ALBERT

Description: The progress, results and future plans for the following objectives are presented: (1) To compare the types, rates, and magnitudes of surficial modification processes that have operated in Northwest China and the Southwestern U.S.; (2) To quantify and understand the basis of the remote sensing signatures of these processes to allow extrapolation from field sites to regional maps and to allow comparisons between widely separated arid regions; (3) To use the resulting chronologies to help define the temporal and spatial distribution of continental climate changes; and (4) Determine the ages of movements on some of the active faults in Northwestern China.

Description: One of the environmental issues affecting the development of a second-generation supersonic commercial transport is the impact of sonic booms on people. Aircraft designers are attempting to design the transport to produce sonic boom signatures that will have minimum impact on the public. Current supersonic commercial aircraft produce an 'N-wave' sonic boom pressure signature that is considered unacceptable by the public. This has resulted in first-generation supersonic transports being banned from flying supersonic over land in the United States, a severe economic constraint. By tailoring aircraft volume and lift distributions, designers hope to produce sonic boom signatures having specific shapes other than 'N-wave' that may be more acceptable to the public. As part of the effort to develop a second-generation supersonic commercial transport, Langley Research Center is conducting research to study people's subjective response to sonic booms. As part of that research, a system was developed for performing studies of the subjective response of people to the occurrence of simulated sonic booms in their homes. The In-Home Noise Generation/Response System (IHONORS) provides a degree of situational realism not available in the laboratory and a degree of control over the noise exposure not found in community surveys. The computer-controlled audio system generates the simulated sonic booms, measures the noise levels, and records the subjects' ratings and can be placed and operated in individual homes for extended periods of time. The system was used to conduct an in-home study of subjective response to simulated sonic booms. The primary objective of the study was to determine the effect on annoyance of the number of sonic boom occurrences in a realistic environment. The effects on annoyance of several other parameters were also examined. Initially, data analyses were based on all the data collected. However, further analyser found that test subjects adapted to the sonic booms during the first few days of exposure. The first eight days of each testing period consisted of eight introductory exposures that were repeated on randomly selected days later in the testing period. Comparison of the introductory exposures with their repeats indicated that the test subjects adapted to the new sonic boom noise environment during the first days of the testing period. Because of the adaptation occurring, the introductory days were deleted from the ds set and the analyses redone. This paper presents the updated analyses. Elimination of the introductory days did not significantly affect the results and conclusions of the initial analyses. This paper also presents analyses of the effects on annoyance of additional factors in the study not previously examined.

Description: The latest CHABA Working Group to have reviewed published information about the effects of high energy impulsive sounds (such as sonic booms) on communities has recommended abandonment of the dosage-response relationship identified by its predecessor in favor of two alternate prediction method. Both of the new assessment methods continue to rely on C-weighted measurements of impulsive sounds One of the two assessment methods retains the standard assumptions of the 'equal energy hypothesis' (the notion that annoyance is governed simply by the product of level, duration, and number noise events), and further assumes that the rate of growth of the prevalence of annoyance is proportional to the rate of growth of loudness with level. The other assessment method, however, assumes a level dependent (non-equal energy) summation of the C-weighted sound exposure levels of individual impulsive events. Since predictions of the second method are distribution-dependent, they are not readily represents graphically in the form of a single dosage-response function. The effects on annoyance predictions of variance in distributions of CSEL values of impulsive sounds are explored in this presentation.

Description: The overall goal of NASA's SCAR (Smoke, Cloud and Radiation) Program is to obtain physical and chemical properties of the smoke produced by biomass burning and the effects of the smoke on the earth's radiation balance and climate. It is a joint project with the Brazilian government and their organizations, including INPE (Instituto Nacional Pesquisas Espaciais) who actively participate in all activities. Appropriate estimates of the biomass buming in the tropics is therefore essential to determine its effect on the atmosphere and on climate. The SCAR series of experiments is designed with that purpose. The present study of evaluating the burnt-out areas is to augment the data collected to date to help evaluate the effect of biomass burning.

Description: Carbonyl Sulfide(OCS) is considered to be one of the major sources of sulfur appearing in the stratosphere due to its relative inertness, about I to 10 yearsl. However, the roles of OCS as well as other reduced sulfur compounds such as carbon disulfide (CS2), hydrogen sulfide (H2S), and dimethyl disulfide(CH3)2S2, are not completely understood in the atmosphenc sulfur cycle. Consequently vely little information is available about the effect of sulfur compounds in the stratosphere. The ability of OCS to penetrate into the stratosphere makes it an excellent tracer for study of the role of the sulfi r cycle in stratospheric chemistry. Previously techniques such as gas chromatography and whole air sampling have been used to measure OCS analytically. Each technique had its drawbacks however, with both being quite slow, and whole air sampling being somewhat unreliable. With molecular spectroscopy, however, it has been found in recent years that the tunable diode laser absorption spectrometer (TDL) provides a very rapid and accurate method of measuring OCS and other trace gases

Description: In this paper we consider microphysical processes which affect the formation of sulfate particles and their size distribution in a dispersing cloud. A model for the dispersion of the Mt. Pinatubo volcanic cloud is described. We then consider a single point in the dispersing cloud and study the effects of nucleation, condensation and coagulation on the time evolution of the particle size distribution at that point.

Description: The Clouds and the Earth's Radiant Energy System (CERES) spacecraft sensors are designed to measure broadband earth-reflected solar shortwave (0.3-5 microns) and earth-emitted longwave (5- 〉 100 microns) radiances at the top of the atmosphere as part of the Mission to Planet Earth program. The scanning thermistor bolometer sensors respond to radiances in the broadband shortwave (0.3-5 microns) and total-wave (0.3- 〉 100 microns) spectral regions, as well as to radiances in the narrowband water vapor window (8-12 microns) region. 'ne sensors are designed to operate for a minimum of 5 years aboard the NASA Tropical Rainfall Measuring Mission and Earth Observing System AM-1 spacecraft platforms that are scheduled for launches in 1997 and 1998, respectively. The flight sensors and the in-flight calibration systems will be calibrated in a vacuum ground facility using reference radiance sources, tied to the international temperature scale of 1990. The calibrations will be used to derive sensor gains, offsets, spectral responses, and point spread functions within and outside of the field of view. The shortwave, total-wave, and window ground calibration accuracy requirements (1 sigma) are +/-0.8, +/-0.6, and +/-0.3 W /sq m/sr, respectively, while the corresponding measurement precisions are +/-O.5% and +/-1.0% for the broadband longwave and shortwave radiances, respectively. The CERES sensors, in-flight calibration systems, and ground calibration instrumentation are described along with outlines of the preflight and in-flight calibration approaches.

Description: The distribution of many chemical constituents of the atmosphere (e.g., ozone) is at least partially determined by the. distribution of net radiative heating in the atmosphere. In this paper, we demonstrate the significant effect of high cirrus clouds on the net radiative heating of the tropical lower stratosphere. A model of tropical lower stratospheric ozone is then used to demonstrate the sensitivity of calculated ozone to the varying cloud cover used in the model. We conclude that calculated ozone is sensitive to the inclusion of clouds In models and that models of the atmosphere should include a realistic description of tropical cirrus clouds in order to accurately simulate the chemical composition of the atmosphere.

Description: The annual flux of freshwater into the Arctic Ocean by the atmosphere and rivers is balanced by the export of sea ice and oceanic freshwater. Two 150-year simulations of a global climate model are used to examine how this balance might change if atmospheric greenhouse gases (GHGs) increase. Relative to the control, the last 50-year period of the GHG experiment indicates that the total inflow of water from the atmosphere and rivers increases by 10% primarily due to an increase in river discharge, the annual sea-ice export decreases by about half, the oceanic liquid water export increases, salinity decreases, sea-ice cover decreases, and the total mass and sea-surface height of the Arctic Ocean increase. The closed, compact, and multi-phased nature of the hydrologic cycle in the Arctic Ocean makes it an ideal test of water budgets that could be included in model intercomparisons.

Description: The Stak-Tracker CEM (Continuous Emission Monitor) Gas Analyzer is an air quality monitor capable of separating the various gases in a bulk exhaust stream and determining the amounts of individual gases present within the stream. The monitor is produced by GE Reuter- Stokes, a subsidiary of GE Corporate Research & Development Center. The Stak-Tracker uses a Langley Research Center software package which measures the concentration of a target gas by determining the degree to which molecules of that gas absorb an infrared beam. The system is environmental-friendly, fast and has relatively low installation and maintenance costs. It is applicable to gas turbines and various industries including glass, paper and cement.

Description: This thesis includes the development and verification of an adsorption model for analysis and optimization of the adsorption processes within the International Space Station multifiltration beds. The fixed bed adsorption model includes multicomponent equilibrium and both external and intraparticle mass transfer resistances. Single solute isotherm parameters were used in the multicomponent equilibrium description to predict the competitive adsorption interactions occurring during the adsorption process. The multicomponent equilibrium description used the Fictive Component Analysis to describe adsorption in unknown background matrices. Multicomponent isotherms were used to validate the multicomponent equilibrium description. Column studies were used to develop and validate external and intraparticle mass transfer parameter correlations for compounds of interest. The fixed bed model was verified using a shower and handwash ersatz water which served as a surrogate to the actual shower and handwash wastewater.

Description: Monitoring of gaseous contaminants stems from the need to ensure a healthy and safe environment. NASA/Ames needs sensors that are able to monitor common atmospheric gas concentrations as well as trace amounts of contaminant gases. To provide an accurate assessment of air quality, a monitoring system would need to be continuous and on-line with full spectrum capabilities, allowing simultaneous detection of all gas components in a sample, including both combustible and non-combustible gases. The system demands a high degree of sensitivity to detect low gas concentrations in the low-ppm and sub-ppm regions. For clean and healthy air ('good' category), criteria established by the EPA requires that contaminant concentrations not exceed 4 ppm of carbon monoxide (CO) in an 8 hour period, 60 ppb of ozone(O3) in a one hour period and 30 ppb of sulfur dioxide (SO2) in a 24 hour period. One step below this is the National Ambient Air Quality Standard ('moderate' category) which requires that contaminant concentrations not exceed 9 ppm of carbon monoxide (CO), 120 ppb of ozone (O3) and 140 ppb of sulfur dioxide (SO2) for their respective time periods. Ideally a monitor should be able to detect the concentrations specified in the 'good' category. To benchmark current abilities of Raman technology in gas phase analysis, laboratory experiments were performed to evaluate the RASCAL II anesthetic gas monitor.

Description: The Florida Scrub-Jay (Aphelocoma coerulescens) is an indicator of ecosystem integrity of Florida scrub, an endangered ecosystem that requires frequent fire. One of the largest populations of this federally threatened species occurs on John F. Kennedy Space Center/Merritt Island National Wildlife Refuge. Population trends were predicted using population modeling and field data on reproduction and survival of Florida Scrub-Jays collected from 1988 - 1995. Analyses of historical photography indicated that habitat suitability has been declining for 30 years. Field data and computer simulations suggested that the population declined by at least 40% and will decline by another 40% in 1 0 years, if habitat management is not greatly intensified. Data and computer simulations suggest that habitat suitability cannot deviate greatly from optimal for the jay population to persist. Landscape trajectories of vegetation structure, responsible for declining habitat suitability, are associated with the disruption of natural fire regimes. Prescribed fire alone can not reverse the trajectories. A recovery strategy was developed, based on studies of Florida Scrub-Jays and scrub vegetation. A reserve design was formulated based on conservation science principles for scrub ecosystems. The strategy emphasizes frequent fire to restore habitat, but includes mechanical tree cutting for severely degraded areas. Pine thinning across large areas can produce rapid increases in habitat quality. Site-specific strategies will need to be developed, monitored, and modified to achieve conditions suitable for population persistence.

