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Laboratory chemistry and stratospheric clouds

Results are presented from laboratory experiments on the chemistry of ice particles to study the role of HCl and ClONO2 from CFCs in stratospheric ozone depletion over Antarctica. It is found that gaseous HCl is scavenged with high efficiency by the ice and the gas phase chlorine nitrate may react with the HCL-containing ice to produce Cl2. Also, consideration is given ot the behavior of solid nitric acid trihydrate and sulfuric acid aerosols.

Molina, Mario J.↗

SO2 on Venus: A final cross-calibration with Pioneer Venus

In our previous report, we noted that we had successfully completed all of the IUE observations which were proposed. A total of 7 Venus spectra were obtained. In the present reporting period, essentially all of the associated data reduction and analysis activities were completed, and Drs. Stern, Barker, and Na met to collaborate on data interpretation. The model atmosphere used in this analysis is similar to the one used in the analysis of the Pioneer Venus observations (Esposito, et al. 1979, 1988) and the previous IUE observations (Na, et al. 1990). In this model, sulfuric acid aerosols with a radius of about 1 micron are mixed uniformly with Rayleigh scattering gases throughout the cloud layer. There are two wavelength-independent absorbers. First, the aerosols are assumed to have a single scattering albedo of 0.98, and second a pure absorbing layer with an optical depth of 0.2 is added at an altitude of 75 mbar. The variable parameters in this model are the mixing ratios of SO2 at the cloud top (40 mbar level), and the scale height of SO2 at the same altitude. Model spectra were calculated using a radiative transfer code utilizing a Markov Chain method. Each model calculation takes into account the multiple scattering and the vertical inhomogeneity of the atmosphere. We reported those initial results at the 1992 meeting of the AAS Division of Planetary Sciences (Barker, Stern, and Na 1992) The important finding we have reached is that the 1991 IUE observations indicate that the long-term decline in Venus SO2 abundance has either halted or reversed. Our simultaneous groundbased measurements made on the McDonald Observatory 2.7 m corroborate this result. We are now preparing a paper describing these IUE results for publication in Icarus. With the IUE results reduced, we are also beginning a project to compare the 1991 IUE results to Pioneer Venus UV spectra made on the same dates.

Stern, S. Alan↗

Tropical ozone loss following the eruption of Mt. Pinatubo

Total Ozone Mapping Spectrometer (TOMS) measurements of equatorial total ozone following the eruption of Mt. Pinatubo show a decrease of up to 6 percent over climatology. Ozone losses begin approximately a month following the eruption, consistent with the time required for the SO2 to convert to sulfuric acid aerosol. The thick aerosol layer interferes with the TOMS retrieval, but this interference is small and easily accounted for in the retrieval. Ozone values remain below climatology until December, 1991. Ozonesonde data from Natal, Brazil taken before and two months after the eruption support TOMS observations of ozone loss. These sondes show that the ozone loss region is confined to a 2-3 km thick layer between 24 and 28 km.

Schoeberl, Mark R.↗

Impact of stratospheric aircraft emissions on ozone: A two dimensional model study

Atmospheric perturbations caused by the emission of nitrogen oxides from a projected fleet of stratospheric aircraft are studied with a two dimensional chemistry, transport model. Photochemistry of the lower stratosphere, the region where these aircraft may fly, is now known to be influenced by heterogeneous reactions involving sulfuric acid aerosols. This study examines the sensitivity of the atmospheric effects of aircraft to heterogeneous reactions. Information of background aerosols based on the SAGE 2 measurements have been used in the parameterization of the heterogeneous conversion rates. It is found that heterogeneous reactions make the lower stratospheric ozone less sensitive to perturbations in the odd nitrogen level. The calculated reduction in global ozone due to NO(x) injection from a fleet of Mach 2.4 aircraft is 1.28 percent if gas phase reactions only are considered in the model, and 0.06 percent if heterogeneous reactions are included.

