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Stedman, D. H.

Publications and source records attributed to Stedman, D. H..

15 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1986

Peroxy radical detection by chemical amplification (PERCA)

Important reactions of atmospheric free radicals are the chain oxidation of NO and CO. Thus: H2O + NO yields OH + NO2; OH + CO yields H + CO2; H + O2 + M yields HO2 + M. In most models, the need to know the free radical concentration could also be described as the need to know the rate of the above oxidation chain in the atmosphere. It is the total rate of this chain (also carried by RO2 and RO) which was measured using the PERCA. The PERCA is thus essentially a RO sub X meter. The PERCA works by adding excess CO (10%) and NO (5ppm) to a stream of air and measuring the NO2 produced after 3s of reaction time. Since other processes produce NO2, the chain reaction is modulated by switching the CO for N2. The chain length is limited by the reaction OH + NO yields HONO and is modeled to be somewhat over 1000. Measured chain lengths agree with the modeled numbers.

Stedman, D. H.↗
NASA NTRS1982

Direct measurements of ozone and nitrogen dioxide photolysis rates in the troposphere

The photolysis frequencies of ozone and nitrogen dioxide were measured under a variety of conditions commonly found in the troposphere. Ozone photolysis frequencies show a strong dependence on solar zenith angle, overhead ozone column, and temperature, but only a weak dependence on altitude (when only downward radiation is detected). Nitrogen dioxide photolysis frequencies also show strong dependence on solar zenith angle, but show little dependence on temperature, pressure, or altitude. Both j values are strongly affected by cloud cover, but aerosol loading has much less effect. The disagreement of measured j(O3) and j(NO2) with many modeled values, especially disagreement over altitude dependence, shows that atmospheric UV radioactive processes are complicated and poorly understood, although experimental conditions may not always be applicable to conditions modeled.

Dickerson, R. R.↗
NASA NTRS1981

Ozone flow visualization techniques

Flow visualization techniques using ozone for tracing gas flows are proposed whereby ozone is detected through its strong absorption of ultraviolet light, which is easily made visible with fluorescent materials, or through its reaction with nitric oxide to form excited nitrogen dioxide, which in relaxing emits detectable light. It is shown that response speeds in the kHz range are possible with an ultraviolet detection system for initial ozone concentrations of about 1%.

Dickerson, R. R.↗
NASA NTRS1980

Precision of NO2 photolysis rate measurements

Gas-phase kinetic calculations indicate that actinometric measurements of the rate of solar photolysis of NO2 in nitrogen can be in error by +5 to -15% or more, unless odd oxygen N2O5 chemistry, and trace oxygen content are considered. A field experiment confirms that the effect of the quartz tube on the measured photolysis rate is less than 1.7%.

Dickerson, R. R.↗
NASA NTRS1979

Actinometric measurements and theoretical calculations of j/O3/, the rate of photolysis of ozone to O/1D/

The paper presents an experimental technique which measures j/O3-O(1-D)/, the rate of solar photolysis of ozone to singlet oxygen atoms. It is shown that a flow actinometer carries dilute O3 in N2O into direct sunlight where the O(1D) formed reacts with N2O to form NO which chemiluminescence detects, with a time resolution of about one minute. Measurements indicate a photolysis rate of 1.2 (+ or - .2) x 10 to the -5/s for a cloudless sky, 45 deg zenith angle, 0.345 cm ozone column and zero albedo. Finally, ground level results compare with theoretical calculations based on the UV actinic flux as a function of ozone column and solar zenith angle.

Dickerson, R. R.↗
NASA NTRS1979

Oxides of nitrogen and the clouds of Venus

Nitric oxide may be produced in the atmosphere of Venus by lightning storms in the clouds. The paper suggests that the odd nitrogen thus formed may play an important part in the chemistry of the clouds. Specifically, production rates for NO2 in the limiting case of high NO concentrations are estimated. If the NO density is high, it is suggested that NO2 may catalyse the production of sulfuric acid aerosol from sulfur dioxide and water vapor, and may also form nitrogen-sulfur compounds such as nitrosyl sulfuric acid, NOHSO4. The large partricles seen by the Pioneer Venus sounder probe may contain considerable quantities of NOHSO4. If this is the case, odd nitrogen must be present in the atmosphere in at least a parts-per-million mixing ratio.

Watson, A. J.↗
NASA NTRS1979

Qualitative and quantitative flow visualization technique using ozone

The paper describes a new flow-visualization technique based on the absorption of ultraviolet light by ozone. Ozone is an excellent tracer, because as a gas it has the same effective physical properties as air. Ozone strongly absorbs the principal line (253.7 nm) of a mercury lamp, so that when an ozone-traced flow passes between a mercury lamp and a fluorescent screen, a sharp, shadow-like image of the ozone tracer is cast on the screen. Quantitative photometry can be carried out by replacing the screen with ultraviolet detectors that yield the path-integrated column density of ozone in the flow. High-speed quantitative point monitoring (10 Hz at 10 ppb O3) is possible with capillary probes and chemiluminescent analysis.

