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Nonflammable, Nonaqueous, Low Atmospheric Impact, High Performance Cleaning Solvents

For many years, chlorofluorocarbon (CFC) and chlorocarbon solvents have played an important part in aerospace operations. These solvents found extensive use as cleaning and analysis (EPA) solvents in precision and critical cleaning. However, CFCs and chlorocarbon solvents have deleterious effects on the ozone layer, are relatively strong greenhouse gases, and some are suspect or known carcinogens. Because of their ozone-depletion potential (ODP), the Montreal Protocol and its amendments, as well as other environmental regulations, have resulted in the phaseout of CFC-113 and 1,1,1-trichloroethane (TCA). Although alternatives have been recommended, they do not perform as well as the original solvents. In addition, some analyses, such as the infrared analysis of extracted hydrocarbons, cannot be performed with the substitute solvents that contain C-H bonds. CFC-113 solvent has been used for many critical aerospace applications. CFC-113, also known as Freon (registered) TF, has been used extensively in NASA's cleaning facilities for precision and critical cleaning, in particular the final rinsing in Class 100 areas, with gas chromatography analysis of rinse residue. While some cleaning can be accomplished by other processes, there are certain critical applications where CFC-113 or a similar solvent is highly cost-effective and ensures safety. Oxygen system components are one example where a solvent compatible with oxygen and capable of removing fluorocarbon grease is needed. Electronic components and precision mechanical components can also be damaged by aggressive cleaning solvents.

Dhooge, P. M.↗

Highly Effective, Low Toxicity, Low Environmental Impact Total Flooding Fire Suppressants

Halon 1301 (CF3Br) has been used for decades as the primary fire suppression agent for areas where powder agents cannot be used because of concerns for sensitive equipment. Halon 1301 is an excellent extinguishing agent, effective at about 3% in air and quite non-toxic. It has an effective exposure limit much greater than its extinguishing concentration, so it can be used in normally occupied areas. The ability of a chemical to destroy stratospheric ozone is its ozone-depletion potential (ODP). ODP is the amount of ozone destroyed per pound of a chemical, relative to the standard CFC-11 with an ODP = 1.0. Because halons have been implicated in stratospheric ozone depletion, their production was stopped at the end of 1995 under the provisions of the Montreal Protocol plus later amendments. In the US, the Clean Air Act Amendments of 1990, Presidential directives, and DoD Directive 6050.9 implemented this phaseout. These regulations and penalties have provided strong incentives for US businesses to decrease CFC use. The Omnibus Budget Reconciliation Act of 1989 mandates high Federal taxes on CFCs and halons, designed to price them out of the market. The taxes also capture for the government the windfall profits that would otherwise go to producers as scarcity drives up prices. Several replacements have been developed for Halon 1301. One is carbon dioxide, which has been used as a firefighting agent for many years. However, a high concentration of carbon dioxide is necessary to inert fuels. The effective concentration for inerting with carbon dioxide is approximately 29%, which is above the concentration lethal to humans. HFC-227ea is being used extensively to replace Halon 1301 systems in nominally occupied areas and some normally unoccupied areas. However, since the effective concentration of HFC-227ea is about three to four times that of Halon 1301 the extinguishing systems have to be larger and new extinguishing systems have to be installed. HFC-125 is also being sold as an extinguishing agent (Nimitz). It has problems similar to HFC-227ea, with a greater concentration needed for effectiveness and the need to use a larger system. This is a particularly onerous penalty in aircraft and spacecraft, where weight and space are extremely important, and substitution is often impossible in existing aircraft due to space limitations.

Glass, S. M.↗

Update: HFC 245fa Blown Foam Development with External Tank Spray Foams

The Marshall Space Flight Center (MSFC) Thermal Protection Systems (TPS) Materials Research Laboratory is currently investigating environmentally friendly blowing agents for use in the insulations of the Space Shuttle's External Tank. The original TPS foam materials of the External Tank were blown with chlorofluorocarbon 11, which is now regulated because of its high Ozone Depletion Potential (ODP). Hydrochlorofluorocarbons (HCFCs), with an ODP that is one tenth that of CFCs, have been widely adopted as an interim blowing agent in urethane insulations. In FY96, Lockheed Martin completed the production qualification and validation of HCFC 141b blown insulations. Because of the expected limited commercial lifetime of HCFC 141b, research efforts are underway to identify and develop alternatives with zero ODP. HFC245fa (1,1,1,3,3-pentaflouropropane) has been chosen by the manufacturer as a third-generation blowing agent to be marketed commercially. Preliminary work evaluating this third-generation candidate has demonstrated promising material mechanical property data. Favorable results from small-scale spray activities have justified evaluations using production foam processing spray parameters. With the scale-up of the spray equipment, however, additional processing issues have been identified. This paper will present data collected to date regarding the use of this blowing agent in External Tank spray foams.