Description: The terrestrial environment is an important forcing function in the design and development of the launch vehicle. The scope of the terrestrial environment includes the following phenomena: Winds; Atmospheric Thermodynamic Models and Properties; Thermal Radiation; U.S. and World Surface Environment Extremes; Humidity; Precipitation, Fog, and Icing; Cloud Characteristics and Cloud Cover Models; Atmospheric Electricity; Atmospheric Constituents; Vehicle Engine Exhaust and Toxic Chemical Release; Occurrences of Tornadoes and Hurricanes; Geological Hazards, and Sea States. One must remember that the flight profile of any launch vehicle is in the terrestrial environment. Terrestrial environment definitions are usually limited to information below 90 km. Thus, a launch vehicle's operations will always be influenced to some degree by the terrestrial environment with which it interacts. As a result, the definition of the terrestrial environment and its interpretation is one of the key launch vehicle design and development inputs. This definition is a significant role, for example, in the areas of structures, control systems, trajectory shaping (performance), aerodynamic heating and take off/landing capabilities. The launch vehicle's capabilities which result from the design, in turn, determines the constraints and flight opportunities for tests and operations.

Description: This report describes the development of a three-dimensional database of aircraft fuel burn and emissions (fuel burned, NOx, CO, and hydrocarbons) from scheduled commercial aircraft for each month of 1992. The seasonal variation in aircraft emissions was calculated for selected regions (global, North America, Europe, North Atlantic, and North Pacific). A series of parametric calculations were done to quantify the possible errors introduced from making approximations necessary to calculate the global emission inventory. The effects of wind, temperature, load factor, payload, and fuel tankering on fuel burn were evaluated to identify how they might affect the accuracy of aircraft emission inventories. These emissions inventories are available for use by atmospheric scientists conducting the Atmospheric Effects of Aviation Project (AEAP) modeling studies. Fuel burned and emissions of nitrogen oxides (NOx as N02), carbon monoxide, and hydrocarbons have been calculated on a 1 degree latitude x 1 degree longitude x 1 kilometer altitude grid and delivered to NASA as electronic files.

Description: A pad for cleaning up liquid spills is described which contains a porous surface covering, and an absorbent interior containing chemically reactive reagents for neutralizing noxious chemicals within the spilled liquid. The porous surface and the absorbent component would normally consist of chemically resistant materials allowing tentative spill to pass. The absorbent interior which contains the neutralizing reagents can but is not required to be chemically resilient and conducts the liquid chemically reactive reagents where the dangerous and undesirable chemicals within the chemical spill are then neutralized as well as removed from the premises.

Description: The work conducted on this grant was devoted to various aspects of the photophysics and photochemistry of the oxygen molecule. Predissociation linewidths were measured for several vibrational levels in the O2(B3 Sigma(sub u)(sup -)) state, providing good agreement with other groups working on this important problem. Extensive measurements were made on the loss kinetics of vibrationally excited oxygen, where levels between v = 5 and v = 22 were investigated. Cavity ring-down spectroscopy was used to measure oscillator strengths in the oxygen Herzberg bands. The great sensitivity of this technique made it possible to extend the known absorption bands to the dissociation limit as well as providing many new absorption lines that seem to be associated with new O2 transitions. The literature concerning the Herzberg band strengths was evaluated in light of our new measurements, and we made recommendations for the appropriate Herzberg continuum cross sections to be used in stratospheric chemistry. The transition probabilities for all three Herzberg band systems were re-evaluated, and we are recommending a new set of values.

Description: This report describes the development of a three-dimensional database of aircraft fuel burn and emissions (fuel burned, NOx, CO, and hydrocarbons) from scheduled commercial aircraft for four months (February, May, August, and November) of 1976 and 1984. Combining this data with earlier published data for 1990 and 1992, trend analyses for fuel burned, NOx, carbon monoxide, and hydrocarbons were calculated for selected regions (global, North America, Europe, North Atlantic, and North Pacific). These emissions inventories are available for use by atmospheric scientists conducting the Atmospheric Effects of Aviation Project (AEAP) modeling studies. Fuel burned and emissions of nitrogen oxides (NOx as NO2), carbon monoxide, and hydrocarbons have been calculated on a 1 degree latitude x 1 degree longitude x 1 kilometer altitude grid and delivered to NASA as electronic files.

Description: The results of monitoring the chemical composition of rain in east-central Florida have shown that the rain is moderately acid. The measured acidity of rain is less than that observed in other regions of the U. S., however, it does suggest that the level of acidity is substantial. The annual chemical composition of rain at UCF and at KSC has shown moderate variability. Extreme daily and monthly variations are observed, however these variations are not addressed here. The total ionic composition of rain collected at FL99 is greater than that for rain collected at UCF, however this can be accounted for by site proximity to the ocean with the accompanying marine influence. Difference in acidity data collected from the UCF and FL99 sites which are separated by 50 km may be due in part to the differences that have been observed between laboratory and field pH measurements. Trend assessment for precipitation composition requires evaluation of data that covers some minimum time period. In fact, the subdivision of the multi-year UCF record into individual 10 year records as described above can lead to the conclusion that a significant increase, a significant decrease or no trend exists for acidity depending upon the time period chosen for evaluation. Trend evaluation has also been accomplished by linear and nonlinear regression analysis using monthly volume weighted average concentrations and deposition using the UCF data set and some of the Florida NADP data set.

Description: Human missions in space, from short-duration shuttle missions lasting no more than several days to the medium-to-long-duration missions planned for the International Space Station, face a number of hazards that must be understood and mitigated for the mission to be carried out safely. Among these hazards are those posed by the internal environment of the spacecraft itself; through outgassing of toxic vapors from plastics and other items, failures or off-nominal operations of spacecraft environmental control systems, accidental exposure to hazardous compounds used in experiments: all present potential hazards that while small, may accumulate and pose a danger to crew health. The first step toward mitigating the dangers of these hazards is understanding the internal environment of the spacecraft and the compounds contained within it. Future spacecraft will have integrated networks of redundant sensors which will not only inform the crew of hazards, but will pinpoint the problem location and, through analysis by intelligent systems, recommend and even implement a course of action to stop the problem. This strategic plan details strategies to determine NASA's requirements for environmental monitoring and control systems for future spacecraft, and goals and objectives for a program to answer these needs.

Description: The report describes the development of a database of fuel burn and emissions from projected High Speed Civil Transport (HSCT) fleets that reflect actual airlines' networks, operational requirement, and traffic flow as operated by simulated world wide airlines for Mach 1.6, 2.0, and 2.4 HSCT configurations. For the year 2015, McDonnell Douglas Corporation created two supersonic commercial air traffic networks consisting of origin-destination city pair routes and associated traffic levels. The first scenario represented a manufacturing upper limit producible HSCT fleet availability by year 2015. The fleet projection of the Mach 2.4 configuration for this scenario was 1059 units with a traffic capture of 70 percent. The second scenario focused on the number of units that can minimally be produced by the year 2015. Using realistic production rates, the HSCT fleet projection amounts to 565 units. The traffic capture associated with this fleet was estimated at 40 percent. The airlines network was extracted from the actual networks of 21 major world airlines. All the routes were screened for suitability for HSCT operations. The route selection criteria included great circle distance, difference between flight path distance and great circle distance to avoid overland operations, and potential flight frequency.

Description: The distribution of many chemical constituents of the atmosphere (e.g., ozone) is at least partially determined by the distribution of net radiative heating in the atmosphere. In this paper, we demonstrate the significant effect of high cirrus clouds on the net radiative heating of the tropical lower stratosphere. A model of tropical lower stratospheric ozone is then used to demonstrate the sensitivity of calculated ozone to the varying cloud cover used in the model. We conclude that calculated ozone is sensitive to the inclusion of clouds in models and that models of the atmosphere should include a realistic description of tropical cirrus clouds in order to accurately simulate the chemical composition of the atmosphere.

Description: This paper reviews the activities at OKSI related to imaging spectroscopy presenting current and future applications of the technology. The authors discuss the development of several systems including hardware, signal processing, data classification algorithms and benchmarking techniques to determine algorithm performance. Signal processing for each application is tailored by incorporating the phenomenology appropriate to the process, into the algorithms. Pixel signatures are classified using techniques such as principal component analyses, generalized eigenvalue analysis and novel very fast neural network methods. The major hyperspectral imaging systems developed at OKSI include the Intelligent Missile Seeker (IMS) demonstration project for real-time target/decoy discrimination, and the Thermal InfraRed Imaging Spectrometer (TIRIS) for detection and tracking of toxic plumes and gases. In addition, systems for applications in medical photodiagnosis, manufacturing technology, and for crop monitoring are also under development.

Description: Design and construction of an in situ sensor for the detection of stratospheric ClONO2, ClO, BrO, and NO2, was conceived as a two-year program. The experiment has two novel components: a resistive silicon thermal dissociation heater used to fragment ClONO2 into ClO and NO2 and a laser-induced fluorescence sensor for N02. These two new components are integrated into an experiment that uses technology developed in our labs for the ER-2 ClO and ER-2 HO(X) instruments. During the first year we reconstructed our laboratory prototypes for ClONO2 and NO2 detection and made substantial improvements in the calibration apparatus. Results from these laboratory experiments have been used to refine the design of the flight instrument. During this year we began the design of all of the long-lead items required to produce a flight instrument: including the design and fabrication of the air flow system used to direct stratospheric air to our halogen sensors, design and prototyping of an aircraft-compatible thermal dissociation heater, and development and test of a new high powered laser system. Finally, we have designed and released for fabrication several subsystems.

Description: Calculations have been carried out for the HEDM species (cyclic O4, cyclic O3, and cubane) using CASSCF/derivative and CASSCF/ICCI methods. Cyclic O4 is of interest both as a potential HEDM species and because of its possible role in the ozone deficit problem in atmospheric chemistry. We have studied the pathway for decomposition from the D(2d) minimum and also have found the approximate location of the singlet triplet crossing. The barrier to decomposition is found to be about 9 kcal/mol and is not limited by the singlet triplet crossing. For cyclic O3 we have focused on the crossings between the lowest five surfaces (X(1)A(1), s(1)A(1), (1)A(2), (1)B(1), and (1)B(2)) to provide some insight into ways to form cyclic O3 photochemically. The crossing region between the X(1)A(1) and 2(1)A(1) surfaces is in agreement with the work of Xantheas et al. The calculations show that vertical excitation from the ground state to the (1)A(2) state leads to a crossing with the (1)A(1) manifold near the crossing region of the X(1)A(1) and 2(1)A(1) surfaces. We have studied the decomposition pathways for cubane to benzene plus acetylene and to cyclooctatetraene. We have also studied the ground and excited states for the photochemical ring closure step. The state which closes to cubane can be described as a double triplet pi to pi* excitation with respect to the ground state. Thus, this state has only a small oscillator strength with respect to the ground state. However, there is a singlet pi to pi* state at nearly the same energy and excitation to this state followed by intersystem crossing could lead to the triplet pi to pi* state.

