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NASA NTRS1987

Infrared spectroscopic measurements of halogenated sink and reservoir gases in the stratosphere with the ATMOS instrument

The Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument recorded 19 sets of interferograms during solar occultations in both the Northern and Southern Hemispheres over the course of the Spacelab 3 mission. The resulting IR spectra furnish concentration profiles for over 25 atmospheric species. Attention is presently given to the volume mixing ratio profiles for HCl and HF in the 15-60-km altitude region, retrieved from northern sunsets and southern sunrises. The HF/HCl ratios deduced are in good agreement with model predictions. The total atmospheric chlorine at 50 km is nearly all in the form of HCl.

Raper, O. F.↗

NASA NTRS1986

Large area space qualified thermoelectrically (TE) cooled HgCdTe MW photovoltaic detectors for the Halogen Occultation Experiment (HALOE)

Large-area, HgCdTe MW photovoltaic detectors have been developed for the NASA-HALOE instrument scheduled for operation on the Upper Atmospheric Research Satellite. The photodiodes will be TE-cooled and were designed to operate in the 5.1-5.4 micron band at 185 K to measure nitric oxide concentrations in the atmosphere. The active area required 15 micron thick devices and a full backside common contact. Reflections from the backside contact doubled the effective thickness of the detectors. Optical interference from reflections was eliminated with a dual layer front surface A/R coating. Bakeout reliability was optimized by having Au metallization for both n and p interconnects. Detailed performance data and a model for the optical stack are presented.

Norton, P. W.↗

NASA NTRS1986

Design and performance of the halogen occultation experiment (HALOE) remote sensor

HALOE is an optical remote sensor that measures extinction of solar radiation caused by the earth's atmosphere in eight channels, ranging in wavelength from 2.5 to 10.1 microns. These measurements, which occur twice each satellite orbit during solar occultation, are inverted to yield vertical distributions of middle atmosphere ozone (O3), water vapor, nitrogen dioxide, nitric oxide, hydrogen fluoride, hydrogen chloride, and methane. A channel located in the 2.7 region is used to infer the tangent point pressure by measuring carbon dioxide absorption. The HALOE instrument consists of a two-axis gimbal system, telescope, spectral discrimination optics and a 12-bit data system. The gimbal system tracks the solar radiometric centroid in the azimuthal plane and tracks the solar limb in the elevation plane, placing the instrument's instantaneous field-of-view 4 arcmin down from the solar top edge. The instrument gathers data for tangent altitudes ranging from 150 km to the earth's horizon. Prior to an orbital sunset and after an orbital sunrise, HALOE automatically performs calibration sequences to enhance data interpretation. The instrument is presently being tested at the NASA Langley Research Center in preparation for launch on the Upper Atmosphere Research Satellite near the end of this decade. This paper describes the instrumenmt design, operation, and functional performance.

Baker, R. L.↗

NASA NTRS1989

Airborne measurements of stratospheric constituents over Antarctica in the austral spring, 1987. II - Halogen and nitrogen trace gases

The IR absorption spectra of the polar stratosphere, recorded by a Fourier transform spectrometer aboard the NASA DC-8 aircraft during the Airborne Antarctic Ozone Experiment, were used to derive vertical column amounts above flight altitude of HCl, HF, NO, NO2, ClONO2, and HNO3 in the region of disturbed ozone chemistry during September 1987. Significant reductions in the amounts of HCl, NO, NO2, and HNO3 were observed within the confines of the polar vortex, compared with amounts outside the vortex. When compared with the springtime observations by the same instrument in the Northern Hemisphere, the HCl and NO2 species displayed the most dramatic depletions. The results obtained are generally in agreement with the earlier ground measurements conducted at the McMurdo Station.

Coffey, M. T.↗

NASA NTRS1989

Solar sensor subsystems alignment check using solar scans for the Halogen Occultation Experiment

The alignment of a dual-axes sun sensor subsystem to a telescope having a multiple sensor subsystem is described. The sun sensor consists of two analog and one digital silicon detectors. The analog detectors are shadow mask type operating in the visible spectrum. The detectors are mounted for azimuth and elevation positioning of biaxial gimbals. The digital detector is a linear diode array that operates at a spectral position of 0.7 micron and is used for elevation positioning. The position signals correspond to relative angles between the sun sensor and the solar disk. These three detectors are aligned on an Invar structure which is mounted to a Cassegrain telescope. This telescope relays solar radiance to an eight channel detector subsystem operating in the infrared range from 2 to 10 microns. The test technique and results to check the boresight alignment of these two subsystems by scanning the solar disk will be reported. The boresight alignment for both the azimuth and elevation axes of the two detector subsystems is verified using this technique.

