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Brewer, D. A.

Publications and source records attributed to Brewer, D. A..

Cumulus cloud venting of mixed layer ozone

Observations are presented which substantiate the hypothesis that significant vertical exchange of ozone and aerosols occurs between the mixed layer and the free troposphere during cumulus cloud convective activity. The experiments utilized the airborne Ultra-Violet Differential Absorption Lidar (UV-DIAL) system. This system provides simultaneous range resolved ozone concentration and aerosol backscatter profiles with high spatial resolution. Evening transects were obtained in the downwind area where the air mass had been advected. Space-height analyses for the evening flight show the cloud debris as patterns of ozone typically in excess of the ambient free tropospheric background. This ozone excess was approximately the value of the concentration difference between the mixed layer and free troposphere determined from independent vertical soundings made by another aircraft in the afternoon.

Ching, J. K. S.↗

The role of isoprene oxidation in the tropospheric ozone budget in the tropics

A comprehensive chemical mechanism for the oxidation of isoprene (a hydrocarbon, C5H8 emitted primarily by vegetation) by OH and O3 in the troposphere was developed and incorporated into a one-dimensional steady-state photochemical model of the troposphere. Flux boundary conditions for NOx (NO + NO2), HNO3, O3, and CO were used to investigate the changes produced in the tropospheric concentrations and integrated column of ozone from including isoprene chemistry in the model. Two calculations were performed at 15 deg N latitude for annual conditions using identical flux boundary conditions for NOx, HNO3, O3, and CO; in one calculation, the chemistry describing isoprene oxidation was included while in the other it was not. Both sets of calculations included reactions describing the chemistry of anthropogenic nonmethane hydrocarbons. The calculations showed decreases in concentrations of ozone throughout the troposphere when isoprene chemistry was included. Concentrations of NOx and HNO3 increased in the lower troposphere and decreased in the upper troposphere while concentrations of CO and PAN increased throughout the troposphere when isoprene chemistry was included. Implications of this study to the budgets of these species in the tropics is discussed.

Brewer, D. A.↗

Cumulus cloud venting of mixed layer ozone

Observations are presented which substantiate the hypothesis that significant vertical exchange of ozone and aerosols occurs between the mixed layer and the free troposphere during cumulus cloud convective activity. The experiments utilized the airborne Ultra-Violet Differential Absorption Lidar (UV-DIAL) system. This system provides simultaneous range resolved ozone concentration and aerosol backscatter profiles with high spatial resolution. Evening transects were obtained in the downwind area where the air mass had been advected. Space-height analyses for the evening flight show the cloud debris as patterns of ozone typically in excess of the ambient free tropospheric background. This ozone excess was approximately the value of the concentration difference between the mixed layer and free troposphere determined from independent vertical soundings made by another aircraft in the afternoon.

Ching, J. K. S.↗

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.↗

The oxidation of isoprene in the troposphere - Mechanism and model calculations

Calculations have been performed for 15 deg N and 45 deg N latitude continental conditions using a one-dimensional, steady state photochemical model that incorporates a chemical mechanism describing the oxidation of isoprene by OH and O3 in the troposphere. At the higher latitude, anthropogenic hydrocarbon emission effects on NO(x) vertical profiles, as well as those of HNO3, overshadow isoprene emissions effects; at the lower latitude, reduced anthropogenic emissions and increased isoprene emissions respectively yield 26 and 4 percent increases in NO(x) and HNO3 column contents. It is suggested that a significant quantity of isoprene goes to the formation of longer carbon chain oxygenated organic species.

Brewer, D. A.↗

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.↗

NASA participation in the 1980 PEPE/NEROS project: Data archive

Eight experimental air quality measurement systems were investigated during July and August 1980 as part of the EPA PEPE/NEROS fiel measurement program. Data from those efforts have been entered into an archive that may be accessed by other researchers. The data sets consists of airborne measurements of regional mixed layer heights and aerosol and ozone distributions as well as point measurements of meteorological parameters and ozone obtained during diurnal transitions in the planetary boundary layer. This report gives a discussion of each measurement system, a preliminary assessment of data quality, a description of the archive format for each data set, and a summary of several proposed scientific studies which will utilize these data.

