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At least 271 records · Page 15

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.↗

High-resolution atmospheric spectroscopy using a diode laser heterodyne spectrometer

A tunable-diode-laser radiometer with a spectral resolution of 0.007/cm was used to obtain IR solar absorption spectra in the 9.1-11.1 micron region. Spectra exhibiting absorption by HNO3, CO2, O3, and H2O were obtained in a piecewise manner using emission modes from a single Pb-salt laser local oscillator. The measured spectra were compared to synthetic atmospheric spectra calculated using a line-by-line model. The results demonstrate that high-resolution IR solar absorption spectroscopy and atmospheric extinction measurements can be routinely performed over wide spectral regions using semiconductor lasers.

Hoell, J. M., Jr.↗

On the siting of noble gases in E-chondrites

Fractions of six E-chondrites were separated by density, grain size, and chemical resistance to determine the siting of noble gases. The samples were taken from the Qingzhen (E3), Indarch (E4), Abee and Saint Saveur (E4-5), and Yilmia and North West Forrest (E6) meteorites. The Ar-rich component of the E6s was concentrated in the enstatite-rich fraction. This subsolar component was resistant to HCl and HNO3 treatment, but could be partially dissolved by HF, implying that the subsolar component is located in the enstatite. The noble gases were transported there by metamorphism. Xe-129 was found in the same regions in the E6s, but was in areas associated with chondrules in the E4s. Additionally, the carbon-rich fraction of the E4 sample displayed Xe and Ne/CCF-Xe isotopic ratios similar to that found in C-chondrites. E3 and E4 primordial gases were analogous, with no subsolar contribution.

Crabb, J.↗

Kinetics of the reaction of hydroxyl radicals with nitric acid

An extensive study was made of the reaction of hydroxyl radicals with nitric acid in a laser photolysis-resonance fluorescence system. A 266 nm laser was used to photolyze HNO3 in the temperature range 225-415 K at pressures of 20-300 torr. A temperature dependence was detected below room temperature, with a leveling off at 298 K and a wide spread in the rate constants. A pressure dependence was observed over the entire range and was more pronounced at lower temperatures. The results are noted to be in agreement with those of previous investigations. However, the wide range of rate constants are suggested to be a problem for stratospheric HO(x) modeling for anthropogenic effects. No explanation could be given of the varying results obtained by other investigators regarding the kinetics of the reactions.

Margitan, J. J.↗

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.↗

The photochemistry of anthropogenic nonmethane hydrocarbons in the troposphere

A lumped, nonmethane hydrocarbon (NMHC) chemical mechanism is presently applied to a one-dimensional photochemical model of the troposphere. The profiles of OH, HO2, NO(x), and HNO3, showed only slight changes when NMHC chemistry was added. The integrated column of peroxyacetylnitrate (PAN), when NMHC chemistry was included, comprised 17 percent of the odd nitrogen budget. Advection is noted as an important possible mechanism for the removal of PAN at midlatitudes. The inclusion of such intermediate lifetime species as aldehydes and olefins has both provided additional sources of short-lived NMHC radicals, such as the peroxyacetyl radical that is the radical precursor of PAN, and offered a more detailed description of the concentrations of short-lived species and the overall NMHC chemistry.

Brewer, D. A.↗

Influence of peroxyacetyl nitrate (PAN) on odd nitrogen in the troposphere and lower stratosphere

Nonmethane hydrocarbon breakdown in the atmosphere produces aldehydes of which a fraction are transferred into peroxyacetyl nitrates (PAN) in the presence of NO and NO2. Since ethane is destroyed photochemically primarily above 1 km, PAN can be introduced into the upper troposphere and lower stratosphere without the need to be transported from the boundary layer where most hydrocarbons are destroyed and where PAN may be lost due to thermal decomposition and heterogeneous loss. Mixing ratios of ethane in the lower troposphere increase by a factor of 4-8 from equatorial to northern mid-latitudes. This difference is directly translatable into a PAN latitude gradient. At mid-latitudes the concentration of PAN below 20 km is 0.1 ppb comparable to and in some instances larger than predicted HO2NO2 mixing ratios. Like HO2NO2 and HNO3, PAN serves as a reservoir for odd nitrogen.

