced with more ease from an atmosphere of carbon dioxide as the dominant carbon species, and from carbonate in solution or sorbed in double layer hydroxide minerals. Potentially more important sources for cyanide and other carbon containing molecules are the partially photoprotected northern and southern auroral ovals where continuous currents reaching several mega-amperes induce ion-molecule reactions, extending into the lower stratosphere. In simulated environments of this kind, the cyanide ion is known to be produced from oxidized carbon species potentially more abundant than methane. Rainout of cyanide and formaldehyde place them in two different geochemical reaction reservoirs. In the anoxic Archean hydrosphere, about 1mM in Fe2(+), the cyanide ion would have been efficiently converted to the stable ferrocyanide complex Fe(CN) sub 6(4-), protecting it from the commonly considered fate of decomposition by hydrolysis, and eventually incorporating it in pyroaurite type minerals, most efficiently in green rust where it converts to insoluble ferriferrocyanide, prussian blue.

Arrhenius, G.↗

Light-Weight Injector Technology for Cryogenic Mars Ascent Engines

Preliminary mission studies for human exploration of Mars have been performed at Marshall Space Flight Center (MSFC). These studies indicate that for chemical rockets only a cryogenic propulsion system would provide high enough performance to be considered for a Mars ascent vehicle. Although the mission is possible with Earth-supplied propellants for this vehicle, utilization of in-situ propellants is highly attractive. This option would significantly reduce the overall mass of launch vehicles. Consequently, the cost of the mission would be greatly reduced because the number and size of the Earth launch vehicle(s) needed for the mission decrease. NASA/Johnson Space Center has initiated several concept studies of in-situ propellant production plants. Liquid oxygen (LOX) is the primary candidate for an in-situ oxidizer. In-situ fuel candidates include methane (CH4), ethylene (C2H4), and methanol (CH3OH). MSFC initiated a technology development program for a cryogenic propulsion system for the Mars human exploration mission in 1998. One part of this technology program is the effort described here: an evaluation of propellant injection concepts for a LOX/liquid methane Mars Ascent Engine (MAE) with an emphasis on light-weight, high efficiency, reliability, and thermal compatibility. In addition to the main objective, hot-fire tests of the subject injectors will be used to test other key technologies including light-weight combustion chamber materials and advanced ignition concepts. This state-of-the-art technology will then be applied to the development of a cryogenic propulsion system that will meet the requirements of the planned Mars sample return (MSR) mission. The current baseline propulsion system for the MSR mission uses a storable propellant combination [monomethyl hydrazine/mixed oxides of nitrogen-25. However, a mission option that incorporates in-situ propellant production and utilization for the ascent stage is being carefully considered as a subscale precursor to a future human mission to Mars.

Trihn, Huu Phuoc↗

Assessing Non-CO2 Climate-Forcing Emissions and Mitigation in Sub-Saharan Africa

There are few direct measurements of anthropogenic climate-forcing emissions in Africa, making it difficult to accurately assess current emissions and to anticipate changes in future emissions. Emissions databases suggest that sub-Saharan Africa (SSA), home to less than 15 of the world's population, is responsible for 11 of anthropogenic methane (CH4) and 18 of anthropogenic nitrous oxide (N2O) emissions globally, though this includes substantial emissions from biomass burning that would occur in the absence of contemporary anthropogenic activity, and which may be over-estimated. SSA is also an important source of precursors to the greenhouse gas tropospheric ozone, and of mineral dust, which has a range of impacts on climate. Eliminating food insecurity and poverty is likely to take priority over greenhouse gas mitigation in the region, so innovations in mitigation must focus on ways to reduce emissions as an ancillary benefit of improving livelihoods.

