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NASA NTRS1994

Present state of knowledge of the upper atmosphere1993: An assessment report, part 2

This document is issued in response to the Clean Air Act Amendment of 1990, Public Law 101-549, which mandates that the National Aeronautics and Space Administration (NASA) and other key agencies submit triennial reports to Congress and the Environmental Protection Agency. NASA is charged with the responsibility to report on the state of our knowledge of the earth's upper atmosphere, particularly the stratosphere. Part 2 (this document) presents summaries of several scientific assessments of our current understanding of the chemical composition and physical structure of the stratosphere, in particular how the abundance and distribution of ozone is predicted to change in the future. These reviews include: (Section B) 'Scientific Assessment of Ozone Depletion: 1991'; (Section C) 'Methyl bromide and the Ozone Layer: A Summary of Current Understanding', published in 1992; (Section D) 'Concentrations, Lifetimes, and Trends of Chlorofluorocarbons (CFC's), Halons, and Related Molecules in the Atmosphere'; (Section E) 'The Atmospheric Effects of Stratospheric Aircraft: Interim Assessment Report of the NASA High-Speed Research Program'; (Section F) 'Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling'; and (Section G) a list of the contributors to this report.

Kurylo, Michael J.↗
NASA NTRS1994

Pilot retrofit test of refrigerant R-134a for GDSCC

NASA has issued an interim policy requiring all of its Centers to eliminate consumption (purchase) of stratospheric ozone-depleting substances, including chlorofluorocarbons (CFC's), by 1995. Also, plans must be outlined for the eventual phase out of their usage. The greatest source of CFC consumption and usage at the Goldstone Deep Space Communications Complex is refrigerant R-12, which is used in many of the facility's air-conditioning systems. A pilot retrofit test shows that retrofitting R-12 air-conditioning systems with hydrofluorocarbon R-13a would be a workable means to comply with the R-12 portion of NASA's policy. Results indicate acceptable cost levels and nearly equivalent system performance.

Albus, J.↗
NASA NTRS1995

The Atmospheric Lifetime Experiment and the Global Atmospheric Gas Experiment (ALE/GAGE)

The ALE/GAGE project was designed to determine the global atmospheric lifetimes of the chlorofluorocarbons CCl3F and CCl2F2 (F-11 and F-12), which had been identified as the main gases that cause stratospheric ozone depletion. The experimental procedures also provided the concentrations of CH3CCl3, CCl4 and N2O. The extended role of the project was to evaluate the mass balances of these gases as well. Methylchloroform (CH3CCl3) serves as a tracer of average atmospheric OH concentrations and hence the oxidizing capacity of the atmosphere. Nitrous oxide (N2O) is a potent greenhouse gas and can also deplete the ozone layer. Measurements of these gases were taken with optimized instruments in the field at a frequency of about 1 sample/hr. Toward the end of the present project methane measurements were added to the program. The final report deals with the research of the Oregon Graduate Institute (OGI) as part of the ALE/GAGE program between 4/1/1988 and 1/31/1991. The report defines the scope of the OGI project, the approach, and the results.

Rasmussen, R. A.↗
NASA NTRS1994

Aqueous alternatives for metal and composite cleaning

For many years the metalworking industry has cleaned metal and composite substrates with chlorinated solvents. Recently, however, health and disposal related environmental concerns have increased regarding chlorinated solvents, including 1,1,1-trichloroethane, trichloroethylene, methylene chloride, or Freon'. World leaders have instituted a production ban of certain ozone depleting chlorofluorocarbons (CFC's) by 1996. The Occupational Safety and Health Administration (OSHA) has instituted worker vapor exposure limitations for virtually all of the solvents used in solvent-based cleaners. In addition, the United States Environmental Protection Agency (EPA) has defined nearly all solvent-based cleaners as 'hazardous'. Cradle to grave waste responsibility is another reason manufacturers are trying to replace chlorinated solvents in their cleaning processes. Because of these factors, there now is a world wide effort to reduce and/or eliminate the use of chlorinated solvents for industrial cleaning. Waterbased cleaners are among the alternatives being offered to the industry. New technology alkaline cleaners are now available that can be used instead of chlorinated solvents in many cleaning processes. These waterbased cleaners reduce the release of volatile organic compounds (VOC's) by as much as 99 percent. (The definition and method of calculation of VOC's now varies from region to region.) Hazardous waste generation can also be significantly reduced or eliminated with new aqueous technology. This in turn can ease worker exposure restrictions and positively impact the environment. This paper compares the chemical and physical properties of this aqueous cleaners versus chlorinated solvents.

