A program of stratospheric research
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Donahue, T. M.↗
Engineering topics
Cicerone, R. J.
Publications and source records attributed to Cicerone, R. J..
Halogen Occultation Experiment (HALOE)
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Russell, J. M., III↗
Radiative equilibrium temperatures in the stratosphere and mesosphere - A comparison for the stellar occultation and BUV ozone data
Recently published ozone densities in the equatorial stratosphere and mesosphere from satellite stellar occultation measurements are appreciably larger than previous independent midlatitude measurements and ozone densities predicted by photochemical theory. Radiative equilibrium temperature profiles with a stratosphere-mesosphere optimized model have been calculated for each of these ozone profiles; it is found that the stellar occultation studies cannot be discounted on energy balance grounds.
Kuhn, W. R.↗
Effects of nonmethane hydrocarbons in the atmosphere
An investigation was conducted to determine whether nonmethane hydrocarbons (NMHC) are abundant enough to have a significant impact upon the ambient photochemistry. The vertical distribution of C2H6, C2H2, C3H8, C4H10, and C5H12 in the altitude range from 0 to 40 km was calculated in this connection. A one-dimensional steady state model with coupled photochemistry and vertical transport was employed in the investigation. The calculations imply that measurable quantities of relatively unreactive NMHC, especially C2H6 and C2H2, may be present in the upper troposphere and stratosphere. The results indicate, however, that NMHC are not likely to have a large impact on the background photochemistry of the troposphere, although local effects near source regions are probable. The findings support the current practice of many modelers who neglect NMHC in their calculations.
Chameides, W. L.↗
Sources and sinks of atmospheric N2O and the possible ozone reduction due to industrial fixed nitrogen fertilizers
The terrestrial and marine nitrogen cycles are examined in an attempt to clarify how the atmospheric content of N2O is controlled. We review available data on the various reservoirs of fixed nitrogen, the transfer rates between the reservoirs, and estimate how the reservoir contents and transfer rates can change under man's influence. It is seen that sources, sinks and lifetime of atmospheric N2O are not understood well. Based on our limited knowledge of the stability of atmospheric N2O we conclude that future growth in the usage of industrial fixed nitrogen fertilizers could cause a 1% to 2% global ozone reduction in the next 50 years. However, centuries from now the ozone layer could be reduced by as much as 10% if soils are the major source of atmospheric N2O.
Liu, S. C.↗
Possible variations in atmospheric methane
A model coupling photochemistry and vertical transport in the troposphere has been used to investigate the magnitude of possible future perturbations to atmospheric CH4. The response of atmospheric CH4 to an increase in the concentration of CO or to a variation in stratospheric O3 is studied. Both of the above mechanisms, which could be caused by man's activities, arise because a change in the concentration of tropospheric OH will lead to a change in the CH4 abundance. The calculations imply that a perturbation of about 30-40% in atmospheric CH4 could occur if stratospheric O3 were perturbed by 10% or if man-made CO continued to increase. The possible consequences of a CH4 perturbation may entail a perturbation in stratospheric photochemistry or in the thermal balance of the atmosphere.
Chameides, W. L.↗
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.↗
Stellar occultation measurements of atmospheric ozone and chlorine from OAO3
The Princeton University telescope on the Orbiting Astronomical Observatory 3 was used for occultation measurements of upper-atmospheric species. The target star, Beta Cen, and observing date were selected so that the line of sight grazed earth's limb at local midnight. Observations at 2580, 2825, 2997, 3100, and 3428 A produced ozone absorption data of high statistical accuracy between 48-km and 114-km tangent altitude. Near-exponential density profiles are obtained up to 85 km. Near 100 km, a significant density excess above the extrapolated low-altitude profile is observed. Near-equatorial observations at altitudes up to approximately 75 km agree well with theoretical calculations. Ozone densities measured at 6.5 to 12.5 deg S latitude above approximately 75 km exceed the theoretical calculations and are not understood at the present time. A search for the 1188-A chlorine line in the 1187-A O2 absorption feature was carried out at tangent altitudes of 96-116 km. An upper limit of 3 ppb to the atomic chlorine mixing ratio at 106 km is found. This upper limit exceeds the expected value for atomic chlorine by a factor of approximately 2.5.
