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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 433 records · Page 24
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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 NTRS1982

Is there any chlorine monoxide in the stratosphere?

A ground based search for the 856.50137/cm R(9.5) and for the 859.76765 R(12.5) transitions of stratospheric (Cl-35)O was made in the solar absorption mode using an infrared heterodyne spectrometer. Lines due to stratospheric HNO3 and tropospheric OCS were detected, at about 0.3% absorption levels. The expected lines of ClO in this same region were not detected, even though the optical depth of the ClO lines should be on the order of 0.2% using currently accepted ClO abundances. These infrared measurements suggest that stratospheric ClO is at least a factor of 7 less abundant than is indicated by indirect in situ fluorescence measurements, and the upper limit of 2.4x10 to the 13th power molecules/sq cm to the integrated column density of ClO is a factor of over 4 less than is indicted by microwave measurements. Results imply that the release of fluorocarbon precursors of ClO may be significantly less important for the destruction of stratospheric ozone than was previously thought.

Rogers, J. D.↗
NASA NTRS1983

Is there any chlorine monoxide in the stratosphere?

A ground-based search for stratospheric 35-ClO was carried out using an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric HNO3 and tropospheric OCS were detected at about 0.2% absorptance levels, but the expected 0.1% lines of ClO in this same region were not seen. We find that stratospheric ClO is at least a factor of seven less abundant than is indicated by in situ measurements, and we set an upper limit of 2.3x10 to the 13th molecules/sq cm at the 95% confidence level for the integrated vertical column density of ClO. Our results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone (O3) than is currently thought.

Mumma, M. J.↗
NASA NTRS1983

Chlorine nitrate - The sole product of the ClO + NO2 + M recombination

A laser operating at 266 nm is used to photolyze the product of the ClO + NO2 + M reaction, and the yield of Cl atoms, measured by resonance fluorescence, is found to be identical with that from equivalent concentrations of ClONO2. This is interpreted as a strong indication that no other isomers are formed in the recombination reaction. Evidence for isomers is surveyed, and the apparent forward-and-reverse-rate constant discrepancy is explained as a probable uncertainty in the thermochemistry.

Margitan, J. J.↗
NASA NTRS1983

Is there any chlorine monoxide in the stratosphere?

A ground-based search for stratospheric 35-ClO was carried out using an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric HNO3 and tropospheric OCS were detected at about 0.2 percent absorptance levels, but the expected 0.1 percent lines of ClO in this same region were not seen. We find that stratospheric ClO is at least a factor of seven less abundant than is indicated by in situ measurements, and we set an upper limit of 2.3 x 10 to the 13th molecules/sq cm at the 95 percent confidence level for the integrated vertical column density of ClO. Our results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone (O3) than is currently thought. Previously announced in STAR as N83-27518

Mumma, M. J.↗
NASA NTRS1986

Application of an atmospheric pressure sampling mass spectrometer to chlorination reactions

An atmospheric pressure mass spectrometric sampling system, based on a free jet expansion was used to study certain M-Cl-O reactions at high temperatures. The apparatus enables the volatile species from a 1-atm chemical process to be directly identified with a mass spectrometer which operates at approx. 10 to the minus 8th power torr. Studies for both pure metals and alloys are discussed. It is shown that this mass spectrometer system aids in identifying the volatile species, and provides fundamental information on the reaction mechanism.

Jacobson, N. S.↗
NASA NTRS1986

Infrared line intensities of chlorine monoxide

Absolute infrared line intensities of several ClO lines in the rotational-vibrational (1-0) band were measured using infrared heterodyne spectroscopy near 12 microns. A measurement technique using combined ultraviolet absorption and infrared line measurements near 9.5 microns and 12 microns permitted an accurate determination of the column densities of O3 and ClO in the absorption cell and thus improved ClO line intensities. Results indicate ClO line and band intensities approximately 2.4 times lower than previous experimental results. Effects of possible failure of local thermodynamic equilibrium conditions in the absorption cell and the implication of the results for stratospheric ClO measurements in the infrared are discussed.

Kostiuk, T.↗
NASA NTRS1986

Reductions of Antarctic ozone due to synergistic interactions of chlorine and bromine

The vertical column density of ozone observed in October over Antarctica has fallen precipitously over the past 10 yr. The concentration at Halley Bay (76 deg S, 27 deg W), expressed conventionally in Dobson units (DU), has dropped from about 300 DU in 1975 to less than 200 DU in 1984. Values in 1985 were even lower, comparable with the lowest values recorded anywhere on earth. It is suggested here that the loss of O3 in Antarctica may be attributed to catalysis of O3 recombination by a scheme in which the rate-limiting step is defined by the reaction of ClO + BrO - Cl + Br + O2. Concentrations of NO2 must be low and heterogeneous reactions involving particles in the polar stratospheric clouds must be an important element of the relevant chemistry. Industrial sources make important contributions to the contemporary budgets of both BrO and ClO and are likely to grow significantly in the future.

