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At least 343 records · Page 19

The potential impact on atmospheric ozone and temperature of increasing trace gas concentrations

The response of the atmosphere to emissions of chlorofluorocarbons (CFCs) and other chlorocarbons, and to increasing concentrations of other radiatively active trace gases such as CO2, CH4, and N2O is calculated by a coupled chemical-radiative transport one-dimensional model. It is shown that significant reductions in the ozone concentration and in the temperature are expected in the upper stratosphere as a result of increasing concentrations of active chlorine produced by photodecomposition of the CFCs. The ozone content is expected to increase in the troposphere, as a consequence of increasing concentrations of methane and nitrogen oxides. Due to enhanced greenhouse effects, the Earth's surface should warm up by several degrees. The amplitude and even the sign of future changes in the ozone column are difficult to predict as they are strongly scenario-dependent. An early detection system to prevent noticeable ozone changes as a result of increasing concentrations of source gases should thus be based on a continuous monitoring of the ozone amount in the upper stratosphere rather than on measurements of the ozone column only. Measurements of NOx, Clx, and HOx are also required for unambiguous trend detection and interpretation.

Brasseur, G.↗

The potential impact on atmospheric ozone and temperature of increasing trace gas concentrations

The response of the atmosphere to emission of chlorofluorocarbons and other chlorocarbons and to increasing concentrations of other radiatively active trace gases is calculated using a coupled, one-dimensional, time-dependent chemical-radiative-transport model. The model predicts future changes in the ozone content and in the temperature based on several possible time-dependent scenarios of future atmospheric emissions. The sensitivity of the atmospheric responses to the values adopted for parameters such as the eddy diffusion coefficient for vertical transport and the atmospheric budget of nitrogen oxides is estimated and discussed.

Brasseur, Guy↗

Seawater strontium isotopes, acid rain, and the Cretaceous-Tertiary boundary

A large bolide impact at the end of the Cretaceous would have produced significant amounts of nitrogen oxides by shock heating of the atmosphere. The resulting acid precipitation would have increased continental weathering greatly and could be an explanation for the observed high ratio of strontium-87 to strontium-86 in seawater at about this time, due to the dissolution of large amounts of strontium from the continental crust. Spikes to high values in the seawater strontium isotope record at other times may reflect similar episodes.

Macdougall, J. D.↗

Mass accommodation coefficient measurements for HNO3, HCl and N2O5 on water, ice and aqueous sulfuric acid droplet surfaces

Preliminary results are reported of the direct measurement of accommodation coefficients for HNO3, N2O5 and HCl on water drops, aqueous sulfuric acid drops and ice particles. The heterogeneous chemistry of these species together with ClONO2 has been implicated in the ozone depletion observed in the Antarctic stratosphere during the spring in the last eight years. The most plausible chemical mechanism involves the removal of nitrogen oxide species via condensation on ice particles in polar stratospheric clouds resulting in a increase in the active chlorine species responsible for the ozone depletion. The observation of low NO2 and high ClO densities in the Antarctic stratosphere last summer appear to be consistent with such a mechanism.

Worsnop, Douglas↗

Response of marine and freshwater algae to nitric acid and elevated carbon dioxide levels simulating environmental effects of bolide impact

One of the intriguing facets of the Cretaceous-Tertiary extinction is the apparently selective pattern of mortality amongst taxa. Some groups of organisms were severely affected and some remained relatively unscathed as they went through the K/T boundary. While there is argument concerning the exact interpretation of the fossil record, one of the best documented extinctions at the Cretaceous-Tertiary boundary is that of the calcareous nannoplankton. These organisms include coccolithic algae and foraminiferans. Attempts to explain their decline at the K/T boundary center around chemistry which could affect their calcium carbonate shells while leaving their silica-shelled cousins less affected or unaffected. Two environmental consequences of an extraterrestrial body impact which were suggested are the production of large quantities of nitrogen oxides generated by the shock heating of the atmosphere and the possible rise in CO2 from the dissolution of CaCO3 shells. Both of these phenomena would acidify the upper layers of the oceans and bodies of freshwater not otherwise buffered. The effects of nitric acid, carbon dioxide, or both factors on the growth and reproduction of calcareous marine coccoliths and non-calcareous marine and freshwater species of algae were considered. These experiments demonstrate that nitric acid and carbon dioxide have significant effects on important aspects of the physiology and reproduction of modern algae representative of extinct taxa thought to have suffered significant declines at the Cretaceous-Tertiary boundary. Furthermore, calcareous species showed more marked effects than siliceous species and marine species tested were more sensitive than freshwater species.