Quitmeyer, Joann↗
NASA NTRS1995

The Oak Ridge Refrigerant Management Program

For many years, chlorofluorocarbons (CFC's) have been used by the Department of Energy's (DOE) Oak Ridge Y-12 Plant in air conditioning and process refrigeration systems. However, Title 6 of the Clean Air Act Amendments (CAAA) and Executive Order 12843 (Procurement Requirements and Policies for Federal Agencies for Ozone Depleting Substances) signed by President Clinton require, as policy, that all federal agencies maximize their use of safe, alternate refrigerants and minimize, where economically practical, the use of Class 1 refrigerants. Unfortunately, many government facilities and industrial plants have no plan or strategy in place to make this changeover, even though their air conditioning and process refrigeration equipment may not be sustainable after CFC production ends December 31, 1995. The Y-12 Plant in Oak Ridge, Tennessee, has taken an aggressive approach to complying with the CAAA and is working with private industry and other government agencies to solve tough manufacturing and application problems associated with CFC and hydrochlorofluorocarbon (HCFC) alternatives. Y-12 was the first DOE Defense Program (DP) facility to develop a long-range Stratospheric Ozone Protection Plan for refrigerant management for compliance with the CAAA. It was also the first DOE DP facility to complete detailed engineering studies on retrofitting and replacing all air conditioning and process refrigeration equipment to enable operation with alternate refrigerants. The management plan and engineering studies are models for use by other government agencies, manufacturing plants, and private industry. This presentation identifies some of the hidden pitfalls to be encountered in the accelerated phaseout schedule of CFC's and explains how to overcome and prevent these problems. In addition, it outlines the general issues that must be considered when addressing the phase-out of ozone depleting substances and gives some 'lessons learned' by Y-12 from its Refrigerant Management Program. Discussion topics include requirements for developing a refrigerant management plan and establishing priorities for cost-effective compliance with the CAAA, as well as ways in which employees can be empowered to develop a comprehensive refrigerant management plan. The result of this employee empowerment was a cooperative labor-management effort that is beneficial for Y-12, DOE, and the environment.

Kevil, Thomas H.↗
NASA NTRS1995

Aqueous cleaning and verification processes for precision cleaning of small parts

The NASA Kennedy Space Center (KSC) Materials Science Laboratory (MSL) has developed a totally aqueous process for precision cleaning and verification of small components. In 1990 the Precision Cleaning Facility at KSC used approximately 228,000 kg (500,000 lbs) of chlorofluorocarbon (CFC) 113 in the cleaning operations. It is estimated that current CFC 113 usage has been reduced by 75 percent and it is projected that a 90 percent reduction will be achieved by the end of calendar year 1994. The cleaning process developed utilizes aqueous degreasers, aqueous surfactants, and ultrasonics in the cleaning operation and an aqueous surfactant, ultrasonics, and Total Organic Carbon Analyzer (TOCA) in the nonvolatile residue (NVR) and particulate analysis for verification of cleanliness. The cleaning and verification process is presented in its entirety, with comparison to the CFC 113 cleaning and verification process, including economic and labor costs/savings.

Allen, Gale J.↗
NASA NTRS1995

Cleaning verification by air/water impingement

This paper will discuss how the Kennedy Space Center intends to perform precision cleaning verification by Air/Water Impingement in lieu of chlorofluorocarbon-113 gravimetric nonvolatile residue analysis (NVR). Test results will be given that demonstrate the effectiveness of the Air/Water system. A brief discussion of the Total Carbon method via the use of a high temperature combustion analyzer will also be given. The necessary equipment for impingement will be shown along with other possible applications of this technology.

