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At least 541 records · Page 30

Intermediates in the Formation of Aromatics in Hydrocarbon Combustion

The formation of the first benzene ring is believed to be the rate limiting step in soot formation. Two different mechanisms have been proposed for formation of cyclic C6 species. The first involves the reaction of two acetylenes to give CH2CHCCH (vinyl acetylene), the loss of a H to give CHCHCCH (n-C41-13) or CH2CCCH (iso-C4H3), and addition of another acetylene to n-C4H3, followed by ring closure to give phenyl radical. Miller and Melius argue that only n-C4H3 leads to phenyl radical and since iso-C4H3 is more stable than n-C4H3 this mechanism is unlikely. An alternative mechanism proposed by them is formation of benzene from the dimerization of two CH2CCH (propargyl) radicals (formed by the reaction of singlet methylene with C2H2). We report reaction pathways and accurate energetics (from CASSCF/internally contracted CI calculations) for the reactions of CH(pi-2) and CH2-1 with acetylene, the reaction of vinylidene with acetylene, and the reaction of n-C4H3 and iso-C4H3 with acetylene. These calculations identify two new reactive intermediates CHCHCH ( a A"-2 ground state in Cs symmetry; spin coupling is a doublet from three singly occupied orbitals) and CHCCH (B-3 ground state in C2 symmetry) from the reaction of CH with acetylene. These species dimerize with no barrier to form benzene and para-benzyne, respectively. CHCCH is proposed as a reactive intermediate which can add to benzene to give higher polynuclear aromatic hydrocarbons or fullerenes. The addition of a C3H2 unit releases two C-C bond energies and thus the resulting addition product contains sufficient energy to break several CH bonds leading to a reduction in the H to C ratio as the cluster size increases. It is found that iso-C4H3 adds to acetylene to initially give a fulvene radical but that this species rearranges to phenyl radical. Thus, the reaction of acetylene with iso-C4H3 does lead to phenyl radical and the cyclization pathway may also contribute to formation of the initial benzene ring.

Walch, Stephen P.↗

Tropical Tropospheric Ozone and Smoke Interactions: Satellite Observations During the 1997 Indonesian Fires

Biomass burning generates hydrocarbons, nitrogen oxides and carbon monoxide that lead to tropospheric ozone pollution. Other combustion products form soot and various aerosol particles that make up smoke. Since early 1997 smoke and tropospheric ozone have been monitored in real-time from TOMS (Total Ozone Mapping Spectrometer) at toms.gsfc.nasa.gov (smoke aerosol) and metosrv2.umd.edu/-tropo (tropospheric ozone). The striking increase in smoke and tropospheric ozone observed during the 1997 Indonesian fires was the first extreme episode observed. During the August-November period, plumes of excess ozone and smoke coincided at times but were decoupled at other times, a phenomenon followed with trajectories. Thus, trans-boundary evolution of smoke and ozone differed greatly. The second discovery of the 1997 TOMS record was a dynamical interaction of ozone with the strong El Nino Southern Oscillation (ENSO) and Indian Ocean Dipole (IOD) that led to a jump in tropospheric ozone in March 1997 over the entire Indian Ocean, well ahead of the intense burning period. A climatology of smoke and tropospheric ozone from a 1980's TOMS instrument shows offsets in the timing of these pollutants - further evidence that factors other than biomass burning exert a strong influence on tropical tropospheric ozone.

Thompson, A. M.↗

Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

Walch, Stephen P.↗

Characterization of the Minimum Energy Paths for the Reactions of CH(X(sup 2 Pi) and (1)CH2 with C2H2

The reactions of CH(sup 2 Pi) and singlet methylene (1)CH2 with acetylene lead to intermediates which may be important in soot formation. CH(sup 2 Pi) + acetylene leads to CHCHCH (C3H3), CHCCH (C3H2), and propargyl (CH2CCH). (1)CH2 + acetylene leads to cyclopropene and propargyl. All of these reaction products are formed with no barrier. Miller and Melius have previously discussed the dimerization of propargyl to give benzene. C3H3 and C3H2 can dimerize with no barrier to give benzene and para-benzyne, respectively. C3H3 and C3H2 can also add to smaller polynuclear aromatic hydrocarbons (PAH), and may be important species in forming larger PAH or fullerenes.