Africa↗

Suppression of Low Strain Rate Nonpremixed Flames by an Agent

The agent concentration required to achieve the suppression of low strain rate nonpremixed flames is an important consideration for fire protection in a microgravity environment such as a space platform. Currently, there is a lack of understanding of the structure and extinction of low strain rate (<20 s(exp -1)) nonpremixed flames. The exception to this statement is the study by Maruta et al., who reported measurements of low strain rate suppression of methane-air diffusion flames with N2 added to the fuel stream under microgravity conditions. They found that the nitrogen concentration required to achieve extinction increased as the strain rate decreased until a critical value was obtained. As the strain rate was further decreased, the required N2 concentration decreased. This phenomenon was termed "turning point" behavior and was attributed to radiation-induced nonpremixed flame extinction. In terms of fire safety, a critical agent concentration assuring suppression under all flow conditions represents a fundamental limit for nonpremixed flames. Counterflow flames are a convenient configuration for control of the flame strain rate. In high and moderately strained near-extinction nonpremixed flames, analysis of flame structure typically neglects radiant energy loss because the flames are nonluminous and the hot gas species are confined to a thin reaction zone. In counterflowing CH4-air flames, for example, radiative heat loss fractions ranging from 1 to 6 percent have been predicted and measured. The objective of this study is to investigate the impact of radiative emission, flame strain, agent addition, and buoyancy on the structure and extinction of low strain rate nonpremixed flames through measurements and comparison with flame simulations. The suppression effectiveness of a number of suppressants (N2, CO2, or CF3Br) was considered as they were added to either the fuel or oxidizer streams of low strain rate methane-air diffusion flames.

Hamins, A.↗

High pressure flame system for pollution studies with results for methane-air diffusion flames

A high pressure flame system was designed and constructed for studying nitrogen oxide formation in fuel air combustion. Its advantages and limitations were demonstrated by tests with a confined laminar methane air diffusion flame over the pressure range from 1 to 50 atm. The methane issued from a 3.06 mm diameter port concentrically into a stream of air contained within a 20.5 mm diameter chimney. As the combustion pressure is increased, the flame changes in shape from wide and convex to slender and concave, and there is a marked increase in the amount of luminous carbon. The height of the flame changes only moderately with pressure.

Miller, I. M.↗

Correlation interferometric measurement of trace species in the atmosphere.

Two correlation interferometers, a breadboard model and an engineering model, have been designed, constructed, and tested for the measurement of selected atmospheric trace species. Test results showed that errors of less than 10% are attainable for atmospheric amounts of carbon monoxide and methane measured at 2.3 microns. Based on these results a program has been undertaken to determine the feasibility of measuring other trace species by correlation interferometry. It shown that in addition to carbon monoxide and methane, carbon dioxide, water vapor, ammonia, nitric oxide, nitrous oxide, nitrogen dioxide, and sulfur dioxide can also be accurately measured with this instrument.

Goldstein, H. W.↗

A high pressure modulated molecular beam mass spectrometric sampling system

The current state of understanding of free-jet high pressure sampling is critically reviewed and modifications of certain theoretical and empirical considerations are presented. A high pressure, free-jet expansion, modulated molecular beam, mass spectrometric sampling apparatus was constructed and this apparatus is described in detail. Experimental studies have demonstrated that the apparatus can be used to sample high temperature systems at pressures up to one atmosphere. Condensible high temperature gaseous species have been routinely sampled and the mass spectrometric detector has provided direct identification of sampled species. System sensitivity is better than one tenth of a part per million. Experimental results obtained with argon and nitrogen beams are presented and compared to theoretical predictions. These results and the respective comparison are taken to indicate acceptable performance of the sampling apparatus. Results are also given for two groups of experiments related to hot corrosion studies. The formation of gaseous sodium sulfate in doped methane-oxygen flames was characterized and the oxidative vaporization of metals was studied in an atmospheric pressure flowing gas system to which gaseous salt partial pressures were added.