Jurczyk, S. G.↗

NASA NTRS1989

Proposed reference models for CO2 and halogenated hydrocarbons

The vertical distribution of carbon dioxide, halocarbons and their sink products, HCl and HF, have become available, mainly by means of balloon measurements. Most measurements were made at northern mid-latutudes, but some constituents were measured at tropical latitudes and in the Southern Hemisphere as well. An attempt is made here to combine the available data for presentation of reference models for CO2, CCl4 CCl3F, CCl2F2, CClF3, CF4, CCl2F-CClF2, CClF2-CClF2, CClF2-CF3, CF3-CF3, CH3Cl, CHClF2, CH3-CCl3, CBrClF2, CBrF3, HCl and HF.

Fabian, P.↗

NASA NTRS1990

Relative effects on global warming of halogenated methanes and ethanes of social and industrial interest

The relative potential global warming effects for several halocarbons (chlorofluorocarbons (CFC's)-11, 12, 113, 114, and 115; hydrochlorofluorocarbons (HCFC's) 22, 123, 124, 141b, and 142b; and hydrofluorocarbons (HFC's) 125, 134a, 143a, and 152a; carbon tetrachloride; and methyl chloroform) were calculated by two atmospheric modeling groups. These calculations were based on atmospheric chemistry and radiative convective models to determine the chemical profiles and the radiative processes. The resulting relative greenhouse warming when normalized to the effect of CFC-11 agree reasonably well as long as we account for differences between modeled lifetimes. Differences among results are discussed. Sensitivity of relative warming values is determined with respect to trace gas levels assumed. Transient relative global warming effects are analyzed.

Fisher, Donald A.↗

NASA NTRS1993

Calibration, testing and orbital performance of the halogen occultation experiment (HALOE) on the upper atmosphere research satellite

HALOE is an occultation viewing radiometer that requires part per million signal precision and characterization. Gas correlation radiometry is used to infer HF HCl, CH4 and NO concentrations, while broad band radiometry is used for temperature, pressure, O3, H2O and NO2. Validated results verify that goals have been met or exceeded in all channels. This was achieved through a comprehensive instrument analysis and calibration process on the ground and in orbit. Components and systems were put through a battery of tests in the lab. In orbit, a variety of exoatmospheric solar disk measurements are used for precise real time inferral of critical calibration parameters. In the end, technical success was based on the close interaction of scientist, engineer and data analysts. The accuracy and precision of HALOE species profiles are equal to any ever achieved from orbiting sensors.

Gordley, Larry L.↗

NASA NTRS1991

An overview of the halogen occultation experiment (HALOE)

The HALOE experiment will fly on the Upper Atmosphere Research Satellite (UARS) in the last quarter of 1991. The experiment uses the solar occultation limb sounding approach, in combination with gas filter and broadband radiometry to provide measurements of temperature profiles and key gases in the ClO(y), NO(y), and HO(y) chemical families of the middle atmosphere. The instrument has been characterized in great detail to determine gains, spectral response, noise, crosstalk, field-of-view, and thermal drift characteristics. A final end-to-end test using a gas cell to simulate the atmosphere demonstrated measurement repeatability to about 1 percent and agreement between measured and calculated signals to within about 1 percent to 3 percent. This latter agreement provides confidence in knowledge of both the hardware as well as the software.

Russell, James M., III↗

NASA NTRS1952

Velocity of action of oxygen, hydrogen sulfide, and halogens on metals

This report discusses a method of determining the rate of surface oxidation of a metal by the change in the color of the surface film produced by reactions with oxygen, chlorine, or iodine. The metals studied included iron, nickel, copper, zinc, cadmium, tin, lead, cobalt, and manganese. Tables are given for surface film thickness versus color for various times.

