Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ATMOSPHERIC CHEMISTRY”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Laboratory studies of low temperature rate coefficients: The atmospheric chemistry of the outer planets

The objectives are to measure laboratory rate coefficients for key reactions of hydrocarbon molecules and radicals at low temperatures, which are relevant to the atmospheric photochemistry of Saturn, Jupiter, and Titan. Upcoming NASA planetary missions, such as Cassini, will probe the atmosphere of Titan in more detail, offering an excellent opportunity to test kinetic models and to establish fiducial standards for using kinetic models to interpret various parameters of the outer planets. Accurate low temperature kinetic data, which are presently lacking, may require crucial revisions to the rates of formation and destruction and are of utmost importance to the success of these efforts. In this program, several key reactions of ethynyl radicals (C2H) with acetylene (C2H2), methane (CH4), and oxygen (O2), down to temperatures of 170 K were successfully investigated. The experimental apparatus developed in our laboratory for measuring reaction kinetics at low temperatures consists of a laser photolysis/infrared probe laser setup. The rate measurements are carried out as a function of (low) temperature with a transverse flow cell designed specifically for these studies. A 193 nm argon fluoride pulsed excimer laser is used to photolyze a suitable precursor molecule, such as acetylene to produce C2H, and a high resolution, tunable infrared F-center laser (2.3-3.35 mu m) probes the transient concentrations of the radical species directly in absorption to extract the kinetic rate coefficients.

Leone, Stephen R.↗
NASA NTRS1990

Global atmospheric chemistry of CFC-123

The compound 1,1-dichloro--2,2,2-trifluoroethane (CFC-123) has been proposed as an industrial substitute for trichlorofluoromethane (CFC-11). The chemical destruction rates of CFC-123 by various processes is calculated here using a three-dimensional global model of the atmosphere, and it is confirmed that the chief sink of CFC-123 is destruction by OH radicals below 12 km, accounting for 88 percent of its loss. The calculated destruction rate is greatest in the equatorial region below 2 km. The calculated steady-state lifetime of CFC-123 is 1.5 years, much shorter than that of CFC-11, the destruction of which is largely confined to the stratosphere. For equal rates of CFC-123 and CFC-11 emission to the atmosphere, the molar content in the atmosphere and the injection rate of chlorine into the stratosphere are, respectively, 48 and 14 times greater for CFC-11 than for CFC-123 in steady state.

Prinn, Ronald G.↗
NASA NTRS2001

Atmospheric Chemistry from Space: Present Status and Future Plans

One of the unqualified successes of the earth observation program is NASA's continuing monitoring of the ozone layer from space. This activity began in the early 70's with research instruments and continues to this day with the TOMS instrument series and the Upper Atmosphere Research Satellite. In the near future, NASA will be launching the EOS Aura spacecraft (launch mid-2003) which will continue our study of the chemical processes that produce stratospheric ozone depletion. In addition, Aura will begin the first global study of lower atmospheric air pollution including urban ozone, aerosols, nitrogen oxides and carbon monoxide. Atmospheric air pollution measurements from earth orbit involve the development of very high precision spectrometer technologies that have never been flown in space. Farther into the future, lower atmospheric ozone and aerosols may be monitored by space based lidars in low earth orbit, by sensors in geostationary orbit and by continuous limb observations instrument from the Lagrange point L2.

Schoeberl, Mark R.↗
NASA NTRS1992

Atmospheric chemistry in the Arctic and subarctic - Influence of natural fires, industrial emissions, and stratospheric inputs

Layers with enhanced concentrations of trace gases intercepted by the NASA Electra aircraft over Alaska during the Arctic Boundary Layer Expedition (ABLE 3A) in July-August 1988 are discussed. Haze layers apparently associated with boreal fires were enriched in hydrocarbons and NO(y), with emission factors corresponding closely to laboratory data for smoldering combustion. It is argued that atmospheric composition was strongly modified by wildfires during several periods of the ABLE 3A mission. The associated enhancement of NO(y) was smaller than observed for most other combustion processes but was nonetheless significant in the context of very low background concentrations. Ozone production in fire plumes was negligible. Ambient O3 was supplied by the stratosphere, with little direct input from midlatitude source during summer. It is argued that NO(y) was supplied about equally by the stratosphere and by wildfires. Hydrocarbons and CO appear to derive from biomass fires and from human activities.