Description: The impact of cirrus clouds on climate is an issue of research interest currently. Whether cirrus clouds heat or cool the Earth-atmosphere system depends on the cloud shortwave albedo and infrared reflectance and absorptance. These in turn are determined by the size distribution, phase, and composition of particles in the clouds. The TOGA-COARE campaign presented an excellent opportunity to study cirrus clouds and their influence on climate. In this campaign, a microphysics instrument package was flown aboard the DC-8 aircraft at medium altitudes in cirrus clouds. This package included a 2D Greyscale Cloud Particle Probe, a Forward Scattering Spectrometer Aerosol Probe, and an ice crystal replicator. At the same time the ER-2 equipped with a radiation measurement system flew coordinated flight tracks above the DC-8 at very high altitude. The radiation measurement made were short and long wave fluxes, as well as narrowband fluxes, both upwelling and downwelling. In addition LIDAR data is available. The existence of these data sets allows for a the comparison of radiation measurement with microphysical measurements. For example, the optical depth and effective radius retrieved from the ER-2 radiation measurements can be compared to the microphysical data. Conversely, the optical properties and fluxes produced by the clouds can be calculated from the microphysical measurements and compared to those measured aboard the ER-2. The assumptions required to make these comparisons are discussed. Typical microphysical results show a prevalence of micron-sized particles, in addition to the cloud particles that exceed 100 mm. The large number of small particles or "haze" cause the effective cloud radii to shift to smaller sizes, leading to changes in optical parameters.

Description: Burning in South Central Africa is primarily responsible for the vast buildup of ozone in the mid-Atlantic noticeable in the Belem, Brazil, ozonesondes, and also visible in analyses using the Total Ozone Mapping Spectrometer (TOMS). We report on full-scale chemistry simulations for the SAFARI/TRACE-A field period of September-October, 1992. These observational programs provided a wealth of comparison data, including spectacular depictions of the vertical structure of ozone and particulate pollution over Africa, South America, and the Equatorial Atlantic [Browell JGR, 1996, submitted] above and below the NASA DC-8 airplane path. These depictions provide strict tests on the ability of a 3-d simulation and its controlling input parameters, most notably the biomass burning emissions strength. We use meteorology from MM5 used as a synoptic assimilation model and our own GRACES Global Regional Air Chemistry Event Simulator. This report will focus on the unique meteorology of the Equatorial Atmosphere around the Gulf of Guinea during the TRACE-A period, which we describe as "the opening of the gate," "the Great African Plume," and the "African Recirculatory System." We expect to assess whether the ozone observed is primarily "transported African smog," the standard view, or whether "re-$NO_[x)$-ification" of the Central Atlantic troposphere (reduction of nitric acid to active nitrogen oxides in clouds or aerosol) may be required for "extended intercontinental ozone production." A status report on a second nitrogen problem, "lower-tropospheric missing NO(y)," in which we find a serious imbalance in the $NO_ {x }$ and $NO_{y}$ budgets when compared with similar atmospheric tracers, will be given. An elaboration of the concepts set off by quotation marks in this abstract will be given in the talk.

Description: Recently it has been determined that the HO/HO2 catalytic cycle accounts for nearly one-half of the total ozone depletion in the lower stratosphere. The catalytic cycle is: (1) HO + O3 yields HO2 + O2; (2) HO2 + O3 yields HO + O2 + O2. The net reaction is 2O3 yields 3O2. The rate limiting step in this process is the reaction of HO2 with ozone. There is a problem extending the experimental measurement of the rate of this reaction over the range 233-400 K down to stratospheric temperatures of 210-220 K. Therefore we have undertaken a project to determine the temperature dependence of the rate constant for this reaction in the low temperature region. The first step in this project, which is described in this poster, is the determination of the relevant potential energy surfaces. The calculations use CASSCF/derivative methods to define the pathways followed by CASSCF/ACPF to determine the energetics. The HO + O3 reaction is found to proceed through an HO4 complex, which is unstable with respect to HO2 + O2. The HO2 +O3 reaction is more complex. One pathway, which has been characterized, is the formation of an HO5 complex which decomposes to HO3 + O2 and subsequently to HO + O2 + O2. Another pathway, which is believed to also play a role, is hydrogen abstraction to give O2 + HO3 and subsequent decomposition of HO3 to HO + O2. Isotopic labeling experiments indicate that the later pathway is dominant. However, so far attempts to locate the saddle point for this pathway have not been successful. We have also characterized the potential energy surfaces for a number of species involved in these reactions, including HO3 and triplet O4. The triplet O4 species is probably involved in the reaction of vibrationally excited O2 with ground state O2 leading to O3 + O. The latter reaction is believed to be important as an additional source of stratospheric ozone.

Description: Pole-to-pole variability of soot aerosol from subsonic aircraft is evidence of two important aspects of stratospheric transport. Vertical transport to 20 km pressure altitude from flight levels near 10-12 km cannot be explained by isentropic mixing. Instead, lofting in the tropics is a possibility. A strong meridional gradient implies that stratospheric soot aerosol residence time is shorter than are mixing times between the hemispheres. Therefore, little if any of exhaust constituents (with residence times similar to that of aircraft soot aerosol), emitted in heavily traveled flight corridors in northern mid-latitudes by a future supersonic fleet, would be transported to the southern hemisphere. However, a significant fraction of NOx could be lofted to altitudes above flight levels where it would dominate ozone depletion.

Description: Recovery of resources from waste streams is essential for future implementation and reliance on a regenerative life support system. The major waste streams of concern are from human activities and plant wastes. Carbon, water and inorganics are the primary desired raw materials of interest. The goal of resource recovery is maintenance of product quality to insure support of reliable and predictable levels of life support function performance by the crop plant component. Further, these systems must be maintained over extended periods of time, requiring maintenance of nutrient solutions to avoid toxicity and deficiencies. Today, reagent grade nutrients are used to make nutrient solutions for hydroponic culture and these solutions are frequently changed during the life cycle or sometimes managed for only one crop life cycle. The focus of this study was to determine the suitability of the ash product following incineration of inedible biomass as a source of inorganic nutrients for hydroponic crop production. Inedible wheat biomass was incinerated and ash quality characterized. The incinerator ash was dissolved in adequate nitric acid to establish a consistent nitrogen concentration in all nutrient solution treatments. Four experimental nutrient treatments were included: control, ash only, ash supplemented to match control, and ash only quality formulated with reagent grade chemicals. When nutrient solutions are formulated using only ash following-incineration of inedible biomass, a balance in solution is established representing elemental retention following incineration and nutrient proportions present in the original biomass. The resulting solution is not identical to the control. This imbalance resulted in suppression of crop growth. When the ash is supplemented with nutrients to establish the same balance as in the control, growth is identical to the control. The ash appears to carry no phytotoxic materials. Growth in solution formulated with reagent grade chemicals but matching the quality of the ash only treatment resulted in growth similar to that of the ash only treatment. The ash product resulting from incineration of inedible biomass appears to be a suitable form for recycle of inorganic nutrients to crop production.

Description: The SSBUV experiment flew eight Space Shuttle missions from October 1989 to January 1996 in conducted eight missions between October 1989 and support of the US long-term ozone monitoring program. Contributions of the SSBUV experiment are reviewed in this paper. SSBUV data are being used to provide and validate the absolute and long-term calibrations of multiple satellite-based ozone monitoring instruments. SSBUV observed a significant decrease in Northern hemisphere total ozone from the winter of 1992 to the following winter, and SSBUV data were combined with Nimbus-7 data to assess long-term ozone changes during the 1980's. SSBUV solar irradiance measurements are being used to determine the absolute solar spectral irradiance in the middle UV, validate solar data from two UARS instruments, and independently measure long-term solar change at wavelengths important for ozone photochemistry. SSBUV data where also used to study the effects of surface reflectivity and rotational Raman scattering on the ozone retrievals, determine the NO column amount and its altitude distribution, measure the UV lunar albedo, and assist in the optimization of wavelengths for new instruments.

Description: The primary focus during the third-phase of our on-going multi-year research effort has been on 3 activities. These are: (1) a global-scale model study of the anthropogenic component of the tropospheric sulfur cycle; (2) process-scale model studies of the factors influencing the distribution of aerosols in the remote marine atmosphere; and (3) an investigation of the mechanism of the OH-initiated oxidation of DMS in the remote marine boundary layer. In this paper, we describe in more detail our research activities in each of these areas. A major portion of our activities during the fourth and final phase of this project will involve the preparation and submission of manuscripts describing the results from our model studies of marine boundary-layer aerosols and DMS-oxidation mechanisms.

Description: The 1783-1784 Laki tholeiitic basalt fissure eruption in Iceland was one of the greatest atmospheric pollution events of the past 250 years, with widespread effects in the northern hemisphere. The degassing history and volatile budget of this event are determined by measurements of pre-eruption and residual contents of sulfur, chlorine, and fluorine in the products of all phases of the eruption. In fissure eruptions such as Laki, degassing occurs in two stages: by explosive activity or lava fountaining at the vents, and from the lava as it flows away from the vents. Using the measured sulfur concentrations in glass inclusions in phenocrysts and in groundmass glasses of quenched eruption products, we calculate that the total accumulative atmospheric mass loading of sulfur dioxide was 122 Mt over a period of 8 months. This volatile release is sufficient to have generated approximately 250 Mt of H2SO4 aerosols, an amount which agrees with an independent estimate of the Laki aerosol yield based on atmospheric turbidity measurements. Most of this volatile mass (approximately 60 wt.%) was released during the first 1.5 months of activity. The measured chlorine and fluorine concentrations in the samples indicate that the atmospheric loading of hydrochloric acid and hydrofluoric acid was approximately 7.0 and 15.0 Mt, respectively. Furthermore, approximately 75% of the volatile mass dissolved by the Laki magma was released at the vents and carried by eruption columns to altitudes between 6 and 13 km. The high degree of degassing at the vents is attributed to development of a separated two-phase flow in the upper magma conduit, and implies that high-discharge basaltic eruptions such as Laki are able to loft huge quantities of gas to altitudes where the resulting aerosols can reside for months, or even 1-2 years. The atmospheric volatile contribution due to subsequent degassing of the Laki lava flow is only 18 wt.% of the total dissolved in the magma, and these emissions were confined to the lowest regions of the troposhere and therefore important only over Iceland. This study indicates that determination of the amount of sulfur degassed from the Laki magma batch by measurements of sulfur in the volcanic products (the petrologic method) yields a result which is sufficient to account for the mass of aerosols estimated by other methods.