Aikin, A. C.↗

Proceedings of a Workshop on Assessment of Techniques for Measuring Tropospheric N sub x O sub y

Human impact on the troposphere, particularly on the regional to global scale is assessed. One area of required research is instrumentation development, which is aimed at improving the capability to measure important trace gases and aerosols which are key species in the major atmospheric biogeochemical cycles. To focus on specific needs, the Instrumentation Workshop for NxOy Tropospheric Species was conducted. The workshop discussed measurement needs and instrument capabilities for NxOy species, including NO, NO2, HNO3, HNO2, PAN, and NO3 aerosols. The status and measurement capabilities of various techniques (operational as well as conceptual) were discussed, along with future instrument and technology needs.

Source record↗

A model study of the effects of intermittent loss on odd nitrogen concentrations in the lower troposphere

A time-dependent box model of the lower troposphere which includes a description of photochemical and physical processes has been developed. This model has been applied to the calculation of nitric acid and NO(x)(NO + NO2) concentrations over a diurnal cycle which includes precipitation. Nitric acid concentrations and the HNO3/NO(x) ratio are found to be highly variable under the assumptions regarding the frequency, duration, and intensity of precipitation employed in this model. The chemistry of odd nitrogen compounds during the night is potentially important in establishing the level of nitric acid in the lower troposphere. These calculations also indicate that relatively large errors may occur when the continuity equation describing nitric acid variations is averaged over a diurnal cycle which includes precipitation. Interpretation of simultaneous measurements of HNO3 and NO(x) will require some knowledge of the history of the observed air mass and may require an improved understanding of nighttime odd nitrogen chemistry.

Stewart, R. W.↗

An investigation of sulfate production in clouds using a flow-through chemical reactor model approach

A flow-through chemical reactor model is developed to describe the mass transfer and chemical processes that atmospheric gases undergo in clouds. The model includes the simultaneous absorption of SO2, NH3, O3, NO(x), HNO3, CO2 and H2O2, the accompanying dissociation and oxidation reactions in cloud water, considers electrical neutrality, and includes qualitative parameterization of cloud microphysics. The model is used to assess the importance of the oxidation reactions H2O2-S(IV), O3-S(IV), and S(IV)-Mn(2+) catalysis, and the effects of cloud parameters such as drop size, rain intensity, liquid water content, and updraft velocity. Both precipitating and nonprecipitating clouds are studied. Model results predict sulfate production rates varying from 3 percent/hr to 230 percent/hr. The actual rate is highly dependent on the chemical composition of the uptake air and the physical conditions of the cloud. Model results also show that both the H2O2 and the O3 oxidation reactions can be significant.

Hong, M. S.↗

Chemical consequences of major impact events on earth

Violent cometary or asteroidal impact events comparable to that which terminated the Cretaceous era must produce large amounts of nitrogen oxides, sufficient to provide NOx mole fractions much larger than 100 ppm over areas of millions of square kilometers. Rapid production of NO2, and subsequent rainout of HNO3 and other strong acids can acidify surface waters, selectively destroying CaCO3 shells. This scenario holds the promise of explaining both the scope of Cretaceous biological extinctions and their extraordinary selectivity.

Lewis, J. S.↗

The photochemistry of a remote marine stratiform cloud

The coupled gas- and aqueous-phase photochemistry of a stratiform cloud in a remote region of the marine atmosphere is investigated with a time-dependent box model. Both scavenging of ambient acidic aerosols and gases as well as aqueous-phase chemical reactions within droplets are found to be important sources of acidity to cloud water and can lead to pH levels in cloud water in the remote marine atmosphere well below 5.6. The major sources of acidity via aqueous-phase chemical reactions are the generation of sulfuric acid from dissolved SO2 and the generation of formic acid from dissolved formaldehyde. In both cases, aqueous-phase free radicals can play a significant role either directly by oxidizing dissolved SO2 and HCHO or indirectly by producing the aqueous-phase oxidant H2O2. The rate of SO2 conversion to sulfuric acid is sensitive to a variety of parameters including the accommodation or sticking coefficient for SO2, H2O2, HO2, and OH, the liquid water content, and the ambient levels of SO2, HNO3, and other acidic or basic gases. Because high levels of SO2 tend to deplete cloud water of H2O3, the possibility exists that the pH of precipitation in polluted regions will respond nonlinearly to reduced SO2 emissions.

