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Observations and theories related to Antarctic ozone changes

In 1985, there was a report of a large, sudden, and unanticipated decrease in the abundance of springtime Antarctic ozone over the last decade. By 1987, ozone decreases of more than 50 percent in the total column, and 95 percent locally between 15 and 20 km, had been observed. The scientific community quickly rose to the challenge of explaining this remarkable discovery; theoreticians soon developed a series of chemical and dynamical hypotheses to explain the ozone loss. Three basic theories were proposed to explain the springtime ozone hole. (1) The ozone hole is caused by the increasing atmospheric loadings of manmade chemicals containing chlorine (chlorofluorocarbons (CFC's) and bromine (halons)). These chemicals efficiently destroy ozone in the lower stratosphere in the Antarctic because of the special geophysical conditions, of an isolated air mass (polar vortex) with very cold temperatures, that exist there. (2) The circulation of the atmosphere in spring has changed from being predominantly downward over Antarctica to upward. This would mean that ozone poor air from the troposphere, instead of ozone rich air from the upper stratosphere, would be transported into the lower Antarctic stratosphere. (3) The abundance of the oxides of nitrogen in the lower Antarctic stratosphere is periodically enhanced by solar activity. Nitrogen oxides are produced in the upper mesosphere and thermosphere and then transported downward into the lower stratosphere in Antarctica, resulting in the chemical destruction of ozone. The climatology and trends of ozone, temperature, and polar stratospheric clouds are discussed. Also, the transport and chemical theories for the Antarctic ozone hole are presented.

Hartmann, D.↗

Upper-atmosphere Aerosols: Properties and Natural Cycles

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

Turco, Richard P.↗

Precision Cleaning Verification of Nonvolatile Residues by Using Water, Ultrasonics, and Turbidity Analyses

Chlorofluorocarbons (CFC's) in the atmosphere are believed to present a major environmental problem because they are able to interact with and deplete the ozone layer. NASA has been mandated to replace chlorinated solvents in precision cleaning, cleanliness verification, and degreasing of aerospace fluid systems hardware and ground support equipment. KSC has a CFC phase-out plan which provides for the elimination of over 90 percent of the CFC and halon use by 1995. The Materials Science Laboratory and KSC is evaluating four analytical methods for the determination of nonvolatile residues removal by water: (1) infrared analyses using an attenuated total reflectance; (2) surface tension analyses, (3) total organic content analyses, and (4) turbidity analyses. This research project examined the ultrasonic-turbidity responses for 22 hydrocarbons in an effect to determine: (1) if ultrasonics in heated water (70 C) will clean hydrocarbons (oils, greases, gels, and fluids) from aerospace hardware; (2) if the cleaning process by ultrasonics will simultaneously emulsify the removed hydrocarbons in the water; and (3) if a turbidimeter can be used successfully as an analytical instrument for quantifying the removal of hydrocarbons. Sixteen of the 22 hydrocarbons tested showed that ultrasonics would remove it at least 90 percent of the contaminated hydrocarbon from the hardware in 10 minutes or less giving a good ultrasonic-turbidity response. Six hydrocarbons had a lower percentage removal, a slower removal rate, and a marginal ultrasonic-turbidity response.

Skinner, S. Ballou↗

On the age of stratospheric air and ozone depletion potentials in polar regions

Observations of the nearly inert, man-made chlorofluorocarbon CFC-115 obtained during January 1989 are used to infer the age of air in the lower stratosphere. These observations together with estimated release rates suggest an average age of high-latitude air at pressure altitudes near 17-21 km of about 3 to 5 yr. This information is used together with direct measurements of HCFC-22, HCFC-142b, CH3Br, H-1301, H-1211, and H-2402 to examine the fractional dissociation of these species within the Arctic polar lower stratosphere compared to that of CFC-11 and hence to estimate their local ozone depletion potentials in this region. It is shown that these HCFCs are much less efficiently dissociated within the stratosphere than CFC-11, lowering their ozone depletion potentials to only about 30-40 percent of their chlorine loading potentials. In contrast, the observations of CH3Br and the Halons considered confirm that they are rapidly dissociated within the stratosphere, with important implications for their ozone depletion potentials.