Davis, S.↗

A Thermal Infrared Radiation Parameterization for Atmospheric Studies

This technical memorandum documents the longwave radiation parameterization developed at the Climate and Radiation Branch, NASA Goddard Space Flight Center, for a wide variety of weather and climate applications. Based on the 1996-version of the Air Force Geophysical Laboratory HITRAN data, the parameterization includes the absorption due to major gaseous absorption (water vapor, CO2, O3) and most of the minor trace gases (N2O, CH4, CFCs), as well as clouds and aerosols. The thermal infrared spectrum is divided into nine bands. To achieve a high degree of accuracy and speed, various approaches of computing the transmission function are applied to different spectral bands and gases. The gaseous transmission function is computed either using the k-distribution method or the table look-up method. To include the effect of scattering due to clouds and aerosols, the optical thickness is scaled by the single-scattering albedo and asymmetry factor. The parameterization can accurately compute fluxes to within 1% of the high spectral-resolution line-by-line calculations. The cooling rate can be accurately computed in the region extending from the surface to the 0.01-hPa level.

Chou, Ming-Dah↗

Contributions of a Tunable Diode Laser Instrument (ATLAS) to the Stratospheric Ozone Depletion Question

The Airborne Tunable Laser Absorption Spectrometer - ATLAS - was designed and built at the NASA Ames Research Center and operates on the NASA ER-2 high altitude research aircraft. ATLAS has taken part in a number of important polar and mid-latitude research campaigns, since 1987, focused on various aspects of stratospheric ozone chemistry and dynamics. The chief measurement carried out by the ATLAS second harmonic diode laser spectrometer is of the important atmospheric tracer N2O. Using N2O as an inert tracer we have been able to gain significant new information on polar vortex dynamics and on the correlations of several important long-lived tracers in the stratosphere. The correlation of N2O with NOy (total reactive nitrogen) has been shown to be linear for a great variety of unperturbed stratospheric conditions, and the breakdown of this correlation has been used to detect denitrification by PSCs in the polar vortex, especially in the Antarctic spring. Denitrification is an important step in the process of ozone hole formation in the austral spring. Correlations of N2O with CFCs and CH4 have led to improved estimates of atmospheric lifetimes of these important molecules. Finally the correlation of N2O with CO2, the latter now being measured with great precision by a new instrument on the ER-2, has led to a significant new tool for studying horizontal and vertical mixing in the lower stratosphere, a tool which is very useful in assessing the potential effects of high speed civil transport aircraft in the lower stratosphere. A new, light-weight version of ATLAS is currently being built for unmanned high altitude aircraft, specifically the new Perseus vehicle. We will give a brief description of this effort.

Loewenstein, Max↗

Monitoring Trace Contaminants in Air Via Ion Trap Mass Spectrometry

Recent passage of the Clean Air Act with its stricter regulation of toxic gas emissions, and the ever-growing number of applications which require faster turnaround times between sampling and analysis are two major factors which are helping to drive the development of new instrument technologies for in-situ, on-line, real-time monitoring. The ion trap, with its small size, excellent sensitivity, and tandem mass spectrometry capability is a rapidly evolving technology which is well-suited for these applications. In this paper, we describe the use of a commercial ion trap instrument for monitoring trace levels of chlorofluorocarbons (CFCs) and volatile organic compounds (VOCs) in air. A number of sample introduction devices including a direct transfer line interface, short column GC, and a cryotrapping interface are employed to achieve increasing levels of sensitivity. MS, MS/MS, and MS/MS/MS methods are compared to illustrate trade-offs between sensitivity and selectivity. Filtered Noise Field (FNF) technology is found to be an excellent means for achieving lower detection limits through selective storage of the ion(s) of interest during ionization. Figures of merit including typical sample sizes, detection limits, and response times are provided. The results indicate the potential of these techniques for atmospheric assessments, the High Speed Research Program, and advanced life support monitoring applications for NASA.