Chameides, W. L.↗

Spectroscopy and transmittances for the LIMS experiment

The Limb Infrared Monitor of the Stratosphere (LIMS) instrument on the Nimbus 7 spacecraft sensed limb emission profiles for 7 months, starting in October 1979. Vertical temperature profiles are inferred from measurements in two CO2 channels, and constituent profiles are obtained form the O3, HNO3, NO2, and water vapor channels. The line parameters used to calculate transmittances in the retrieval algorithm are presented. Their adequacy for LIMS and for other applications are assessed, and recommendations for future investigations are outlined.

Drayson, S. R.↗

The variability of stratospheric and mesospheric NO2 in the polar winter night observed by LIMS

The LIMS experiment sounded the upper atmosphere from late October 1978 to late May 1979 and provided vertical profiles of atmospheric temperature, 03, H2O, HNO3, and NO2. Radiance averaging was used before retrieval to measure the altitude distribution of NO2 over the altitude range from the lower stratosphere into the mesosphere. Observations in the polar winter night region northward of about 70 deg N reveal NO2 levels near 175 ppbv at about 70 km, and they show a significant longitudinal variability (factor of 4 to 7). A definite temporal trend exists, showing a buildup of mesospheric and stratospheric NO2 during the polar night and a subsequent slowing of the increase of decline after sunlight returns, depending on altitude. The data represent the first experimental evidence that the thermosphere is an NO(x) source for the mesosphere and stratosphere.

Russell, M. J., III↗

Surface effects of corrosive media on hardness, friction, and wear of materials

Hardness, friction, and wear experiments were conducted with magnesium oxide exposed to various corrosive media and also with elemental iron and nickel exposed to water and NaOH. Chlorides such as MgCl2 and sodium containing films were formed on cleaved magnesium oxide surfaces. The MgCl2 films softened the magnesium oxide surfaces and caused high friction and great deformation. Hardness was strongly influenced by the pH value of the HCl-containing solution. The lower the pH, the lower the microhardness. Neither the pH value of nor the immersion time in NaOH containing, NaCl containing, and HNO3 containing solutions influenced the microhardness of magnesium oxide. NaOH formed a protective and low friction film on iron surfaces. The coefficient of friction and the wear for iron were low at concentrations of NaOH higher than 0.01 N. An increase in NaOH concentration resulted in a decrease in the concentration of ferric oxide on the iron surface. It took less NaOH to form a protective, low friction film on nickel than on iron.

Miyoshi, K.↗

Optical Studies of Nitrogen Oxides in the Stratosphere

Several observational approaches were used to study the oxides of nitrogen in the stratosphere. Two species are accessible in the visible range: NO2 (400 to 450 nm) and NO3 (620 to 670 nm). In the infrared NO, NO2 and HNO3 can be studied easily only if measurements are made from above the tropopause where the water density becomes low. Measurements were carried out both by ground-based techniques as well as aircraft and balloons.

Noxon, J. F.↗

MAP/GLOBUS campaign 1983

The major scientific objectives of the campaign are the accurate measurement of ozone and its short-term variability together with the determination of members of the NO sub x family as NO, NO2, NO3, N2O5, and HNO3. Related important solar fluxes (including scattered fluxes) shall be measured as much as possible. Other important trace species (as H2O) shall be determined simultaneously. The detailed scientific objectives for the ozone and NO sub x measurements are given. A further scientific objective is the study of atmospheric dynamics, especially of the meteorological background. Therefore special analysis will be performed of the data of respective network stations and satellites. Local wind and turbulence measurements will also be performed.

Offerman, D.↗

Tropospheric sources of NO(x) - Lightning and biology

Laboratory tests were performed to quantify the expected NO(x) production by lightning and biological processes. Attention was focused on energy deposition by lightning and the oxygen partial pressure of soil, and one-dimensional photochemical models were defined for the tropospheric distributions of NO and HNO3 for various NO source strengths. The Lightning Facility data were compared with air samples of N2O production gathered during over 2 yr of flights through storms. Soil NO(x) productions were studied in terms of nitrification processes involving Nitrosomonas europaea and Alcaligenes faecalis bacteria, which change ammonium to nitrite and release NO and N2O as byproducts. The results indicate that atmospheric NO(x) is generated at two tropospheric levels, with lightning and soil bacteria being significant contributors.

Levine, J. S.↗