Walch, Stephen P.↗

Environmental Perturbations Caused by the Impacts of Comets and Asteroids on Earth

The extinction mechanisms proposed at the Cretaceous-Tertiary geological boundary are reviewed and related to the impact of asteroids or comets in general. For impact energies below 10(exp 4) Megatons (less than 6 x 10(exp 4) years; asteroid diameter less than 650 m), blast, earthquake, and fire may destroy local areas up to 10(exp 5) square m. Tidal waves could flood a kilometer inland over entire ocean basins. The energy range from 105 to 106 Megatons (less than 2 x 10(exp 6) years; asteroid diameter less than 3 km) is transitional. Dust lifted, sulfur released from within impacting asteroids, and soot from fires started by comets can produce climatologically significant optical depths of 10. At energies beyond 10(exp 7) Megatons, blast and earthquake damage is regional (10(exp 6) square cm). Tsunami cresting to 100 m and flooding 20 km inland will sweep the coastal zones of the world's oceans. Fires will be set globally. Light levels may drop so low from the smoke, dust and sulfate that vision is not possible. At energies approaching 10(exp 9) Megatons the ocean surface waters may be acidified by sulfur. The combination of these effects would be devastating.

Toon, Owen B.↗

Computed Potential Energy Surfaces and Minimum Energy Pathways for Chemical Reactions

Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. For some dynamics methods, global potential energy surfaces are required. In this case, it is necessary to obtain the energy at a complete sampling of all the possible arrangements of the nuclei, which are energetically accessible, and then a fitting function must be obtained to interpolate between the computed points. In other cases, characterization of the stationary points and the reaction pathway connecting them is sufficient. These properties may be readily obtained using analytical derivative methods. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives usefull results for a number of chemically important systems. The talk will focus on a number of applications including global potential energy surfaces, H + O2, H + N2, O(3p) + H2, and reaction pathways for complex reactions, including reactions leading to NO and soot formation in hydrocarbon combustion.

Walch, Stephen P.↗

Dust Aerosols at the Source Region During ACE-ASIA: A Surface/Satellite Perspective

ACE (Aerosol Characterization Experiment)-Asia is designed to study the compelling variability in spatial and temporal scale of both pollution-derived and naturally occurring aerosols, which often exist in high concentrations over eastern Asia and along the rim of the western Pacific. The phase-I of ACE-Asia was conducted from March-May 2001 in the vicinity of the Gobi desert, East Coast of China, Yellow Sea, Korea, and Japan, along the pathway of Kosa (severe events that blanket East Asia with yellow desert dust, peaked in the Spring season). Asian dust typically originates in desert areas far from polluted urban regions. During transport, dust layers can interact with anthropogenic sulfate and soot aerosols from heavily polluted urban areas. Added to the complex effects of clouds and natural marine aerosols, dust particles reaching the marine environment can have drastically different properties than those from the source. Thus, understanding the unique temporal and spatial variations of Asian dust is of special importance in regional-to-global climate issues such as radiative forcing, the hydrological cycle, and primary biological productivity in the mid-Pacific Ocean. During ACE-Asia we have measured continuously aerosol physical/optical/radiative properties, column precipitable water amount, and surface reflectivity over homogeneous areas from surface. The inclusion of flux measurements permits the determination of dust aerosol radiative flux in addition to measurements of loading and optical thickness. At the time of the Terra/MODIS, SeaWiFS, TOMS and other satellite overpasses, these ground-based observations can provide valuable data to compare with satellite retrievals over land. Preliminary results will be presented and discussed their implications in regional climatic effects.

Tsay, Si-Chee↗

Minimum Energy Pathways for Chemical Reactions

Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives useful results for a number of chemically important systems. The talk will focus on a number of applications to reactions leading to NOx and soot formation in hydrocarbon combustion.