Palmer, Peter T.↗

Upper Tropospheric/Lower Stratospheric Distribution of Reactive Nitrogen and Ozone

In-situ measurements of a large number of trace chemicals from upper troposphere/lower stratosphere (UT/LS) were performed with the NASA DC-8 aircraft during February/March 1994 over the Pacific Ocean (10 S to 60 N). Mixing ratios in the UT were relatively low in the warm tropical and subtropical air south of the polar jetstream (approx. =28 N) but increased sharply with latitude in the cold polar air north of the jetstream. At about 45 N, high concentrations of PAN (300 ppt) coexisted with extremely low (approx. = 20 ppt) concentrations of NOx. Elevated NOx levels in the UT did not always correspond to continental outflow conditions. Deepest penetrations into the stratosphere (550 ppb O3, 279 ppb NOx, and 350 K potential temperature) corresponded to a region that has been defined as the 'lowermost stratosphere' (LS) by Holton et al. Analysis of data shows that the mixing ratios of long-lived tracer species (e.g., CH4, HNO3, NOy, CFCs, HCFCs) are linearly correlated with those of O3 and N2O. A delta-NOY/delta-O3 of 0.0054 ppb/ppb and delta-NOy/delta-N2O of -0.081 ppb/ppb is in good agreement with other reported measurements from the DC-8. These slopes are however, somewhat steeper than those reported from the ER-2 studies. We find that the reactive nitrogen budget in the UT/LS is largely balanced with shortfalls that are no greater than 15%. A number of oxygenated species (e.g., acetone, H2O2) are present and may provide an important in-situ source of HOx in the UT/LS region.

Singh, H. S.↗

Evaluation of Chemistry-Climate Model Results using Long-Term Satellite and Ground-Based Data

Chemistry-climate models attempt to bring together our best knowledge of the key processes that govern the composition of the atmosphere and its response to changes in forcing. We test these models on a process by process basis by comparing model results to data from many sources. A more difficult task is testing the model response to changes. One way to do this is to use the natural and anthropogenic experiments that have been done on the atmosphere and are continuing to be done. These include the volcanic eruptions of El Chichon and Pinatubo, the solar cycle, and the injection of chlorine and bromine from CFCs and methyl bromide. The test of the model's response to these experiments is their ability to produce the long-term variations in ozone and the trace gases that affect ozone. We now have more than 25 years of satellite ozone data. We have more than 15 years of satellite and ground-based data of HC1, HN03, and many other gases. I will discuss the testing of models using long-term satellite data sets, long-term measurements from the Network for Detection of Stratospheric Change (NDSC) , long-term ground-based measurements of ozone.

Stolarski, Richard S.↗

Change in ozone trends at southern high latitudes

Long-term ozone variations at 60-70degS in spring are investigated using ground-based and satellite measurements. Strong positive correlation is shown between year-to-year variations of ozone and temperature in the Antarctic collar region in Septembers and Octobers. Based on this relationship, the effect of year-to-year variations in vortex dynamics has been filtered out. This process results in an ozone time series that shows increasing springtime ozone losses over the Antarctic until the mid-1990s. Since approximately 1997 the ozone losses have leveled off. The analysis confirms that this change is consistent across all instruments and is statistically significant at the 95% confidence level. This analysis quantifies the beginning of the recovery of the ozone hole, which is expected from the leveling off of stratospheric halogen loading due to the ban on CFCs and other halocarbons initiated by the Montreal Protocol.