Natarajan, M.↗

Biospheric effects of volatiles produced by the Chicxulub Cretaceous/Tertiary impact

The meteorite impact that formed the Chicxulub crater 65 million years ago caused a mass extinction of life. Analyses indicate that the projectile was either a 9.4-16.8 km diameter asteroid or a 14.2-24.0 km diameter comet. We estimate that 200 gigatons each of S02 and H2O were deposited globally in the stratosphere by the impact into water saturated sulfate-rich sediments. Conversion of these gases into sulfuric acid aerosols blocked an average of 68 percent of the sun's radiation for a period of 12 years. Global average temperatures probably dropped to near freezing in 5 years and remained near or below freezing for 7 years. Greenhouse warming due to impact-generated C02 was negligible, hence global cooling from sulfates was the major cause of climate change and contributed greatly to the mass extinction.

Pope, Kevin O.↗

Impact Cratering Calculations

Understanding the physical processes of impact cratering on planetary surfaces and atmospheres as well as collisions of finite-size self-gravitating objects is vitally important to planetary science. The observation has often been made that craters are the most ubiquitous landform on the solid planets and the satellites. The density of craters is used to date surfaces on planets and satellites. For large ringed basin craters (e.g. Chicxulub), the issue of identification of exactly what 'diameter' transient crater is associated with this structure is exemplified by the arguments of Sharpton et al. (1993) versus those of Hildebrand et al. (1995). The size of a transient crater, such as the K/T extinction crater at Yucatan, Mexico, which is thought to be the source of SO,-induced sulfuric acid aerosol that globally acidified surface waters as the result of massive vaporization of CASO, in the target rock, is addressed by our present project. The impact process excavates samples of planetary interiors. The degree to which this occurs (e.g. how deeply does excavation occur for a given crater diameter) has been of interest, both with regard to exposing mantle rocks in crater floors, as well as launching samples into space which become part of the terrestrial meteorite collection (e.g. lunar meteorites, SNC's from Mars). Only in the case of the Earth can we test calculations in the laboratory and field. Previous calculations predict, independent of diameter, that the depth of excavation, normalized by crater diameter, is d(sub ex)/D = 0.085 (O'Keefe and Ahrens, 1993). For Comet Shoemaker-Levy 9 (SL9) fragments impacting Jupiter, predicted excavation depths of different gas-rich layers in the atmosphere, were much larger. The trajectory and fate of highly shocked material from a large impact on the Earth, such as the K/T bolide is of interest. Melosh et al. (1990) proposed that the condensed material from the impact upon reentering the Earth's atmosphere induced. radiative heating, and producing global firestorms. The observed reentry splash of the SL-9 impact-induced plumes that reimpact Jupiter (Boslough et al., 1994) supported Melosh's K/T model. The fate of early primitive planetary atmospheres during the latter stages of planetary accretion, resulting from impactors in the 100 to 103 km diameter require modeling, e.g. Newman et al. (1997). Ahrens (1990; 1993) and Chen and Ahrens (1997) found that upon delivery of most of the impact energy to the solid planet, very large ground motions arise, which couple sufficient kinetic energy to the atmosphere to cause substantial atmospheric escape. The trade-off of this model with that of Cameron (1997) who suggests that atmospheric blow-off occurs as a result of the massive impact-induced heating of the atmosphere and Pepin (1997) who uses this heating event to model differential hydrodynamic loss of lighter atmospheric gases, requires further research.

Ahrens, Thomas J.↗

The Role of HO(x) in Super- and Subsonic Aircraft Exhaust Plumes

The generation of sulfuric acid aerosols in aircraft exhaust has emerged as a critical issue in determining the impact of supersonic aircraft on stratospheric ozone. It has long been held that the first step in the mechanism of aerosol formation is the oxidation of SO2, emitted from the engine by OH in the exhaust plume. We report in situ measurements of OH and HO, in the exhaust plumes of a supersonic (Air France Concorde) and a subsonic (NASA ER-2) aircraft in the lower stratosphere. These measurements imply that reactions with OH are responsible for oxidizing only a small fraction of SO2 (2%), and thus cannot explain the large number of particles observed in the exhaust wake of the Concorde.