TIN↗

NASA NTRS1982

Matrix isolation infrared spectra of hydrogen halide and halogen complexes with nitrosyl halides

Matrix isolation infrared spectra of nitrosyl halide (XNO) complexes with HX and X2 (X = Cl, Br) are presented. The relative frequency shifts of the HX mode are modest (ClNO H-Cl, delta-nu/nu = -0.045; BrNO H-Br, delta-nu/nu = -0.026), indicating weak hydrogen bonds 1-3 kcal/mol. These shifts are accompanied by significant shifts to higher frequencies in the XN-O stretching mode (CIN-O HCl, delta-nu/nu = +0.016; BrN-O HBr, delta-nu/nu = +0.011). Similar shifts were observed for the XN-O X2 complexes (ClN-O Cl2, delta-nu/nu = +0.009; BrN-O-Br2, delta-nu/nu = +0.013). In all four complexes, the X-NO stretching mode relative shift is opposite in sign and about 1.6 times that of the NO stretching mode. These four complexes are considered to be similar in structure and charge distribution. The XN-O frequency shift suggests that complex formation is accompanied by charge withdrawal from the NO bond ranging from about .04 to .07 electron charges. The HX and X2 molecules act as electron acceptors, drawing electrons out of the antibonding orbital of NO and strengthening the XN-O bond. The implications of the pattern of vibrational shifts concerning the structure of the complexes are discussed.

Allamandola, Louis J.↗

NASA NTRS1993

Measurements of halogenated organic compounds near the tropical tropopause

The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude mid-troposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

Schauffler, S. M.↗

NASA NTRS1996

A Comparison of Measurements from ATMOS and Instruments Aboard the ER-2 Aircraft: Tracers of Atmospheric Transport and Halogenated Gases

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.

Chang, A. Y.↗

NASA NTRS1993

Measurements of Halogenated Organic Compounds near the Tropical Tropopause

The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8 deg N and 25.3 deg N during AASE 2. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 +/- 0.06 ppbv and 21.1 +/- 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude midtroposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

Schauffler, S. M.↗

NASA NTRS1997

Halogen and Sulfur Reactions Relevant to Polar Chemistry

It is widely hypothesized that catalytic cycles involving BrO(x) species play an important role in the episodic destruction of ground-level ozone which is observed in the springtime Arctic boundary layer, although the exact mechanism for production of BrO(x) radicals remains an open question [Barrie et al., Bottenheim et al.; Finlayson-Pitts et al., McConnell et al.] The critical evidence linking ozone depletion with BrO(x) chemistry is an observed negative correlation between ozone and filterable bromine [Bottenheim et al., Kieser et al.] In a recent field study of springtime Arctic boundary layer chemistry [Kieser et al.] ozone concentrations and ethane concentrations were found to be correlated; this observation suggests chlorine atoms (which react rapidly with ethane) may also be an important catalyst for ozone destruction under springtime Arctic conditions.

Wine, Paul H.↗

NASA NTRS1998

An Investigation of Aerosol Measurements from the Halogen Occultation Experiment: Validation, Size Distributions, Composition, and Relation to Other Chemical Species

The efforts envisioned within the original proposal (accepted February 1994) and the extension of this proposal (accepted February 1997) included measurement validations, the retrieval of aerosol size distributions and distribution moments, aerosol correction studies, and investigations of polar stratospheric clouds. A majority of the results from this grant have been published. The principal results from this grant are discussed.

Deshler, Terry↗

NASA NTRS1960

Adsorption of Halogenated Fire-Extinguishing Agents on Powders

The amounts of four different Freons adsorbed by carbon, silica gel, alumina, and molecular sieves were determined at pressures up to 225 lb/sq in. The carbon adsorbed 50 to 100 percent and the silica gels, 30 to 50 percent of their own weight of Freon. Several adsorbed systems were tested in a standard dry-powder extinguisher on a 5-sq-ft gasoline fire for their effectiveness in putting out a fire. One of the Freons (bromotrifluoromethane) and carbon extinguished fires about as well as bicarbonate powder and nitrogen.

Barduhn, Allen J.↗

NASA NTRS1999

Tropospheric Diagnostic Modeling Studies of PEM-Tropics Field Data: Investigation of the HO(x)/NO(x)/O3 Photochemical System and Its Coupling to Sulfur and Halogen Chemistry

Over the time period of this NASA grant the PI has helped plan and execute in the PEM-Tropics A field program. He has also helped organize and co-chair three data workshops which have focused on the detailed analysis of PEM-Tropics A data. His direct participation in these analyses has led to his major involvement in 10 manuscripts, 5 of which are in print, 3 in press, and 2 submitted. A complete list of papers is included in the report.

Davis, Douglas D.↗