Riegler, G. R.↗
Effect of water vapor on the destruction of ozone in the stratosphere perturbed by ClX or NOx pollutants
Results are presented for a self-consistent one-dimensional coupled flow calculation for Ox, NOx, HOx, ClX, H2O, H2, CH4, H2O2, and N2O densities between 10 and 120 km. The results agree well with observations for the normal midlatitude atmosphere over this altitude range. ClX, NOx, and H2O are varied independently in the model considered. It is shown that the effect of depletion of ozone by ClX is to remove ozone preferentially above 30 km and to lower the altitude of maximum ozone density. This leads to enhanced solar heating of the lower stratosphere and tropopause and suggests the possibility of an increased flux of water into the stratosphere. Increasing water vapor in the stratosphere greatly enhances the rate of destruction of O3 by ClX and also causes an increase in the rate of destruction of O3 in the NOx-perturbed atmosphere.
Liu, S. C.↗
Effect of odd hydrogen on ozone depletion by chlorine reactions
The present paper discusses how the shape of the ozone layer changes under the influence of injected ClX for several choices of two key HOx reaction rates. The two HOx reactions are: OH + HO2 yields H2O + O2 and O + HO2 yields OH + O2. Results of calculations are presented which show that the two reaction rates determine the stratospheric concentrations of OH and HO2, and that these concentrations regulate the amount by which the stratospheric ozone column can be reduced due to injections of odd chlorine. It is concluded that the amount of ozone reduction by a given mixing ratio of ClX will remain very uncertain until the significance of several possible feedback effects involving HOx in a chlorine-polluted atmosphere are determined and measurements of the reaction rates and HOx concentrations are made at the relevant temperatures.
Donahue, T. M.↗
Comment on 'Volcanic emissions of halides and sulfur compounds to the troposphere and stratosphere' by R. D. Cadle
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Cicerone, R. J.↗
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.↗
Minor constituents in the stratosphere and mesosphere
This paper is a brief survey of a portion of the research on trace constituents in the stratosphere and mesosphere between 1971 and 1974. A primary motivation for much of the stratospheric research came from the realization that man's activities may influence global climate and the atmospheric ozone content, our shield against certain UV wavelengths. A great deal of progress has been reported in understanding both the present background stratosphere and the responses to be expected from additions of nitrogen oxides, water, and chlorine oxides, especially with respect to ozone. Trace constituents in the mesosphere have been modeled and measured to increase our understanding of the physics and chemistry of the mesosphere but also to relate mesospheric composition and transport to ionospheric processes at higher altitudes, to D region ion chemistry, and to upper stratospheric composition.
Cicerone, R. J.↗
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.↗
Chlorine compounds and stratospheric ozone
A report by Cicerone et al. (1974) concerned with the potential size of the atmospheric perturbation produced by man-made chlorofluoromethanes is considered, giving attention to a number of errors made in the first investigation and their correction. However, the corrections do not significantly change the results reported. It had been found that chlorine oxides which arise from chlorofluoromethane usage will within 10 or 15 years provide a sink for stratospheric ozone which will dominate the natural sinks for ozone.
Cicerone, R. J.↗
Stratospheric ozone destruction by man-made chlorofluoromethanes
Calculations indicate that chlorofluoromethanes produced by man can greatly affect the concentrations of stratospheric ozone in future decades. This effect follows the release of chlorine from these compounds in the stratosphere. Present usage levels of chlorofluoromethanes can lead to chlorine-catalyzed ozone destruction rates that will exceed natural sinks of ozone by 1985 or 1990.
Cicerone, R. J.↗
Thermalization and transport of photoelectrons - A comparison of theoretical approaches.
Three methods of studying ionospheric photoelectron thermalization, in which transport effects are evaluated in different ways, are outlined and compared. One method uses a diffusion equation formulation, the second proceeds from a two-stream approximation to the general particle transfer equation, and the third employs a Monte Carlo technique to simulate electron paths. The methods are compared by applying them to identically prepared models. The methods are in close agreement for altitudes in the region of local energy loss, but higher altitudes reveal a discrepancy of as much as a factor of 2 in the net flux of photoelectrons. The discrepancy is removed by appropriately modifying the computational techniques.
Cicerone, R. J.↗
Impact of space shuttle orbiter reentry on mesospheric NOx.
Shuttle orbiter reentry will produce large amounts of nitric oxide (NO) through shock heating at mesospheric altitudes. The effects of this reentry are modeled by considering an impulsive source of NO in time-dependent equations including photochemistry and transport. The model uses an odd-nitrogen approach similar to Strobel's. Parameterized flux boundary conditions are imposed at the mesopause and stratopause and concentrations of the odd nitrogen species (NO, NO2, NO+, N(4S) and N(2D) are found numerically by a finite difference scheme. A localized disturbance can last many hours, depending on the effectiveness of eddy transport. Although the model is one-dimensional, effects of horizontal transport are also included approximately.
Stolarski, R. S.↗