Yang, E.-S.↗

On detecting a trend in the residual circulation from observations of column HCl

The troposphere is the part of the atmosphere where people live. The troposphere goes up to about 12 km above the earth over places at middle latitudes like Washington, D.C. The next layer of air up in the atmosphere is called the stratosphere. The tropopause separates the troposphere and stratosphere. Most of the ozone in the atmosphere is in the stratosphere where it protects people from the harmful rays in sunlight. Near the earth s surface, ozone is a pollutant. In general, air travels from the troposphere to the stratosphere through upward motion in the tropics. Most of the air comes back down to the troposphere at middle latitudes. The so-called "stratospheric residual circulation" moves the air in the stratosphere from the tropics to the middle latitudes. In this way, the amount of air that moves out of the stratosphere into the troposphere at middle latitudes depends on the strength of the residual circulation. This overturning of the atmosphere is important as it brings chemicals produced by the activities of people into the stratosphere. Most notable are chlorofluorocarbons (CFCs) that destroy stratospheric ozone. The transport of air out of the stratosphere removes ozone-destroying chemicals, but also brings ozone into the troposphere.

Olsen, M. A.↗

The Governing Processes and Timescales of Stratosphere-to-Troposphere Transport and its Contribution to Ozone in the Arctic Troposphere

We used the seasonality of a combination of atmospheric trace gases and idealized tracers to examine stratosphere-to-troposphere transport and its influence on tropospheric composition in the Arctic. Maximum stratosphere-to-troposphere transport of CFCs and O3 occurs in April as driven by the Brewer-Dobson circulation. Stratosphere-troposphere exchange (STE) occurs predominantly between 40 deg N to 80 deg N with stratospheric influx in the mid-latitudes (30-70 deg N) accounting for 67.81 percent of the air of stratospheric origin in the Northern Hemisphere extratropical troposphere. Transport from the lower stratosphere to the lower troposphere (LT) takes three months on average, one month to cross the tropopause, the second month to travel from the upper troposphere (UT) to the middle troposphere (MT), and the third month to reach the LT. During downward transport, the seasonality of a trace gas can be greatly impacted by wet removal and chemistry. A comparison of idealized tracers with varying lifetimes suggests that when initialized with the same concentrations and seasonal cycles at the tropopause, trace gases that have shorter lifetimes display lower concentrations, smaller amplitudes, and earlier seasonal maxima during transport to the LT. STE contributes to O3 in the Arctic troposphere directly from the transport of O3 and indirectly from the transport of NOy . Direct transport of O3 from the stratosphere accounts for 78 percent of O3 in the Arctic UT with maximum contributions occurring from March to May. The stratospheric contribution decreases significantly in the MT/LT (20.25 percent of total O3) and shows a very weak March.April maximum. Our NOx budget analysis in the Arctic UT shows that during spring and summer, the stratospheric injection of NO y-rich air increases NOx concentrations above the 20 pptv threshold level, thereby shifting the Arctic UT from a regime of net photochemical ozone loss to one of net production with rates as high as +16 ppbv/month.

Liang, Q.↗

Chemical Loss of Polar Ozone: Present Understanding and Remaining Uncertainties

Not long after the discovery of the Antarctic ozone hole, it was established that halogen compounds, supplied to the atmosphere mainly by anthropogenic activities, are the primary driver of polar ozone loss. We will briefly review the chemical mechanisms that cause polar ozone loss and the early evidence showing the key role played by anthropogenic halogens. Recently, stratospheric halogen loading has leveled off, due to adherence to the Montreal Protocol and its amendments that has essentially banned CFCs (chlorofluorocarbons) and other halocarbons. We will describe recent reports of the first stage of recovery of the Antarctic ozone hole (e.g., a statistically significant slowing of the downward trend), associated with the leveling off of stratospheric halogens. Despite this degree of understanding, we will discuss the tendency of photochemical models to underestimate the observed rate of polar ozone loss and a hypothesis that has recently been put forth that might resolve this discrepancy. Finally, we will briefly discuss chemical loss of Arctic ozone, which

