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Photochemistry of the atmosphere of Titan - Comparison between model and observations

Updated chemical schemes and estimates of key rate coefficients are used in the present investigation of the photochemistry of Titan atmosphere C- H- and O-atom containing simple molecules, according to a model incorporating exospheric boundary conditions, vertical transport, and condensation processes at the tropopause. It is suggested that the composition, climatology, and evolution of the Titan atmosphere are controlled by five major processes: CH4 photolysis and photosensitized dissociation, H-to-H2 conversion and hydrogen escape, higher hydrocarbon synthesis, nitrogen and hydrocarbon coupling, and oxygen and hydrocarbon coupling. The model accounts for the minor species concentrations observed by Voyager instruments. Implications of abiotic organic synthesis on Titan for the origin of life on earth are briefly discussed.

Yung, Y. L.

Water and the photochemistry of the troposphere

A discussion is presented concerning the role of water in its liquid and gaseous states in the chemistry and photochemistry of the earth's troposphere, with attention to the formation of the hydroxyl radical, oxidation chains involving the gases methane, carbon monoxide and ammonia, the atmospheric chemistry of the sulfur, hydrogen, halogen and nitrogen species, and the function of lightning as a source of tropospheric species. The phenomena of 'rainout', 'washout', and the aqueous chemistry of cloud an rain droplets and of water-covered aerosols, are noted. A section is devoted to the past and anticipated impact of anthropogenic activities on the chemistry and composition of the earth's atmosphere.

Levine, J. S.

A diabatic circulation two-dimensional model with photochemistry - Simulations of ozone and long-lived tracers with surface sources

Numerous studies have been concerned with the possibility of a reduction of the stratospheric ozone layer. Such a reduction could lead to an enhanced penetration of ultraviolet (UV) radiation to the ground, and, as a result, to damage in the case of several biological processes. It is pointed out that the distributions of many trace gases, such as ozone, are governed in part by transport processes. The present investigation presents a two-dimensional photochemistry-transport model using the residual circulation. The global distribution of both ozone and components with ground sources computed in this model is in good agreement with the observations even though slow diffusion is adopted. The agreement is particularly good in the Northern Hemisphere. The results provide additional support for the idea that tracer transport in the stratosphere is mainly of advective nature.

Stordal, F.

The photochemistry of atmospheres: Earth, the other planets, and comets

Papers on the photochemistry of the early atmosphere, the troposphere, stratosphere, and upper atmosphere are presented. Consideration is given to the effect of chemical constituents on the climate and atmosphere. Topics discussed include the composition of the atmospheres of Venus, Mars, the outer planets and their satellites, and the chemical changes which occur in comets.

Levine, J. S.

The photochemistry of the atmospheres of the outer planets and their satellites

The thermal structure and composition of Uranus, Neptune, Saturn, Jupiter, Titan, and Io are described. Molecular hydrogen is the dominant constituent in the atmosphere of the outer planets. The hydrogen and helium, methane, ammonia and phosphine, and carbon monoxide photochemical reactions of the outer planets are studied. The importance of Jupiter's lightning as a source of organic matter is examined. The aerosol and haze layers of the stratosphere of Jupiter, Saturn, Neptune, and Uranus are observed. The photochemistry of Titan's atmosphere, which includes nitrogen, methane, carbon monoxide, and carbon dioxide reactions, is analyzed. The SO2 atmosphere on Io is discussed.

Strobel, D. F.

The photochemistry of synoptic-scale ozone synthesis Implications for the global tropospheric ozone budget

The oxidation of nonmethane hydrocarbons represents a source of tropospheric ozone that is primarily confined to the boundary layers of several highly industrialized regions. (Each region has an area greater than one million km/sq cm). Using a photochemical model, the global tropospheric ozone budget is reexamined by including the in-situ production from these localized regimes. The results from these calculations suggest that the net source due to this photochemistry, which takes place on the synoptic scale, is approximately as large as the amount calculated for global scale photochemical processes which consider only the oxidation of methane and carbon monoxide. Such a finding may have a considerable impact on our understanding of the tropospheric ozone budget. The model results for ozone show reasonable agreement with the climatological summer distribution of ozone and the oxides of nitrogen at the surface and with the vertical distribution of ozone and nonmethane hydrocarbons obtained during a 1980 field program.