Description: Atmospheric aerosol particles, both natural and anthropogenic, are important to the earth's radiative balance. They scatter the incoming solar radiation and modify the shortwave reflective properties of clouds by acting as Cloud Condensation Nuclei (CCN). Although it has been recognized that aerosols exert a net cooling influence on climate (Twomey et al. 1984), this effect has received much less attention than the radiative forcings due to clouds and greenhouse gases. The radiative forcing due to aerosols is comparable in magnitude to current anthropogenic greenhouse gas forcing but opposite in sign (Houghton et al. 1990). Atmospheric aerosol particles generated from biomass burning, dust storms and forest fires are important regional climatic variables. A recent study by Penner et al. (1992) proposed that smoke particles from biomass burning may have a significant impact on the global radiation balance. They estimate that about 114 Tg of smoke is produced per year in the tropics through biomass burning. The direct and indirect effects of smoke aerosol due to biomass burning could add up globally to a cooling effect as large as 2 W/sq m. Ackerman and Chung (1992) used model calculations and the Earth Radiation Budget Experiment (ERBE) data to show that in comparison to clear days, the heavy dust loading over the Saudi Arabian peninsula can change the Top of the Atmosphere (TOA) clear sky shortwave and longwave radiant exitance by 40-90 W/sq m and 5-20 W/sq m, respectively. Large particle concentrations produced from these types of events often are found with optical thicknesses greater than one. These aerosol particles are transported across considerable distances from the source (Fraser et al. 1984). and they could perturb the radiative balance significantly. In this study, the regional radiative effects of aerosols produced from biomass burning, dust storms and forest fires are examined using the Advanced Very High Resolution Radiometer (AVHRR) Local Area Coverage (LAC) data and the instantaneous scanner ERBE data from the NOAA-9 and NOAA-10 satellites.

Description: Mission to Planet Earth's (MTPE's) first Strategic Enterprise Plan, issued in May 1995, defined the Agency's major goals and objectives as well as constraints. This update of the Strategic Enterprise Plan identifies the following major changes: a focused Science Research Plan that integrates space-based and in situ observational critical science to address critical science uncertainties; a technology infusion plan to reduce the cost of future missions; a series of flight opportunities to infuse new science into the overall program; and a tighter coupling between NASA and NOAA to reduce costs and to improve the overall program. Three important new initiatives are also under development and are described briefly in this plan: MTPE Education Strategy, MTPE Commercial Strategy, and an emerging concept for an Integrated Global Observing Strategy. This first update to the MTPE Strategic Enterprise Plan captures these new developments, and takes a significant step forward in planning this complex Earth system science endeavor. The plan and other information on MTPE may be viewed via the Internet at http://www.hq.nasa.gov/office/mtpe/.

Description: Using results from a time-dependent photochemical model to calculate the diurnal variation of NO and NO2, we have corrected Atmospheric Trace MOlecule Spectroscopy (ATMOS) solar-occultation retrievals of the NO and NO2 abundances at 90' solar zenith angle. Neglecting to adjust for the rapid variation of these gases across the terminator results in potential errors in retrieved profiles of approximately 20% for NO2 and greater than 100% for NC at altitudes below 25 km. Sensitivity analysis indicates that knowledge of the local 03 and temperature profiles, rather than zonal mean or climatological conditions of these quantities, is required to obtain reliable retrievals of NO and NO2 in the lower stratosphere. Extremely inaccurate 03 or temperature values at 20 km can result in 50% errors in retrieved NO or NO2. Mixing ratios of NO in the mid-latitude, lower stratosphere measured by ATMOS during the November 1994 ATLAS-3 mission compare favorably with in situ ER-2 observations, providing strong corroboration of the reliability of the adjusted space-borne measurements.

Description: This report summarizes research done under NASA Grant NAGW-2541 from April 1, 1996 through March 31, 1997. The research performed during this reporting period includes development and maintenance of scientific software for the GOME retrieval algorithms, consultation on operational software development for GOME, consultation and development for SCIAMACHY near-real-time (NRT) and off-line (OL) data products, and development of infrared line-by-line atmospheric modeling and retrieval capability for SCIAMACHY. SAO also continues to participate in GOME validation studies, to the limit that can be accomplished at the present level of funding. The Global Ozone Monitoring Experiment was successfully launched on the ERS-2 satellite on April 20, 1995, and remains working in normal fashion. SCIAMACHY is currently in instrument characterization. The first two European ozone monitoring instruments (OMI), to fly on the Metop series of operational meteorological satellites being planned by Eumetsat, have been selected to be GOME-type instruments (the first, in fact, will be the refurbished GOME flight spare). K. Chance is the U.S. member of the OMI Users Advisory Group.

Description: This project had four initial objectives: (1) to create a realistic coupled surface-atmosphere model to investigate the aggregate description of heterogeneous surfaces; (2) to develop a simple heuristic model of surface-atmosphere interactions; (3) using the above models, to test aggregation rules for a variety of realistic cover and meteorological conditions; and (4) to reconcile biosphere-atmosphere transfer scheme (BATS) land covers with those that can be recognized from space; Our progress in meeting these objectives can be summarized as follows. Objective 1: The first objective was achieved in the first year of the project by coupling the Biosphere-Atmosphere Transfer Scheme (BATS) with a proven two-dimensional model of the atmospheric boundary layer. The resulting model, BATS-ABL, is described in detail in a Masters thesis and reported in a paper in the Journal of Hydrology Objective 2: The potential value of the heuristic model was re-evaluated early in the project and a decision was made to focus subsequent research around modeling studies with the BATS-ABL model. The value of using such coupled surface-atmosphere models in this research area was further confirmed by the success of the Tucson Aggregation Workshop. Objective 3: There was excellent progress in using the BATS-ABL model to test aggregation rules for a variety of realistic covers. The foci of attention have been the site of the First International Satellite Land Surface Climatology Project Field Experiment (FIFE) in Kansas and one of the study sites of the Anglo-Brazilian Amazonian Climate Observational Study (ABRACOS) near the city of Manaus, Amazonas, Brazil. These two sites were selected because of the ready availability of relevant field data to validate and initiate the BATS-ABL model. The results of these tests are given in a Masters thesis, and reported in two papers. Objective 4: Progress far exceeded original expectations not only in reconciling BATS land covers with those that can be recognized from space, but also in then applying remotely-sensed land cover data to map aggregate values of BATS parameters for heterogeneous covers and interpreting these parameters in terms of surface-atmosphere exchanges.

Description: This research is aimed at producing a fundamental new research tool for characterizing the source strength of the most important compound controlling the hemispheric and global scale distribution of tropospheric ozone. Specifically, this effort seeks to demonstrate the proof-of-concept of a new general purpose laser-induced fluorescence based spectrometer for making airborne eddy-correlation flux measurements of nitric oxide (NO) and other reactive nitrogen compounds. The new all solid-state laser technology being used in this advanced sensor will produce a forerunner of the type of sensor technology that should eventually result in highly compact operational systems. The proof-of-concept sensor being developed will have over two orders-of-magnitude greater sensitivity than present-day instruments. In addition, this sensor will offer the possibility of eventual extension to airborne eddy-correlation flux measurements of nitrogen dioxide (NO2) and possibly other compounds, such as ammonia (NH3), peroxyradicals (HO2), nitrateradicals (NO3) and several iodine compounds (e.g., I and IO). Demonstration of the new sensor's ability to measure NO fluxes will occur through a series of laboratory and field tests. This proof-of-concept demonstration will show that not only can airborne fluxes of important ultra-trace compounds be made at the few parts-per-trillion level, but that the high accuracy/precision measurements currently needed for predictive models can also. These measurement capabilities will greatly enhance our current ability to quantify the fluxes of reactive nitrogen into the troposphere and significantly impact upon the accuracy of predictive capabilities to model O3's distribution within the remote troposphere. This development effort also offers a timely approach for producing the reactive nitrogen flux measurement capabilities that will be needed by future research programs such as NASA's planned 1999 Amazon Biogeochemistry and Atmospheric Chemistry Experimental portion of LBA.

Description: A new radiative transfer model combining the efforts of three groups of researchers is discussed. The model accurately computes radiative transfer in a inhomogeneous absorbing, scattering and emitting atmospheres. As an illustration of the model, results are shown for the effects of dust on the thermal radiation.

Description: The photochemistry of the troposphere over the South Atlantic basin is examined by modeling of aircraft observations up to 12-km altitude taken during the TRACE A expedition in September-October 1992. A close balance is found in the 0 to 12-km column between photochemical production and loss Of O3, with net production at high altitudes compensating for weak net loss at low altitudes. This balance implies that O3 concentrations in the 0-12 km column can be explained solely by in situ photochemistry; influx from the stratosphere is negligible. Simulation of H2O2, CH3OOH, and CH2O concentrations measured aboard the aircraft lends confidence in the computations of O3 production and loss rates, although there appears to be a major gap in current understanding of CH2O chemistry in the marine boundary layer. The primary sources of NO(x) over the South Atlantic Basin appear to be continental (biomass burning, lightning, soils). There is evidence that NO(x) throughout the 0 to 12-km column is recycled from its oxidation products rather than directly transported from its primary sources. There is also evidence for rapid conversion of HNO3 to NO(x) in the upper troposphere by a mechanism not included in current models. A general representation of the O3 budget in the tropical troposphere is proposed that couples the large scale Walker circulation and in situ photochemistry. Deep convection in the rising branches of the Walker circulation injects NO(x) from combustion, soils, and lightning to the upper troposphere, leading to O3 production; eventually, the air subsides and net O3 loss takes place in the lower troposphere, closing the O3 cycle. This scheme implies a great sensitivity of the oxidizing power of the atmosphere to NO(x) emissions in the tropics.

Description: A summary of the first order scientific conclusions that emerged from the research done under this grant are as follows: (1) For the first time, the concentration of the key hydrogen and halogen radicals OH, H02, ClO and BrO were determined on a global scale extending from the arctic circle to the antarctic circle, over the altitude domain of the ER-2. That domain extends from 15-20 km altitude, covering a critical part of the lower stratosphere; (2) Simultaneous, in situ measurements of the concentrations of OH, H02, ClO, BrO, NO and NO2 demonstrate the predominance of odd-hydrogen and halogen free radical catalysis in determining the rate of removal of ozone in the lower stratosphere over the complete ASHOE mission. This extends to the global scale the "first look" data obtained during the NASA Stratospheric Photochemistry and Dynamics Experiment (SPADE), executed out of Ames Research Center in June 1993. This represents a major rearrangement of our understanding with respect to the hierarchy of dominant catalytic cycles controlling ozone loss in the lower stratosphere. For the past twenty years, it has been assumed that nitrogen radicals dominate the destruction rate of ozone in the lower stratosphere; (3) Throughout the altitude and latitude range covered by ASHOE, it was determined that a single catalytic cycle, HO2 + O3 yields OH + 2O2, accounted for one half of the total O3 removal in this region of the atmosphere. Halogen radical catalytic cycles were found to account for one third of the ozone loss, and nitrogen radicals were found to account for 20% of the loss; (4) Simultaneous observations of the full complement of radicals, tracers, ozone, and water vapor during ASHOE demonstrated quantitatively the coupling that exists between the rate limiting radicals and other reactive species in the photochemical reaction network. Specifically, the concentrations of ClO and HO2 are inversely correlated with the concentration of NOx. This carries the implication that the NOx effluent from the proposed High Speed Civil Transport may be less destructive to stratospheric ozone than had previously been thought. ASHOE brought this conclusion forward for the first time on a global basis; and (5) The density of BrO was measured on a global scale during ASHOE in the lower stratosphere. It was found that bromine is responsible for 55-65% of the local rate of catalytic destruction of ozone by reactions involving bromine and chlorine. Normalizing calculated loss rates to total available inorganic bromine and chlorine explicitly demonstrates that bromine is 60-80 times more efficient than chlorine in removing ozone in the lower stratosphere. An inferred value of total inorganic bromine is in excellent agreement with measurements of their source species, organic bromine compounds in the troposphere.