Walch, S. P.↗

Overview of ACE-Asia Spring 2001 Investigations on Aerosol Radiative Effects and Related Aerosol Properties

A primary, ACE-Asia objective was to quantify the interactions between aerosols and radiation in the Asia-Pacific region. Toward this end, radiometric and related aerosol measurements were made from ocean, land, air and space platforms. Models that predict aerosol fields guided the measurements and are helping integrate and interpret results. Companion overview's survey these measurement and modeling components. Here we illustrate how these components were combined to determine aerosol radiative. impacts and their relation to aerosol properties. Because clouds can obscure or change aerosol direct radiative effects, aircraft and ship sorties to measure these effects depended on predicting and finding cloud-free areas and times with interesting aerosols present. Pre-experiment satellite cloud climatologies, pre-flight aerosol and cloud forecasts, and in-flight guidance from satellite imagery all helped achieve this. Assessments of aerosol regional radiative impacts benefit from the spatiotemporal coverage of satellites, provided satellite-retrieved aerosol properties are accurate. Therefore, ACE-Asia included satellite retrieval tests, as part of many comparisons to judge the consistency (closure) among, diverse measurements. Early results include: (1) Solar spectrally resolved and broadband irradiances and optical depth measurements from the C-130 aircraft and at Kosan, Korea yielded aerosol radiative forcing efficiencies, permitting comparisons between efficiencies of ACE-Asia and INDOEX aerosols, and between dust and "pollution" aerosols. Detailed results will be presented in separate papers. (2) Based on measurements of wavelength dependent aerosol optical depth (AOD) and single scattering albedo the estimated 24-h a average aerosol radiative forcing efficiency at the surface for photosynthetically active radiation (400 - 700 nm) in Yulin, China is approx. 30 W sq m per AOD(500 nm). (3) The R/V Brown cruise from Honolulu to Sea of Japan sampled an aerosol optical depth gradient, with AOD(500 nm) extremes from 0.1 to 1.1. On the Pacific transit from Honolulu to Hachijo AOD(500 nm) averaged 0.2, including increases to 0.4 after several storms, suggesting the strong impact of wind-generated seasalt. The AOD maximum, found in the Sea of Japan, was influenced by dust and anthropogenic sources. (4) In Beijing, single scattering albedo retrieved from AERONET sun-sky radiometry yielded midvisible SSA=0.88 with strong wavelength dependence, suggesting a significant black carbon component. SSA retrieved during dust episodes was approx. 0.90 and variable but wavelength neutral reflecting the presence of urban haze with the dust. Downwind at Anmyon Island SSA was considerably higher, approx. 0.94, but wavelength neutral for dust episodes and spectrally dependent during non dust periods. (5) Satellite retrievals show major aerosol features moving from Asia over the Pacific; however, determining seasonal-average aerosol effects is hampered by sampling frequency and large-scale cloud systems that obscure key parts of aerosol patterns. Preliminary calculations using, satellite-retrieved AOD fields and initial ACE-Asia aerosol properties (including sulfates, soot, and dust) yield clear-sky aerosol radiative effects in the seasonal-average ACE-Asia plume exceeding those of manmade greenhouse gases. Quantifying all-sky direct aerosol radiative effects is complicated by the need to define the height of absorbing aerosols with respect to cloud decks.

Russell, Philip B.↗

Subsonic Aircraft Contrail and Cloud Effects Special Study (SUCCESS)

