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Review of the currently available knowledge on Titan's atmosphere, based on the report of the 1973 Titan Atmosphere Workshop. The atmosphere composition, clouds, haze, and thermal structure are discussed, along with the photochemistry, escape, and recycling of the atmosphere.
Electron spin resonance (ESR) spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170 C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 adsorbed on silica gel at -170 C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, reirradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals. Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precursors of formic acid. These results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth, and on dust grains in the interstellar medium.
The work presented here is directed toward assessment of environmental effects of the supersonic transport (SST). The model used for the purpose includes vertical eddy transport and the photochemistry of the O-H-N system. It is found that the flight altitude has a pronounced effect on ozone depletion. The largest ozone reduction occurs for NO deposition above an altitude of 20 km.
Some areas of D and E region research are examined, with particular reference to the photochemistry and transport of minor neutral constitutents in the mesosphere and lower thermosphere. The review shows that the D and E regions become more complex physical and chemical systems as research progresses, so that some previous views on these regions have to be revised. In particular, the lower ionosphere appears to be hydrodynamically coupled to the lower atmosphere and electrodynamically coupled to the magnetosphere.
A three-year integration of a global three-dimensional model including dynamics and simple photochemistry is used to predict ozone. Good agreement with observation is obtained for stratospheric motion patterns, meridional circulations, ozone density as a function of height and latitude, eddy transports of ozone, surface destruction of ozone, and correlations of ozone with other variables. The annual cycle of columnar ozone in high latitudes is present, but at a smaller amplitude than observed. Vertical transport of ozone downward from the main generation level at 30 km is accomplished primarily by small-scale eddy diffusion between 20 and 30 km and again near the ground; large-scale vertical transport dominates in between. The model predicts a secondary maximum in ozone mixing ratio at 45 km somewhat equatorward of the winter polar-night zone. This feature, recently observed from satellite measurements, is thought to be caused by the temperature dependence of reaction rates in the Chapman scheme. The principal deficiency of the model is an underprediction of the spring ozone concentration in high latitudes in the lower stratosphere.
A time-dependent, one-dimensional model of the coupled chemistry and vertical mixing of the atmosphere is used to compute the distribution for many atmospheric constituents of the troposphere and stratosphere. The model treats the photochemistry of the carbon-hydrogen-oxygen-nitrogen system and is (with the exception of H2O) self-consistent in the sense of requiring no assumptions regarding minor constituent distributions.
A study of the chemistry and photochemistry of the recently discovered phosphine in the atmosphere of Jupiter suggests that the red colorations on this planet result from photochemical production of red phosphorus particles. Chemical-dynamical models of this red phosphorus haze imply that the intensity of the red coloration is a strong function of the strength of vertical turbulent mixing in the atmosphere. If the Jovian Great Red Spot is a region of considerable dynamical activity our model provides a self-consistent explanation for the redness of this region in comparison to the rest of the planet.
Tabulated data on solar flux measurements are presented. The measurements, taken from balloons, rockets and satellites, are not new data, but have been critically re-evaluated. The eleven year sunspot cycle is discussed. Also discussed is the brightness temperature. The effect of solar radiation at various wavelengths, on the photochemistry of stratospheric ozone is briefly discussed.
The possibility that predictions of atmospheric photochemistry/transport models are sensitive to uncertainties in reaction rates and other inputs stresses the need for rapid numerical integration schemes in rate photochemistry problems. Reducing the computational burden has a major merit in facilitating sensitivity studies to assess the effect of uncertainties on predicted ozone diminutions from NOx (NO + NO2) in the exhaust plume of SST engines. The paper discusses the validity of an algorithmic approach to integration of rate chemistry problems in combustion, developed by Rubel and Baronti for an approximate calculation of the production rate of the i-th chemical species involved. An analysis of two projected SST engines confirms the validity of the proposed algorithm. Because of the relative arithmetical simplicity, it may be easier to treat diffusion rate chemistry calculations using the Rubel and Baronti approximation than would be possible by other approaches.
A comprehensive review is given of the chemistry and spectroscopic studies of the Jovian atmosphere. Thermochemical equilibrium models for determining atmospheric composition are considered along with possible disequilibrating processes, and studies of the photochemistry of H2, CH4, NH3, H2S, and PH3 using the modeling methods are summarized. It is shown that photodissociation and advection are the major disequilibrating processes in Jupiter's atmosphere, that lightning and charged-particle bombardment are relatively minor factors in the planet's bulk chemistry, and that the existence of living organisms on the planet is highly improbable. Spectroscopic investigations of Jupiter are discussed, emphasizing recent observations of absorption bands due to CH4, NH3, H2, He, and D. Spectroscopic abundance determinations are examined for H2, HD, CH4, CH3D, NH3, C2H6, C2H2, and PH3. Upper limits are given for the abundances of several unobserved gases in the visible atmosphere, including H2S, HCl, SiH4, benzene, purines, pyrimidines, and their derivatives.
