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At least 109 records · Page 6

Measurements of Nitric Acid and Aerosol Species Aboard the NASA DC-8 Aircraft During the SASS OZone and Nitrogen Oxide Experiment (SONEX)

The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the north Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of total reactive nitrogen (NO(y)) in the upper troposphere (8 - 12 km altitude). The median measured NO(y) mixing ratio was 425 parts per trillion by volume (pptv). Two different methods were used to measure HNO3: (1) the mist chamber technique and, (2) chemical ionization mass spectrometry. Two merged data sets using these HNO3 measurements were used to calculate NO(y) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing the resultant values to measured NO(y) (gold catalytic reduction method). Both comparisons showed good agreement in the two quantities (slope greater than 0.9 and r(sup 2) greater than 0.9). Thus, the total reactive nitrogen budget in the upper troposphere over the North Atlantic can be explained in a general manner as a simple mixture of NO(x). (NO + NO2), HNO3, and PAN. Median values of NO(x)/NO(y) were approx. = 0.25, HNO3/NO(y) approx. = 0.35 and PAN/NO(y) approx. = 0.17. Particulate NO3 and alkyl nitrates together composed less than 10% of NO(y), while model estimated HNO4 averaged 12%.

Talbot, Robert W.↗

Progress and Challenges in Quantifying Wildfire Smoke Emissions, Their Properties, Transport, and Atmospheric Impacts

Wildfire is a natural and integral ecosystem process that is necessary to maintain species composition, structure, and ecosystem function. Extreme fires have been increasing over the last decades, which have a substantial impact on air quality, human health, the environment, and climate systems. Smoke aerosols can be transported over large distances, acting as pollutants that affect adjacent and distant downwind communities and environments. Fire emissions are a complicated mixture of trace gases and aerosols, many of which are short‐lived and chemically reactive, and this mixture affects atmospheric composition in complex ways that are not completely understood. We present a review of the current state of knowledge of smoke aerosol emissions originating from wildfires. Satellite observations, from both passive and active instruments, are critical to providing the ability to view the large‐scale influence of fire, smoke, and their impacts. Progress in the development of fire emission estimates to regional and global chemical transport models has advanced, although significant challenges remain, such as connecting ecosystems and fuels burned with dependent atmospheric chemistry. Knowledge of the impact of smoke on radiation, clouds, and precipitation has progressed and is an essential topical research area. However, current measurements and parameterizations are not adequate to describe the impacts on clouds of smoke particles (e.g., CNN, INP) from fire emissions in the range of representative environmental conditions necessary to advance science or modeling. We conclude by providing recommendations to the community that we believe will advance the science and understanding of the impact of fire smoke emissions on human and environmental health, as well as feedback with climate system.

I N Sokolik↗

Contributions of a Tunable Diode Laser Instrument (ATLAS) to the Stratospheric Ozone Depletion Question

The Airborne Tunable Laser Absorption Spectrometer - ATLAS - was designed and built at the NASA Ames Research Center and operates on the NASA ER-2 high altitude research aircraft. ATLAS has taken part in a number of important polar and mid-latitude research campaigns, since 1987, focused on various aspects of stratospheric ozone chemistry and dynamics. The chief measurement carried out by the ATLAS second harmonic diode laser spectrometer is of the important atmospheric tracer N2O. Using N2O as an inert tracer we have been able to gain significant new information on polar vortex dynamics and on the correlations of several important long-lived tracers in the stratosphere. The correlation of N2O with NOy (total reactive nitrogen) has been shown to be linear for a great variety of unperturbed stratospheric conditions, and the breakdown of this correlation has been used to detect denitrification by PSCs in the polar vortex, especially in the Antarctic spring. Denitrification is an important step in the process of ozone hole formation in the austral spring. Correlations of N2O with CFCs and CH4 have led to improved estimates of atmospheric lifetimes of these important molecules. Finally the correlation of N2O with CO2, the latter now being measured with great precision by a new instrument on the ER-2, has led to a significant new tool for studying horizontal and vertical mixing in the lower stratosphere, a tool which is very useful in assessing the potential effects of high speed civil transport aircraft in the lower stratosphere. A new, light-weight version of ATLAS is currently being built for unmanned high altitude aircraft, specifically the new Perseus vehicle. We will give a brief description of this effort.