Wofsy, S. C.↗
NASA NTRS2005

Mars Atmospheric Chemistry in Electrified Dust Devils and Storms

Laboratory studies, simulations and desert field tests all indicate that aeolian mixing dust can generate electricity via contact electrification or "triboelectricity". In convective structures like dust devils or storms, grain stratification (or charge separation) occurs giving rise to an overall electric dipole moment to the aeolian feature, similar in nature to the dipolar electric field generated in terrestrial thunderstorms. Previous simulation studies [1] indicate that this storm electric field on Mars can approach atmospheric breakdown field strength of 20 kV/m. In terrestrial dust devils, coherent dipolar electric fields exceeding 20 kV/m have been measured directly via electric field instrumentation. Given the expected electrostatic fields in Martian dust devils and storms, electrons in the low pressure CO2 gas can be energized via the electric field to values exceeding the electron dissociative attachment energy of both CO2 and H2O, resulting in the formation of new chemical products CO and O- and OH and H- within the storm. Using a collisional plasma physics model we present a calculation of the CO/O- and OH/H- reaction and production rates. We demonstrate that these rates vary geometrically with ambient electric field, with substantial production of dissociative products when fields approach breakdown levels of 20-30 kV/m.

Farrell, W. M.↗
NASA NTRS1993

First observations of CO and HCN on Neptune and Uranus at millimeter wavelengths and the implications for atmospheric chemistry

Observations are presented which show that CO is present in both the troposphere and stratosphere of Neptune, whereas is confined to the Neptune stratosphere with a mean mole fraction in the 0.003-30 mbar pressure level range of 1.0 x 10 exp -9. CO is present in both the stratosphere and in the troposphere with a uniformly mixed model fraction of 1.2 x 10 exp -6. Upper limits of 1.0 x 10 exp -10 and 3.0 x 10 exp -8 mole fractions are derived for HCN and CO respectively on Uranus. The origin of these species in the atmosphere of Neptune and their nondetection in that of Uranus are discussed in detail. It is concluded that the most plausible scenario involves upward convection of CO and N2 from Neptune's deep interior and a failure of chemical equilibrium at deep atmospheric levels, allowing excess CO and presumably N2 to reach the upper atmosphere. Nondetection in Uranus may be explained by the lack of a significant internal heat source in the planet and consequent suppression of vertical convection.

Marten, A.↗
NASA NTRS1995

Photodissociation of cyanoacetylene: Application to the atmospheric chemistry of Titan

The quantum yield and reaction threshold for the photochemical dissociation of cyanoacetylene into a hydrogen atom and the cyanoethynyl radical have been determined. The quantum yield at 185 nm is approximately 0.09. The threshold is approximately 240 nm. Combination of this data with literature values shows that production of excited-state cyanoacetylene is the major primary process resulting from irradiation between 185 and 254 nm. Also determined are the relative rate constants for the abstraction of a hydrogen atom from hydrogen, methane, and ethane by the cyanoethynyl radical (k(H2):k(CH4):k(C2H6) = 1:9.3:63). Implications of these results for the proposal that hydrogen abstraction plays an important role in the conversion of methane to ethane and in the protection of unsaturated compounds from photoconsumption in the atmosphere of Titan are discussed.

Clarke, David W.↗
NASA NTRS1982

Research in atmospheric chemistry and transport

The carbon monoxide cycle was studied by incorporating the known CO sources and sinks in a tracer model which used the winds generated by a general circulation model. The photochemical production and loss terms, which depended on OH radical concentrations, were calculated in an interactive fashion. Comparison of the computed global distribution and seasonal variations of CO with observations was used to yield constraints on the distribution and magnitude of the sources and sinks of CO, and the abundance of OH radicals in the troposphere.

Yung, Y. L.↗
NASA NTRS1982

Atmospheric chemistry of ethane and ethylene

It is shown by a study of ethane and ethylene photochemistry that the loss of ethane is controlled by OH in the troposphere and Cl in the stratosphere. Ethane observations indicating free Cl concentrations below 30 km that are only 10% of the value predicted by the present model calculations cannot be explained by heterogeneous aerosol concentration processes, and contradict current stratospheric photochemistry. The chemical destruction of ethane and ethylene leads to the generation of such compounds as carbon monoxide and formaldehyde, and it is found that the tropospheric concentrations of the latter are enhanced by nearly a factor of three for an ethylene mixing ratio of 2 ppb.