Pollock, W. H.↗

Flexible Sandwich Diaphragms Are Less Permeable

Diaphragms for use in refrigerator compressors made as laminates of commercially available elastomers and metals. Diaphragms flexible, but less permeable by chlorofluorocarbon refrigerant fluids than diaphragms made of homogeneous mixtures of materials.

Michalovic, John G.↗

Evaluation of ultrasonic cavitation of metallic and non-metallic surfaces

1,1,2 trichloro-1,2,2 trifluoro ethane (CFC-113) commercially known as Freon-113 is the primary test solvent used for validating the cleaned hardware at the Kennedy Space Center (KSC). Due to the ozone depletion problem, the current United States policy calls for the phase out of Freons by 1995. NASAs chlorofluorocarbon (CFC) replacement group at KSC has opted to use water as a replacement fluid for the validation process since water is non-toxic, inexpensive, and is environmentally friendly. The replacement validation method calls for the ultrasonification of the small parts with water at 52 C for a cycle or two of 10 min duration wash using commercial ultrasonic baths. In this project, experimental data was obtained to assess the applicability of the proposed validation method for any damage of the metallic and non-metallic surfaces resulting from ultrasonic cavitation.

Mehta, Narinder K.↗

Life cycles of transient planetary waves

In recent years there has been an increasing effort devoted to understanding the physical and dynamical processes that govern the global-scale circulation of the atmosphere. This effort has been motivated, in part, from: (1) a wealth of new satellite data; (2) an urgent need to assess the potential impact of chlorofluorocarbons on our climate; (3) an inadequate understanding of the interactions between the troposphere and stratosphere and the role that such interactions play in short and long-term climate variability; and (4) the realization that addressing changes in our global climate requires understanding the interactions among various components of the earth system. The research currently being carried out represents an effort to address some of these issues by carrying out studies that combine radiation, ozone, seasonal thermal forcing and dynamics. Satellite and ground-based data that is already available is being used to construct basic states for our analytical and numerical models. Significant accomplishments from 1991-1992 are presented and include the following: ozone-dynamics interaction; (2) periodic local forcing and low frequency variability; and (3) steady forcing and low frequency variability.

Nathan, Terrence↗

The atmospheric effects of stratospheric aircraft. Report of the 1992 Models and Measurements Workshop. Volume 1: Workshop objectives and summary

This Workshop on Stratospheric Models and Measurements (M&M) marks a significant expansion in the history of model intercomparisons. It provides a foundation for establishing the credibility of stratospheric models used in environmental assessments of chlorofluorocarbons, aircraft emissions, and climate-chemistry interactions. The core of the M&M comparisons involves the selection of observations of the current stratosphere (i.e., within the last 15 years): these data are believed to be accurate and representative of certain aspects of stratospheric chemistry and dynamics that the models should be able to simulate.

Prather, Michael J.↗

The atmospheric effects of stratospheric aircraft. Report of the 1992 Models and Measurements Workshop. Volume 2: Comparisons with global atmospheric measurements

This Workshop on Stratospheric Models and Measurements (M&M) marks a significant expansion in the history of model intercomparisons. It provides a foundation for establishing the credibility of stratospheric models used in environmental assessments of chlorofluorocarbons, aircraft emissions, and climate-chemistry interactions. The core of the M&M comparisons involves the selection of observations of the current stratosphere (i.e., within the last 15 years): these data are believed to be accurate and representative of certain aspects of stratospheric chemistry and dynamics that the models should be able to simulate.

