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Two-step photochemical process prevents yellowing of polycarbonate plastics. Use of polycarbonate plastics growing in windows, aircraft glazing, and streetlight globes. New photochemical process causes formation of stabilizers bound to polymer chains and therefore cannot be leached out.
Atmospheric interactions involving the nitrogen species are varied and complex. These interactions include photochemical reactions, initiated by the absorption of solar photons and chemical kinetic reactions, which involve both homogeneous (gas-to-gas reactions) and heterogeneous (gas-to-particle) reactions. Another important atmospheric interaction is the production of nitrogen oxides by atmospheric lightning. The nitrogen cycle strongly couples the biosphere and atmosphere. Many nitrogen species are produced by biogenic processes. Once in the atmosphere nitrogen oxides are photochemically and chemically transformed to nitrates, which are returned to the biosphere via precipitation, dry deposition and aerosols to close the biosphere-atmosphere nitrogen cycle. The sources, sinks and photochemistry/chemistry of the nitrogen species; atmospheric nitrogen species; souces and sinks of nitrous oxide; sources; sinks and photochemistry/chemistry of ammonia; seasonal variation of the vertical distribution of ammonia in the troposphere; surface and atmospheric sources of the nitrogen species, and seasonal variation of ground level ammonia are summarized.
Progress on modeling the spatial distributions of cometary radicals is described. The Monte Carlo particle-trajectory model was generalized to include the full time dependencies of initial comet expansion velocities, nucleus vaporization rates, photochemical lifetimes and photon emission rates which enter the problem through the comet's changing heliocentric distance and velocity. The effect of multiple collisions in the transition zone from collisional coupling to true free flow were also included. Currently available observations of the spatial distributions of the neutral radicals, as well as the latest available photochemical data were re-evaluated. Preliminary exploratory model results testing the effects of various processes on observable spatial distributions are also discussed.
Correlations between ozone and temperature are commonly used to investigate the photochemical and dynamical aspects of satellite-derived ozone data. In this paper, the dynamical contributions to the ozone temperature correlations are examined using simple analytic and numerical models. It is shown that the phase differences between ozone and temperature waves caused by dynamical forcing can mimic the phase relationships predicted for photochemical equilibrium. Furthermore, the dynamical contribution to the phase relationship between ozone and temperature waves is routinely significant for chemistry time scales of approximately 0.5 days and is potentially important for time scales as short as 2 hours during stratospheric warmings. The model results are highly relevant to the analysis of the limb infrared monitor of the stratosphere and solar backscatter ultraviolet data taken during the winter of 1979.
To investigate the occurrence of low temperatures and the formation of noctilucent clouds in the summer mesosphere, a one-dimensional time-dependent photochemical-thermal numerical model of the atmosphere between 50 and 120 km has been constructed. The model self-consistently solves the coupled photochemical and thermal equations as perturbation equations from a reference state assumed to be in equilibrium and is used to consider the effect of variability in water vapor in the lower mesosphere on the temperature in the region of noctilucent cloud formation. It is found that change in water vapor from an equilibrium value of 5 ppm at 50 km to a value of 10 ppm, a variation consistent with observations, can produce a roughly 15 K drop in temperature at 82 km. It is suggested that this process may produce weeks of cold temperatures and influence noctilucent cloud formation.
The types of models used in assessment of possible chemical perturbations to the stratosphere are reviewed. The statue of one and two dimensional models are discussed. The problem of model validation is covered before the status of photochemical modeling efforts is discussed. A hierarchy of tests for photochemical models is presented.
The data for chemical kinetics rate constants and photochemical cross sections taken from a compilation prepared in early 1985, entitled Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, is presented.