Jones, Lisa L.↗
NASA NTRS1995

The effect of environmental initiatives on NASA specifications and standards activities

The NASA Operational Environment Team (NOET) has conducted a survey of NASA centers specifications and standards that require the use of Ozone Depleting Substances (ODS's) (Chlorofluorocarbons (CFCs), Halons, and chlorinated solvents). The results of this survey are presented here, along with a pathfinder approach utilized at Marshall Space Flight Center (MSFC) to eliminate the use of ODS's in targeted specifications and standards. Presented here are the lessons learned from a pathfinder effort to replace CFC-113 in a significant MSFC specification for cleaning and cleanliness verification methods for oxygen, fuel and pneumatic service, including Shuttle propulsion elements.

Griffin, Dennis↗
NASA NTRS1995

Development of a CFC Critical Area Response (CAR) package

During the past two years, the NASA Marshall Space Flight Center (MSFC) has studied means to improve the transfer of technology from a major federal lab to a significant portion of an industrial segment. In the past, technology transfers had taken place with individual firms, or small groups of firms. This method of 'customized' transfer is often time consuming and can reduce the effectiveness of a response. Thus, a method was achieved to develop a standardized package on replacement of Chlorofluorocarbons (CFC's) that could be sent out to a large number of firms with minimum follow-up.

Mccain, J. Wayne↗
NASA NTRS1994

Age as a diagnostic of stratospheric transport

Estimates of stratospheric age from observations of long-lived trace gases with increasing tropospheric concentrations invoke the implicit assumption that an air parcel has been transported intact from the tropopical tropopause. However, because of rapid and irreversible mixing in the stratosphere, a particular air parcel cannot be identified with one that left the troposphere at some prior time. The parcel contains a mix of air with a range of transit times, and the mean value over this range is the most appropriate definition of age. The measured tracer concentration is also a mean over the parcel, but its value depends both on the transit time distribution and the past history of the tracer in the troposphere. In principle, only if the tropospheric concentration is increasing linearly can the age be directly inferred. We illustrate these points by employing both a one-dimensional diffusive analog of stratospheric transport, and the general circulation model (GCM) of the Goddard Institute for Space Studies (GISS). Within the limits of the GCM, we estimate the time over which tropospheric tracer concentrations must be approximately linear in order to determine stratospheric age unambiguously; the concentration of an exponentially increasing tracer is a function only of age if the growth time constant is greater than about 7 years, which is true for all the chlorofluorocarbons. More rapid source variations (for example, the annual cycle in CO2) have no such direct relationship with age.

Hall, Timothy M.↗
NASA NTRS1993

A two-dimensional model with coupled dynamics, radiative transfer, and photochemistry. 2: Assessment of the response of stratospheric ozone to increased levels of CO2, N2O, CH4, and CFC

The impact of increased levels of carbon dioxide (CO2), chlorofluorocarbons (CFCs), and other trace gases on stratospheric ozone is investigated with an interactive, two-dimensional model of gas phase chemistry, dynamics, and radiation. The scenarios considered are (1) a doubling of the CO2 concentration, (2) increases of CFCs, (3) CFC increases combined with increases of nitrous oxide (N2O) and methane CH4, and (4) the simultaneous increase of CO2, CFCs, N2O, and CH4. The radiative feedback and the effect of temperature and circulation changes are studied for each scenario. For the double CO2 calculations the tropospheric warming was specified. The CO2 doubling leads to a 3.1% increase in the global ozone content. Doubling of the CO2 concentrations would lead to a maximum cooling of about 12 C at 45 km if the ozone concentration were held fixed. The cooling of the stratosphere leads to an ozone increase with an associated increase in solar heating, reducing the maximum temperature drop by about 3 C. The CFC increase from continuous emissions at 1985 rate causes a 4.5% loss of ozone. For the combined perturbations a net loss of 1.3% is calculated. The structure of the perturbations shows a north-south asymmetry. Ozone losses (when expressed in terms of percent changes) are generally larger in the high latitudes of the southern hemisphere as a result of the eddy mixing being smaller than in the northern hemisphere. Increase of chlorine leads to ozone losses above 30 km altitude where the radiative feedback results in a cooler temperature and an ozone recovery of about one quarter of the losses predicted with a noninteractive model. In all the cases, changes in circulation are small. In the chlorine case, circulation changes reduce the calculated column depletion by about one tenth compared to offline calculations.