During recent years interest in the impact of commercial aircraft on the climate has increased. Aircraft might impact climate in a number of ways. Contrails are clearly a direct radiative forcing mechanism. Exhaust emissions, principally soot and sulfate, might indirectly force the climate by modifying the radiative properties of cirrus clouds. The SUCCESS program was carried out to investigate these issues. It also has several other goals including: better understanding the emissions from aircraft, better understanding the formation of cirrus clouds: better understanding the radiative properties of contrails and clouds and their remote sensing; better understanding the heterogeneous chemistry in the upper atmosphere; and developing new instruments of importance to atmospheric chemistry and cloud physics. SUCCESS took place during April and May of 1997. The NASA DC-8, ER-2, T-39, and 757 aircraft were used as in situ sampling, remote sensing, near field sampling, and emission sources respectively. Most of the operations occurred near the DOE's Atmospheric Radiation Measurement Site in Northern Oklahoma. The DOE operated several other aircraft so that on some days as many as six research aircraft flew together. Numerous new instruments functioned during the mission. This talk will present an overview of SUCCESS from the operational point of view, and provide some of the overall scientific highlights.

Toon, O.B.↗

Optical Scattering Characterization for the Glennan Microsystems Microscale Particulate Classifier

Small sensors that are tolerant to mechanically and thermally harsh environments present the possibility for in-situ particle characterization in propulsion, industrial, and planetary science applications. Under a continuing grant from the Glennan Microsystems Initiative to the Microgravity Fluids Physics Branch of the NASA-Glenn Research Center, a Microscale Particle Classifier (MiPAC) instrument is being developed. The MiPAC instrument will be capable of determining the size distribution of airborne particles from about 1 nm to 30 micrometers, and will provide partial information as to the concentration, charge state, shape, and structure of the particles, while being an order of magnitude smaller in size and lighter in weight than presently commercially available instruments. The portion of the instrument that will characterize the nm-range particles will employ electrical mobility techniques and is being developed under a separate grant to Prof. David Pui of the University of Minnesota. The portion of the instrument that will characterize the micrometer-size particles such as dirt, pollens, spores, molds, soot, and combustion aerosols will use light scattering techniques. The development of data analysis techniques to be employed in the light scattering portion of the instrument is covered by this grant.

Lock, James A.↗

Subsonic Aircraft Contrail and Cloud Effects Special Study (SUCCESS)

During recent years interest in the impact of commercial aircraft on the climate has increased. Aircraft might impact climate in a number of ways. Contrails are clearly a direct radiative forcing mechanism. Exhaust emissions, principally soot and sulfate, might indirectly radiative force the climate by modifying the properties of cirrus clouds. The SUCCESS program was carried out to investigate these issues. It also had several other goals including: better understanding the emissions from aircraft, better understanding the formation of cirrus clouds: better understanding the radiative properties of contrail and clouds and their remote sensing; better understanding the heterogeneous chemistry in the upper atmosphere; and developing new instruments of importance to atmospheric chemistry and cloud physics. SUCCESS took place during April and May of 1996. The NASA DC-8, ER-2, T-39, and 757 aircraft were used as in situ sampling, remote sensing, near field sampling, and emission sources respectively. Most of the operations occurred near the DOE's Atmospheric Radiation Measurement Site in Northern Oklahoma. The DOE operated several other aircraft so that on some days as many as six research aircraft operated together. Numerous new instruments operated during the mission. This talk will present an overview of SUCCESS from the operational point of view, and provide some of the overall scientific highlights.

Toon, O. B.↗

Characteristics of Interstellar and Circumstellar Dust

This paper will review our current knowledge of circumstellar and interstellar dust from an astronomical point of view. About half of the interstellar dust volume consists of amorphous silicates. The remainder has to be made up of an carbonaceous component such as graphite, amorphous carbon (i.e., soot), Polycyclic Aromatic Hydrocarbon molecules (PAHs), and/or organic grain mantles (i.e., mixed polymers). The observational evidence for these components will be reviewed and their relative importance assessed. The emphasis will be on recent observations using the Infrared Space Observatory. Most of these dust components are formed in the outflows from stars in the late stages of their evolution (i.e., red giants, planetary nebulae, novae, supergiants, Wolf Rayet stars, and supernovae). Indeed, observation of such objects indicate an even richer spectrum of stardust components, including also SiC, MgS, and aluminates and crystalline silicates. These observations will be briefly discussed. The stardust budget of the galaxy will be reviewed and the relative importance of the various birth sites assessed. Finally, in recent years, isotopic composition studies have shown that some circumstellar and interstellar dust grains have been incorporated into solar system bodies such as planetary dust particles and meteorites without totally losing their identity. Among the components identified are SiC, graphite, diamonds, PAHs, aluminum oxides, as well as various trace element carbides. Studies of this kind have opened up a new window on the composition and structure of interstellar dust. These different sources of information on interstellar and circumstellar dust will be briefly contrasted.