The distribution of gases in the prebiologial paleoatmosphere is investigated using photochemical models. A chart of the photochemical and chemical reactions and reaction rates for CH4, NH3, H2S, N2O, and CO atmospheric gases is given. Mixing ratios and surface mixing ratios for CH4, NH3, CO, and N2O are obtained using thermodynamic equilibrium calculations; an increase in CH4 and N2O is observed. The reactions, which explain the photochemistry of the gases studied, are presented. The sources of these gases and their concentration with regards to altitude are examined. Graphs of the vertical distribution of CH4, NH3, H2S, CO, O2, and N2O in prebiological paleoatmosphere are provided. The data reveals the presence of only N2, CO2, and N2O in the early atmosphere; with the evolution of life, sources of atmospheric gases increased and their influence on the photochemistry of the troposphere and stratosphere increased.
An attempt is made to explain the fact that the large variation in Venus CO abundance with planetary phase using a combination of photochemical and kinematical models. Present knowledge about the Venus mesosphere is first summarized, emphasizing the more completely measured lower and upper atmosphere. The predictions of Dickinson and Ridley's (1977) hydrodynamic modeling are compared to the results of microwave observations of CO. It is noted that the nightside CO bulge above 90-95 km altitude indicated by microwave measurements is a primary characteristic of these models, whereas the opposite phase behavior of CO between 80 and 90 km is not predicted by them. The result of diurnal photochemical models for the Venus mesosphere are presented and an attempt is made to reproduce the phase behavior of CO between 80 and 90 km in the Venus mesosphere. Possible diurnal variations due to chemistry and vertical eddy diffusion are considered.
A novel photochemical method for liquid-phase deposition of metal films is described. In the liquid phase deposition scheme, a metal containing compound and a metal-metal bonded carbonyl complex are dissolved together in a polar solvent and the mixture is irradiated using a UV laser. The optical arrangement consists of a HeCd laser which provides 7 mW of power at a wavelength of 325 nm in the TEM(OO) mode. The beam is attenuated and may be expanded to a diameter of 5-20 mm. Experiments with photochemical deposition of silver films onto glass and quartz substrates are described in detail. Mass spectrometric analysis of deposited silver films indicated a deposition rate of about 1 A/s at incident power levels of 0.01 W/sq cm. UV laser-induced copper and palladium films have also been obtained. A black and white photograph showing the silver Van Der Pauw pattern of a solution-deposited film is provided.
Difficulties arise in connection with the verification of multidimensional chemical models of the stratosphere. The present study shows that LIMS data, together with a photochemical equilibrium model, may be used to infer concentrations of a variety of zonally averaged trace Ox, OHx, and NOx species over much of the stratosphere. In the lower stratosphere, where the photochemical equilibrium assumption for HOx species breaks down, inferred concentrations should still be accurate to about a factor of 2 for OH and 2.5 for HO2. The algebraic nature of the considered model makes it possible to see easily to the first order the effect of variation of any model input parameter or its uncertainty on the inferred concontration of the HOx species and their uncertainties.
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.
Measurements of limb radiance from the Solar Mesosphere Explorer (SME) satellite are used to infer the NO2 density at the 10- and 16-mbar pressure levels from January 1 to March 31 of 1982. A photochemical-dynamical model is developed using the presently accepted chemistry of the NO(x) family. The dynamical model produces isentropic trajectories which simulate the history of air parcels. From the trajectories the photochemical model calculates NO2 densities, which are compared to those observed by SME. Although the model generally reproduces the spatial and temporal variations rather well, some disagreement was noted for conditions of exceptionally low temperatures. Further analysis indicates that the temperature sensitivity of the N2O5 photolysis cross sections may be overestimated at low temperatures.