Loewenstein, Max↗

The effects of the diffuse radiation fields due to multiple scattering and thermal reradiation by dust on the dynamics and thermodynamics of a dusty cometary atmosphere

A self-consistent model of a dirty, clathrate cometary nucleus is extended to account for diffuse radiation fields caused by multiple scattering and thermal reradiation of the solar continuum by dust. The model is configured to fit conditions expected for the various spacecraft which will encounter Halley's comet at 0.89 AU. The atmosphere is assumed a chemically reactive dust-gas mixture in quasi-steady spherically symmetric expansion. The effect of electron-neutral ion collisions is accounted for, along with rate constants of the various species of clathrate ice particles and radiative transfer of the solar input in the UV, visible and near-IR intervals. The opacity of the circumnuclear dust is projected to be an order of magnitude greater than previous estimates, which severely impacts the potential visibility of the nucleus to the cameras of the flyby satellites.

Marconi, M. L.↗

Graben and extension in northern Tharsis, Mars

A morphometric analysis of north-south trending graben at 35 deg N in northern Tharsis is used to provide the first quantitative measurements of crustal extension in and strain for areas of the Martian crust that have undergone both extreme and mild deformation. These estimates also demonstrate the viability of the Viking data for making such quantitative assessment. Graben in the region accommodate about 8 km of post Early Amazonian east-west extension. This extension corresponds to a net regional strain of 0.45-0.61 percent; local strains vary from less than 1 percent to 5 percent. Extension is nonuniform and localized near 110 deg (south of Alba Patera and north of Ceraunius Fossae) because of reactivation of preexisting fractures in underlying basement and possibly due to superposition of stress fields from Tharsis and Alba Patera. A major mechanical discontinuity in the shallow crust, probably representing the base of or a strength contrast within the megaregolith, is observed. It occurs at a depth of 2 km on the profile flanks and is depressed to about 7.5 km near 110 deg due to loading of the crust by the volcano.

Plescia, J. B.↗

U-937 Toxicity Testing of Lunar Dust Stimulant (JSC-1A-vf)

With NASA planning to extend the human presence to the moon by 2020, the dangers of the lunar environment must be assessed and appropriate countermeasures must be developed. Possible toxic effects of the lunar dust are of particular importance to human health because of the dust's chemical composition, reactivity, and small size. This project focuses on the toxicity of lunar dust stimulant (JSC-1A-vf), in both its active and passive forms, using U-937 human monocyte cells. Simulant was mechanically activated from its passive form by grinding, and its ability to produce hydroxyl radicals was determined. To test for toxicity, active and passivated simulant was diluted in media and applied to the cells for various time periods. Toxicity was then estimated using flow cytometry on the Guava Personal Cell Analysis system. Preliminary results suggest that passivated stimulant is slightly toxic, with an increase in toxicity for activated stimulant. Toxicity results may be affected by cell lysing behavior and quenching of hydroxyl radical production by the cell media.

Bales, Kristyn↗

Prebiotic phosphorus chemistry reconsidered

The available evidence indicates that the origin of life on Earth certainly occurred earlier than 3.5 billion years ago and perhaps substantially earlier. The time available for the chemical evolution which must have preceded this event is more difficult to estimate. Both endogenic and exogenic contributions to chemical evolution have been considered; i.e., from chemical reactions in a primitive atmosphere, or by introduction in the interiors of comets and/or meteorites. It is argued, however, that the phosphorus chemistry of Earth's earliest hydrosphere, whether primarily exogenic or endogenic in origin, was most likely dominated by compounds less oxidized than phosphoric acid and its esters. A scenario is presented for the early production of a suite of reactive phosphonic acid derivatives, the properties of which may have foreshadowed the later appearance of biophosphates.