climate change↗

Permanent Sequestration of Emitted Gases in the Form of Clathrate Hydrates

Underground sequestration has been proposed as a novel method of permanent disposal of harmful gases emitted into the atmosphere as a result of human activity. The method was conceived primarily for disposal of carbon dioxide (CO2, greenhouse gas causing global warming), but could also be applied to CO, H2S, NOx, and chorofluorocarbons (CFCs, which are super greenhouse gases). The method is based on the fact that clathrate hydrates (e.g., CO2 6H2O) form naturally from the substances in question (e.g., CO2) and liquid water in the pores of sub-permafrost rocks at stabilizing pressures and temperatures. The proposed method would be volumetrically efficient: In the case of CO2, each volume of hydrate can contain as much as 184 volumes of gas. Temperature and pressure conditions that favor the formation of stable clathrate hydrates exist in depleted oil reservoirs that lie under permafrost. For example, CO2-6H2O forms naturally at a temperature of 0 C and pressure of 1.22 MPa. Using this measurement, it has been calculated that the minimum thickness of continuous permafrost needed to stabilize CO2 clathrate hydrate is only about 100 m, and the base of the permafrost is known to be considerably deeper at certain locations (e.g., about 600 m at Prudhoe Bay in Alaska). In this disposal method, the permafrost layers over the reservoirs would act as impermeable lids that would prevent dissociation of the clathrates and diffusion of the evolved gases up through pores.

Duxbury, N.↗

Identifying the Molecular Origin of Global Warming

We have investigated the physical characteristics of greenhouse gases (GHGs) to assess which properties are most important in determining the efficiency of a GHG. Chlorofluorcarbons (CFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), nitrogen fluorides, and various other known atmospheric trace molecules have been included in this study. Compounds containing the halogens F or Cl have in common very polar X-F or X-Cl bonds, particularly the X-F bonds. It is shown that as more F atoms bond to the same central atom, the bond dipoles become larger as a result of the central atom becoming more positive. This leads to a linear increase in the total or integrated XF bond dipole derivatives for the molecule, which leads to a non-linear (quadratic) increase in infrared (IR) intensity. Moreover, virtually all of the X-F bond stretches occur in the atmospheric IR window as opposed to X-H stretches, which do not occur in the atmospheric window. It is concluded that molecules possessing several F atoms will always have a large radiative forcing parameter in the calculation of their global warming potential. Some of the implications for global warming and climate change are discussed.

Bera, Partha P.↗

Overview of the Airborne Tropical TRopopause EXperiment (ATTREX)

The NASA Airborne Tropical TRopopause EXperiment (ATTREX) is a series of airborne campaigns focused on understanding physical processes in the Tropical Tropopause Layer (TTL) and their role in atmospheric chemistry and climate. ATTREX is using the high-altitude, long-duration NASA Global Hawk Unmanned Air System to make in situ and remote-sensing measurements spanning the Pacific. A particular ATTREX emphasis is to better understand the dehydration of air as it passes through the cold tropical tropopause region. The ATTREX payload contains 12 in situ and remote sensing instruments that measure water vapor, clouds, multiple gaseous tracers (CO, CO2, CH4, NMHC, SF6, CFCs, N2O), reactive chemical compounds (O3, BrO, NO2), meteorological parameters, and radiative fluxes. ATTREX flight series have been conducted in the fall of 2011 from Armstrong Flight Research Center (AFRC) in California, in the winter of 2013 from AFRC, and in the winter/spring of 2014 from Guam. The first two flight series provided extensive sampling of the central and eastern Pacific, whereas the last flight series permitted sampling in the western Pacific. The sampling strategy has primarily involved repeated ascents and descents through the depth of the TTL (about 13-19 km). Over 100 TTL profiles were obtained on each flight series. The ATTREX dataset includes TTL water vapor measurements with unprecedented accuracy, ice crystal size distributions and habits. The cloud and water measurements provide unique information about TTL cloud formation, the persistence of super-saturation with respect to ice, and dehydration. The plethora of tracers measured on the Global Hawk flights are providing unique information about TTL transport pathways and time scales. The meteorological measurements are revealing dynamical phenomena controlling the TTL thermal structure, and the radiation measurements are providing information about heating rates associated with TTL clouds and water vapor. This presentation will provide an overview of the ATTREX flights, examples of measurements from the flights, and plans for modeling/analysis of the ATTREX dataset.

