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The Halogen Occultation Experiment (HALOE) Hydrogen Fluoride (HF) channel on the Upper Atmospheric Research Satellite (UARS) is providing the first global measurements of stratospheric HF, the dominant flourine reservoir in the atmosphere. This paper describes the latitudinal and seasonal variations of HALOE-observed HF in terms of vertical profiles, altitude/latitude cross sections, and column abundances. The HF global distribution shows a 'tracerlike' structure and its column amount increases with latitude, in agreement with previous aircraft measurements of the HF column amount. A comparison between the HALOE HF column above 20 km and the ATMOS 1985 measurements is used to estimate the annual rate of increase of stratospheric HF. Exponential rates of 4.9-6.6%/yr and linear growth rates of 6-8.6%/yr in 1985 and 4.3-5.5%/yr in 1992-1993 are found. HALOE HF measurements during the 1993 Antarctic spring are briefly described. This species behaves like a conserved tracer and its distribution shows an area of enhanced mixing ratios correlated with the polar vortex that has a clear latitude boundary. Finally, simulated HF distributions by the National Center for Atmospheric Research (NCAR) two-dimensional model are used to compare with HALOE observations of HF. Reasonable agreements in the global structure and the absolute amount of HF are found. The differences between the model and the observed results indicate the need for improving treatment of atmospheric dynamics and fluorine-related chemical parameters in the model simulations.

A global three-dimensional chemical tracer model of the distribution and seasonal cycles of the surface concentration of CH3CCl3 is compared with surface observations from the Atmospheric Lifetime Experiment (ALE) for the years 1980-1985. Two-dimensional OH distributions calculated by a photochemical model are empirically adjusted from observed trends in the global average and the interhemispheric ratio of methyl chloroform. The effects of the recently discovered ocean sink for methyl chloroform were investigated. The model simulates the 5-year record of observations made at the five ALE sampling sites to generally within +/- 5 percent of the observed mean. The calculated average global lifetime of methyl chloroform is 5.7 +/- 0.3 years. The estimated global mean OH concentration is 6.5 +/- 0.4 x 10 exp 5/cu cm. However, the inclusion of the ocean sink does not significantly improve the simulation of the observed interhemispheric gradient of methyl chloroform. Atmospheric transport dominates the simulated CH3CCl3 seasonal cycle throughout the Northern Hemisphere but is less important in the Southern Hemisphere.

Sources and sinks of methane and methyl chloroform are investigated using a global three-dimensional Lagrangian tropospheric tracer transport model with parameterized hydroxyl and temperature fields. Using the hydroxyl radical field calibrated to the methyl chloroform observations, the globally averaged release of methane and its spatial and temporal distribution were investigated. Two source function models of the spatial and temporal distribution of the flux of methane to the atmosphere were developed. The first model was based on the assumption that methane is emitted as a proportion of net primary productivity (NPP). The second model identified source regions for methane from rice paddies, wetlands, enteric fermentation, termites, and biomass burning based on high-resolution land use data. The most significant difference between the two models were predictions of methane fluxes over China and South East Asia, the location of most of the world's rice paddies, indicating that either the assumption that a uniform fraction of NPP is converted to methane is not valid for rice paddies, or that NPP is underestimated for rice paddies, or that present methane emission estimates from rice paddies are too high.

Source gases are defined as those gases that, by their breakdown, introduce into the stratosphere halogen, hydrogen, and nitrogen compounds that are important in stratospheric ozone destruction. Given here is an update of the existing concentration time series for chlorocarbons, nitrous oxide, and methane. Also reviewed is information on halogen containing species and the use of these data for establishing trends. Also reviewed is evidence on trends in trace gases that influence tropospheric chemistry and thus the tropospheric lifetimes of source gases, such as carbon dioxide, carbon monoxide, or nitrogen oxides. Much of the information is given in tabular form.