Schneider, Hans R.↗
NASA NTRS1994

Northern middle-latitude ozone profile features and trends observed by SBUV and Umkehr, 1979-1990

A comparison of Umkehr ozone profile data with the reprocessed solar backscatter ultraviolet (SBUV) ozone data in the northern middle-latitude region, 30 deg to 50 deg N, is reported. Although significant biases exist between the two types of observations, the long-term variations and least squares linear regression trends agree remarkably well over the comparison period of 1979 to 1990. The ozone trend in the upper stratosphere is of the order of -0.9%/yr. Near 25 km, little if any trend appears, but a larger negative trend is seen in the lower stratosphere near 15 km. Comparisons show that the average annual ozone cycles in the profiles also agree well. The upper stratospheric ozone results are consistent with photochemical model predictions of ozone depletion near 40 km that are due to the release of anthropogenically produced chlorofluorocarbons. The lower stratospheric ozone trend results are in reasonable agreement with published ozonesonde data trends. It is shown that the ozone trends in the lower stratospheric layers impact significantly on the total ozone trend of the order of -0.47%/yr. The good agreement now seen between the two types of observations suggest that the combined ground-based and satellite approach could provide a valuable database for long-term monitoring of stratospheric ozone for trends and extraordinary variations.

Deluisi, J. J.↗
NASA NTRS1994

Climatic consequences of observed ozone loss in the 1980s: Relevance to the greenhouse problem

Recently published findings using satellite and ground-based observations indicate a large winter and summertime decrease in the column abundance of ozone at high and middle latitudes during the last decade. Using a simple ozone depletion profile reflecting the observed decrease in ozone column abundance, Ramaswamy et al. (1992) showed that the negative radiative forcing that results from the ozone decrease between 1979 and 1990 approximately balanced the greenhouse climate forcing due to the chlorofluorocarbons emitted during the same period. Here, we extend the forcing analyses by calculating the equilibrium surface temperature response explicitly, using an updated version of the Atmospheric and Environmental Research two-dimensional radiative-dynamical seasonal model. The calculated steady state responses suggest that the surface cooling due to the ozone depletion in the lower stratosphere offsets about 30% of the surface warming due to greenhouse gases emitted during the same decade. The temperature offset is roughly a factor of 2 larger than the corresponding offset obtained from forcing intercomparisons. This result appears to be related to the climate feedback mechanisms operating in the model troposphere, most notably that associated with atmospheric meridional heat transport. Thus a comprehensive assessment of ozone change effects on the predicted greenhouse warming cannot be accomplished based on forcing evaluations alone. Our results also show that calculations adopting a seasonally and latitudinally dependent ozone depletion profile produce a negative forcing about 50% smaller than that calculated for the depletion profile used by Ramaswamy et al. (1992).

Molnar, G. I.↗
NASA NTRS1995

Supersonic-Spray Cleaner

Spraying system for cleaning mechanical components uses less liquid and operates at pressures significantly lower. Liquid currently used is water. Designed to replace chlorofluorocarbon (CFC) solvent-based cleaning and cleanliness verification methods. Consists of spray head containing supersonic converging/diverging nozzles, source of gas at regulated pressure, pressurized liquid tank, and various hoses, fittings, valves, and gauges. Parameters of nozzles set so any of large variety of liquids and gases combined in desired ratio and rate of flow. Size and number of nozzles varied so system built in configurations ranging from small hand-held spray heads to large multinozzle cleaners. Also used to verify part adequately cleaned. Runoff liquid from spray directed at part collected. Liquid analyzed for presence of contaminants, and part recleaned if necessary.