In spite of the excellent agreement between various laboratory measurements of the recombination rate of O2(+) with electrons, it is still questionable whether the laboratory results apply in the ionosphere, because although the radiative lifetime of vibrating O2(+) is not well known, indications are that it may be very long. Whether the laboratory results apply in the atmosphere depends on whether the recombination rate is dependent on the vibrational state of the O2(+) ion and on whether the ions are deactivated (or not) in both the laboratory experiments and the atmosphere prior to recombination. To obtain reliable answers to these questions, the present study was carried out to determine the recombination of O2(+) in the ionosphere from in situ measurements of the relevant temperatures and densities made by the open source mass spectrometer carried by the AE-C satellite. The photochemistry involved is discussed. The results show that the ionospheric determination of the recombination rate of O2(+) with electrons agrees with the laboratory measurements of Walls and Dunn (1974) for electron temperatures between 1200 and 2000 K.
Fast flow can be used to create the population inversion required for lasing action, or can be used to improve laser operation, for example by the removal of waste heat. It is pointed out that at the present time all lasers which are capable of continuous high-average power employ flow as an indispensable aspect of operation. High power laser systems are discussed, taking into account the gasdynamic laser, the HF supersonic diffusion laser, and electric discharge lasers. Aerodynamics and high power lasers are considered, giving attention to flow effects in high-power gas lasers, aerodynamic windows and beam manipulation, and the Venus machine. Applications of high-power laser technology reported are related to laser material working, the employment of the laser in controlled fusion machines, laser isotope separation and photochemistry, and laser power transmission.
The mesosphere is an atmospheric region characterized by a negative gradient of solar energy absorption and temperature. Although the distribution of most minor constituents is dominated by photochemistry, vertical transport does have a pronounced effect on many of them. The basic dynamic principles are discussed along with their application to the important mesospheric motions: acoustic-gravity waves, tides, planetary-scale waves, and eddy motions. Oxides of nitrogen and hydrogen are also examined which strongly influence the balance of odd oxygen (O and O3). Brief discussions of the chemistry of carbon compounds and of excited species are also included. The chemistry of ionic species in the mesosphere is very important because it strongly influences the propagation and absorption of radio waves. Because of ion clustering and negative-ion formation, such chemistry is extremely complex. The current state of knowledge is discussed in some detail. The principles involved in constructing models for predicting the distribution of minor constituents, both neutral and ionic, are presented.
The impact of atmospheric and cloud-structure models on the nonequilibrium chemical behavior of the atmospheres of the Jovian planets is discussed. Quantitative constraints on photochemical, lightning, and charged-particle production of organic matter and chromophores are emphasized whenever available. These considerations imply that inorganic chromophore production is far more important than that of organic chromophores, and that lightning is probably a negligibly significant process relative to photochemistry on Jupiter. Production of complex molecules by gas-phase disequilibrium processes on Saturn, Uranus, and Neptune is severely limited by condensation of even simple intermediates.
An estimate has been made of the methylamine concentration in the Jupiter atmosphere on the basis of the possible overlap between the regions of hydrocarbon and ammonia photochemistry. It was found that the maximum production rate of 6 x 10 to the 4th/cu cm/Jovian day occurs in the vicinity of 60 km above the ammonia cloud layer. The volumetric mixing ratio is 3 x 10 to the -11th, if the downward transport of methylamine equals the production rate.
The rate coefficient for the reaction O(+) + N2 yields NO(+) + N is determined as a function of temperature from the photochemistry of NO(+) for both day and night conditions by using a large sample of simultaneous measurements of ion and neutral concentrations and temperatures made by the Atmosphere Explorer C satellite. The results cover the ion temperature range from 500 to 1200 K. Using recent flow-drift-tube results, the rate coefficient is calculated as a function of ion temperature and mean ion drift velocity for ionospheric conditions. The satellite and laboratory determinations are found to be in good agreement. Using this temperature dependence, an earlier determination of the dissociative recombination coefficient of NO(+) with electrons is refined.
A more comprehensive model for stratospheric chemistry and transport theory was developed for the purpose of aiding predictions of changes in the stratospheric ozone content as a consequence of natural and anthropogenic processes. This new and more advanced stratospheric model is time dependent and the dependent variables are zonal means of the relevant meteorological quantities which are functions of latitude and height. The model was constructed by the best mathematical approach on a large IBM S360 in American National Standard FORTRAN. It will be both a scientific tool and an assessment device used to evaluate other models. The interactions of dynamics, photochemistry and radiation in the stratosphere can be governed by a set of fundamental dynamical equations.
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.