NASA Discipline Exobiology↗

Electrospray Thruster Performance with Microfabricated Emitter Arrays and Indium Propellant

The feasibility of a microfabricated indium-fueled electrospray thruster with excellent performance was demonstrated. High efficiency electrospray thrusters with microfabricated components are under development for very compact, distributable propulsion systems that can be employed on both very small and large spacecraft with 10X improvement over SOA in mass, volume and specific impulse The critical components of this technology are the microfabricated emitter arrays and the capillary force driven indium feed system. Grey scale electron-beam lithography patterning and reactive ion dry etching provided the required micron-scale etch precision and uniformity across an array of 400 emitters in 1 cm2. Initial tests of single microfabricated silicon emitters demonstrated better performance than industry standard single emitters and the performance required to achieve 200 micronewtons when scaled up to a thruster with 400 emitters in 1 cm2. Arrays of emitters tested in a preliminary prototype Microfluidic Electrospray Propulsion (MEP) thruster assembly demonstrated stable performance at estimated thrust levels of 5, 50, and 120 µN at extraction voltages less than 4 kV. Current stability was within 0.15 % at 120 µN with only 1.5% of the emitter current collected by the extractor electrode. Post-test inspections revealed that more than 99% of the 400 emitters were electrospraying during the test. Specific impulse was estimated to be >3100 s from measurements of total charge and consumed indium mass at an emitter voltage of 1470 V. The results of this investigation suggest that microfabricated indium electrospray thruster technology is both feasible and capable of excellent performance as a highly compact microthruster.

Marrese-Reading, Colleen M.↗

Comprehensive investigation of HgCdTe metalorganic chemical vapor deposition

The principal objective of this experimental and theoretical research program was to explore the possibility of depositing high quality epitaxial CdTe and HgCdTe at very low pressures through metalorganic chemical vapor deposition (MOCVD). We explored two important aspects of this potential process: (1) the interaction of molecular flow transport and deposition in an MOCVD reactor with a commercial configuration, and (2) the kinetics of metal alkyl source gas adsorption, decomposition and desorption from the growing film surface using ultra high vacuum surface science reaction techniques. To explore the transport-reaction issue, we have developed a reaction engineering analysis of a multiple wafer-in-tube ultrahigh vacuum chemical vapor deposition (UHV/CVD) reactor which allows an estimate of wafer or substrate throughput for a reactor of fixed geometry and a given deposition chemistry with specified film thickness uniformity constraints. The model employs a description of ballistic transport and reaction based on the pseudo-steady approximation to the Boltzmann equation in the limit of pure molecular flow. The model representation takes the form of an integral equation for the flux of each reactant or intermediate species to the wafer surfaces. Expressions for the reactive sticking coefficients (RSC) for each species must be incorporated in the term which represents reemission from a wafer surface. The interactions of MOCVD precursors with Si and CdTe were investigated using temperature programmed desorption (TPD) in ultra high vacuum combined with Auger electron spectroscopy (AES). These studies revealed that diethyltellurium (DETe) and dimethylcadmium (DMCd) adsorb weakly on clean Si(100) and desorb upon heating without decomposing. These precursors adsorb both weakly and strongly on CdTe(111)A, with DMCd exhibiting the stronger interaction with the surface than DETe.

Raupp, Gregory B.↗

Production of pulsed atomic oxygen beams via laser vaporization methods

Energetic pulsed atomic oxygen beams were generated by laser-driven evaporation of cryogenically frozen ozone/oxygen films and thin films of indium-tin oxide (ITO). Mass and energy characterization of beams from the ozone/oxygen films were carried out by mass spectrometry. The peak flux, found to occur at 10 eV, is estimated from this data to be 3 x 10(20) m(-2) s(-1). Analysis of the time-of-flight data indicates a number of processes contribute to the formation of the atomic oxygen beam. The absence of metastable states such as the 2p(3) 3s(1) (5S) level of atomic oxygen blown off from ITO films is supported by the failure to observe emission at 777.3 nm from the 2p(3) 3p(1) (5P sub J) levels. Reactive scattering experiments with polymer film targets for atomic oxygen bombardment are planned using a universal crossed molecular beam apparatus.