Three independent examples are discussed which suggest that photochemical ozone production in the troposphere can be observed in the tropics from an analysis of total ozone data. The first finding shows that the seasonal cycle of total columnar ozone is dominated by the seasonal cycle of tropospheric ozone, even though tropospheric ozone accounts for only 5-15 percent of the total ozone. Second, a case study is presented which shows that enhanced total ozone observed over the Amazon Basin can be associated with the presence of biomass burning. In situ measurements have confirmed that biomass burning does result in the production of photochemically generated ozone, analogous to the formation of 'smog' near industrialized areas. Third, an analysis of the distribution of carbon monoxide obtained from a Space Shuttle platform is strongly correlated with the concurrent distribution of total ozone between 5 deg S and 10 deg N. Because all of the sources of carbon monoxide are located in the troposphere, this finding likewise suggests that the gradients of total ozone at low latitudes must also reflect processes occurring in the troposphere.
Possible dynamical influences on the diurnal behavior of ozone are investigated. A time dependent one-dimensional photochemical model is developed for this purpose; all model calculations are made at 70 deg N during summer. It is shown that the vertical diffusion can vary as much as 1 order of magnitude within a day as a result of large changes in the zonal wind induced by atmospheric thermal tides. It is found that by introducing a dissipation time scale for turbulence produced by breaking gravity waves, the agreement with Poker Flat echo data is improved. Comparisons of results from photochemical model calculations, where the vertical diffusion is a function of height only, with those in which the vertical diffusion coefficient is changing in time show large differences in the diurnal behavior of ozone between 70 and 90 km. By including the dynamical effect, much better agreement with the Solar Mesosphere Explorers data is obtained. The results are, however, sensitive to the background zonally averaged wind. The influence of including time-varying vertical diffusion coefficient on the OH densities is also large, especially between 80 and 90 km. This suggests that dynamical effects are important in determining the diurnal behavior of the airglow emission from the Meinel bands.
An earlier theory of ionization of C-rich circumstellar envelopes based on the photochemical model is extended to include the temperature dependence of ion-molecule reactions with polar molecules, particularly HCN, and line self-shielding of CO dissociating radiation. The results are applied to the abundances of HCO(+) and HNC in C-rich circumstellar envelopes. With standard parameters for IRC + 10216, the model is found to be consistent with the new upper limit to the antenna temperature of the J = 1-0 line of HCO(+) obtained with the IRAM 30-m telescope. The photochemical model provides a natural explanation of the relatively large ratio of HCN to HNC observed for C-rich circumstellar envelopes, and good agreement is obtained for the H(C-13)N/HNC antenna temperature ratio measured for IRC + 10216.
The 1-1/2-D model of Holton (1986), which is actually a highly truncated two-dimensional model, describes latitudinal variations of tracer mixing ratios in terms of their projections onto second-order Legendre polynomials. The present study extends the work of Holton by including tracers with photochemical production in the stratosphere (O3 and NOy). It also includes latitudinal variations in the photochemical sources and sinks, improving slightly the calculated global mean profiles for the long-lived tracers studied by Holton and improving substantially the latitudinal behavior of ozone. Sensitivity tests of the dynamical parameters in the model are performed, showing that the response of the model to changes in vertical residual meridional winds and horizontal diffusion coefficients is similar to that of a full two-dimensional model. A simple ozone perturbation experiment shows the model's ability to reproduce large-scale latitudinal variations in total ozone column depletions as well as ozone changes in the chemically controlled upper stratosphere.
Ozone depletions associated with solar proton events have now been observed in nine events: November 1969, January and September 1971, August 1972, June and August 1979, October 1981, and July and December 1982. Since the proton fluxes during these events are fairly well known from satellite observations, modelers have been able to compare model predictions with observations of ozone behavior during these events to test the validity of atmospheric photochemical models. Ozone decreases initially follow approximately their theoretically predicted behavior below about 45 km (where NOx is thought to cause the ozone decrease), but after about two weeks the observed decrease appears to be larger than the computed decrease. Above 45 km, where HOx is thought to cause the ozone decrease, the picture of model validity is not as clear. The observed ozone decreases between about 45 and 60 km are substantially more than that predicted by present photochemical models while between about 60 and 85 km the observed ozone decrease is approximately equal to that predicted.