Prather, Michael J.↗

The atmospheric effects of stratospheric aircraft. Report of the 1992 Models and Measurements Workshop. Volume 3: Special diagnostic studies

This Workshop on Stratospheric Models and Measurements (M&M) marks a significant expansion in the history of model intercomparisons. It provides a foundation for establishing the credibility of stratospheric models used in environmental assessments of chlorofluorocarbons, aircraft emissions, and climate-chemistry interactions. The core of the M&M comparisons involves the selection of observations of the current stratosphere (i.e., within the last 15 years): these data are believed to be accurate and representative of certain aspects of stratospheric chemistry and dynamics that the models should be able to simulate.

Prather, Michael J.↗

The HITRAN molecular data base - Editions of 1991 and 1992

We describe in this paper the modifications, improvements, and enhancements to the HITRAN molecular absorption database that have occurred in the two editions of 1991 and 1992. The current database includes line parameters for 31 species and their isotopomers that are significant for terrestrial atmospheric studies. This line-by-line portion of HITRAN presently contains about 709,000 transitions between 0 and 23,000/cm and contains three molecules not present in earlier versions: COF2, SF6, and H2S. The HITRAN compilation has substantially more information on chlorofluorocarbons and other molecular species that exhibit dense spectra which are not amenable to line-by-line representation. The user access of the database has been advanced, and new media forms are now available for use on personal computers.

Rothman, Laurence S.↗

Measurement of volatile organic chemicals at selected sites in California

Urban air concentrations of 24 selected volatile organic chemicals that may be potentially hazardous to human health and environment were measured during field experiments conducted at two California locations, at Houston, and at Denver. Chemicals measured included chlorofluorocarbons, halomethanes, haloethanes, halopropanes, chloroethylenes, and aromatic hydrocarbons. With emphasis on California sites, data from these studies are analyzed and interpreted with respect to variabilities in ambient air concentrations, diurnal changes, relation to prevailing meteorology, sources and trends. Except in a few instances, mean concentrations are typically between 0 and 5 ppb. Significant variabilities in atmospheric concentrations associated with intense sources and adverse meteorological conditions are shown to exist. In addition to short-term variability, there is evidence of systematic diurnal and seasonal trends. In some instances it is possible to detect declining trends resulting from the effectiveness of control strategies.

Singh, Hanwant B.↗

An aircraft instrument design for in situ tropospheric OH measurements by laser induced fluorescence at low pressures

The hydroxyl radical (OH) is important for many processes involved in tropospheric chemistry. For instance, it initiates the photochemical degradation of gases that cause global climate change, such as methane and the chlorofluorocarbon substitutes (HCFCs). Because of its reactivity, its abundances are less than 0.1 pptv. Thus, OH has been very difficult to measure accurately, despite its importance. Techniques have evolved, however, so that good measurements of tropospheric OH abundances are now possible. One of these techniques that is adaptable to aircraft measurements is the laser induced fluorescence detection of the OH radical in a detection chamber at low pressures. The current ground-based instrument, which can be readily adapted to aircraft, can detect OH abundances of 1.4 x 10 exp 5 OH molecules/cu cm with S/N = 2 in 30 sec, and 5 x 10 exp 4/cu cm in 5 min.

Brune, William H.↗

Using Water To Analyze Greasy Residues

Water found useful as substitute for chlorofluorocarbon (CFC) solvents in tests to measure amounts of nonvolatile residues of contaminants (e.g., hydrocarbon greases) on equipment after it has been cleaned. Water does not harm environment and much cheaper than CFCs.

Hoppesch, Charles W.↗

Self-Calibrating, Variable-Flow Pumping System

Pumping system provides accurate, controlled flows of two chemical liquids mixed in spray head and react to form rigid or flexible polyurethane or polyisocyanurate foam. Compatible with currently used polyurethane-based coating materials and gas-bubble-forming agents (called "blowing agents" in industry) and expected to be compatible with materials that used in near future. Handles environmentally acceptable substitutes for chlorofluorocarbon foaming agents.