Brinza, David E.↗

Seasonal variations in the atmospheric distribution of a reactive chlorine compound, tetrachloroethene (CCl2 = CCl2)

Tropospheric mixing ratios of CCl2 = CCl2 were measured at remote surface locations in the Pacific between 71 deg N and 47 deg S during September and December of 1989, and March and June of 1990. The observed gradient of decreasing concentrations from the northern to the southern hemisphere, and very low concentrations in the southern hemisphere throughout the year, indicates a predominant input from the northern hemisphere. Seasonal measurements in the northern hemisphere showed maximum CCl2 = CCl2 concentrations occurring in the late summer. This distinct seasonal variation is strongly coupled to the atmompheric abundance of hydroxyl radical, the only important species responsible for CCl2 = CCl2 removal. With the estimated global CCl2 =CCl2 emissions, the lifetime is calculated to be about 5.4 months which is in good agreement with the 4.0 month estimate obtained from the inverse ratio of its measured hydroxyl reaction rate constant compared with that of methyl-chloroform CH3CCl3.

Wang, Charles J.-L.↗

Measurements of Nitric Acid and Aerosol Species Aboard the NASA DC-8 Aircraft During the SASS Ozone and Nitrogen Oxide Experiment (SONEX)

The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the North Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of total reactive nitrogen (NO(sub y)) in the upper troposphere (8 - 12 km altitude). The median measured NO(sub y) mixing ratio was 425 parts per trillion by volume (pptv). Two different methods were used to measure HNO3: (1) the mist chamber technique and, (2) chemical ionization mass spectrometry. Two merged data sets using these HNO3 measurements were used to calculate NO(sub y) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing the resultant values to measured NO(sub y) (gold catalytic reduction method). Both comparisons showed good agreement in the two quantities (slope > 0.9 and r(exp 2) > 0.9). Thus, the total reactive nitrogen budget in the upper troposphere over the North Atlantic can be explained in a general manner as a simple mixture of NO(sub x). (NO + NO2), HNO3, and PAN. Median values of NO(sub x)/NO(sub y) were approximately equal to 0.25, HNO3/NO(sub y) were approximately equal to 0.35 and Peroxyacetyl Nitrate (PAN)/NO(sub y) were approximately equal to 0. 17. Particulate NO3 and alkyl nitrates together composed <10 % of NO(sub y), while model estimated HNO4 averaged 12%.

Talbot, Robert W.↗

Deposition of ozone to tundra

Eddy correlation measurements of O3 deposition fluxes to tundra during the Arctic Boundary Layer Expedition (ABLE 3A) are reported. The mean O3 deposition velocity was 0.24 cm/s in the daytime and 0.12 cm/s at night. The day-to-day difference in deposition velocity was driven by both atmospheric stability and surface reactivity. The mean surface resistance to O3 deposition was 2.6 s/cm in the daytime and 3.4 s/cm at night. The relatively low surface resistance at night is attributed to light-insensitive uptake of O3 at dry upland tundra surfaces. The small day-tonight difference in surface resistance is attributed to additional stomatal uptake by wet meadow tundra plants in the daytime. The mean O3 deposition flux to the world north of 60 deg N in July-August is estimated at 8.2 x 10 exp 10 molecules/sq cm/s. Suppression of photochemical loss by small anthropogenic inputs of nitrogen oxides could have a major effect on O3 concentrations in the summertime Arctic troposphere.

