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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
NASA NTRS1978

Ozone profiles and chemical loss rates in the tropical stratosphere deduced from backscatter ultraviolet measurements

Analysis of data obtained by the backscatter ultraviolet (BUV) experiment on the Atmosphere Explorer E satellite has provided equatorial ozone mixing ratio profiles for equinox and solstice conditions. The combination of these results with a pure oxygen chemical model yields the rate of odd oxygen loss due to the sum of the odd hydrogen, nitrogen, and chlorine cycles. Use of recent mid-latitude stratospheric measurements of HO(x), NO(x), and ClO(x) with the BUV data provides an independent calculation of the catalytic loss. Below 45 km the agreement between the two sets of loss rates is satisfactory. At higher altitudes the odd hydrogen cycle provides far more O(x) loss than can be tolerated by the BUV measurements if the photodissociation of O2 is the only source and has the currently accepted magnitude. The results suggest either a tropical HO(x) concentration smaller than is now believed or the presence of a very large source of odd oxygen in the upper stratosphere and lower mesosphere.

Frederick, J. E.↗
NASA NTRS1979

The photolysis of chlorine in the presence of ozone, nitric acid and nitrogen dioxide

The following three systems were investigated: the Cl2-O3 system, the Cl2-O2-NO system and the Cl2-NO2-M system. In the first system, the reaction between ClO and O3, the reaction between OClO and O3, and the mechanism of the Cl2-O3 system were studied. In the second system, the reaction between ClOO and NO was investigated. In the last system, the reaction between Cl and NO2 was investigated as well as the kinetics of the chemiluminescence of the Cl-NO2-O3 reaction. In the first system, Cl2 was photolyzed at 366 nm in the presence of O3 within the temperature range 254-297 K. O3 was removed with quantum yields of 5.8 + or - 0.5, 4.0 + or - 0.3, 2.9 + or - 0.3 and 1.9 + or - 0.2 at 297, 283, 273, and 252 K respectively, invariant to changes in the initial O3 or Cl2 concentration, the extent of conversion or the absorbed intensity, I sub a. The addition of nitrogen had no effect on -phi(03). The Cl2 removal quantum yields were 0.11 + or - 0.02 at 297 K for Cl2 conversions of about 30%, much higher than expected from mass balance considerations based on the initial quantum yield of 0.089 + or - 0.013 for OClO formation at 297 K. The final chlorine-containing product was Cl2O7. It was produced at least in part through the formation of OClO as an intermediate which was also observed with an initial quantum yield of phi sub i(OClO) = 2500 exp(-(3025 + or - 625)/T) independent of (O3) or I sub a.

Stuper, W. W.↗
NASA NTRS1978

Stratospheric-related research using the shock tube

The capabilities of shock tubes used in stratospheric-related research are considered, and the results of three independent shock tube research projects are reported. The studies are concerned with the evaluation of stratospheric ozone depletion. In the first experiment, photoabsorption cross sections of Freon 11 and 12 at stratospheric temperatures were measured using rarefaction waves. In the second experiment, reaction-rate coefficients were determined from measurements made behind reflected shock waves. In the third experiment, electronic-transition moments of the O2 Schumann-Runge system and the A2Pi-X2Pi system of ClO were deduced from intensity measurements made behind the incident shock.

Cooper, D. M.↗
NASA NTRS1978

The reaction of ClOO with NO

Reactions of ClOO with NO were studied by photolyzing Cl2 in the presence of NO and O2 with or without added N2. Steady-state photolysis results show that two reactions of ClOO and NO can occur, one forming ClO and the other forming ClNO. The rate constants for the reactions are calculated, and their values indicate that the reactions are probably not important in the stratosphere.

Wongdontri-Stuper, W.↗
NASA NTRS1979

Rate constant measurements for the reaction Cl + CH2O yields HCl + CHO Implications regarding the removal of stratospheric chlorine

The flash photolysis resonance fluorescence technique was employed to investigate the rate constant for the reaction Cl + CH2O yields HCl + CHO from 223 to 323 K. An Arrhenius fit of the data gives a rate constant equal to (1.09 + or - 0.40) x 10 to the -10th exp/-(131 + or - 98)/T/ in units of cu cm/molecule per sec. The results are compared to two very recent kinetic studies and are assessed in view of the reaction's role in disrupting the Cl-ClO stratospheric ozone depletion chain.

Anderson, P. C.↗
NASA NTRS1980

Sensitivity studies and laboratory measurements for the laser heterodyne spectrometer experiment

Several experiments involving spectral scanning interferometers and gas filter correlation radiometers (ref. 2) using limb scanning solar occultation techniques under development for measurements of stratospheric trace gases from Spacelab and satellite platforms are described. An experiment to measure stratospheric trace constituents by Laser Heterodyne Spectroscopy, a summary of sensitivity analyses, and supporting laboratory measurements are presented for O3, ClO, and H2O2 in which the instrument transfer function is modeled using a detailed optical receiver design.