Hanisco, T. F.↗

The Role of HO(x) in Super- and Subsonic Aircraft Exhaust Plumes

The generation of sulfuric acid aerosols in aircraft exhaust has emerged as a critical issue in determining the impact of supersonic aircraft on stratospheric ozone. It has long been held that the first step in the mechanism of aerosol formation is the oxidation of SO2 emitted from the engine by OH in the exhaust plume. We report in situ measurements of OH and HO2 in the exhaust plumes of a supersonic (Air France Concorde) and a subsonic (NASA ER-2) aircraft in the lower stratosphere. These measurements imply that reactions with OH are responsible for oxidizing only a small fraction of SO2 (2%), and thus cannot explain the large number of particles observed in the exhaust wake of the Concorde.

Hanisco, T. F.↗

Electrochemical Measurement of Atmospheric Corrosion

Corrosion of Shuttle thruster components in atmospheres containing high concentrations of nitrogen tetroxide (NTO) and water is an important issue in ground operations of bipropellant systems in humid locations. Measurements of the corrosivities of NTO-containing atmospheres and the responses of different materials to these atmospheres have been accomplished using an electrochemical sensor. The sensor is composed of alternating aluminum/titanium strips separated by thin insulating layers. Under high humidity conditions a thin film of water covers the surface of the sensor. Added NTO vapor reacts with the water film to form a conductive medium and establishes a galvanic cell. The current from this cell can be integrated with respect to time and related to the corrosion activity. The surface layer formed from humid air/NTO reacts in the same way as an aqueous solution of nitric acid. Nitric acid is generally considered an important agent in NTO corrosion situations. The aluminum/titanium sensor is unresponsive to dry air, responds slightly to humid air (> 75% RH), and responds strongly to the combination of humid air and NTO. The sensor response is a power function (n = 2) of the NTO concentration. The sensor does not respond to NTO in dry air. The response of other materials in this type of sensor is related to position of the material in a galvanic series in aqueous nitric acid. The concept and operation of this electrochemical corrosion measurement is being applied to other corrosive atmospheric contaminants such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, and acidic aerosols.

DeArmond, Anna H.↗

The Role of HOx in Super-and Subsonic Aircraft Exhaust Plumes

The generation of sulfuric acid aerosols in aircraft exhaust has emerged as a critical issue in determining the impact of supersonic aircraft on stratospheric ozone. It has long been held that the first step in the mechanism of aerosol formation is the oxidation of SO2 emitted from the engine by OH in the exhaust plume. We report in situ measurements of OH and HO2 in the exhaust plumes of a supersonic (Air France Concorde) and a subsonic (NASA ER-2) aircraft in the lower stratosphere. These measurements imply that reactions with OH are responsible for oxidizing only a small fraction of SO2 (2%), and thus cannot explain the large number of particles observed in the exhaust wake of the Concorde.

Hanisco, T. F.↗

How do Polar Stratospheric Clouds Form?

SOLVE measurements have been compared with results from a microphysical model to understand the composition and formation of the polar stratospheric clouds (PSCs) observed during SOLVE. Evidence that the majority of the particles remain liquid throughout the winter will be presented. However, a small fraction of the particles do freeze, and the presence of these frozen particles can not be explained by current theories, in which the only freezing mechanism is homogeneous freezing to ice below the ice frost point. Alternative formation mechanisms, in particular homogeneous freezing above the ice frost point and heterogeneous freezing, have been explored using the microphysical model. Both nitric acid trihydrate (NAT) and nitric acid dihydrate (NAD) have been considered as possible compositions for the solid-phase nitric acid aerosols. Comparisons between the model results and the SOLVE measurements will be used to constrain the possible formation mechanisms. Other effects of these frozen particles will also be discussed, in particular denitrification.