Jacob, D. J.↗

Airborne derivation of microburst alerts from ground-based Terminal Doppler Weather Radar information: A flight evaluation

An element of the NASA/FAA windshear program is the integration of ground-based microburst information on the flight deck, to support airborne windshear alerting and microburst avoidance. NASA conducted a windshear flight test program in the summer of 1991 during which airborne processing of Terminal Doppler Weather Radar (TDWR) data was used to derive microburst alerts. Microburst information was extracted from TDWR, transmitted to a NASA Boeing 737 in flight via data link, and processed to estimate the windshear hazard level (F-factor) that would be experienced by the aircraft in each microburst. The microburst location and F-factor were used to derive a situation display and alerts. The situation display was successfully used to maneuver the aircraft for microburst penetrations, during which atmospheric 'truth' measurements were made. A total of 19 penetrations were made of TDWR-reported microburst locations, resulting in 18 airborne microburst alerts from the TDWR data and two microburst alerts from the airborne reactive windshear detection system. The primary factors affecting alerting performance were spatial offset of the flight path from the region of strongest shear, differences in TDWR measurement altitude and airplane penetration altitude, and variations in microburst outflow profiles. Predicted and measured F-factors agreed well in penetrations near microburst cores. Although improvements in airborne and ground processing of the TDWR measurements would be required to support an airborne executive-level alerting protocol, the practicality of airborne utilization of TDWR data link data has been demonstrated.

Hinton, David A.↗

On the paragenetic modes of minerals: A mineral evolution perspective

A systematic survey of 57 different paragenetic modes distributed among 5659 mineral species reveals patterns in the diversity and distribution of minerals related to their evolving formational environments. The earliest minerals in stellar, nebular, asteroid, and primitive Earth contexts were dominated by relatively abundant chemical elements, notably H, C, O, Mg, Al, Si, S, Ca, Ti, Cr, and Fe. Significant mineral diversification subsequently occurred via two main processes, first through gradual selection and concentration of rarer elements by fluid-rock interactions (for example, in hydrothermal metal deposits, complex granite pegmatites, and agpaitic rocks), and then through near-surface biologically mediated oxidation and weathering. We find that 3349 mineral species (59.2%) are known from only one paragenetic context, whereas another 1372 species (24.2%) are associated with two paragenetic modes. Among the most genetically varied minerals are pyrite, albite, hornblende, corundum, magnetite, calcite, hematite, rutile, and baryte, each with 15 or more known modes of formation. Among the most common paragenetic modes of minerals are near-surface weathering/oxidation (1998 species), subsurface hydrothermal deposition (859 species), and condensation at volcanic fumaroles (459 species). In addition, many species are associated with compositionally extreme environments of highly differentiated igneous lithologies, including agpaitic rocks (726 species), complex granite pegmatites (564 species), and carbonatites and related carbonate-bearing magmas (291 species). Biological processes lead to at least 2707 mineral species, primarily as a consequence of oxidative weathering but also through coal-related and other taphonomic minerals (597 species), as well as anthropogenic minerals, for example as byproducts of mining (603 minerals). However, contrary to previous estimates, we find that only ~34% of mineral species form exclusively as a consequence of biological processes. By far the most significant factor in enhancing Earth’s mineral diversity has been its dynamic hydrological cycle. At least 4583 minerals—81% of all species—arise through water-rock interactions. A timeline for mineral-forming events suggests that much of Earth’s mineral diversity was established within the first 250 million years. If life is rare in the universe, then this view of a mineralogically diverse early Earth provides many more plausible reactive pathways over a longer timespan than previous models. If, however, life is a cosmic imperative that emerges on any mineral- and water-rich world, then these findings support the hypothesis that life on Earth developed rapidly in the early stages of planetary evolution

Robert M. Hazen↗

Status of the Delco Systems Operations forward looking windshear detection program