Stearns, C. A.↗

Liquid Methane/Liquid Oxygen Injectors for Potential Future Mars Ascent Engines

Preliminary mission studies for human exploration of Mars have been performed at Marshall Space Flight Center (MSFC). These studies indicate that for chemical rockets only a cryogenic propulsion system would provide high enough performance to be considered for a Mars ascent vehicle. Although the mission is possible with Earth-supplied propellants for this vehicle, utilization of in-situ propellants is highly attractive. This option would significantly reduce the overall mass of launch vehicles. Consequently, the cost of the mission would be greatly reduced because the number and size of the Earth launch vehicle(s) needed for the mission would decrease. NASA/Johnson Space Center has initiated several concept studies of in-situ propellant production plants. Liquid oxygen (LOX) is the primary candidate for an in-situ oxidizer. In-situ fuel candidates include methane (CH4), ethylene (C2H4), and methanol (CH3OH). MSFC initiated a technology development program for a cryogenic propulsion system for the Mars human exploration mission in 1998. One part of this technology program is the effort described here: an evaluation of propellant injection concepts for a LOX/liquid methane Mars Ascent Engine (MAE) with an emphasis on light-weight, high efficiency, reliability, and thermal compatibility. In addition to the main objective, hot-fire tests of the subject injectors will be used to test other key technologies including light-weight combustion chamber materials and advanced ignition concepts. This paper will address the results of the liquid methane/LOX injector study conducted at MSFC. A total of four impinging injector configurations were tested under combustion conditions in a modular combustor test article (MCTA), equipped with optically accessible windows. A series of forty hot-fire tests, which covered a wide range of engine operating conditions with the chamber pressure varied from 320 to 510 and the mixture ratio from 1.5 to 3.5, were performed. The test matrix also included a variation in the combustion chamber length for the purpose of investigating its effects on the combustion performance and stability.

Trinh, Huu Phuoc↗

Ecosystem Modeling of Biological Processes to Global Budgets

From an ecological perspective, the search for life on distant planets begins from several key assumptions. The first of these is that, viewed from a remote location in space, the signature of life on a distant planet will be the result of net gas exchange of organisms with their environment. On the basis of extensive biogeochemical measurements and biogenic trace gas fluxes in modem Earth environments, it is probable that certain groups of organisms both produce and consume the same trace gas(es) within a single bioprofile of Solid (porous) substrate or surface water. The net gas exchange rate with the atmosphere measured at the living surface is frequently the result of competing metabolic reactions, which may carried out by different functional groups of organisms located at dissimilar 'climatic' or chemical microsites within the same bioprofile. Biogenic gases produced at one (deep) level of a bioprofile may be consumed by another functional group of organisms located closer to the level of surface exchange with the atmosphere. A second key assumption is that the net biogenic fluxes of atmospheric gases on Earth can be used to infer relative abundance and functional composition of the major organisms on a distant planet. Examples of this principle include the presence of methanogenic microorganisms abundant today in freshwater ecosystems worldwide, which are major source of atmospheric methane and its seasonal variability in Earth's atmosphere. A third assumption is that scaling up biogenic gas fluxes from a single biological community to the planetary level requires flux measurements at the whole ecosystem level. This implies that measurements of biogenic gas exchange with the global atmosphere cannot be easily inferred from measurements of gas production rates of single organisms, which may have been isolated in some manner from the setting of their native ecosystem. Hence, the unit of biological organization used in modern Earth Science for scaling up to biosphere effects on atmospheric composition is the ecosystem level. These assumptions are the foundation for developing modern emission budgets for biogenic gases such as carbon dioxide, methane, carbon monoxide, isoprene, nitrous and nitric oxide, and ammonia. Such emission budgets commonly include information on seasonal flux patterns, typical diurnal profiles, and spatial resolution of at least one degree latitude/longitude for the globe. On the basis of these budgets, it is possible to compute 'base emission rates' for the major biogenic trace gases from both terrestrial and ocean sources, which may be useful benchmarks for defining the gas production rates of organisms, especially those from early Earth history, which are required to generate a detectable signal on a global atmosphere. This type of analysis is also the starting point for evaluation of the 'biological processes to global gas budget' extrapolation procedure described above for early Earth ecosystems.