Brewer, D. A.↗

PAN and the NOx budget of the troposphere

The present investigation has the objective to examine the interaction of NOx with the nonmethane hydrocarbons (NMHCs) photochemistry. Attention is given to the influence of temperature, transport, and hydrocarbon radical reactions on the profiles of peroxyacylnitrates (PANs) and NO2. A lumped NMHC chemical reaction scheme was used in a one-dimensional photochemical model of the global troposphere. Model calculations were performed with various temperature profiles and the corresponding solar zenith angles to examine seasonal variations in the profiles of PAN and NOx. A study of the effects of changing temperature and solar zenith angle on the profiles of PAN and NOx showed that the amount of NO2 tied up in PAN increased as temperature decreased.

Brewer, D. A.↗

The chlorine budget of the troposphere

It has been hypothesized that chlorine compounds in the stratosphere could photodissociate and release atomic chlorine which catalytically destroys ozone. For an accurate assessment of the possibility of stratospheric ozone depletion, it will be necessary to know the chlorine budget of the entire atmosphere, including the troposphere and the stratosphere. Most chlorine species in the atmosphere are emitted at the surface and diffuse upward. Measurements involving chlorine are reviewed and photochemical calculations are discussed. It is found that between 0.1-1.0 ppbv of inorganic chlorine is present at the surface and about 0.02 ppbv (parts per billion by volume) at the tropopause. Most of the inorganic chlorine is believed to be in the form of HCl, and thus natural in origin. For organic chlorine the corresponding numbers are 1.9 ppbv and 1.7 ppbv, respectively. At the surface approximately 32% of the organic chlorine is natural and 68% anthropogenic.

Augustsson, T. R.↗

A diagnostic model for studying daytime urban air quality trends

A single cell Eulerian photochemical air quality simulation model was developed and validated for selected days of the 1976 St. Louis Regional Air Pollution Study (RAPS) data sets; parameterizations of variables in the model and validation studies using the model are discussed. Good agreement was obtained between measured and modeled concentrations of NO, CO, and NO2 for all days simulated. The maximum concentration of O3 was also predicted well. Predicted species concentrations were relatively insensitive to small variations in CO and NOx emissions and to the concentrations of species which are entrained as the mixed layer rises.

Brewer, D. A.↗

Ab initio projected-unrestricted Hartree-Fock calculation of some potential energy curves for carbonyl fluoride

Some potential energy curves for CF2O were calculated using projected-unrestricted Hartree-Fock (PUHF) theory. The calculations employed a contracted (4s 3p) Gaussian-type atomic orbital basis set. Bound states were found for the X-tilde 1A1 and 1,3A2 states while the 1,3B1 and 1,3B2 states were repulsive in the valence representation. The merits of the PUHF treatment for excited states are discussed. The results are discussed in terms of available experimental information and previous calculations with particular emphasis on the question of the photolysis channels open in the solar spectral region.

Brewer, D. A.↗

Air quality model studies with application for southeastern Virginia

A single-cell photochemical air quality model incorporating (1) a published chemical mechanism, (2) advection, and (3) entrainment and emissions processes was constructed and compared with data from the EPA Regional Air Pollution Study. While agreement with measured CO and NO2 was established, O3 production was found to occur too rapidly and in excess. Calculated O3 levels improved when a 20% reduction in photolytic rate constants and a doubling of wind speed were applied. The results of the model sensitivity studies are being incorporated into the design and conduct of field measurement programs for the characterization of the vertical and horizontal homogeneity of an air quality region.

Brewer, D. A.↗

The 1977 emissions inventory for southeastern Virginia

Regional tropospheric air pollution modeling and data compilation to simulate the time variation of species concentrations in and around an urban area is discussed. The methods used to compile an emissions inventory are outlined. Emissions factors for vehicular travel in the urban area are presented along with an analysis of the emission gases. Emission sources other than vehicular including industrial wastes, residential solid waste disposal, aircraft emissions, and emissions from the railroads are investigated.

Brewer, D. A.↗

A survey of kinetic data of compounds containing flourine

Chlorofluoromethanes may have a significant effect on the level of ozone in the atmosphere. However, the role of fluroine-containing compounds has not been examined fully. A tabulation of a search of the chemical kinetic literature published between 1953 and July 1975, is presented. The data are then evaluated with respect to acceptability and importance to the overall reaction balance in the atmosphere. Possible future research to elucidate important reaction processes is discussed.

Brewer, D. A.↗