Delco Systems Operations, a division of General Motors Hughes Electronics Corporation, is developing a Forward Looking Windshear Detection System based on the integration of infrared remote sensing and accelerometer reactive sensing technologies. The infrared sensor is a multi-spectral, scanning radiometer operating in the 8 to 14 micron region. A 2 x 5 detector array with parallel-serial scanning produces 60 degrees horizontal and 10 degrees vertical-fields of view. Using multiple wavelength signals, azimuth temperature gradients are analyzed for characteristic signatures of thermally induced windshear phenomena. Elevation temperature gradients are processed through an atmosphere model to continuously compute a stability index for arming microburst detection criteria. The atmosphere model and proprietary computer processing algorithms combine to generate coarse estimates of disturbance ranges based on multiple wavelength radiance data with different extinction coefficients. Computer outputs of atmospheric stability, disturbance intensity, and azimuth and range information provide a situation display capability. A ground operated, experimental radiometer has been developed and is being used to verify the detection and discrimination concepts at an atmospheric and simulated rain test facility in Milwaukee. A prototype airborne radiometer is being developed for flight test evaluation during the summer of 1989.

Gallagher, Brian J.↗

Analysis of the Atmospheric Distribution, Sources, and Sinks of Oxygenated Volatile Organic Chemicals Based on Measurements over the Pacific during TRACE-P

Airborne measurements of a large number of oxygenated volatile organic chemicals (OVOC) were carried out in the Pacific troposphere (0.1-12 km) in winter/spring of 2001 (24 February to 10 April). Specifically, these measurements included acetone (CH3COCH3), methylethyl ketone (CH3COC2H5, MEK), methanol (CH3OH), ethanol (C2H5OH), acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), peroxyacylnitrates (PANs) (C(sub n)H(sub 2n+1)COO2NO2), and organic nitrates (C(sub n)H(sub 2n+1)ONO2). Complementary measurements of formaldehyde (HCHO), methyl hydroperoxide (CH3OOH), and selected tracers were also available. OVOC were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Background mixing ratios were typically highest in the lower troposphere and declined toward the upper troposphere and the lowermost stratosphere. Their total abundance (Summation of OVOC) was nearly twice that of nonmethane hydrocarbons (Summation of C2-C8 NMHC). Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NMHC. A comparison of these data with western Pacific observations collected some 7 years earlier (February-March 1994) did not reveal significant differences. Mixing ratios of OVOC were strongly correlated with each other as well as with tracers of fossil and biomass/biofuel combustion. Analysis of the relative enhancement of selected OVOC with respect to CH3Cl and CO in 12 plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. A three-dimensional global model that uses state of the art chemistry and source information is used to compare measured and simulated mixing ratios of selected OVOC. While there is reasonable agreement in many cases, measured aldehyde concentrations are significantly larger than predicted. At their observed levels, acetaldehyde mixing ratios are shown to be an important source of HCHO (and HO x ) and PAN in the troposphere. On the basis of presently known chemistry, measured mixing ratios of aldehydes and PANs are mutually incompatible. We provide rough estimates of the global sources of several OVOC and conclude that collectively these are extremely large (150-500 Tg C / yr) but remain poorly quantified.

Singh, H. B.↗

Thermodynamics of the Lu2O3 – SiO2 system and comparison to other Rare Earth Silicates

Environmental barrier coatings are necessary to protect SiC based ceramics and composites from water vapor degradation in harsh engine environments. Currently, rare earth (RE) silicates are the most promising systems to protect SiC based ceramics and composites. This protection is largely based on reduced silica activity in these rare earth silicates which results in a lowered reactivity with water vapor. To that end, previous Knudsen effusion mass spectrometry (KEMS) studies have explored RE = Yb, Y silicates to measure the reduced silica activity and subsequent water vapor reactivity. Similarly, this work employs the KEMS technique to measure the SiO(g) vapor pressure in Lu containing RE silicates to calculate the activity of silica within the monosilicate [log(a(SiO2)) = -2351.1*1/T-1.6731] and the disilicate (log(a(SiO2)) = -4884.0*1/T + 2.2208) as a function of temperature. The enthalpies of formation for Lu monosilicate from the oxides and the elements were calculated to be -45±3 kJ/mol at 1550 K and -2831.1±12 kJ/mol at 298 K, respectively. The measured enthalpy of formation and those found in literature are compared to modeled values from density functional theory and those estimated using electronegativity.

Knudesen Effusion Mass Spectrometry↗