Description: Biomass burning is considered to be a major source of trace gas species and aerosol particles which play a vital role in tropospheric chemistry and climate. Anthropogenic biomass burning has largely expanded in the last 15 years, due to increased deforestation practices in the Amazon Basin, as well as to clear land for shifting cultivation in South America, southern Asia, and Africa. Biomass burning produces large amounts of carbon dioxide, carbon monoxide (CO), water, hydrocarbons, nitrous oxides, and smoke particles.

Description: As a significant industrial pollutant, cadmium is implicated as the cause of itai-itai disease. For biological detection of cadmium toxicity, an assay device has been developed using the motile response of the protozoa species, Tetrahymena pyriformis. This mobile protozoa measures 50 microns in diameter, swims at 10 body lengths per second, and aggregates into macroscopically visible patterns at high organism concentrations. The assay demonstrates a Cd(+2) sensitivity better than 1 micro-M and a toxicity threshold to 5 micro-M, thus encouraging the study of these microbial cultures as viable pollution detectors. Using two-dimensional diffraction patterns within a Tetrahymena culture, the scattered light intensity varies with different organism densities (population counts). The resulting density profile correlates strongly with the toxic effects at very low dosages for cadmium (less than 5 ppm) and then for poison protection directly (with nickel and copper antagonists competing with cadmium absorption). In particular, copper dosages as low as 0.1-0.5 mM Cu have shown protective antagonism against cadmium, have enhanced density variability for cultures containing 1 mM Cd(+2) and therefore have demonstrated the sensitivity of the optical detection system. In this way, such microbial diffraction patterns give a responsive optical measure of biological culture changes and toxicity determination in aqueous samples of heavy metals and industrial pollutants.

Description: Stratospheric measurements of H2O and CH4 by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer on the ATLAS-3 shuttle flight in November 1994 have been examined to investigate the altitude and geographic variability of H2O and the quantity H = (H2O + 2CH4) in the tropics and at mid-latitudes (8 to 49 deg N) in the northern hemisphere. The measurements indicate an average value of 7.24 plus or minus 0.44 ppmv for H between altitudes of about 18 to 35 km, corresponding to an annual average water vapor mixing ratio of 3.85 plus or minus 0.29 ppmv entering the stratosphere. The H2O vertical distribution in the tropics exhibits a wave-like structure in the 16- to 25-km altitude range, suggestive of seasonal variations in the water vapor transported from the troposphere to the stratosphere. The hygropause appears to be nearly coincident with the tropopause at the time of observations. This is consistent with the phase of the seasonal cycle of H2O in the lower stratosphere, since the ATMOS observations were made in November when the H2O content of air injected into the stratosphere from the troposphere is decreasing from its seasonal peak in July - August.

Description: Simultaneous stratospheric volume mixing ratios (VMR's) measured inside and outside the Antarctic vortex by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument in November 1994 reveal previously unobserved features in the distributions of total reactive nitrogen (NO(y)) and total hydrogen (H2O + 2CH4). Maximum removal of NO(y) due to sedimentation of polar stratospheric clouds (PSC's) inside the vortex occurred at a potential temperature (Theta) of 500-525 K (approximately 20 km), where values were 5 times smaller than measurements outside. Maximum loss of H2O + 2CH4 due to PSC's occurred in the vortex at 425-450 K, approximately 3 km lower than the peak NO(y) loss. At that level, H2O + 2CH4 VMR's inside the vortex were approximately 70% of corresponding values outside. The Antarctic and April 1993 Arctic measurements by ATMOS show no significant differences in H2O + 2CH4 VMR's outside the vortices in the two hemispheres. Elevated NO(y) VMRs were measured inside the vortex near 700 K. Recent model calculations indicate that this feature results from downward transport of elevated NO(y) produced in the thermosphere and mesosphere.

Description: We compare volume mixing ratio profiles of N2O, O3, NO(y), H2O, CH4, and CO in the mid-latitude lower stratosphere measured by the ATMOS Fourier transform spectrometer on the ATLAS-3 Space Shuttle Mission with in situ measurements acquired from the NASA ER-2 aircraft during Nov 1994. ATMOS and ER-2 observations of (N2O) show good agreement, as do measured correlations of (O3), (NO(y)), (H2O), and (CH4) with (N2O). Thus a consistent measure of the hydrogen (H2O, CH4) content of the lower stratosphere is provided by the two platforms. The similarity of (NO(y)) determined by detection of individual species by ATMOS and the total (NOy) measurement on the ER-2 provides strong corroboration for the accuracy of both techniques. A 25% discrepancy in lower stratospheric (CO) observed by ATMOS and the ER-2 remains unexplained. Otherwise, the agreement for measurements of long-lived tracers demonstrates the ability to combine ATMOS data with in situ observations for quantifying atmospheric transport.

Description: Stratospheric mixing ratios of CH3D from 100 mb to 17mb (approximately equals 15 to 28 km)and HDO from 100 mb to 10 mb (approximately equals 15 to 32 km) have been inferred from high resolution solar occultation infrared spectra from the Atmospheric Trace MOlecule Spectroscopy (ATMOS) Fourier-transform interferometer. The spectra, taken on board the Space Shuttle during the Spacelab 3 and ATLAS-1, -2, and -3 missions, extend in latitude from 70 deg S to 65 deg N. We find CH3D entering the stratosphere at an average mixing ratio of (9.9 +/- 0.8) x 10(exp -10) with a D/H ratio in methane (7.1 +/- 7.4)% less than that in Standard Mean Ocean Water (SMOW) (1 sigma combined precision and systematic error). In the mid to lower stratosphere, the average lifetime of CH3D is found to be (1.19 +/- 0.02) times that of CH4, resulting in an increasing D/H ratio in methane as air 'ages' and the methane mixing ratio decreases. We find an average of (1.0 +/- 0.1) molecules of stratospheric HDO are produced for each CH3D destroyed (1 sigma combined precision and systematic error), indicating that the rate of HDO production is approximately equal to the rate of CH3D destruction. Assuming negligible amounts of deuterium in species other than HDO, CH3D and HD, this limits the possible change in the stratospheric HD mixing ratio below about 10 mb to be +/- 0.1 molecules HD created per molecule CH3D destroyed.

Description: Vertical enrichment profiles of stratospheric O-16O-16O-18 and O-16O-18O-16 (hereafter referred to as (668)O3 and (686)O3 respectively) have been derived from space-based solar occultation spectra recorded at 0.01 cm(exp-1) resolution by the ATMOS (Atmospheric Trace MOlecule Spectroscopy) Fourier transform infrared (FTIR) spectrometer. The observations, made during the Spacelab 3 and ATLAS-1, -2, and -3 shuttle missions, cover polar, mid-latitude and tropical regions between 26 to 2.6 mb inclusive (approximately 25 to 41 km). Average enrichments, weighted by molecular (48)O3 density, of (15 +/- 6)% were found for (668)O3 and (10 +/- 7)% for (686)O3. Defining the mixing ratio of (50)O3 as the sum of those for (668)O3 and (686)O3, an enrichment of (13 plus or minus 5)% was found for (50)O3 (1 sigma standard deviation). No latitudinal or vertical gradients were found outside this standard deviation. From a series of ground-based measurements by the ATMOS instrument at Table Mountain, California (34.4 deg N), an average total column (668)O3 enrichment of (17 +/- 4)% (1 sigma standard deviation) was determined, with no significant seasonal variation discernable. Possible biases in the spectral intensities that affect the determination of absolute enrichments are discussed.

Description: Total reactive nitrogen (NO(y)), nitrous oxide (NO2), methane (CH4), and ozone (03) were measured on board a balloon launched from Aire sur l'Adour (44 deg N, 0 deg W), France on October 12, 1994. Generally, NO(y) was highly anti-correlated with N2O and CH4 at altitudes between 15 and 32 km. The linear NO(y) - N2O and NO(y) - CH4 relationships obtained by the present observations are very similar to those obtained on board ER-2 and DC-8 aircraft previously at altitude below 20 km in the northern hemisphere. They also agree well with the data obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument at 41 deg N in November 1994. Slight departures from linear correlations occurred around 29 km, where N2O and CH4 mixing ratios were larger than typical midlatitude values, suggesting horizontal transport of tropical airmasses to northern midlatitudes in a confined altitude region.

Description: Partitioning between HCl and ClONO2 and among the main components of the reactive nitrogen family (NO, NO2, HNO3, ClONO2, N2O5, and HO2NO2) has been studied inside and outside the Antarctic stratospheric vortex based on ATMOS profiles measured at sunrise during the 3-12 November 1994 ATLAS-3 Shuttle mission. Elevated mixing ratios of HCl in the lower stratosphere with a peak of approximately 2.9 ppbv (10(exp -9) parts per volume) were measured inside the vortex near 500 K potential temperature (approximately 19 km). Maximum ClONO2 mixing ratios of approximately 1.2, approximately 1.4, and approximately 0.9 ppbv near 700 K (approximately 25 km) were measured inside, at the edge, and outside the vortex, respectively. Model calculations reproduce the higher levels of HCl and NO(x) (NO + NO2) inside the lower stratospheric vortex both driven by photochemical processes initiated by low O3. The high HCl at low O3 results from chemical production of HC1 via the reaction of enhanced Cl with CH4, limited production of ClONO2, and the descent of inorganic chlorine from higher altitudes.

Description: Measured stratospheric mixing ratios of HCl, ClNO3, and ClO from ATMOS and MAS are poorly reproduced by models using recommended kinetic parameters. This discrepancy is not resolved by new rates for the reactions Cl+CH4 and OH+HCl derived from weighted fits to laboratory measurements. A deficit in modeled [HCl] and corresponding overprediction of [ClNO3] and [ClO], which increases with altitude, suggests that production of HCl between 20 and 50 km is much faster than predicted from recommended rates.

Description: Volume mixing ratio (VMR) profiles of OCS, HCN, SF6, and CHClF2 (HCFC-22) have been measured near 30 deg N latitude by the Atmospheric Trace Molecule Spectroscopy Fourier transform spectrometer during shuttle flights on 29 April - 6 May 1985 and 3-2 November 1994. The change in the concentration of each molecule in the lower stratosphere has been derived for this 9 1/2-year period by comparing measurements between potential temperatures of 395 to 800 K (approximately 17 to 30 km altitude) relative to simultaneously measured values of the long-lived tracer N2O. Exponential rates of increase inferred for 1985-to 1994 from these comparisons are (0.1 plus or minus 0.4)% yr(exp-1) for OCS, (1.0 plus or minus 1.0)% yr(exp-1) for HCN, (8.0 +/- 0.7)% yr(exp-1) for SF6, and (8.0 +/- 1.0)% yr(exp-1) for CHClF2 (HCFC-22), 1 sigma. The lack of an appreciable trend for OCS suggests the background (i.e. nonvolcanic) source of stratospheric aerosol was the same during the two periods. These results are compared with trends reported in the literature.

Description: Stratospheric volume mixing ratio profiles of carbon tetrafluoride, CF4, obtained with the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument during the ATLAS (Atmospheric Laboratory for Applications and Science) -3 mission of 1994 are reported. Overall the profiles are nearly constant over the altitude range 20 to 50 km, indicative of the very long lifetime of CF4 in the atmosphere. In comparison to the stratospheric values of CF4 inferred from the ATMOS/Spacelab 3 mission of 1985, the 1994 concentrations are consistent with an exponential increase of (1.6 +/- 0.6)% yr(exp -1). This increase is discussed with regard to previous results and likely sources of CF4 at the ground. Further, it is shown that simultaneous measurements of N2O and CF4 provide a means of constraining the lower limit of the atmospheric lifetime of CF4 at least 2,300 years, two sigma.