Mcelroy, M. B.↗
NASA NTRS1986

The Antarctic ozone minimum - Relationship to odd nitrogen, odd chlorine, the final warming, and the 11-year solar cycle

Photochemical calculations along 'diabatic trajectories' in the meridional phase are used to search for the cause of the dramatic springtime minimum in Antarctic column ozone. The results indicate that the minimum is principally due to catalytic destruction of ozone by high levels of total odd nitrogen. Calculations suggest that these levels of odd nitrogen are transported within the polar vortex and during the polar night from the middle to upper stratosphere and lower mesosphere to the lower stratosphere. The possibility that these levels are related to the 11-year solar cycle and are increased by enhanced formation in the thermosphere and mesosphere during solar maximum conditions is discussed.

Callis, L. B.↗
NASA NTRS1986

The formation of volatile corrosion products during the mixed oxidation-chlorination of cobalt at 650 C

The reaction of cobalt with 1 pct Cl2 in 1, 10, and 50 pct O2/Ar atmospheres has been studied at 650 C with thermogravimetry and mass spectrometry. The principal vapor species appear to be CoCl2 and CoCl3. In all cases, CoCl2(s) forms at the oxide/metal interface and equilibration of the volatile chlorides with Co3O4 does not occur in the early stages of the reaction. In the 1 pct Cl2 1 pct O2-Ar case, continuous volatilization occurs. In the 1 pct Cl2-10 pct O2-Ar and 1 pct CL2-50 pct O2-Ar cases, volatilization occurs only in the first few minutes of reaction. Afterwards, the reaction is predominantly oxidation.

Jacobson, N. S.↗
NASA NTRS1988

Antarctic chlorine chemistry - Possible global implications

Occurrence of heterogeneous reactions on the surface of polar stratospheric clouds (PSC) is a necessary component of the Cl-related chemical mechanisms proposed to explain the recently observed decrease of O3 during Antarctic spring. A one-dimensional model is used to assess the impact of these heterogeneous reactions on future global O3 trends if they were to occur on the global aerosol layer. The impact of these reactions on the concentration of Cl species in the present-day atmosphere is also calculated. The reaction (ClNO3 + HCl) could have a large impact on stratospheric O3. A fast rate for this reaction would greatly enhance the present concentration of ClO and reduce the abundance of HCl in the lower stratosphere. Because of the large differences between the Antarctic and global environments, the calculated global O3 trends are smaller than those calculated for Antarctica.

Rodriguez, Jose M.↗
NASA NTRS1988

In situ observations of ClO in the Antarctic: Evidence for chlorine catalyzed destruction of ozone

Results from a series of 12 ER-2 aircraft flights into the Antarctic polar vortex are summarized. These in situ data define the spatial and temporal distribution of ClO as the aircraft flew at an altitude of approx. 18 km from Punta Arenas (54 deg S latitude) to the base of the Palmer Peninsula (72 deg S latitude), executed a rapid descent to approx. 13 km, turned north and climbed bach to approximately 18 km, returning to Punta Arenas. A general pattern in the ClO distribution is reported: mixing ratios of approximately 10 ppt are found at altitude in the vicinity of 55 deg S increasing to 50 ppt at 60 degrees S. In the vicinity of 65 deg S latitude a steep gradient in the ClO mixing ratio is observed. At a fixed potential temperature, the ClO mixing ratio through this sharp transition increases by an order of magnitude within a very few degrees of latitude, thus defining the edge of the chemical containment vessel. From the edge of that containment vessel to the southern extension of the flights, 72 deg S, a dome of slowly increasing ClO best describes the distribution. Conclusion are drawn from the data.

Anderson, J. G.↗
NASA NTRS1989

Chemistry and transport in a three-dimensional stratospheric model - Chlorine species during a simulated stratospheric warming

The distributions in the stratosphere of a variety of chemical species were calculated for a 6-day period during the February 1979 stratospheric major warming, using winds derived from a spectral forecast model which included O(x), NO(x), HO(x), and ClO(x) chemistries as well as longitudinally varying reaction rate coefficients and photolysis rates for these molecules. The results obtained indicate a particular importance of chemistry and transport for the Cl-containing species ClO, ClONO2, HCl, and HOCl. Dynamical effects dominate the variability of HCl, while diurnal effects dominate that of ClONO2 and ClO. The effects of strong planetary wave activity may be seen in terms of large longitudinal variability of the total HCl and ClONO columns in the stratosphere; in the middle and high northern latitudes, it is sufficiently large to exceed the diurnal variability of the column.

Kaye, Jack A.↗