Walls, Joe T.↗

Design of a vehicle based system to prevent ozone loss

Reduced quantities of ozone in the atmosphere allow greater levels of ultraviolet light (UV) radiation to reach the earth's surface. This is known to cause skin cancer and mutations. Chlorine liberated from Chlorofluorocarbons (CFC's) and natural sources initiate the destruction of stratospheric ozone through a free radical chain reaction. The project goals are to understand the processes which contribute to stratospheric ozone loss, examine ways to prevent ozone loss, and design a vehicle-based system to carry out the prevention scheme. The 1992/1993 design objectives were to accomplish the first two goals and define the requirements for an implementation vehicle to be designed in detail starting next year. Many different ozone intervention schemes have been proposed though few have been researched and none have been tested. A scheme proposed by R.J. Cicerone, Scott Elliot and R.P.Turco late in 1991 was selected because of its research support and economic feasibility. This scheme uses hydrocarbon injected into the Antarctic ozone hole to form stable compounds with free chlorine, thus reducing ozone depletion. Because most polar ozone depletion takes place during a 3-4 week period each year, the hydrocarbon must be injected during this time window. A study of the hydrocarbon injection requirements determined that 100 aircraft traveling Mach 2.4 at a maximum altitude of 66,000 ft. would provide the most economic approach to preventing ozone loss. Each aircraft would require an 8,000 nm. range and be able to carry 35,000 lbs. of propane. The propane would be stored in a three-tank high pressure system. Missions would be based from airport regions located in South America and Australia. To best provide the requirements of mission analysis, an aircraft with L/D(sub cruise) = 10.5, SFC = 0.65 (the faculty advisor suggested that this number is too low) and a 250,000 lb TOGW was selected as a baseline. Modularity and multi-role functionality were selected to be key design features. Modularity provides ease of turnaround for the down-time critical mission. Multi-role functionality allows the aircraft to be used beyond its design mission, perhaps as an High Speed Civil Transport (HSCT) or for high altitude research.

Lynn, Sean R.↗

Technology transfer initiatives

This report summarizes the University of Alabama in Huntsville (UAH) technology transfer activities with the Marshall Space Flight Center (MSFC) for the period of April 1993 through December 1993. Early in 1993, the MSFC/TUO and UAH conceived of the concept of developing stand-alone, integrated data packages on MSFC technology that would serve industrial needs previously determined to be critical. Furthermore, after reviewing over 500 problem statements received by MSFC, it became obvious that many of these requests could be satisfied by a standard type of response. As a result, UAH has developed two critical area response (CAR) packages: CFC (chlorofluorocarbon) replacements and modular manufacturing and simulation. Publicity included news releases, seminars, articles and conference papers. The Huntsville Chamber of Commerce established the Technology Transfer Subcommittee with the charge to identify approaches for the Chamber to assist its members, as well as non-members, access to the technologies at the federal laboratories in North Alabama. The Birmingham Chamber of Commerce has expressed interest in establishing a similar technology transfer program. This report concludes with a section containing a tabulation of the problem statements, including CAR packages, submitted to MSFC from January 1992 through December 1993.

Mccain, Wayne↗

Report on concentrations, lifetimes, and trends of CFCs, halons, and related species

The atmospheric lifetimes of molecules containing chlorine and bromine are the dominant parameters influencing their ability to promote enhanced ozone destruction in the stratosphere. The purpose of this report is to assess the present state of knowledge of the lifetimes of halocarbons using two complementary approaches. First, a time series of measurements of gas concentrations is used together with information on their emissions histories and a computational model of atmospheric circulation and chemistry to infer lifetimes through a mass balance approach. Second, an atmospheric chemical-dynamical model is used with detailed information on the chemistry and spectroscopy of the molecules of interest to calculate lifetimes. The lifetimes determined by these two methods are then compared. Attention is focused most closely on fully halogenated chlorine- and bromine-containing molecules, primarily the chlorofluorocarbons, and the halons, because of their ability to deliver chlorine and bromine to the stratosphere. Some attention will be given to those molecules containing hydrogen, which are subject to removal in the troposphere primarily by reaction with OH and by other processes.

Kaye, J. A.↗