Drdla, Katja↗

Review of HxPyOz-Catalyzed H + OH Recombination in Scramjet Nozzle Expansions; and Possible Phosphoric Acid Enhancement of Scramjet Flameholding, from Extinction of H3PO4 + H2 - Air Counterflow Diffusion Flames

Recent detailed articles by Twarowski indicate that small quantities of phosphorus oxides and acids in the fuel-rich combustion products of H2 + phosphine (PH3) + air should significantly catalyze H, OH and O recombination kinetics during high-speed nozzle expansions -- to reform H2O, release heat, and approach equilibrium more rapidly and closely than uncatalyzed kinetics. This paper is an initial feasibility study to determine (a) if addition of phosphoric acid vapor (H3PO4) to a H2 fuel jet -- which is much safer than using PH3 -- will allow combustion in a high-speed scramjet engine test without adverse effects on localized flameholding, and (b) if phosphorus-containing exhaust emissions are environmentally acceptable. A well-characterized axisymmetric straight-tube opposed jet burner (OJB) tool is used to evaluate H3PO4 addition effects on the air velocity extinction limit (flame strength) of a H2 versus air counterflow diffusion flame. Addition of nitric oxide (NO), also believed to promote catalytic H-atom recombination, was evaluated for comparison. Two to five mass percent H3PO4 in the H2 jet increased flame strength 4.2%, whereas airside addition decreased it 1%. Adding 5% NO to the H2 caused a 2% decrease. Products of H-atom attack on H3PO4 produced an intense green chemiluminescence near the stagnation point. The resultant exothermic production of phosphorus oxides and acids, with accelerated H-atom recombination, released sufficient heat near the stagnation point to increase flame strength. In conclusion, the addition of H3PO4 vapor (or more reactive P sources) to hydrogen in scramjet engine tests may positively affect flameholding stability in the combustor and thrust production during supersonic expansion -- a possible dual benefit with system design / performance implications. Finally, a preliminary assessment of possible environmental effects indicates that scramjet exhaust emissions should consist of phosphoric acid aerosol, with gradual conversion to phosphate aerosol. This is compared to various natural abundances and sources.

Pellett, Gerald↗

Dual Balloon Concept for Lifting Payloads from the Surface of Venus

Introduction: Two high-rated Venus mission concepts proposed in the National Science Foundation Decadal Survey require a balloon to lift payloads from Venusian surface to high altitudes: Venus Surface Sample Return (VESSR) and Venus In-Situ Explorer (VISE). In case of VESSR the payload is a canister with the surface sample plus a Venus ascent vehicle (VAV), which is a rocket that takes the sample into orbit for rendezvous with an Earth return vehicle. VISE is envisioned as a more limited precursor mission where the surface sample is only taken to high altitudes so that non time-critical analyses can be performed. From the balloon point of view, the only difference between these two missions is that the VESSR payload to be lifted is very much larger than VISE because of the inclusion of the VAV. A key problem is that at the time the decadal survey was published, no high temperature balloon technology existed to implement either mission. Prior technology development efforts had concentrated on a single balloon that could operate across the entire 0-60 km altitude range, tolerating both the sulfuric acid aerosols and the extreme temperatures of -10 to +460 C. However, this problem was unsolved because no combination of sufficiently lightweight balloon material and manufacturing (seaming) technology was ever found to tolerate the high temperatures at the surface.

Kerzhanovich, Viktor V.↗

Emissions of Trace Gases and Particles from Savanna Fires in Southern Africa

Airborne measurements made on initial smoke from 10 savanna fires in southern Africa provide quantitative data on emissions of 50 gaseous and particulate species, including carbon dioxide, carbon monoxide, sulfur dioxide, nitrogen oxides, methane, ammonia, dimethyl sulfide, nonmethane organic compounds, halocarbons, gaseous organic acids, aerosol ionic components, carbonaceous aerosols, and condensation nuclei (CN). Measurements of several of the gaseous species by gas chromatography and Fourier transform infrared spectroscopy are compared. Emission ratios and emission factors are given for eight species that have not been reported previously for biomass burning of savanna in southern Africa (namely, dimethyl sulfide, methyl nitrate, five hydrocarbons, and particles with diameters from 0.1 to 3 microns). The emission factor that we measured for ammonia is lower by a factor of 4, and the emission factors for formaldehyde, hydrogen cyanide, and CN are greater by factors of about 3, 20, and 3 - 15, respectively, than previously reported values. The new emission factors are used to estimate annual emissions of these species from savanna fires in Africa and worldwide.