Fishman, J.

Photochemistry of methane and the formation of hydrocyanic acid (HCN) in the earth's early atmosphere

A one-dimensional photochemical model is used to analyze the photochemistries of CH4 and HCN in the primitive terrestrial atmosphere. CH4, N2, and HCN photolysis are examined. The background atmosphere and boundary conditions applied in the analysis are described. The formation of HCN as a by-product of N2 and CH4 photolysis is investigated; the effects of photodissociation and rainfall on HCN is discussed. The low and high CH4 mixing ratios and radical densities are studied.

Zahnle, K. J.

Photochemistry and clouds of Jupiter, Saturn and Uranus

Photochemistry of ammonia, methane, phosphine, hydrogen sulfide, methylamine, hydrogen cyanide and carbon monoxide in the atmospheres of Jupiter, Saturn and Uranus is discussed. Condensation of ammonia, ammonium hydrosulfide, water, methane, ethane and acetylene below and near the tropopause of these planets is formulated. Whenever necessary, new calculations are included. Candidates for the upper atmospheric hazes, and the reddish-brown chromosphore in the clouds of Jupiter and Saturn are discussed.

Atreya, S. K.

Clouds, aerosols, and photochemistry in the Jovian atmosphere

An assessment is made of the development status of concepts for cloud and aerosol compositions, vertical and horizontal distributions, and microphysical properties, in the Jovian upper troposphere and stratosphere. Attention is given to several key photochemical species' relationships to aerosol formation as well as their transport process implications, treating photochemistry in the context of comparative planetology and noting differences and similarities among the outer planet atmospheres; since this approach emphasizes observational data, a variegated assortment of ground-based and spacecraft observations is assembled. Current views on the tropospheric distribution of clouds are challenged, and a rationale is presented for alternative accounts.

West, R. A.

Sensitivity of an atmospheric photochemistry model to chlorine perturbations including consideration of uncertainty propagation

Models of stratospheric photochemistry are generally tested by comparing their predictions for the composition of the present atmosphere with measurements of species concentrations. These models are then used to make predictions of the atmospheric sensitivity to perturbations. Here the problem of the sensitivity of such a model to chlorine perturbations ranging from the present influx of chlorine-containing compounds to several times that influx is addressed. The effects of uncertainties in input parameters, including reaction rate coefficients, cross sections, solar fluxes, and boundary conditions, are evaluated using a Monte Carlo method in which the values of the input parameters are randomly selected. The results are probability distributions for present atmosheric concentrations and for calculated perturbations due to chlorine from fluorocarbons. For more than 300 Monte Carlo runs the calculated ozone perturbation for continued emission of fluorocarbons at today's rates had a mean value of -6.2 percent, with a 1-sigma width of 5.5 percent. Using the same runs but only allowing the cases in which the calculated present atmosphere values of NO, NO2, and ClO at 25 km altitude fell within the range of measurements yielded a mean ozone depletion of -3 percent, with a 1-sigma deviation of 2.2 percent. The model showed a nonlinear behavior as a function of added fluorocarbons. The mean of the Monte Carlo runs was less nonlinear than the model run using mean value of the input parameters.

Stolarski, R. S.

A study of the ozone photochemistry in the upper stratosphere using LIMS data

LIMS data at vernal equinox conditions are used to study the photochemistry of the upper stratosphere. The results indicate, and it has been recently reported, that with the use of recommended reaction rates, current models underestimate ozone mixing ratio by 20-40 percent. For ozone, good agreement with data is realized with the modification of six key reaction rates within the published limits of uncertainty. These modifications also yield better agreement with data for daytime NO2. Model results for other parameters such as the ratio HNO3/NO2, OH mixing ratio, and the temperature sensitivity of O3 are compared with data.