Caimi, Raoul E. B.↗
NASA NTRS1995

Vapor Degreasing Of A Large Tank

Vapor degreasing procedure provides for removal of relatively non-volatile oils and greases from insides of large vessels. Solvent refluxed to concentrate less volatile contaminants at bottom. Procedure ensures required degrees of cleaniness in high-purity chemical processing and high-vacuum processing vessels. Devised for cleaning complexly-shaped stainless-steel vacuum chamber containing numerous difficult-to-clean features like screw holes and abutting surfaces. Solvent can be chlorofluorocarbon, if means provided to recover most and minimize portion escaping into air. Alternatively, hydrocarbon or other flammable solvent used, provided flammability tolerable in particular application.

Frazer, Robert E.↗
NASA NTRS1995

Replacements For Ozone-Depleting Foaming Agents

Fluorinated ethers used in place of chlorofluorocarbons and hydrochlorofluorocarbons. Replacement necessary because CFC's and HCFC's found to contribute to depletion of ozone from upper atmosphere, and manufacture and use of them by law phased out in near future. Two fluorinated ethers do not have ozone-depletion potential and used in existing foam-producing equipment, designed to handle liquid blowing agents soluble in chemical ingredients that mixed to make foam. Any polyurethane-based foams and several cellular plastics blown with these fluorinated ethers used in processes as diverse as small batch pours, large sprays, or double-band lamination to make insulation for private homes, commercial buildings, shipping containers, and storage tanks. Fluorinated ethers proved useful as replacements for CFC refrigerants and solvents.

Blevins, Elana↗
NASA NTRS1994

Increase in Levels of Stratospheric Chlorine and Fluorine Loading between 1985 and 1992

Mixing ratios of 3.44 ppbv (parts per billion by volume) and 1.23 ppbv for HCl and HF above 50 km, surrogates for total chlorine and fluorine, have been measured by the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment on a March 1992 flight of the Space Shuttle. Compared to the measured values obtained on a 1985 flight, these correspond to a 37% and 62% increase for HCl and HF, respectively. The derived trend in HCl (approx. 0.13 ppbv per year) is in good agreement with the model-predicted increase in chlorine loading of 0.13 ppbv per year, and with the measured trends in HCl total column abundance from reported ground-based observations. The main source of this change can be attributed to the release of man-made chlorofluorocarbons (CFC's) and hydro-chloro-fluoro-carbons (HCFC's). This new value for HCl represents an upper limit to the inorganic chlorine concentration in the stratosphere available for participation in photochemical processes which destroy ozone.

Gunson, M. R.↗
NASA NTRS1995

Development of CFC-Free Cleaning Processes at the NASA White Sands Test Facility

The NASA White Sands Test Facility (WSTF) is developing cleaning and verification processes to replace currently used chlorofluorocarbon-113- (CFC-113-) based processes. The processes being evaluated include both aqueous- and solvent-based techniques. The presentation will include the findings of investigations of aqueous cleaning and verification processes that are based on a draft of a proposed NASA Kennedy Space Center (KSC) cleaning procedure. Verification testing with known contaminants, such as hydraulic fluid and commonly used oils, established correlations between nonvolatile residue and CFC-113. Recoveries ranged from 35 to 60 percent of theoretical. WSTF is also investigating enhancements to aqueous sampling for organics and particulates. Although aqueous alternatives have been identified for several processes, a need still exists for nonaqueous solvent cleaning, such as the cleaning and cleanliness verification of gauges used for oxygen service. The cleaning effectiveness of tetrachloroethylene (PCE), trichloroethylene (TCE), ethanol, hydrochlorofluorocarbon-225 (HCFC-225), tert-butylmethylether, and n-Hexane was evaluated using aerospace gauges and precision instruments and then compared to the cleaning effectiveness of CFC-113. Solvents considered for use in oxygen systems were also tested for oxygen compatibility using high-pressure oxygen autoignition and liquid oxygen mechanical impact testing.

Beeson, Harold↗