ATTREX↗

Overview of the Airborne Tropical TRopopause EX

The NASA Airborne Tropical TRopopause EXperiment (ATTREX) is a series of airborne campaigns focused on understanding physical processes in the Tropical Tropopause Layer (TTL) and their role in atmospheric chemistry and climate. ATTREX is using the high-altitude, long-duration NASA Global Hawk Unmanned Air System to make in situ and remote-sensing measurements spanning the Pacific. A particular ATIREX emphasis is to better understand the dehydration of air as it passes through the cold tropical tropopause region. The ATTREX payload contains 12 in situ and remote sensing instruments that measure water vapor, clouds, multiple gaseous tracers (CO, CO2, CH4, NMHC, SF6, CFCs, N2O), reactive chemical compounds (O3, BrO, NO2), meteorological parameters, and radiative fluxes. ATTREX flight series have been conducted in the fall of 2011 from Armstrong Flight Research Center (AFRC) in California, in the winter of 2013 from AFRC, and in the winter/spring of 2014 from Guam. The first two f light series provided extensive sampling of the central and eastern Pacific, whereas the last flight series permitted sampling in the western Pacific. The sampling strategy has primarily involved repeated ascents and descents through the depth of the TTL (about 13-19 km). Over 100 TTL profiles were obtained on each flight series. The ATTREX dataset includes TTL water vapor measurements with unprecedented accuracy, ice crystal size distributions and habits. The cloud and water measurements provide unique information about TTL cloud formation, the persistence of supersaturation with respect to ice, and dehydration. The plethora of tracers measured on the Global Hawk flights are providing unique information about TTL transport pathways and time scales. The meteorological measurements are revealing dynamical phenomena controlling the TTL thermal structure, and the radiation measurements are providing information about heating rates associated with TTL clouds and water vapor. This presentation will provide an overview of the ATTREX flights, examples of measurements from the flights, and plans for modeling/analysis of the ATTREX dataset.

Airborne↗

Concerns for Ozone Recovery

Reactive halogen gases containing chlorine (Cl) or bromine (Br) can destroy stratospheric ozone via catalytic cycles. The main sources of atmospheric reactive halogen are the long-lived synthetic chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), carbon tetrachloride (CCl4), methyl chloroform (CH3CCl3), and bromine-containing halons, all of which persist in the atmosphere for years. These ozone-depleting substances are now controlled under the Montreal Protocol and its amendments. Natural methyl bromide (CH3Br) and methyl chloride (CH3Cl) emissions are also important long-lived sources of atmospheric reactive halogen. Rising concentrations of very-short-lived substances (VSLSs) with atmospheric lifetimes of less than half a year may also contribute to future stratospheric ozone depletion. A greater concern for ozone layer recovery is incomplete compliance with the Montreal Protocol, which will impact stratospheric ozone for many decades, as well as rising natural emissions as a result of climate change.

VSLS↗

Overview of the NASA Airborne Tropical TRopopause EXperiment (ATTREX)

The NASA Airborne Tropical TRopopause EXperiment (ATTREX) is a series of airborne campaigns focused on understanding physical processes in the Tropical Tropopause Layer (TTL) and their role in atmospheric chemistry and climate. ATTREX is using the high-altitude, long-duration NASA Global Hawk Unmanned Air System to make in situ and remote-sensing measurements spanning the Pacific. A particular ATTREX emphasis is to better understand the dehydration of air as it passes through the cold tropical tropopause region. The ATTREX payload contains 12 in situ and remote sensing instruments that measure water vapor, clouds, multiple gaseous tracers (CO, CO2, CH4, NMHC, SF6, CFCs, N2O), reactive chemical compounds (O3, BrO, NO2), meteorological parameters, and radiative fluxes.ATTREX flight series have been conducted in the fall of 2011 from Armstrong Flight Research Center (AFRC) in California, in the winter of 2013 from AFRC, and in the winterspring of 2014 from Guam. The first two flight series provided extensive sampling of the central and eastern Pacific, whereas the last flight series permitted sampling in the western Pacific. The sampling strategy has primarily involved repeated ascents and descents through the depth of the TTL (about 13-19 km). Over 100 TTL profiles were obtained on each flight series. The ATTREX dataset includes TTL water vapor measurements with unprecedented accuracy, ice crystal size distributions and habits. The cloud and water measurements provide unique information about TTL cloud formation, the persistence of supersaturation with respect to ice, and dehydration. The plethora of tracers measured on the Global Hawk flights are providing unique information about TTL transport pathways and time scales. The meteorological measurements are revealing dynamical phenomena controlling the TTL thermal structure, and the radiation measurements are providing information about heating rates associated with TTL clouds and water vapor.This presentation will provide an overview of the ATTREX flights, examples of measurements from the flights, and plans for modelinganalysis of the ATTREX dataset.

Jensen, Eric J.↗