Tielens, A. G. G. M.↗

Dust, Pollution, and Biomass Burning Aerosols in Asian Pacific: A Column Surface/Satellite Perspective

Many recent field experiments are designed to study the compelling variability in spatial and temporal scale of both pollution-derived and naturally occurring aerosols, which often exist in high concentrations over eastern/southeastern Asia and along the rim of the western Pacific. For example, the phase-I of ACE-Asia was conducted from March-May 2001 in the vicinity of the Gobi desert, East Coast of China, Yellow Sea, Korea, and Japan, along the pathway of Kosa (severe events that blanket East Asia with yellow desert dust, peaked in the Spring season). Asian dust typically originates in desert areas far from polluted urban regions. During transport, dust layers can interact with anthropogenic sulfate and soot aerosols from heavily polluted urban areas. Springtime is also the peak season for biomass burning in southeastern Asia. Added to the complex effects of clouds and natural marine aerosols, dust particles reaching the marine environment can have drastically different properties than those from the source. Thus, understanding the unique temporal and spatial variations of Asian aerosols is of special importance in regional-to-global climate issues such as radiative forcing, the hydrological cycle, and primary biological productivity in the mid-Pacific Ocean. During ACE-Asia we have measured continuously aerosol physical/optical/radiative properties, column precipitable water amount, and surface reflectivity over homogeneous areas from surface. The inclusion of flux measurements permits the determination of aerosol radiative flux in addition to measurements of loading and optical depth. At the time of the Terra/MODIS (Moderate Resolution Imaging Spectroradiometer), SeaWiFS (Sea-viewing Wide Field-of-view Sensor), TOMS (Total Ozone Mapping Spectrometer) and other satellite overpasses, these ground-based observations can provide valuable data to compare with satellite retrievals over land. A column satellite-surface perspective of Asian aerosols will be presented and will discuss their implications in regional-to-global effects on climate, fresh water redistribution, and health issues. (to be presented in Hawaii, April 28 - May 3, and Beijing, China, May 6 - 10, 2002)

Tsay, Si-Chee↗

Combustion Temperature Measurement by Spontaneous Raman Scattering in a Jet-A Fueled Gas Turbine Combustor Sector

Spontaneous vibrational Raman scattering was used to measure temperature in an aviation combustor sector burning jet fuel. The inlet temperature ranged from 670 K (750 F) to 756 K (900 F) and pressures from 13 to 55 bar. With the exception of a discrepancy that we attribute to soot, good agreement was seen between the Raman-derived temperatures and the theoretical temperatures calculated from the inlet conditions. The technique used to obtain the temperature uses the relationship between the N2 anti-Stokes and Stokes signals, within a given Raman spectrum. The test was performed using a NASA-concept fuel injector and Jet-A fuel over a range of fuel/air ratios. This work represents the first such measurements in a high-pressure, research aero-combustor facility.

Hicks, Yolanda R.↗

Airborne Sunphotometer Measurements of Aerosol Optical Depth and Water Vapor in ACE-Asia and Their Comparisons to Correlative Measurements