The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

A photochemical model is used to predict temporal trends in atmospheric CO, CH4, and OH. The model is described, including the choice of model inputs and boundary conditions for three cases: low NOx, midlatitude; high NOx, midlatitude; and low NOx, low latitude. Basic features of CO and CH4 perturbation calculations are presented. The model is used to predict CH4, CO, and OH over the next 50 years and to assess possible CH4-CO-OH perturbations from 1860 to 1985. An attempt is made to discern whether increasing global sources of CO or increasing sources of CH4, or both, are responsible for the recent apparent increases of these gases.

An analysis of the possible dissociation of metastable oxygen molecules subject ot constraints imposed by selection rules for molecular transitions, airglow observations, and atmospheric chemistry leads to the following conclusions. Dissociation of O2(b1Sigma g +) must produce a negligible number of oxygen atoms at all altitudes in the earth's atmosphere. However, if the dissociation cross section of O2(a1Delta g) has a maximum value in the range 10 to the -20th to 10 to the -19th/sq cm, then the process O2(a1Delta g) + h(nu) yields O2(C3Delta u) yields O(3P) + O(3P) will constitute a significant, and potentially the major, source of odd oxygen in the uppermost stratosphere and mesosphere.

Trace gas concentrations in the atmosphere reflect in part the overall metabolism of the biosphere, and in part the broad range of human activities such as agriculture, production of industrial chemicals, and combustion of fossil fuels and biomass. There is compelling evidence that the composition of the atmosphere is now changing. Observed trends in trace gas levels are reviewed and implications for the chemistry of the atmosphere are discussed. Throughout the discussion, particular emphasis is given to those species which are now increasing in the atmosphere.

The predictions of several one-dimensional models were examined for a number of prescribed scenarios in steady-state or time-dependent approximations. A small number of two-dimensional steady-state calculations for a limited number of scenarios were compared with the results of one-dimensional models. The sensitivity of the calculated predictions to the values of input parameters were examined in order to assess recognized uncertainties in these predictions.

Measurements are reported of four gas-phase, brominated organic species found in the Arctic atmosphere during March and April 1983. Volume mixing ratios for CH3Br, CH2BrCH2Br, CHBr3, and CH2Br2 were determined by gas chromatography/mass spectrometry analysis from samples taken Arctic wide, including at the geographic North Pole and during a tropopause folding event over Baffin Bay near Thule, Greenland. Methyl bromide mixing ratios were reasonably constant at 11 plus or minus 4 pptv, while the other three brominated organics showed a high degree of variability. Bromoform (2 to 46 pptv) was found to be the dominant contributor to gaseous organic bromine to the Arctic troposphere at 38 plus or minus 10 percent followed by CH2Br2 (3 to 60 pptv) at 29 plus or minus 6 percent. Both CH3Br and CH2BrCH2Br (1 to 37 pptv) reservoirs contained less than 20 percent of the organically bound bromine. Stratospheric samples, taken during a tropopause folding event, showed mixing ratios for all four species at levels high enough to support a stratospheric total volume mixing ratio of 249 pptv Br (888 ngBr/SCM).

A modeling study of the effects of clouds and wet removal on the chemistry of the remote marine troposphere is described. Using a time-dependent model with parameterized vertical transport to calculate trace-gas concentrations, it is found that large variations in key species (e.g., HNO3, H2CO, and H2O2) result from simulations of sporadic rainfall, changes in cloud cover, and external inputs such as surface NO sources. Depending on the frequency and intensity of an event, the effects of these perturbations may persist for several days, thereby invalidating assumptions of photochemical equilibrium in the interpretation of measurements. Long-term integrations with fixed boundary conditions and regularly occurring cloud and rain episodes demonstrate a strong sensitivity of the mean concentration of longer-lived soluble gases to precipitation frequency but also confirm the validity of using properly chosen parameterizations of wet removal in steady state calculations.

Estimates are made showing that, as a consequence of rocket activity in the earth's upper atmosphere in the Shuttle era, average ice nuclei concentrations in the upper atmosphere could increase by a factor of two, and that an aluminum dust layer weighing up to 1000 tons might eventually form in the lower atmosphere. The concentrations of Space Shuttle ice nuclei (SSIN) in the upper troposphere and lower stratosphere were estimated by taking into account the composition of the particles, the extent of surface poisoning, and the size of the particles. Calculated stratospheric size distributions at 20 km with Space Shuttle particulate injection, calculated SSIN concentrations at 10 and 20 km altitude corresponding to different water vapor/ice supersaturations, and predicted SSIN concentrations in the lower stratosphere and upper troposphere are shown.