Allario, F.↗
NASA NTRS1980

Atmospheric bromine and ozone perturbations in the lower stratosphere

The role of bromine compounds in the photochemistry of the natural and perturbed stratosphere has been reexamined using an expanded reaction scheme and the results of recent laboratory studies of several key reactions. The most important finding is that through the reaction BrO + ClO yielding Br + Cl + O2 there is a synergistic effect between bromine and chlorine which results in an efficient catalytic destruction of ozone in the lower stratosphere. One-dimensional photochemical model results indicate that BrO is the major bromine species throughout the stratosphere, followed by BrONO2, HBr, HOBr and Br. It is shown from the foregoing that bromine is more efficient than chlorine as a catalyst for destroying ozone, and the implications for stratospheric ozone of possible future growth in the industrial and agricultural use of bromine are discussed. Bromine concentrations of 20 pptv (2 x 10 to the -11th power), as suggested by recent observations, can decrease the present-day integrated ozone column density by 2.4%, and can enhance ozone depletion from steady-state chlorofluoromethane release at 1973 rates by a factor of 1.1-1.2.

Yung, Y. L.↗
NASA NTRS1980

Possible existence and chemistry of ClO.O2 in the stratosphere

The influence of the existence and chemistry of the possible atmospheric constituent ClO.O2 on current models of stratospheric photochemistry is discussed. It is suggested that the formation of an asymmetric ClO.O2 complex may explain the observed suppression of the quantum yield in the chlorine-photosensitized decomposition of ozone in the presence of O2, and that the presence of the ClO.O2 formed may account for the current discrepancy between measurements and theoretical predictions of stratospheric ClO mixing ratio profiles. The presence of stratospheric ClO.O2 is also invoked as a possible mitigating influence on present estimates of ozone destruction due to chlorofluoromethane release.

Prasad, S. S.↗
NASA NTRS1980

Stratospheric free chlorine measured by balloon-borne in situ resonance fluorescence

Eight balloon-borne in situ measurements of ClO in the stratosphere are analyzed and are compared with recent model calculations. While the use of in situ stratospheric studies of free radicals to test models by comparing observed and predicted concentration profiles is essential for a prognosis of changes in stratospheric ozone, resulting from future changes in stratospheric ozone, such studies provide only limited insight into the nature of stratospheric photochemistry, because natural variability and the large number of fast reactions which compete in the coupling among the key radicals frustrate a detailed comparison between a mean distribution provided by the models and an instantaneous distribution provided by a single observation.

Anderson, J. G.↗
NASA NTRS1981

Stratospheric trace constituent profile retrievals using laser heterodyne radiometer IR limb sensing spectra

A retrieval technique for high resolution IR solar occultation limb sensing data is described for profiling stratospheric trace constituents. Remote measurement of ClO during sunset in the 24-45-km region with a 2-km height resolution is chosen as an example. Two types of instruments are considered: a laser heterodyne radiometer with line resolving spectral resolution and an interferometer spectrometer with a fixed slit width of 0.02/cm. It is pointed out that a multichannel approach is necessary with the heterodyne instrument for improved retrieval accuracy. The error analysis indicates the relative sizes of instrument noise and other sources of error in the retrieval of altitude profiles with high (2-km) vertical resolution.

Majumdar, A. K.↗
NASA NTRS1981

AFGL trace gas compilation - 1980 version

A new edition of the AFGL trace gas compilation is now available. Absorption line parameters of positions, intensities, and half-widths are given for the major bands of thirteen gases covering the spectral region from 0 to 10,000/cm. In addition to updating the original gases (NO, SO2, NO2, and NH3), the molecules HNO3, OH, HF, HCl, HBr, HI, ClO, OCS, and H2CO have been added to the compilation. The sources for the additions and modifications are described.

Rothman, L. S.↗
NASA NTRS1981

Atlas of absorption lines from 0 to 17 900 cm(-1)

Plots of absorption line strength versus line position for wavenumbers from 0 to 17,900 cm(-1) are shown for 20 atmospheric gases (H2O, CO2, O3, N2O, CO, CH4, O2, NO, SO2, NO2, NH3, HNO3, OH, HF, HCl, HBr, HI, ClO, OCS, H2CO). Also shown are similar plots of lower-state energy values for adsorption lines for the strongly adsorbing atmospheric gases (H2O, CO2, O3, and CH4) for wavenumbers from 0 to 5000 cm(-1).

Park, J. H.↗
NASA NTRS1981

Ground-based mm-wave emission spectroscopy for the detection and monitoring of stratospheric ozone

The molecular rotational spectrum of ozone is quite rich in the mm-wave region from 50 to 300 GHz. An apparatus, which was developed primarily for detection and measurement of stratospheric ClO and other trace molecules, is found to be well suited also for the observation of ozone lines. The collecting antenna of the apparatus is a simple mm-waveguide feedhorn. The detector is a superheterodyne mixer using a special high frequency Schottky diode and a klystron local oscillator. The spectrometer is a 256 channel filter bank with 1 MHz resolution per channel. The apparatus is believed to be the first ground-based mm-wave instrument having the capability of obtaining data of sufficient quality to make use of the inversion technique. The ground based radio technique is most sensitive to changes in vertical distribution in the region above 25 km, a region which is difficult to sample by other techniques.