Description: Observations of the long-lived tracers N2O, CH4 and HF obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument in early November 1994 are used to estimate average descent rates during winter in the Antarctic polar vortex of 0.5 to 1.5 km/month in the lower stratosphere, and 2.5 to 3.5 km/month in the middle and upper stratosphere. Descent rates inferred from ATMOS tracer observations agree well with theoretical estimates obtained using radiative heating calculations. Air of mesospheric origin (N2O less than 5 ppbV) was observed at altitudes above about 25 km within the vortex. Strong horizontal gradients of tracer mixing ratios, the presence of mesospheric air in the vortex in early spring, and the variation with altitude of inferred descent rates indicate that the Antarctic vortex is highly isolated from midlatitudes throughout the winter from approximately 20 km to the stratopause. The 1994 Antarctic vortex remained well isolated between 20 and 30 km through at least mid-November.

Description: Measurements of the long-lived tracers CH4, N2O, and HF from the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument during the Atmospheric Laboratory for Science and Applications-2 (ATLAS-2) Space Shuttle mission in April 1993 are used to infer average winter descent rates ranging from 0.8 km/month at 20 km to 3.2 km/month at 40 km in the Arctic polar vortex during the 1992-93 winter. Descent rates in the mid-stratosphere are similar to those deduced for the Antarctic vortex using ATMOS/ATLAS-3 measurements in November 1994, but the shorter time period of descent in the Arctic leads to smaller total distances of descent. Strong horizontal gradients observed along the vortex edge indicate that the Arctic vortex remains a significant barrier to transport at least until mid-April in the lower to middle stratosphere.

Description: The Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument is a high resolution Fourier transform spectrometer that measures atmospheric composition from low Earth orbit with infrared solar occultation sounding in the limb geometry. Following an initial flight in 1985, ATMOS participated in the Atmospheric Laboratory for Applications and Science (ATLAS) 1, 2, and 3 Space Shuttle missions in 1992, 1993, and 1994 yielding a total of 440 occultation measurements over a nine year period. The suite of more than thirty atmospheric trace gases profiled includes CO2, O3, N2O, CH4, H2O, NO, NO2, HNO3, HCl, HF, ClONO2, CCl3F, CCl2F2, CHF2Cl, and N2O5. The analysis method has been revised throughout the mission years culminating in the 'version 2' data set. The spectroscopic error analysis is described in the context of supporting the precision estimates reported with the profiles; in addition, systematic uncertainties assessed from the quality of the spectroscopic database are described and tabulated for comparisons with other experiments.

Description: The Shuttle SBUV (SSBUV) conducted its fourth and fifth flights in late March 1992 and early April 1993 along with the ATLAS-1 and ATLAS-2 Shuttle missions, respectively. The two successive SSBUV flights yielded ozone data nearly one year apart. An analysis of the meteorological conditions, namely temperature and winds, during the two flight periods indicate that the conditions in the stratosphere were very similar. The temperatures had significantly warmed from winter throughout most of the stratosphere and the circulation was approaching normal summertime conditions for both periods. SSBUV-4, flown in 1992, measured ozone from approximately 30S to 60N while SSBUV-5, flown in 1993, measured ozone from approximately 55S to 60N. Zonal average column ozone amounts were derived from the two flights and compared to determine if a systematic change in ozone could be detected despite the fact that only a few days from each year were sampled. The comparison indicates that in the latitude range 30N to 60N total ozone was lower in 1993 than in 1992 by about 12%. This change is larger than the observational errors and the expected interannual variations. This result verifies similar data taken from ground and satellites.

Description: Ozone profile measurements were made by three instruments, ATMOS, MAS, and SSBUV, using distinctly different observing techniques, as part of the ATLAS Space Shuttle missions in March 1992, April 1993, and November 1994. ATMOS makes solar-occultation observations of infrared spectra using a Fourier transform interferometer. MAS uses a limb-scanning antenna to measure emission spectra at millimeter wavelengths. SSBUV is a nadir-viewing instrument measuring the transmission of scattered solar ultraviolet radiation modified by ozone absorption. A sample of zonal-mean mixing ratio profiles indicates that these three ATLAS instruments generally agree to within 10%, although a few potential biases have been noted. There are significant differences in the character of the agreement between ATLAS 1 and ATLAS 2 which will require further study.

Description: Labeling, feature selection, and the choice of classifier are critical elements for classification of scenes and for image understanding. This study examines several methods for feature selection in polar regions, including the list, of a fuzzy logic-based expert system for further refinement of a set of selected features. Six Advanced Very High Resolution Radiometer (AVHRR) Local Area Coverage (LAC) arctic scenes are classified into nine classes: water, snow / ice, ice cloud, land, thin stratus, stratus over water, cumulus over water, textured snow over water, and snow-covered mountains. Sixty-seven spectral and textural features are computed and analyzed by the feature selection algorithms. The divergence, histogram analysis, and discriminant analysis approaches are intercompared for their effectiveness in feature selection. The fuzzy expert system method is used not only to determine the effectiveness of each approach in classifying polar scenes, but also to further reduce the features into a more optimal set. For each selection method,features are ranked from best to worst, and the best half of the features are selected. Then, rules using these selected features are defined. The results of running the fuzzy expert system with these rules show that the divergence method produces the best set features, not only does it produce the highest classification accuracy, but also it has the lowest computation requirements. A reduction of the set of features produced by the divergence method using the fuzzy expert system results in an overall classification accuracy of over 95 %. However, this increase of accuracy has a high computation cost.

Description: During October 19-20, 1991, one flight of the NASA Global Tropospheric Experiment (GTE) Pacific Exploratory Mission (PEM-West A) mission was conducted near Hawaii as an intercomparison with ground-based measurements of the Mauna Loa Observatory Photochemistry Experiment (MLOPEX 2) and the NOAA Climate Modeling and Diagnostics Laboratory (CMDL). Ozone, reactive nitrogen species, peroxides, hydrocarbons, and halogenated hydrocarbons were measured by investigators aboard the DC-8 aircraft and at the ground site. Lidar cross sections of ozone revealed a complex air mass structure near the island of Hawaii which was evidenced by large variation in some trace gas mixing ratios. This variation limited the time and spatial scales for direct measurement intercomparisons. Where differences occurred between measurements in the same air masses, the intercomparison suggested that biases for some trace gases was due to different calibration scales or, in some cases, instrumental or sampling biases. Relatively large uncertainties were associated with those trace gases present in the low parts per trillion by volume range. Trace gas correlations were used to expand the scope of the intercomparison to identify consistent trends between the different data sets.

Description: A Final Report of a project to measure ClO and BrO from scientific balloons launched during the Second European Stratospheric Arctic and Midlatitude Expedition (SESAME) is presented. A successful launch was initiated on February 3, 1995 in Kiruna, Sweden. A second launch on March 6, 1995 resulted in the retrieval of a partial altitude profile of these species, and a full engineering characterization of a new instrument designed for lightweight balloons.

Description: The chemical characteristics of air parcels over the tropical South Atlantic during September - October 1992 are summarized by analysis of aged marine and continental outflow classifications. Positive correlations between CO and CH3CL and minimal enhancements of C2CL40, and various ChloroFluoroCarbon (CFC) species in air parcels recently advected over the South Atlantic basin strongly suggest an impact on tropospheric chemistry from biomass burning on adjacent continental areas of Brazil and Africa. Comparison of the composition of aged Pacific air with aged marine air over the South Atlantic basin from 0.3 to 12.5 km altitude indicates potential accumulation of long-lived species during the local dry season. This may amount to enhancements of up to two-fold for C2H6, 30% for CO, and 10% for CH3Cl. Nitric oxide and NO(x) were significantly enhanced (up to approx. 1 part per billion by volume (ppbv)) above 10 km altitude and poorly correlated with CO and CH3Cl. In addition, median mixing ratios of NO and NO(x) were essentially identical in aged marine and continental outflow air masses. It appears that in addition to biomass burning, lightning or recycled reactive nitrogen may be an important source of NO(x) to the upper troposphere. Methane exhibited a monotonic increase with altitude from approx. 1690 to 1720 ppbv in both aged marine and continental outflow air masses. The largest mixing ratios in the upper troposphere were often anticorrelated with CO, CH3Cl, and CO2, suggesting CH, contributions from natural sources. We also argue, based on CH4/CO ratios and relationships with various hydrocarbon and CFC species, that inputs from biomass burning and the northern hemisphere are unlikely to be the dominant sources of CO, CH4 and C2H6 in aged marine air. Emissions from urban areas would seem to be necessary to account for the distribution of at least CH4 and C2H6. Over the African and South American continents an efficient mechanism of convective vertical transport coupled with large-scale circulations conveys biomass burning, urban, and natural emissions to the upper troposphere over the South Atlantic basin. Slow subsidence over the eastern South Atlantic basin may play an important role in establishing and maintaining the rather uniform vertical distribution of long-lived species over this region. The common occurrence of values greater than 1 for the ratio CH3OOH/H2O2 in the upper troposphere suggests that precipitation scavenging effectively removed highly water soluble gases (H2O2, HNO3, HCOOH, and CH3COOH) and aerosols during vertical convective transport over the continents. However, horizontal injection of biomass burning products over the South Atlantic, particularly water soluble species and aerosol particles, was frequent below 6 km altitude.

Description: We present a study of the growth of ternary solution (nitric acid, sulfuric acid and water) droplets in the stratosphere. The growth mechanism is hetero-molecular condensation in which the particle is assumed to be in equilibrium with environmental water vapor. Model results are in reasonable agreement with the averaged extinction ratio obtained by the SAM II satellite system.

Description: Validation of stratospheric ClO measurements by the Microwave Limb Sounder (MLS) on the Upper Atmosphere Research Satellite (UARS) is described. Credibility of the measurements is established by (1) the consistency of the measured ClO spectral emission line with the retrieved ClO profiles and (2) comparisons of ClO from MLS with that from correlative measurements by balloon-based, ground-based, and aircraft-based instruments. Values of "noise" (random), "scaling" (multiplicative), and "bias" (additive) uncertainties are determined for the Version 3 data, in the first version public release of the known artifacts in these data are identified. Comparisons with correlative measurements indicate agreement to within the combined uncertainties expected for MLS and the other measurements being compared. It is concluded that MLS Version 3 ClO data, with proper consideration of the uncertainties and "quality" parameters produced with these data, can be used for scientific analyses at retrieval surfaces between 46 and 1 hPa (approximately 20-50 km in height). Future work is planned to correct known problems in the data and improve their quality.

Description: A new radiative transfer model combining the efforts of three groups of researchers is discussed. The model accurately computes radiative transfer in a inhomogeneous absorbing, scattering and emitting atmospheres. As an illustration of the model, results are shown for the effects of dust on the thermal radiation.