Infrared atmospheric absorption spectra at 0.02/cm resolution were obtained during a balloon flight on March 23, 1981 from the Holloman AFB, New Mexico. The absorption features, attributed to C2H2, were used to derive a preliminary mixing ratio of about 25 pptv near 9 km, accurate to + or - 40%. This mixing ratio falls into the range of values calculated for the upper troposphere C2H2 in a photochemical/transport model. However, previous measurements from aircraft grab sampling (Cronn and Robinson, 1979) show four to twelve times this C2H2 concentration 1.5 km below the tropopause.

Field measurements of methane fluxes from rice paddies, fresh water lakes, and saltwater marshes have been made to infer estimates of the size of these sources of atmospheric methane. The rice-paddy measurements, the first of their kind, show that the principal means of methane escape is through the plants themselves as opposed to transport across the water-air interface via bubbles or molecular diffusion. Nitrogen-fertilized plants release much more methane than unfertilized plants but even these measured rates are only one fourth as large as those inferred earlier by Koyama (1963, 1964) and on which all global extrapolations have been based to date. Measured methane fluxes from lakes and marshes are also compared to similar earlier data and it is found that extant data and flux-measurement methods are insufficient for reliable global extrapolations.

The aeronomic implications of a preliminary observation of weak OCS photoabsorption above 270 nm are investigated. It is argued that the measured cross section is consistent with a forbidden transition in this wavelength region. Model calculations are made for the OCS photodissociation rates in daylight, the OCS and SO2 distributions in the upper atmosphere, and the budgets of sulfur in the stratosphere and OCS in the troposphere, assuming various extrapolations of the measured OCS absorption cross sections and quantum yields to longer wavelengths. It is shown that weak OCS absorption above 300 nm can have important consequences for all of these quantities. Laboratory and field experiments are identified which might lead to a better understanding of the atmospheric OCS cycle.

Atmospheric halogen measurement data are presented for: (1) inorganic and organic gaseous compounds of chlorine, fluorine, bromine and iodine; and (2) chloride, fluoride, bromide and iodine in particulate form and in precipitation. The roles that these data and other, unavailable data play in the determination of the global cycles of the halogens are discussed. It is found that the speciation of the halogen gases in the troposphere is uncertain, with the only inorganic species detected by species-specific methods being HC1 and SF6. It is shown that heterogeneous reactions, both gas-to-particle and particle-to-gas processes, precipitation removal, and sea-salt aerosol generation and fractionation processes, need quantitative investigation to allow progress in estimating halogen sources and sinks. Where practical, quantitative comparisons are made between measured and predicted concentrations.

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.

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.

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.

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.

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.

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.

The present work reviews the current state of knowledge regarding the contribution from all sources, both natural and anthropogenic, of HCl in the troposphere and in the stratosphere. Some recent estimates on the number of grams per year from each source are presented, and assumptions made in obtaining these figures are discussed. The present lack of measurement data regarding gaseous chlorine compounds in the atmosphere is pointed out.

(O-18)(O-16) is the sixth most abundant gas in the atmosphere after (N-14)(N-14), (O-16)(O-16), Ar, (N-15)(N-14) and H2O. From available data on line positions in the Schumann-Runge (S-R) bands (175 to 205 nm) of (O-18)(O-16) its atmospheric photodissociation rates are estimated. In the high stratosphere and mesosphere this proposed source of O and O3 could be significant compared to photodissociation of (O-16)(O-16) although the estimates are subject to several uncertainties that are discussed. The transmission of solar radiation is calculated through the S-R bands of (O-18)(O-16) and (O-16)(O-16) with transmission functions averaged over individual S-R bands.

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.

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.

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.

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.

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.

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.

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.

Positive ion concentration in D region, using spherical stationary electrostatic probe in weakly ionized collision dominated gas

Positive ion collection by highly negative spherical electrostatic probe in collision dominated plasma

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.