Christopher, Potter S.↗

Analysis of 1970-1995 Trends in Tropospheric Ozone at Northern Hemisphere Midlatitudes with the GEOS-CHEM Model

I ] The causes of trends in tropospheric ozone at Northern Hemisphere midlatitudes from 1970 to 1995 are investigated with the GEOS-CHEM model, a global three-dimensional model of the troposphere driven by assimilated meteorological observations from the Goddard Earth Observing System (GEOS). This model is used to investigate the sensitivity of tropospheric ozone with respect to (1) changes in the anthropogenic emission of nitrogen oxides and nonmethane hydrocarbons, (2) increases in methane concentrations, (3) variations in the stratospheric source of ozone, (4) changes in solar radiation resulting from stratospheric ozone depletion, and ( 5 ) increases in tropospheric temperatures. Model results indicate that local increases in NO, emissions have caused most of the increases seen in lower tropospheric ozone over Europe and Japan. Increases in methane are responsible for roughly one fifth of the anthropogenically induced increase in tropospheric ozone at northern midlatitudes. However, changes in ozone precursors do not adequately explain either the spatial differences in observed ozone trends across midlatitudes or the observed decreases in ozone over Canada throughout the troposphere. We argue that ozone depletion in the lowermost stratosphere is likely to have reduced the stratospheric source by as much as 30% from the early 1970s to the mid 1990s. Model simulations that account for such a reduction along with reported changes in anthropogenic emissions show steep declines of ozone in the upper troposphere and variable increases in the lower troposphere that are more consistent with observations. Differential temperature trends in summer between North America and Europe may account for at least some of the remaining spatial variation in tropospheric ozone trends. Increases in ultraviolet (UV) radiation due to stratospheric ozone depletion do not appear to significantly reduce tropospheric ozone, except at midlatitudes in the Southern Hemisphere following the breakup of the ozone hole.

Fusco, Andrew C.↗

Development of a Batch Fabrication Process for Chemical Nanosensors: Recent Advancements at NASA Glenn Research Center

A major objective in aerospace sensor development is to produce sensors that are small in size, easy to batch fabricate and low in cost, and have low power consumption. Chemical sensors involving nanostructured materials can provide these characteristics as well as the potential for the development of sensor systems with unique properties and improved performance. However, the fabrication and processing of nanostructures for sensor applications currently is limited by the ability to control their location on the sensor platform, which in turn hinders the progress for batch fabrication. This presentation will discuss the following: the development of a novel room temperature methane (CH4) sensor fabricated using porous tin oxide (SnO2) nanorods as the sensing material, the advantages of using nanomaterials in sensor designs, the challenges encountered with the integration of nanostructures into microsensordevices, and the different methods that have been attempted to address these challenges. An approach for the mass production of sensors with nanostructures using a method developed by our group at the NASA Glenn Research Center to control the alignment of nanostructures onto a sensor platform will also be described.

Nanotechnology↗

Airborne Tropical TRopopause EXperiment (ATTREX) 2014 Western Pacific Campaign

The NASA Airborne Tropical TRopopause EXperiment (ATTREX) is a series of airborne campaigns focused on understanding physical processes in the Tropical Tropopause Layer (TTL) and their role in atmospheric chemistry and climate. ATTREX is using the high-altitude, long-duration NASA Global Hawk Unmanned Air System to make in situ and remote-sensing measurements spanning the Pacific. A particular ATTREX emphasis is to better understand the dehydration of air as it passes through the cold tropical tropopause region. The ATTREX payload contains 12 in situ and remote sensing instruments that measure water vapor, carbon dioxide, methane, nonmethane hydrocarbons, sulfur hexafluoride, chlorofluorocarbons, nitrous oxide), reactive chemical compounds (ozone, bromine, nitrous oxide), meteorological parameters, and radiative fluxes. During January-March, 2014, the Global Hawk was deployed to Guam for ATTREX flights. Six science flights were conducted from Guam (in addition to the transits across the Pacific), resulting in over 100 hours of Western Pacific TTL sampling and about 180 vertical profiles through the TTL. I will provide an overview of the dataset, with examples of the measurements including meteorological parameters, clouds and water vapor, and chemical tracers.