Description: The present experimental study examines the performance of a novel fuel injector/burner configuration with respect to reduction in nitrogen oxide NOx emissions. The lobed injector/burner is a device in which very rapid initial mixing of reactants can occur through strong streamwise vorticity generation, producing high fluid mechanical strain rates which can delay ignition and thus prevent the formation of stoichiometric diffusion flames. Further downstream of the rapid mixing region. this flowfield produces a reduced effective strain rate, thus allowing ignition to occur in a premixed mode, where it is possible for combustion to take place under locally lean conditions. potentially reducing NOx emissions from the burner. The present experiments compare NO/NO2/NOx emissions from a lobed fuel injector configuration with emissions from a straight fuel injector to determine the net effect of streamwise vorticity generation. Preliminary results show that the lobed injector geometry can produce lean premixed flame structures. while for comparable flow conditions, a straight fuel injector geometry produces much longer. sooting diffusion flames or slightly rich pre-mixed flames. NO measurements show that emissions from a lobed fuel injector/burner can be made significantly lower than from a straight fuel injector under comparable flow conditions.

Description: An important objective of the Pacific Exploratory Mission-West A (PEM-West A) was the chemical characterization of the outflow of tropospheric trace gases and aerosol particles from the Asian continent over the western Pacific Ocean. This paper summarizes the chemistry of this outflow during the period September - October 1991. The vertical distributions of CO, C2H6, and NO(x), showed regions of outflow at altitudes below 2 km and from 8 to 12 km. Mixing ratios of CO were approx. equals 130 parts per billion by volume (ppbv), approx. equals 1OOO parts per trillion by volume (pptv) for C2H6, and approx. equals 100 pptv for NO(x) in both of these regions. Direct outflow of Asian industrial materials was clearly evident at altitudes below 2 km, where halocarbon tracer compounds such as CH3CCl3 and C2Cl4 were enhanced about threefold compared to aged Pacific air. The source attribution of species outflowing from Asia to the Pacific at 8-12 km altitude was not straightforward. Above 10 km altitude there were substantial enhancements of NO(y), O3, CO, CH4, SO2, C2H6, C3H8, C2H2, and aerosol Pb-210 but not halocarbon industrial tracers. These air masses were rich in nitrogen relative to sulfur and contained ratios of C2H2/CO and C3H8/C2H6 (approx. equals l.5 and 0.1 respectively) indicative of several- day-old combustion emissions. It is unclear if these emissions were of Asian origin, or if they were rapidly transported to this region from Europe by the high wind speeds in this tropospheric region (60 - 70 m/s). The significant cyclonic activity over Asia at this time could have transported to the upper troposphere emissions from biomass burning in Southeast Asia or emissions from the extensive use of various biomass materials for cooking and space heating. Apparently, the emissions in the upper troposphere were brought there by wet convective systems since water-soluble gases and aerosols were depleted in these air masses. Near 9 km altitude there was a distinct regional outflow that appeared to be heavily influenced by biogenic processes on the Asian continent, especially from the southeastern area. These air masses contained CH4 in excess of 1800 ppbv, while CO2 and OCS were significantly depleted (349 - 352 ppmv and 450 - 500 pptv, respectively). This signature seemingly reflected CH4 emissions from wetlands and rice paddies with coincident biospheric uptake of tropospheric CO2 and OCS.

Description: Aerosol samples collected over the western Pacific during the NASA/Global Tropospheric Experiment Pacific Exploratory Mission (PEM-West A) expedition (September - October 1991) revealed mean Pb-210 concentrations in the free troposphere in the 5-10 fCi m(exp -3) STP range. Most soluble ionic aerosol-associated species were near detection limits [much less than 40 parts per trillion by volume (pptv)] in these same samples. The altitude distribution of O3 near Asia closely resembled that of Pb-210, while no relationship was found between the concentrations of O3 and Be-7. Free tropospheric air over the western Pacific was depleted in soluble aerosol-associated species but enriched in Pb-210 and O3, indicative of deep wet convection over the Asian continent. The influence of Asian air on the composition of the free troposphere over the western Pacific was evident on most of the PEM-West A flights. However, evidence of continental influence was largely restricted to those species that are relatively insoluble (or have insoluble precursors), hence escape scavenging during vertical transport from the boundary layer into the free troposphere by wet convective activity.

Description: The feasibility of using microwave power to thermally regenerate sorbents loaded with water vapor, CO2, and organic contaminants has been rigorously demonstrated. Sorbents challenged with air containing 0.5% CO2, 300 ppm acetone, 50 ppm trichloroethylene, and saturated with water vapor have been regenerated, singly and in combination. Microwave transmission, reflection, and phase shift has also been determined for a variety of sorbents over the frequency range between 1.3-2.7 GHz. This innovative technology offers the potential for significant energy savings in comparison to current resistive heating methods because energy is absorbed directly by the material to be heated. Conductive, convective and radiative losses are minimized. Extremely rapid heating is also possible, i.e., 1400 C in less than 60 seconds. Microwave powered thermal desorption is directly applicable to the needs of Advance Life Support in general, and of EVA in particular. Additionally, the applicability of two specific commercial applications arising from this technology have been demonstrated: the recovery for re-use of acetone (and similar solvents) from industrial waste streams using a carbon based molecular sieve; and the separation and destruction of trichloroethylene using ZSM-5 synthetic zeolite catalyst, a predominant halocarbon environmental contaminant. Based upon these results, Phase II development is strongly recommended.

Description: The research objectives that were achieved during the course of our studies include the following: (1) Over the last few years, a model has been developed in the Atmospheric Chemistry and Dynamics Branch at Ames Research Center in collaboration with the Physics Department at San Jose State University. It is referred to as the Global/Regional Atmospheric Chemistry Event Simulator (GRACES). Currently, the GRACES model system combines an atmospheric chemistry and transport model, and a regional mesoscale meteorological model. Therefore this system is suitable for simulating the conditions observed by the tropical observation missions, such as the Pacific Exploratory Mission in the 'Tropics (PEM-Tropics), Study of Ozone and Nitrogen oxides Experiment (SONEX), and other periods. Specifically, the research carried out included the evaluation of the behavior of several components of the MM5 (I.e., Meteorological Model 5, version 2) and the GRACES combined modeling system. We initiated research on (a) the ability of the MM5 model to assimilate downward vertical velocities at least as high as the analyses, (b) the ability of the Graces model to incorporate the vertical velocities from MM5, and (c) other factors related to transport patterns required to transport CO in the observed manner. We carried out improved calculations of the transport of tracers for both NASA airborne missions, SONEX and PEM-Tropics. We also made improved source strength estimates fopr isoprene dust, and similar emissions from the Earths surface. This required the use of newly available databases on the Earth's surface and vegetation. We completed atmospheric chemistry simulations of radicals and nitrogen oxide species. We have greatly improved the handling of cumulonimnbus convection by modifing an existing scheme.

Description: This report covers the Tropospheric Trace Gas and Airborne Measurement Group's (TTGAMG) participation in the NASA Global Tropospheric Experiment (GTE) Pacific Exploratory Mission: Tropics A (PEM-TA) field measurement program. With other university and NASA centers, the Georgia Institute of Technology Airborne Laser Induced Fluorescence Experiment (GITALIFE) was deployed on the NASA Ames DC-8 aircraft for the measurement of NO and NO2 One of the PEM-TA objectives was to collect the data and interpret the fast photo-chemical processes taking place in the remote and relatively pristine environment over Hawaii, Tahiti, Easter Island, New Zealand, and Fiji.

Description: We present calculations of the radiative forcing of the Mt. Pinatubo aerosols as a function of latitude and time after the eruption and compare the results with GOES satellite data. The results from the model indicate that the net effect of the aerosol was to cool the earth-atmosphere system with the most significant radiative effect in the tropics (corresponding to the location of the tropical stratospheric reservoir) and at latitudes greater than 60 deg. The high-latitude maximum is a combined effect of the high-latitude peak in optical depth (Trepte et al 1994) and the large solar zenith angles. The comparison of the predicted and measured net flux shows relatively good agreement, with the model consistently under predicting the cooling effect of the aerosol.

Description: The Earth is in the midst of rapid and unprecedented change, much of it caused by the enormous reproductive and resource acquisition success of the human population. For the first time in Earth's history, the actions of one species-humans-are altering the atmospheric, climatic, biospheric, and edaphic processes on a scale that rivals natural processes. How will ecosystems, involving those manipulated and managed by humans largely for human use, respond to these changes? Clearly ecosystems have been adjusting to change throughout Earth's history and evolving in ways to adapt and to maintain self-organizing behavior. And in this process, the metabolic activity of the biosphere has altered the environmental conditions it experiences. I am going to confine this presentation to a few thoughts on the present state of terrestrial ecosystems and the urgency that changes in it is bringing to all of us.

Description: The history of life on Earth is a rich tapestry of adaptation and innovation which was shaped, at least in part, by the changing surface environment of our planet. To the extent that all rocky planets have followed similar evolutionary paths, studies of our own biosphere can guide us in our search for extraterrestrial life. Understanding the nature, timing, and causes of long-term changes in the global environment is a key objective.

Description: An asymptotic plume growth method based on a time-accurate three-dimensional computational fluid dynamics formulation has been developed to assess the exhaust-plume pollutant environment from a simulated RD-170 engine hot-fire test on the F1 Test Stand at Marshall Space Flight Center. Researchers have long known that rocket-engine hot firing has the potential for forming thermal nitric oxides, as well as producing carbon monoxide when hydrocarbon fuels are used. Because of the complex physics involved, most attempts to predict the pollutant emissions from ground-based engine testing have used simplified methods, which may grossly underpredict and/or overpredict the pollutant formations in a test environment. The objective of this work has been to develop a computational fluid dynamics-based methodology that replicates the underlying test-stand flow physics to accurately and efficiently assess pollutant emissions from ground-based rocket-engine testing. A nominal RD-170 engine hot-fire test was computed, and pertinent test-stand flow physics was captured. The predicted total emission rates compared reasonably well with those of the existing hydrocarbon engine hot-firing test data.

Description: Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.

Description: Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration, (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control, and (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.

Description: This document is the first report from the Office of Aeronautics Advanced Subsonic Technology (AST) Program's Subsonic Assessment (SASS) Project. This effort, initiated in late 1993, has as its objective the assessment of the atmospheric effects of the current and predicted future aviation fleet. The two areas of impact are ozone (stratospheric and tropospheric) and radiative forcing. These are driven, respectively, by possible perturbations from aircraft emissions of NOX and soot and/or sulfur-containing particles. The report presents the major questions to which project assessments will be directed (Introduction) and the status of six programmatic elements: Emissions Scenarios, Exhaust Characterization, Near-Field Interactions, Kinetics and Laboratory Studies, Global Modeling, and Atmospheric Observations (field studies).

Description: Measurements of the isotopic composition of stratospheric water by the ATMOS instrument are used to infer the convective history of stratospheric air. The average water vapor entering the stratosphere is found to be highly depleted of deuterium, with delta-D(sub w) of -670 +/- 80 (67% deuterium loss). Model calculations predict, however, that under conditions of thermodynamic equilibrium, dehydration to stratospheric mixing ratios should produce stronger depletion to delta-D(sub w) of -800 to 900 (80-90% deuterium loss). Deuterium enrichment of water vapor in ascending parcels can occur only in conditions of rapid convection; enrichments persisting into the stratosphere require that those conditions continue to near-tropopause altitudes. We conclude that either the predominant source of water vapor to the uppermost troposphere is enriched convective water, most likely evaporated cloud ice, or troposphere-stratosphere transport occurs closely associated with tropical deep convection.