In the Spring 2001 phase of the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia), the 6-channel NASA Ames Airborne Tracking Sunphotometer (AATS-6) operated on 15 of the 19 research flights of the NCAR C-130, while its 14-channel counterpart (AATS-14) flew successfully on all 19 research flights of the CIRPAS Twin Otter. ACE-Asia studied aerosol outflow from the Asian continent to the Pacific basin. It was designed to integrate suborbital and satellite measurements and models to reduce the uncertainty in calculations of the climate forcing due to aerosols. AATS-6 and AATS-14 measured solar beam transmission at six and 14 wavelengths (380-1021 and 354-1558 nm, respectively), yielding aerosol optical depth (AOD) spectra and columnar water vapor (CWV). Vertical differentiation in profiles yielded aerosol extinction spectra and water vapor concentration. In this paper, we plan to present examples of the following, preliminary findings that are based in part on our airborne sunphotometer measurements: (1) The wavelength dependence of sunphotometer-derived AOD and extinction indicates that supermicron dust was often a major component of the aerosol, frequently extending to high altitudes. The percentage of full-column AOD (525 nm) that Jay above 3 km was typically 34+/-13%. In contrast, the analogous percentage of columnar water vapor was only 10+/-4%; (2) Initial comparison studies between AOD data obtained by AATS-6 and AATS-14 during coordinated low-level flight legs show agreement well within the instruments' error bars; (3) Aerosol extinction has been derived from airborne in situ measurements of scattering (nephelometers) and absorption (particle soot/ absorption photometer, PSAP) or calculated from particle size distribution measurements (mobility analyzers and aerodynamic particle sizers). Comparison with corresponding extinction values derived from the Ames airborne sunphotometer measurements shows good agreement for the vertical distribution of aerosol layers. However, the level of agreement in absolute magnitude of the derived aerosol extinction/optical depth varied among the aerosol layers sampled; (4) Initial comparisons of sunphotometer and satellite-derived AOD using SeaWiFS, MISR and AVHRR show promising results. We also plan to include comparisons with MODIS and TOMS: (5) Initial comparisons of sunphotometer-derived AOD and aerosol extinction profiles with lidars in Tokyo and on a ship show reasonable agreement.

Schmid, B.↗

Sensitivity of Stratocumulus Optical Depths to Droplet Concentrations: Satellite Observations and Large-Eddy Simulations

A number of observations and simulations have shown that increased droplet concentrations in ship tracks increase their total cross-sectional area, thereby enhancing cloud albedo and providing a negative (cooling) radiative forcing at the surface and the top of the atmosphere. In some cases cloud water has been found to be enhanced in ship tracks, which has been attributed to suppression of drizzle and implies an enhanced susceptibility of cloud albedo to droplet concentrations. However, observations from aircraft and satellite indicate that on average cloud water is instead reduced in daytime ship tracks. Such a reduction in liquid water may be attributable to cloud-burning caused by solar heating by soot within the ship exhaust, or by increased precipitation resulting from giant nuclei in the ship exhaust. We will summarize the observational evidence and present results from large-eddy simulations that evaluate these mechanisms. Along the way we will present our insights into the interpretation of satellite retrievals of cloud microphysical properties.

Ackerman, A. S.↗

Effects of Aircraft On Aerosol Abundance in the Upper Troposphere

A significant increase in sulfuric acid aerosol concentration was detected above 10 km pressure altitude during a cross-corridor flight out of Shannon on October 23, 1997. The source of this aerosol is ascribed to commercial aircraft operations in flight corridors above 10 km, because (1) a stable atmosphere prevented vertical air mass exchanges and thus eliminated surface sources, (2) air mass back trajectories documented the absence of remote continental sources, and (3) temperature profiler data showed the tropopause at least one kilometers above flight altitude throughout the flight. Particle volatility identified 70% H2SO4, 20% (NH4)2SO4 and 10% nonvolatile aerosol in the proximity of flight corridors, and (10-30)% H2SO4, up to 50% (NH4)2SO4, and (40-60)% nonvolatile aerosols in air that was not affected by aircraft operations below 10 km. Only a very small fraction of the nonvolatile particles (determined with a condensation nucleus counter) could be morphologically identified as soot aerosol (validated by scanning electron microscopy of wire impactor samples). The newly formed H2SO4 particles did not measurably affect surface area and volume of the background aerosol due to their small size, hence did not affect radiative transfer directly.

Ferry, G. V.↗