Boston, P. J.↗

Low NO(x) potential of gas turbine engines

Nitrogen oxide levels of low gas turbine engine emissions are correlated in this paper. The predictions of NO(x) emissions are based on a review of the literature of previous low NO(x) combustor programs and analytical chemical kinetic calculations. Concepts included in the literature review consisted of Lean-Premixed-Prevaporized (LPP), Rich Burn/Quick Quench/Lean/Burn (RQL), and Direct Injection. The NO(x) emissions were found to be an exponential function of adiabatic combustion temperature over a wide range of inlet temperatures, pressures and (lean) fuel-air ratios. It is stated that the low NO(X) potential of LPP is offset by the operational disadvantages of its narrow stability limits and its susceptibility to autoignition/ flashback. The RQL and the Direct Injection concepts have the advantage of wider stability limits comparable to conventional combustors. Results were obtained primarily with gaseous fuels and it is noted that the challenge will be to produce the same low levels of NO(x) with liquid fuels.

Tacina, Robert R.↗

The atmospheric effects of stratospheric aircraft: A current consensus

In the early 1970's, a fleet of supersonic aircraft flying in the lower stratosphere was proposed. A large fleet was never built for economic, political, and environmental reasons. Technological improvements may make it economically feasible to develop supersonic aircraft for current markets. Some key results of earlier scientific programs designed to assess the impact of aircraft emissions on stratospheric ozone are reviewed, and factors that must be considered to assess the environmental impact of aircraft exhaust are discussed. These include the amount of nitrogen oxides injected in the stratosphere, horizontal transport, and stratosphere/troposphere assessment models are presented. Areas in which improvements in scientific understanding and model representation must be made to reduce the uncertainty in model calculations are identified.

Douglass, A. R.↗

Airborne sulfur trace species intercomparison campaign: Sulfur dioxide, dimethylsulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide

Results from an airborne intercomparison of techniques to measure tropospheric levels of sulfur trace gases are presented. The intercomparison was part of the NASA Global Tropospheric Experiment (GTE) and was conducted during the summer of 1989. The intercomparisons were conducted on the Wallops Electra aircraft during flights from Wallops Island, Virginia, and Natal, Brazil. Sulfur measurements intercompared included sulfur dioxide (SO2), dimethylsulfide (DMS), hydrogen sulfide (H2S), carbon disulfide (CS2), and carbonyl sulfide (OCS). Measurement techniques ranged from filter collection systems with post-flight analyses to mass spectrometer and gas chromatograph systems employing various methods for measuring and identifying the sulfur gases during flight. Sampling schedules for the techniques ranged from integrated collections over periods as long as 50 minutes to one- to three-minute samples every ten or fifteen minutes. Several of the techniques provided measurements of more than one sulfur gas. Instruments employing different detection principles were involved in each of the sulfur intercomparisons. Also included in the intercomparison measurement scenario were a host of supporting measurements (i.e., ozone, nitrogen oxides, carbon monoxide, total sulfur, aerosols, etc.) for purposes of: (1) interpreting results (i.e., correlation of any noted instrument disagreement with the chemical composition of the measurement environment); and (2) providing supporting chemical data to meet CITE-3 science objectives of studying ozone/sulfur photochemistry, diurnal cycles, etc. The results of the intercomparison study are briefly discussed.

Gregory, Gerald L.↗

Analytical combustion/emissions research related to the NASA high-speed research program

Increasing the pressure and temperature of the engines of new generation supersonic airliners increases the emissions of nitrogen oxides to a level that would have an adverse impact on the Earth's protective ozone layer. In the process of implementing low emissions combustor technologies, NASA Lewis Research Center has pursued a combustion analysis program to guide combustor design processes, to identify potential concepts of greatest promise, and to optimize them at low cost, with short turn-around time. The approach is to upgrade and apply advanced computer programs for gas turbine applications. Efforts have been made to improve the code capabilities of modeling the physics. Test cases and experiments are used for code validation. To provide insight into the combustion process and combustor design, two-dimensional and three-dimensional codes such as KIVA-II and LeRC 3D have been used. These codes are operational and calculations have been performed to guide low emissions combustion experiments.

Nguyen, H. Lee↗

Ozone trends in Atlanta, Georgia - Have emission controls been effective?