Natarajan, M.

The photochemistry of some possible cometary CN parent species

Laboratory work on the photochemistry of HC3N, C4N2, and CH3CN in relation to their possible role as CN parent molecules in comets is discussed. Photodissociation of HC3N, photolysis of C4N2, and quantum yields of excited CN(B) and CN(A) radicals from the VUV photolysis of CH3CN are considered.

Halpern, Joshua B.

Determination of O2(a1Delta g) and O2(b1Sigma + g) yields in the reaction O + ClO yields Cl + O2 - Implications for photochemistry in the atmosphere of Venus

A discharge flow apparatus with a chemiluminescence detector was used to investigate the reaction O + ClO yields Cl + O2(asterisk), where O2(asterisk) = O2(a1Delta g) or O2(b1Sigma + g). It is found that the observed O2(a1Delta g) airglow of Venus cannot be explained in the framework of standard photochemistry using the experimental results obtained here and those reported in the recent literature. The possibility of an alternative source of O atoms derived from SO2 photolysis in the Venus mesosphere is suggested.

Leu, Ming-Taun

Photochemistry of planetary ionospheres

The dominant photochemical reactions taking place in the ionospheres of Venus, Saturn, and Comet P/Halley are presented. It is shown that the differences in the ionospheres of these celestial bodies result from the different chemistry, energetics, and dynamics of the respective atmospheres. The role of photochemistry in the formation of the individual ionospheres is discussed.

Nagy, Andrew F.

Photochemistry Of 2,5-Diacyl-1, 4-Dimethylbenzenes

Experiments described in report revealed potentially useful aspects of photochemistry of 2,5-dibenzoyl-1, 4-dimethylbenzene (DBX) and 2,5-diacetyl-1, 4-dimethylbenzene (DAX). Behavior of these compounds reminiscent of orthoalkylphenyl ketones, studied from similar perspective for more than two decades.

Meador, Michael A.

Photochemistry and vertical mixing

Earth-based observations relevant to the question of photochemistry and vertical mixing are discussed. Phytolysis of methane, the only known photochemically active volatile in the Uranian atmosphere, produces heavier hydrocarbons, the most abundant of which are ethane, acetylene, and the polyacetylenes. Unlike Jupiter and Saturn, these hydrocarbon products condense at the low temperatures prevalent in the middle atmosphere. Contrary to the pre-Voyager notion that the atmosphere of Uranus is remarkable clear, it is found that the aerosols are widely and extensively distributed. Despite its photodestruction, methane remains stable in the Uranian atmosphere. The vertical mixing on Uranus is found to be the least efficient of any of the planetary atmospheres.

Atreya, S. K.

Photochemistry of biogenic gases

The relationship between the biosphere and the atmosphere is examined, emphasizing the composition and photochemistry and chemistry of the troposphere and stratosphere. The reactions of oxygen, ozone, and hydroxyl are reviewed and the fate of the biogenic gases ammonia, methane, reduced sulfur species, reduced halogen species, carbon monoxide, nitric oxide, nitrous oxide, nitrogen, and carbon dioxide are described. A list is given of the concentration and sources of the various gases.

Levine, Joel S.

The ultraviolet photochemistry of diacetylene - Direct detection of primary products of the metastable C4H2* + C4H2 reaction

The products of diacetylene's ultraviolet photochemistry over the 245-220 nm region were directly determined in experiments where C4H2 was excited within a small reaction tube attached to a pulsed nozzle. The products formed in the collisions of C4H2* with C4H2 were subsequently ionized by vacuum UV radiation (at 118 nm) in the ion source of a time-of-flight mass spectrometer. It was found that the reaction of C4H2* with C4H2 produces C6H2 (+C2H2), C8H2 (+2H,H2), and C8H3 (+H), confirming the results of Glicker and Okabe (1987). Under certain conditions, secondary products were observed. Mechanisms for the observed reactions are proposed.

Bandy, Ralph E.