Parrish, A.↗
NASA NTRS1981

Spectral line inversion for sounding of stratospheric minor constituents by infrared heterodyne technique from balloon altitudes

A combination of two different techniques for the inversion of infrared laser heterodyne measurements of tenuous gases in the stratosphere by solar occulation is presented which incorporates the advantages of each technique. An experimental approach and inversion technique are developed which optimize the retrieval of concentration profiles by incorporating the onion peel collection scheme into the spectral inversion technique. A description of an infrared heterodyne spectrometer and the mode of observations for solar occulation measurement is presented, and the results of inversions of some synthetic ClO spectral lines corresponding to solar occulation limb-scans of the stratosphere are examined. A comparison between the new techniques and one of the current techniques indicates that considerable improvement in the accuracy of the retrieved profiles can be achieved. It is found that noise affects the accuracy of both techniques but not in a straightforward manner since there is interaction between the noise level, noise propagation through inversion, and the number of scans leading to an optimum retrieval.

Abbas, M. M.↗
NASA NTRS1982

A stratospheric chemical instability

The equations which determine partitioning of Cl(x) in steady state have multiple (three) solutions under conditions which might arise in the high-latitude winter stratosphere. Two of these solutions are stable, one is unstable, to infinitesimal perturbations. The relative stability of solutions is examined by subjecting the system to finite perturbations. The more stable solution is found to eliminate the less stable when semi-infinite volumes of the two solutions are placed in contact. The high-ClO, low NO2 solution is more stable under most conditions. Transitions from less to more stable states are slow in winter but may occur more rapidly when the seasonal variation of insolation is taken into account.

Fox, J. L.↗
NASA NTRS1983

A two-dimensional photochemical model of the atmosphere. I Chlorocarbon emissions and their effect on stratospheric ozone

A two-dimensional photochemical model is used to examine changes to the ozone layer caused by emissions of CFCl3, CF2Cl2, CH3CCl3 and CCl4. The influence of a possible secular increase in tropospheric methane up to 2 percent per year was found to be small, although it acts to mask decreases in total ozone caused by the chlorocarbons. Increasing NO(x) emissions caused by industralization also tend to mask decreases in total ozone and may have caused total ozone to increase by about 1 percent. The model-calculated ozone decreases are estimated to be about 3 percent by 1980. This estimate is higher than estimates by similar models, although it is noted that CCl4 and CH3CCl3 emissions are included in the model in addition to CFCl3 and CF2Cl2. This is significant because the model indicates that CCl4 has dominated the ozone depletions so far, and knowledge of the historical emission rate of CCl4 to the atmosphere is incomplete. There remain sufficient significant disagreements between theoretical and observed concentrations and variabilities, particularly for odd nitrogen and ClO, to caution against assigning too much confidence in the calculated ozone depletion.

Gidel, L. T.↗
NASA NTRS1983

The retrieval of atmospheric constituent mixing-ratio profiles from solar absorption spectra

Methods used to determine various atmospheric gas distributions are summarized. The experimentally determined mixing ratio profiles (the mixing ratio of a gas is the ratio of the number of gas molecules to the number of air molecules) of some atmospheric gases are shown. In most in situ experiments stratospheric gas samples are collected at several altitudes by balloon, aircraft, or rocket. These samples are then analyzed by various methods. Mixing ratio profiles of Ci, ClO, and OH were determined by laser induced fluorescence of samples. Others have analyzed gas samples by gas chromatography in order to determine the molecular abundances of CCl2F2, CCl4, CCl3F, CFCl3, CF2Cl2, CHClF2, CH3CCl3, CH4, CO, C2Cl3F3, C2Cl4, C2HCl3, C2H2, C2H4, C2H6, C3H8, C6H6, C7H8, H2, and N2O.

Shaffer, W. A.↗
NASA NTRS1984

Passive microwave remote sensing of the atmosphere from satellites

Present and future satellite atmospheric sounding is discussed. Although present systems sound principally the temperature profile and the water vapor and precipitation abundances over ocean, future systems will measure other constituents such as O3, H2O2, and ClO, and will provide improved spatial resolution, retrieval accuracy, and altitude coverage for temperature and humidity. Present systems with only a few channels will be replaced by systems with 20 or more, and larger antennas with more sensitive radiometers will permit horizontal resolutions of 15 to 50 km or less, even from geosynchronous orbit. The success of imaging microwave spectrometers in penetrating clouds and in yielding uniquely accurate measurements ensure a growing role in operational and research systems for these remote sensing techniques.

Staelin, D. H.↗