Airborne↗

Prebiotic Chemistry and Atmospheric Warming of Early Earth by an Active Young Sun

Nitrogen is a critical ingredient of complex biological molecules. Molecular nitrogen, however, which was outgassed Into the Earth's early atmosphere, is relatively chemically inert and nitrogen fixation into more chemically reactive compounds requires high temperatures. Possible mechanisms of nitrogen fixation include lightning, atmospheric shock heating by meteorites, and solar ultraviolet radiation. Here we show that nitrogen fixation in the early terrestrial atmosphere can be explained by frequent and powerful coronal mass ejection events from the young Sun -- so-called superflares. Using magnetohydrodynamic simulations constrained by Kepler Space Telescope observations, we find that successive superflare ejections produce shocks that accelerate energetic particles, which would have compressed the early Earth's magnetosphere. The resulting extended polar cap openings provide pathways for energetic particles to penetrate into the atmosphere and, according to our atmospheric chemistry simulations, initiate reactions converting molecular nitrogen, carbon dioxide and methane to the potent greenhouse gas nitrous oxide as well as hydrogen cyanide, an essential compound for life. Furthermore, the destruction of N2, C02 and CH, suggests that these greenhouse gases cannot explain the stability of liquid water on the early Earth. Instead, we propose that the efficient formation of nitrous oxide could explain a warm early Earth.

Airapetian, V. S.↗

Modeling Modern Methane Emissions from Natural Wetlands: Interannual Variations 1982-1993 - 2

A global run of a process-based methane model [Walter et al., this issue] is performed using high-frequency atmospheric forcing fields from ECMWF reanalyses of the period from 1982 to 1993. We calculate global annual methane emissions to be 260 Tg/ yr. 25% of methane emissions originate from wetlands north of 30 deg. N. Only 60% of the produced methane is emitted, while the rest is re-oxidized. A comparison of zonal integrals of simulated global wetland emissions and results obtained by an inverse modeling approach shows good agreement. In a test with data from two wetlands, the seasonality of simulated and observed methane emissions agrees well. The effects of sub-grid scale variations in model parameters and input data are examined. Modeled methane emissions show high regional, seasonal and interannual variability. Seasonal cycles of methane emissions are dominated by temperature in high latitude wetlands, and by changes in the water table in tropical wetlands. Sensitivity tests show that +/- 1 C changes in temperature lead to +/- 20 % changes in methane emissions from wetlands. Uniform changes of +/- 20% in precipitation alter methane emissions by about +/- 18%. Limitations in the model are analyzed. Simulated interannual variations in methane emissions from wetlands are compared to observed atmospheric growth rate anomalies. Our model simulation results suggest that contributions from other sources than wetlands and/or the sinks are more important in the tropics than north-of 30 deg. N. In higher northern latitudes, it seems that a large part, of the observed interannual variations can be explained by variations in wetland emissions. Our results also suggest that reduced wetland emissions played an important role in the observed negative methane growth rate anomaly in 1992.