Aikin, A. C.↗
NASA NTRS1993

Ab initio characterization of ClOOH - Implications for atmospheric chemistry

The equilibrium structure, dipole moment, harmonic vibrational frequencies, and infrared intensities of ClOOH are determined using the CCSD(T) (singles and doubles coupled-cluster theory plus a perturbational estimate of the effects of connected triple excitations) electronic structure method in conjunction with a TZ2P (triple xi plus double polarization) basis set. The heat of formation of CIOOH is determined (using two different isodesmic reactions) to be +1.5 +/- 1 kcal/mol at 0 K or +0.2 +/- 1 kcal/mol at 298.15 K. Using the computed heat of formation, we examined the stability of ClOOH with respect to the ClO + OH, ClOO + H, and HOO + Cl dissociation limits. Since ClOOH is found to be quite stable, it is argued that the chemistry of ClOOH should be included in any accurate modeling of the stratosphere.

Lee, Timothy J.↗
NASA NTRS1994

Comparison and analysis of aircraft measurements and mesoscale atmospheric chemistry model simulations of tropospheric ozone

The Regional Acid Deposition Model (RADM) has been applied to several of the field experiments which were part of the Acid Models Operational and Diagnostic Evaluation Study (Acid MODES). The experiment which was of particular interest with regards to ozone photochemistry involved horizontal zig-zag flight patterns (ZIPPER) over an area from the eastern Ohio River valley to the Adirondacks of New York. Model simulations by both the standard resolution RADM (delta x = 80 km) and the nested grid RADM (delta x = 26.7 km) compare well to measurements in the low emission regions in central Pennsylvania and upstate New York, but underestimate in the high emission upper Ohio River valley. The nested simulation does considerably better, however, than the coarse grid simulation in terms of horizontal pattern and concentration magnitudes. Analysis of NO(x) and HO(x) concentrations and photochemical products rates of ozone show that the model's response to large point source emissions is very unsystematic both spatially and temporally. This is due to the models instability to realistically simulate the small scale (subgrid) gradients in precursor concentrations in and around large point source plumes.

Pleim, Jonathan E.↗
NASA NTRS1993

Multiple steady states in atmospheric chemistry

The equations describing the distributions and concentrations of trace species are nonlinear and may thus possess more than one solution. This paper develops methods for searching for multiple physical solutions to chemical continuity equations and applies these to subsets of equations describing tropospheric chemistry. The calculations are carried out with a box model and use two basic strategies. The first strategy is a 'search' method. This involves fixing model parameters at specified values, choosing a wide range of initial guesses at a solution, and using a Newton-Raphson technique to determine if different initial points converge to different solutions. The second strategy involves a set of techniques known as homotopy methods. These do not require an initial guess, are globally convergent, and are guaranteed, in principle, to find all solutions of the continuity equations. The first method is efficient but essentially 'hit or miss' in the sense that it cannot guarantee that all solutions which may exist will be found. The second method is computationally burdensome but can, in principle, determine all the solutions of a photochemical system. Multiple solutions have been found for models that contain a basic complement of photochemical reactions involving O(x), HO(x), NO(x), and CH4. In the present calculations, transitions occur between stable branches of a multiple solution set as a control parameter is varied. These transitions are manifestations of hysteresis phenomena in the photochemical system and may be triggered by increasing the NO flux or decreasing the CH4 flux from current mean tropospheric levels.