Sinha, Parikhit↗

Influence of Tropospheric SO2 Emissions on Particle Formation and the Stratospheric Humidity

Stratospheric water vapor plays an important role in the chemistry and radiation budget of the stratosphere. Throughout the last decades stratospheric water vapor levels have increased and several processes have been suggested to contribute to this trend. Here we present a mechanism that would link increasing anthropogenic SO2 emissions in southern and eastern Asia with an increase in stratospheric water. Trajectory studies and model simulations suggest that the SO2 increase results in the formation of more sulfuric acid aerosol particles in the upper tropical troposphere. As a consequence, more ice crystals of smaller size are formed in the tropical tropopause, which are lifted into the stratosphere more readily. Our model calculations suggest that such a mechanism could increase the amount of water that entered the stratosphere in the condensed phase by up to 0.5 ppmv from 1950-2000.

Notholt, J.↗

Influence of the Mt. Pinatubo Eruption on the Stratospheric Circulation

On June 15th, 1991 the eruption of Mt. Pinatubo in the Philippines injected about 20 Tg of sulfur dioxide in the stratosphere, which was transformed into sulfuric acid aerosol. Even though stratospheric winds climatologically tend to hinder the air mixing between the two hemispheres, observations have shown that a large part of the SO2 emitted by Mt. Pinatubo have been transported from the Northern to the Southern Hemisphere. We show how the absorption of radiation by sulfate aerosol is responsible for the spreading to the southern hemisphere through a middle stratospheric channel. We simulate the eruption of Mt. Pinatubo with the Goddard Earth Observing System (GEOS) version 5 general circulation model, coupled to the aerosol module GOCART and the stratospheric chemistry module StratChem. Our simulations are in good agreement with SAGE-II and AVHRR data. We perform two ensembles of simulations: the first ensemble consists of runs without coupling between aerosol and radiation. In these simulations the plume of aerosols is treated as a passive tracer and the atmosphere is unperturbed. In the second ensemble of simulations aerosols and radiation are coupled. We show that the set of runs with interactive aerosol produces a larger cross-equatorial transport of the Pinatubo cloud, in agreement with the observations. At first, the volcanic cloud is transported from the latitude of the eruption to both hemispheres through a lower stratospheric pathway. Additionally, in the interactive simulations the absorption of long wave radiation from the volcanic sulfate induces a lofting of the cloud to the middle atmosphere and, at the same time, a divergent motion from the center of the cloud. Such motion spreads the volcanic cloud across the equator and to the tropics, where the background circulation carry it to higher latitudes.

Aquila, V.↗

Prototype Development of a Variable Altitude Venus Aerobot

This paper presents the design methodology and results from the first subscale prototype jointly developed by JPL and Near Space Corporation for a variable altitude Venus aerobot. This vehicle is based on the principle of a two-part balloon for which pumping helium gas between the balloons can modulate buoyancy and thereby control the altitude of the vehicle. The intended mission application at Venus is a cloud-level exploration across an altitude range of 52 to 62 kilometers for weeks or months, circumnavigating the planet multiple times and carrying an approximately 100 kg payload module containing all scientific instruments, avionics and other vehicle support systems. The first prototype is approximately one-third scale (4 m diameter) and serves as a proof-of-concept test article allowing for evaluation of manufacturing approaches and laboratory testing to evaluate performance. Two key design features of the prototype as built are the use of Teflon film on the outside of the balloon to protect it from the sulfuric acid aerosols in the Venusian atmosphere and second surface metallization of that film to reflect most incident sunlight and thereby limit diurnal temperature and the associated temperature-driven pressure fluctuations. This prototyping effort has been complemented with a detailed vehicle simulation activity that incorporates the relevant balloon physics and thereby models the expected dynamic behavior of the aerobot in both the Earth and Venus atmospheres. Data obtained in laboratory tests of the prototype have been used to validate, verify and update that simulation model as described in the paper.

Turner, Caleb↗