Dickerson, R. R.↗
NASA NTRS1977

Atomic chlorine and the chlorine monoxide radical in the stratosphere - Three in situ observations

Three simultaneous observations of atomic chlorine (Cl) and the clorine monoxide radical (ClO) are reported which encompass the altitude interval between 25 and 45 kilometers. Together, Cl and ClO form a gas-phase catalytic cycle potentially capable of depleting stratospheric ozone. Observed Cl and ClO densities, although variable, imply that chlorine compounds constitute an important part of the stratospheric ozone budget. The results are compared with recent models of stratospheric photochemistry which have been used as a basis for predicting ozone depletion resulting from fluorocarbon release.

Anderson, J. G.↗
NASA NTRS1977

Tropospheric ozone - Coupling transport and photochemistry

The budget of tropospheric ozone is re-examined in the light of lower observed nitrogen oxide densities and revised reaction rates. To estimate the relative importance of transport and photochemistry, model calculations are presented which determine one-dimensional vertical ozone profiles at midlatitudes for equinoctial conditions. These calculations imply that both photochemistry and transport are important in controlling the abundance of tropospheric ozone. It is estimated that photochemical processes produce about 0.6 times 10 to the eleventh and destroy about 1.4 times 10 to the eleventh tropospheric ozone molecules per sq cm per sec, while mixing processes transport about 1.4 times 10 to the eleventh ozone molecules per sq cm per sec from the stratosphere into the troposphere and ground level fluxes destroy about 0.6 times 10 to the eleventh ozone molecules per sq cm per sec. The sensitivity of our model calculations to transport parameters, key rate coefficients, and nitrogen oxide densities are discussed.

Chameides, W. L.↗
NASA NTRS1977

NOx production in lightning

The rate of odd nitrogen (NOx) production by electrical discharge through air was theoretically and experimentally estimated to be about 60,000 trillion NOx molecules per joule. The theoretical treatment employed a cylindrical shock-wave solution to calculate the rate of NOx production in high temperature reactions. The limits obtained were experimentally verified by subjecting a regulated air flow to electrical discharges followed by a measurement of NOx production using chemiluminescence. These measurements also indicated that water vapor content has no detectable effect on the NOx production rate. The results imply that lightning is a significant source of NOx, producing about 30-40 megatons NOx-N per year and possibly accounting for as much as 50% of the total atmospheric NOx source.

Chameides, W. L.↗
NASA NTRS1975

The vertical distribution of soluble gases in the troposphere

The thermodynamic properties of several water-soluble gases are reviewed to determine the likely effect of the atmospheric water cycle on their vertical profiles. It is found that gaseous HCl, HNO3, and HBr are sufficiently soluble in water to suggest that their vertical profiles in the troposphere have a similar shape to that of water vapor. It is predicted that HCl, HNO3, and HBr exhibit a steep negative gradient with altitude roughly equal to the altitude gradient of water vapor. Therefore, ground-based sources of inorganic chlorine, odd nitrogen, and inorganic bromine compounds are not likely to affect the stratosphere directly in the mean. Calculations also show that while SO2 and NH3 are significantly affected by the atmospheric water cycle, their abundances may not decrease with altitude as rapidly as does that of water vapor.

Stedman, D. H.↗
NASA NTRS1975

Estimate of late 1974 stratospheric concentration of gaseous chlorine compounds /ClX/

The total concentration (ClX) versus altitude of Cl-containing molecules (principally HCl, Cl, ClO) is estimated. It is shown that the predicted present stratospheric concentrations are due to photolysis near 30 km of man-made CF2Cl2 and CFCl3, and CCl4 from a ground-level source, either man-made or natural. The contribution of CH3Cl to stratospheric ClX is evaluated from preliminary measurements of the compound at ground level. Although ground-level sources of HCl and Cl2 are large, tropospheric processes preclude significant impact on the stratosphere.

Cicerone, R. J.↗
NASA NTRS1974

Chemiluminescent measurement of atmospheric acid

The design and construction of a gas phase acid sensitive analyzer are reported. These studies showed that the chemical system was a practical analytical method. A complete instrument was developed and prepared for field testing. A Titan 3-C rocket was scheduled for launching on February 11, 1974. Through preparations made by NASA Langley the instrument was set up to monitor the acid concentration in the rocket exhaust. Due to adverse wind conditions no acid was detected. This entire trip is described in detail.

Stedman, D. H.↗
NASA NTRS1973

Assessment of possible environmental effects of space shuttle operations

The potential of shuttle operations to contribute to atmospheric pollution is investigated. Presented in this interim report are results of the study to date on rocket exhaust inventory, exhaust interactions, dispersion of the ground cloud, detection and measurement of hydrochloric acid and aluminum oxide, environmental effects of hydrochloric acid and aluminum oxide, stratospheric effects of shuttle effluents, and mesospheric and ionospheric effects of orbiter reentry. The results indicate space shuttle operation will not result in adverse environmental effects if appropriate launch constraints are met.

Cicerone, R. J.↗