Nine years of summertime ozone data from the Atlanta metropolitan area are analyzed and compared to local emissions of volatile organic carbon and nitrogen oxides. Trends from 1979 to 1987 were studied for the number of days per year ozone exceeded the NAAQS standard, the second-highest ozone level observed per year, and the first quartile summertime average ozone observed, as well as the mean difference between the ozone level observed downwind and upwind of the city. Because this last parameter is sensitive to chemical factors but relatively insensitive to the number of days each year with meteorological conditions conducive to ozone formation, its trend may be best suited for determining how effective emission controls have been in reducing O3 in the Atlanta area. In spite of the fact that sizeable reductions have been claimed for volatile organic carbon emissions over the past several years, the data give no indication that ozone levels have decreased and in fact, imply that summertime ozone production may have increased. The results imply that either emissions have not decreased as much as has been claimed or that ozone is not sensitive to anthropogenic volatile organic carbon emissions.

Lindsay, Ronald W.↗

The Tropospheric Lifetimes of Halocarbons and Their Reactions with OH Radicals: an Assessment Based on the Concentration of CO-14

Chemical reaction with hydroxyl radicals formed in the troposphere from ozone photolysis in the presence of methane, carbon monoxide and nitrogen oxides provides an important removal mechanism for halocarbons containing C-H and C = C double bonds. The isotropic distribution in atmospheric carbon monoxide was used to quantify the tropospheric hydroxyl radical distribution. Here, this methodology is reevaluated in the light of recent chemical kinetic data evaluations and new understandings gained in the life cycles of methane and carbon monoxide. None of these changes has forced a significant revision in the CO-14 approach. However, it is somewhat more clearly apparent how important basic chemical kinetic data are to the accurate establishment of the tropospheric hydroxyl radical distribution.

Derwent, Richard G.↗

Upper-atmosphere Aerosols: Properties and Natural Cycles

The middle atmosphere is rich in its variety of particulate matter, which ranges from meteorite debris, to sulfate aerosols, to polar stratospheric ice clouds. Volcanic eruptions strongly perturb the stratospheric sulfate (Junge) layer. High-altitude 'noctilucent' ice clouds condense at the summer mesopause. The properties of these particles, including their composition, sizes, and geographical distribution, are discussed, and their global effects, including chemical, radiative, and climatic roles, are reviewed. Polar stratospheric clouds (PSCs) are composed of water and nitric acid in the form of micron-sized ice crystals. These particles catalyze reactions of chlorine compounds that 'activate' otherwise inert chlorine reservoirs, leading to severe ozone depletions in the southern polar stratosphere during austral spring. PSCs also modify the composition of the polar stratosphere through complex physiocochemical processes, including dehydration and denitrification, and the conversion of reactive nitrogen oxides into nitric acid. If water vapor and nitric acid concentrations are enhanced by high-altitude aircraft activity, the frequency, geographical range, and duration of PSCs might increase accordingly, thus enhancing the destruction of the ozone layer (which would be naturally limited in geographical extent by the same factors that confine the ozone hole to high latitudes in winter). The stratospheric sulfate aerosol layer reflects solar radiation and increases the planetary albedo, thereby cooling the surface and possibly altering the climate. Major volcanic eruptions, which increase the sulfate aerosol burden by a factor of 100 or more, may cause significant global climate anomalies. Sulfate aerosols might also be capable of activating stratospheric chlorine reservoirs on a global scale (unlike PCSs, which represent a localized polar winter phenomenon), although existing evidence suggests relatively minor perturbations in chlorine chemistry. Nevertheless, if atmospheric concentrations of chlorine (associated with anthropogenic use of chlorofluorocarbons) continue to increase by a factor of two or more in future decades, aircraft emissions of sulfur dioxide and water vapor may take on greater significance.

Turco, Richard P.↗

Photochemistry of biogenic gases

The relationship between the biosphere and the atmosphere is examined, emphasizing the composition and photochemistry and chemistry of the troposphere and stratosphere. The reactions of oxygen, ozone, and hydroxyl are reviewed and the fate of the biogenic gases ammonia, methane, reduced sulfur species, reduced halogen species, carbon monoxide, nitric oxide, nitrous oxide, nitrogen, and carbon dioxide are described. A list is given of the concentration and sources of the various gases.