Walter, Bernadette P.↗

Modeling Modern Methane Emissions from Natural Wetlands: Model Description and Results - 1

Methane is an important greenhouse gas which contributes about 22 percent to the present greenhouse effect. Natural wetlands currently constitute the biggest methane source and were the major source in preindustrial times. Wetland emissions depend highly on the climate, i.e., on soil temperature and water table. To investigate the response of methane emissions from natural wetlands to climate variations, a process-based model that derives methane emissions from natural wetlands as a function of soil temperature, water table, and net primary productivity is used. For its application on the global scale, global data sets for all model parameters are generated. In addition, a simple hydrologic model is developed in order to simulate the position of the water table in wetlands. The hydrologic model is tested against data from different wetland sites, and the sensitivity of the hydrologic model to changes in precipitation is examined. The global methane­ hydrology model constitutes a tool to study temporal and spatial variations in methane emissions from natural wetlands. The model is applied using high-frequency atmospheric forcing fields from European Center for Medium-range Weather Forecasts (ECMWF) re-analyses of the period from 1982 to 1993. We calculate global annual methane emissions from wetlands to be 260 teragrams per year. Twenty-five percent of these methane emissions originate from wetlands north of 30 degrees North Latitude. Only 60 percent of the produced methane is emitted, while the rest is re-oxidized. A comparison of zonal integrals of simulated global wetland emissions and results obtained by an inverse modeling approach shows good agreement. In a test with data from two wetlands the seasonality of simulated and observed methane emissions agrees well.

Biogeochemical processes↗

Dimethoxymethane: A Fuel For Direct-Oxidation Fuel Cells

Dimethoxymethane (DMM) identified as one of several high-energy fuels for direct-oxidation fuel cells. Found to undergo facile electro-oxidation to carbon dioxide and water, with methanol as possible intermediate product. Fuel electro-oxidized at sustained high rates without poisoning electrodes. Performance superior to that of methanol at same temperature. Synthesized from natural gas (methane) and is thus viable alternative to methanol in direct-oxidation fuel cells. Better performance expected at higher temperature and by use of Pt/Sn catalyst. Alternatively, low boiling temperature of DMM also makes it candidate for gas-feed operation.

Olah, George A.↗

Novel diode laser-based sensors for gas sensing applications

The development of compact spectroscopic gas sensors and their applications to environmental sensing will be described. These sensors employ mid-infrared difference-frequency generation (DFG) in periodically poled lithium niobate (PPLN) crystals pumped by two single-frequency solid state lasers such as diode lasers, diode-pumped solid state, and fiber lasers. Ultrasensitive, highly selective, and real-time measurements of several important atmospheric trace gases, including carbon monoxide, nitrous oxide, carbon dioxide, formaldehyde [correction of formaldehye], and methane, have been demonstrated.

NASA Discipline Life Sciences Technologies↗

Attribution of Stratospheric and Tropospheric Ozone Changes Between 1850 and 2014 in CMIP6 Models

We quantify the impacts of halogenated ozone-depleting substances (ODSs), greenhouse gases (GHGs), and short-lived ozone precursors on ozone changes between 1850 and 2014 using single-forcing perturbation simulations from several Earth system models with interactive chemistry participating in the Coupled Model Intercomparison Project Aerosol and Chemistry Model Intercomparison Project. We present the responses of ozone to individual forcings and an attribution of changes in ozone columns and vertically resolved stratospheric and tropospheric ozone to these forcings. We find that whilst substantial ODS-induced ozone loss dominates the stratospheric ozone changes since the 1970s, in agreement with previous studies, increases in tropospheric ozone due to increases in short-lived ozone precursors and methane since the 1950s make increasingly important contributions to total column ozone (TCO) changes. Increases in methane also lead to substantial extra-tropical stratospheric ozone increases. Impacts of nitrous oxide and carbon dioxide on stratospheric ozone are significant but their impacts on TCO are small overall due to several opposing factors and are also associated with large dynamical variability. The multi-model mean (MMM) results show a clear change in the stratospheric ozone trends after 2000 due to now declining ODSs, but the trends are generally not significantly positive, except in the extra-tropical upper stratosphere, due to relatively small changes in forcing over this period combined with large model uncertainty. Although the MMM ozone compares well with the observations, the inter-model differences are large primarily due to the large differences in the models' representation of ODS-induced ozone depletion.

Halogenated ozone-depleting substances↗