Description: Collocated measurements from the Advanced Very High Resolution Radiometer (AVHRR) and the Earth Radiation Budget Experiment (ERBE) scanner are used to examine the radiative forcing of atmospheric aerosols generated from biomass burning for 13 images in South America. Using the AVHRR, Local Area Coverage (LAC) data, a new technique based on a combination of spectral and textural measures is developed for detecting these aerosols. Then, the instantaneous shortwave, longwave, and net radiative forcing values are computed from the ERBE instantaneous scanner data. Results for the selected samples from 13 images show that the mean instantaneous net radiative forcing for areas with heavy aerosol loading is about -36 W/sq m and that for the optically thin aerosols are about -16 W/sq m. These results, although preliminary, provide the first estimates of radiative forcing of atmospheric aerosols from biomass burning using satellite data.

Description: Work performed during the second half of Year 1 of the contract is summarized. The primary objective of the work is to derive global dayside thermospheric oxygen concentrations from DE-1 far ultraviolet imaging data which we are considering under both magnetically quiet and disturbed times. Work to date has been more qualitative in producing maps showing intensity variations beyond those that can be explained by changes in solar zenith angle (SZA) and look angle across an image (Craven et al., 1995; Meier et al., 1994; Gladstone, 1994). In meeting our primary objective, four tasks have been addressed during the reporting period: (1) Investigating the uniqueness of the relationship between the dayglow emission seen using DE-1's 123 filter (dominated by OI 130.4 nm emission) and the column abundance of O relative to N2 referenced to an N2 depth of 10(exp 17) cm(exp 2); (2) Completion of the algorithm for rapid conversion of DE-1 disk dayglow measurements to O/N2 values; (3) Applying the algorithm to a simulation in which a model DE image was constructed using TIGCM atmospheres. The retrieved image of O/N2 was compared to TIGCM O/N2 obtained by integrations of the TIGCM densities; and (4) Applying the algorithm to selected DE-1 data.

Description: 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.

Description: Collocated measurements from the Advanced Very High Resolution Radiometer (AVHRR) and the Earth Radiation Budget Experiment (ERBE) scanner are used to examine the radiative forcing of atmospheric aerosols generated from biomass burning for 13 images in South America. Using the AVHRR, Local Area Coverage (LAC) data, a new technique based on a combination of spectral and textural measures is developed for detecting these aerosols. Then, the instantaneous shortwave, longwave, and net radiative forcing values arc computed from the ERBE instantaneous scanner data. Results for the selected samples from 13 images show that the mean instantaneous net radiative forcing for areas with heavy aerosol loading is about -36 W/square meter and that for the optically thin aerosols are about -16 W/square meter. These results, although preliminary, provide the first estimates of radiative forcing of atmospheric aerosols from biomass burning using satellite data.

Description: Collocated measurements from the Advanced Very High Resolution Radiometer (AVHRR) and the Earth Radiation Budget Experiment (ERBE) scanner are used to examine the radiative forcing of atmospheric aerosols generated from biomass burning for 13 images in South America. Using the AVHRR, Local Area Coverage (LAC) data, a new technique based on a combination of spectral and textural measures is developed for detecting these aerosols. Then, the instantaneous shortwave, longwave, and net radiative forcing values are computed from the ERBE instantaneous scanner data. Results for the selected samples from 13 images show that the mean instantaneous net radiative forcing for areas with heavy aerosol loading is about -36 W/sq m and that for the optically thin aerosols are about -16 W/sq m. These results, although preliminary, provide the first estimates of radiative forcing of atmospheric aerosols from biomass burning using satellite data.

Description: The proposed research involves the application of multispectral satellite data in combination with ground truth measurements to monitor surface properties of the Greenland Ice Sheet which are essential for describing the energy and mass of the ice sheet. Several key components of the energy balance are parameterized using satellite data and in situ measurements. The analysis has been done for a 6 to 17 year time period in order to analyze the seasonal and interannual variations of the surface processes and the climatology. Our goal was to investigate to what accuracy and over what geographic areas large scale snow properties and radiative fluxes can be derived based upon a combination of available remote sensing and meteorological data sets. For the understanding of the surface processes a field program was designed to collect information on spectral albedo, specular reflectance, soot content, grain size and the physical properties of different snow types. Further, the radiative and turbulent fluxes at the ice/snow surface were monitored for the parameterization and interpretation of the satellite data. Highlights include AVHRR time series and surface based radiation measurements, passive microwave time series, and geodetic results from the ETH/CU camp.

Description: This paper describes the validation of ozone data from the Upper Atmosphere Research Satellite (UARS) Microwave Limb Sounder (MLS). The MLS ozone retrievals are obtained from the calibrated microwave radiances (emission spectra) in two separate bands, at frequencies near 205 and 183 GHz. Analyses described here focus on the MLS Version 3 data (the first set of files made publicly available). We describe results of simulations performed to assess the quality of the retrieval algorithms, in terms of both mixing ratio and radiance closure. From actual MLS observations, the 205-GHz ozone retrievals give better closure (smaller radiance residuals) than that from the 183-GHz measurements and should be considered more accurate from the calibration aspects. However, the 183-GHz data are less noise limited in the mesosphere and can provide the most useful scientific results in that region. We compare the retrieved 205-GHz ozone profiles in the middle-to lower stratosphere to ozonesonde measurements at a wide range of latitudes and seasons. Ground-based lidar data from Table Mountain, California, provide a good reference for comparisons at higher altitudes. Based on these analyses, comparisons with balloon-borne measurements and others, as well as a detailed budget of estimated uncertainties, MLS results appear to be generally of high quality, with some biases worth mentioning. Results for the lowermost stratosphere (approx. 50 to 100 bPa) are still in need of improvement. A set of estimated precision and accuracy values is derived for the MLS ozone data sets. We also comment on recent updates in the retrieval algorithms and their impact on ozone values.

Description: This research project involved the investigation of vertical profiles of temperature and moisture in convective regimes, using moist available energy as a guide. The results have been used to develop an improved cumulus parameterization.

Description: The three-dimensional, spectral transport model used in the current project was first successfully integrated over climatological time scales by Dr. Guang Ping Lou for the simulation of atmospheric N2O using the United Kingdom Meteorological Office (UKMO) 4-dimensional, assimilated wind and temperature data set. A non-parallel, FORTRAN version of this integration using a fairly simple N2O chemistry package containing only photo-chemical reactions was used to verify our initial parallel model results. The integrations reproduced the gross features of the observed stratospheric climatological N2O distributions but also simulated the structure of the stratospheric Antarctic vortex and its evolution. Subsequently, Dr. Thomas Kindler, who produced much of the parallel version of our model, enlarged the N2O model chemistry package to include N2O reactions involving O(D-1) and also introduced assimilated wind data from NASA as well as UKMO. Initially, transport calculations without chemistry were run using Carbon-14 as a non-reactive tracer gas with the result that large differences in the transport properties of the two assimilated wind data sets were apparent from the resultant Carbon-14 distributions. Subsequent calculations for N2O, including its chemistry, with the two input winds data sets with verification from UARS satellite observations have refined the transport differences between the two such that the model's steering capabilities could be used to infer the correct climatological vertical velocity fields required to support the N2O observations. During this process, it was also discovered that both the NASA and the UKMO data contained spurious values in some of the higher frequency wave components, leading to incorrect local transport calculations and ultimately affecting the large scale properties of the model's N2O distributions, particularly at tropical latitudes. Subsequent model runs with wind data that had been filtered to remove some of the high frequency components produced much more realistic N2O distributions. During the past few months, the UKMO wind data base for a complete two-year period was processed into spectral form for model use. This new version of the input transport data base now includes complete temperature fields as well as the necessary wind data. This was done to facilitate advanced chemical calculations in the parallel model which often depend upon temperature. Additional UKMO data is being added as it becomes available.

Description: In Part 1 of this study, monthly 2.5 deg. gridpoint anomalies in the TIROS-N (Television and Infrared Operational Satellite-N) series Microwave Sounding Unit (MSU) channel 2 brightness temperatures during 1979-88 are evaluated with multiple satellites and radiosonde data for their climate temperature monitoring capability. The MSU anomalies we computed about a 10-year mean annual cycle at each grid point, with the MSUs intercalibrated to a common arbitrary level. The intercalibrations remove relative biases between instruments of up to several tenths of a degree celsius. The monthly gridpoint anomaly agreement between concurrently operating satellites reveals single-satellite precision on generally better than 0.07 C in the tropics and better than 0.15 C at higher latitudes. Monthly anomalies in radiosonde channel 2 brightness temperatures computed with the radiative transfer equation compare very closely to the MSU measured anomalies in all climate zones, with correlations generally from 0.94 to 0.98 and standard errors of 0.15 C in the tropics to 0.30 C at high latitudes. Simplification of these radiative transfer calculations to a static weighting profile applied to the radiosonde temperature profile leads to an average degradation of only 0.02 deg. in the monthly skill. In terms of a more traditionally measured quantity, the MSU channel 2 anomalies match best with either the radiosonde 100-20-kPa or 100-15-kPa layer anomalies. No significant spurious trends were found in the 10-yr satellite dataset compared to the radiosondes that would indicate a calibration drift in either system. Thus, sequentially launched, overlapping passive microwave radiometers provide a useful system for monitoring intraseasonal to interannual climate anomalies and offer hope for monitoring of interdecadal trends from space. The Appendix includes previously unpublished details of the MSU gridpoint anomaly dataset construction. Part II of this study addresses the removal from channel 2 of the temperature influence above the 30-kPa level, providing a sharper and thus potentially more useful weighting function for monitoring lower tropospheric temperatures.

Description: The contribution from the chlorine and bromine species in the formation of the Antarctic ozone hole is evaluated. Since chlorine and bromine compounds are of different industrial origin, it is desirable, from a policy point of view, to be able to attribute chlorine-catalyzed loss of ozone with those reactions directly involving chlorine species, and likewise for bromine-catalyzed loss. In the stratosphere, however, most of the chemical families are highly coupled, and, for example, changes in the chlorine abundance will alter the partitioninig in other families and thus the rate of ozone loss. This modeling study examines formation of the Antarctic ozone hole for a wide range of bromine concentrations (5 - 25 pptv) and for chlorine concentrations typical of the last two decades (1.5, 2.5 and 3.5 ppbv). We follow the photochemical evolution of a single parcel of air, typical of the inner Antarctic vortex (50 mbar, 70 deg. S, NO(sub y) = 2 ppbv, with Polar Stratospheric Clouds(PSC)) from August 1 to November 1. For all of these ranges of chlorine and bromine loading, we would predict a substantial ozone hole (local depletion greater than 90%) within the de-nitrified, PSC- perturbed vortex. The contributions of the different catalytic cycles responsible for ozone loss are tabulated. The deep minimum in ozone is driven primarily by the chlorine abundance. As bromine levels decrease, the magnitude of the chlorine-catalyzed ozone loss increases to take up the slack. This is because bromine suppresses ClO by accelerating the conversion of ClO an Cl2O2 back to HCI. For this range of conditions, the local relative efficiency of ozone destruction per bromine atom to that per chlorine atom (alpha-factor) ranges from 33 to 55, decreasing with increase of bromine.