Stewart, Richard W.↗
NASA NTRS1994

Influence of plumes from biomass burning on atmospheric chemistry over the equatorial and tropical South Atlantic during CITE 3

During all eight flights conducted over the equatorial and tropical South Atlantic in the course of the Chemical Instrumentation Test and Evaluation (CITE 3) experiment, we observed haze layers with elevated concentrations of aerosols, O3, CO, and other trace gases related to biomass burning emissions. They occurred at altitudes between 1000 and 5200 m and were usually only some 100-300 m thick. These layers extended horizontally over several 100 km and were marked by the presence of visible brownish haze. Air mass trajectories indicate that these layers originate in the biomass burning regions of Africa and South America and typically have aged at least 10 days since the time of emission. In the haze layers, O3 and CO concentrations up to 90 and 210 ppb were observed, respectively. The two species were highly correlated. The ratio concentrations in plume minus background concentrations of O3/CO is typically in the range 0.2-0.7, much higher than the ratios in the less aged plumes investigated previously in Amazonia. In most cases, aerosol (0.12-3 micrometer diameter) number concentrations were also elevated by up to 400/cu cm in the layers; aerosol enrichments were also strongly correlated with elevated CO levels. Clear correlations between CO and NO(x) enrichments were not apparent due to the age of the plumes, in which most NO(x) would have already reacted away within 1-2 days. Only in some of the plumes could clear correlations between NO(y) and CO be identified; the absence of a general correlation between NO(y) and CO may be due to instrumental limitations and to variable sinks for NO(y). The average enrichment of the ratio concentrations in plume minus background concentrations of NO(y)/CO was quite high, consistent with the efficient production of ozone observed in the plumes. The chemical characteristics of the haze layers, together with remote sensing information and trajectory calculations, suggest that fire emissions (in Africa and/or South America) are the primary source of the haze layer components.

Andreae, M. O.↗
NASA NTRS1996

Ab Initio Calculation of Accurate Vibrational Frequencies for Molecules of Interest in Atmospheric Chemistry

Due to advances in quantum mechanical methods over the last few years, it is now possible to determine ab initio potential energy surfaces in which fundamental vibrational frequencies are accurate to within +/- 8 cm(sup -1) on average, and molecular bond distances are accurate to within +/- 0.001-0.003 A, depending on the nature of the bond. That is, the potential energy surfaces have not been scaled or empirically adjusted in any way, showing that theoretical methods have progressed to the point of being useful in analyzing spectra that are not from a tightly controlled laboratory environment, such as rovibrational spectra from the interstellar medium. Some recent examples demonstrating this accuracy win be presented and discussed. These include the HNO, CH4, C2H4, and ClCN molecules. The HNO molecule is interesting due to the very large H-N anharmonicity, while ClCN has a very large Fermi resonance. The ab initio studies for the CH4 and C2H4 molecules present the first accurate full quartic force fields of any kind (i.e., whether theoretical or empirical) for a five-atom and six-atom system, respectively.

Lee, Timothy J.↗
NASA NTRS2002

Atmospheric Chemistry Insights from the SHADOZ Data: An IGAC Paradigm

The first climatological overview of total, stratospheric and tropospheric ozone in the southern hemisphere tropical and subtropics is based on ozone sounding data from ten sites comprising the Southern Hemisphere Additional Ozonesondes (SHADOZ) network. The period covered is 1998-2000. Observations were made over: Ascension Island; Nairobi, Kenya; Irene, South Africa; Reunion Island; Watukosek, Java; Fiji; Tahiti; American Samoa; San Cristobal, Galapagos; Natal, Brazil. Campaign data were collected on a Trans-Atlantic oceanographic cruise and during SAFARI-2000 in Zambia. The ozone data, with simultaneous temperature profiles to approx. 7 hPa and relative humidity to approx. 200 hPa, reside at: http://code9l6.gsfc.nasa.gov/ Data-services/shadoz. SHADOZ ozone time-series and profiles give a perspective on tropical total, stratospheric and tropospheric ozone in 1998-2000. Prominent features are highly variable tropospheric ozone, a zonal wave-one pattern in total (and tropospheric) column ozone, and signatures of the Quasi-Biennial Oscillation (QBO) in stratospheric ozone. Total, stratospheric and tropospheric column ozone amounts peak between August and November and are lowest between March and May. Tropospheric ozone variability over the Indian and Pacific Ocean displays influences of the Indian Ocean Dipole, and convective mixing. Pollution transport from Africa, South American and the Maritime Continent is a seasonal feature. Tropospheric ozone seasonality over the Atlantic Basin shows effects of regional subsidence and recirculation as well as biomass burning. Dynamical and chemical influences appear to be of comparable magnitude though model studies are needed to quantify this.

Thompson, Anne M.↗