Levine, Joel S.↗

Measurements of nitric acid, carboxylic acids, and selected aerosol species for the NASA/GTE Pacific Mission - West (PEM-WEST)

The research investigation funded through this grant to the University of New Hampshire was performed during a major field expedition conducted by the NASA Tropospheric Chemistry Program. The NASA Global Tropospheric Experiment (GTE) executed an airborne science mission (PEM-WEST A) aboard the NASA Ames DC-8 over the Pacific Ocean during Sep./Oct. 1981. The atmosphere over the central Pacific Ocean is the only major region in the Northern Hemisphere that is relatively free from direct anthropogenic influence. Thus, this environment is ideally suited to study the natural biogeochemical cycles of carbon, nitrogen, ozone, sulfur, and aerosols without serious confounding problems related to anthropogenic emissions. Asian sources account for about 17 percent of the global budgets of nitrogen oxides (NO(x)) and sulfur dioxide (SO2). The Pacific Rim region therefore provides the opportunity to study the anthropogenic impact on natural atmospheric chemical cycles. The PEM-WEST A flights were focused on contrasting the chemistry of 'clean' air over the central Pacific with anthropogenically impacted air advected off the Asian continent. The principal objectives of PEM-WEST A were to investigate the atmospheric chemistry of ozone (O3) and its precursors, and to study important aspects of the atmospheric sulfur cycle over the western Pacific Ocean. Measurements conducted by the University of New Hampshire contributed directly to both of these objectives. Subsequent PEM-WEST field missions are planned by GTE in the mid-1990's to contrast atmospheric chemistry documented during PEM-WEST A with other time periods. This report presents preliminary findings from the PEM-WEST A field mission. Data interpretation is currently ongoing with the goal of manuscript submission of scientific results to a special issue of the Journal of Geophysical Research-Atmospheres in Feb. 1994. The reader is strongly encouraged to review this suite of profession articles to appreciate the overall scientific findings and benefits of the PEM-WEST A field mission.

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.↗

Twisted Vanes Would Enhance Fuel/Air Mixing In Turbines

Computations of flow show performance of high-shear airblast fuel injector in gas-turbine engine enhanced by use of appropriately proportioned twisted (instead of flat) dome swirl vanes. Resultant more nearly uniform fuel/air mixture burns more efficiently, emitting smaller amounts of nitrogen oxides. Twisted-vane high-shear airblast injectors also incorporated into paint sprayers, providing advantages of low pressure drop characteristic of airblast injectors in general and finer atomization of advanced twisted-blade design.

Nguyen, H. Lee↗

Combustor technology for future small gas turbine aircraft

Future engine cycles proposed for advanced small gas turbine engines will increase the severity of the operating conditions of the combustor. These cycles call for increased overall engine pressure ratios which increase combustor inlet pressure and temperature. Further, the temperature rise through the combustor and the corresponding exit temperature also increase. Future combustor technology needs for small gas turbine engines is described. New fuel injectors with large turndown ratios which produce uniform circumferential and radial temperature patterns will be required. Uniform burning will be of greater importance because hot gas temperatures will approach turbine material limits. The higher combustion temperatures and increased radiation at high pressures will put a greater heat load on the combustor liners. At the same time, less cooling air will be available as more of the air will be used for combustion. Thus, improved cooling concepts and/or materials requiring little or no direct cooling will be required. Although presently there are no requirements for emissions levels from small gas turbine engines, regulation is expected in the near future. This will require the development of low emission combustors. In particular, nitrogen oxides will increase substantially if new technologies limiting their formation are not evolved and implemented. For example, staged combustion employing lean, premixed/prevaporized, lean direct injection, or rich burn-quick quench-lean burn concepts could replace conventional single stage combustors.

Lyons, Valerie J.↗

Theoretical study of thermodynamic properties and reaction rates of importance in the high-speed research program

One of the primary goals of NASA's high-speed research program is to determine the feasibility of designing an environmentally safe commercial supersonic transport airplane. The largest environmental concern is focused on the amount of ozone destroying nitrogen oxides (NO(x)) that would be injected into the lower stratosphere during the cruise portion of the flight. The limitations placed on NO(x) emission require more than an order of magnitude reduction over current engine designs. To develop strategies to meet this goal requires first gaining a fundamental understanding of the combustion chemistry. To accurately model the combustor requires a computational fluid dynamics approach that includes both turbulence and chemistry. Since many of the important chemical processes in this regime involve highly reactive radicals, an experimental determination of the required thermodynamic data and rate constants is often very difficult. Unlike experimental approaches, theoretical methods are as applicable to highly reactive species as stable ones. Also our approximation of treating the dynamics classically becomes more accurate with increasing temperature. In this article we review recent progress in generating thermodynamic properties and rate constants that are required to understand NO(x) formation in the combustion process. We also describe our one-dimensional modeling efforts to validate an NH3 combustion reaction mechanism. We have been working in collaboration with researchers at LeRC, to ensure that our theoretical work is focused on the most important thermodynamic quantities and rate constants required in the chemical data base.

Langhoff, Stephen↗