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At least 541 records · Page 30

The influence of NO and ClO variations at twilight on the interpretation of solar occultation measurements

Measurement of short-lived photochemically-produced species in the stratosphere by solar occultation is difficult because the rapid variation of such species near the terminator introduces ambiguities in interpreting the measured absorption in terms of meaningful atmospheric abundances. These variations produce tangent path concentrations that are asymmetric relative to the tangent point, as opposed to the symmetrical distribution usually assumed in most inversion algorithms. Neglect of this asymmetry may yield an inverted profile that deviates significantly from the true sunset/sunrise profile. In the present paper, the influence of this effect on solar occultation measurements of ClO and NO is examined. The results show that average inhomogeneity factors, which measure the concentration variation along the tangent path and which can be calculated from a photochemical model, can indicate which species require more careful data analysis.

Boughner, R.↗

Preliminary calculations concerning the maintenance of the zonal mean ozone distribution in the Northern Hemisphere

Results from a three-dimensional photochemical-dynamical model of ozone are presented and a qualitative description of the maintenance of the ozone distribution and its seasonal variations below 1 mb is given. The transition between photochemical and transport control of the ozone distribution is emphasized. Between 1 and 10 mb, transport by the eddies seems to play only a minor role at mid-latitudes in producing the observed ozone distribution despite the zero correlation between ozone and temperature which occurs in that region. In the lower stratosphere, mean and eddy contributions to ozone change generally strongly offset one another. The buildup and decay of the springtime ozone maximum is discussed. Emphasis is given to the mechanism of ozone transport by the mid-latitude eddies, which play an important role in the springtime accumulation of ozone.

Cunnold, D. M.↗

Modeling of a solar-pumped iodine laser

The direct conversion in space of solar radiation into laser radiation for power transmission to earth, satellites, or deep space probes shows promise as a reasonably simple technology and may have cost advantage in deployment and greater reliability compared to other methods of space power generation and transmission. The main candidates for solar pumping are the gas dynamic, photochemical, and direct photoexcited lasers. Here consideration is given to the photochemical reaction of alkyliodides which predominantly excite the I(2P1/2) state which then lases at 1.315 microns. The iodine ground state is eventually lost to reconstituting the gas or in the formation of molecular iodine. The rates at which the gas is required to be recycled through the laser system are modest. The side exposure at 100-fold solar concentration of a 100-m long tube with a 1 sq m cross section is estimated to provide 20 kW of continuous laser output. Scaling laws and optimum operating conditions of this system are discussed.

Wilson, J. W.↗

Ozone in the upper stratosphere and mesosphere

A detailed photochemical model of the upper stratosphere and mesosphere is compared with three extensive sets of ozone observations: Atmospheric Explorer-E backscattered ultraviolet experiment (BUV), Nimbus-4 BUV, and rocket flights from Wallops Flight Center (ROCOZ). The Nimbus-4 and rocket observations are most sensitive to ozone between 30 and 50 km, whereas observations from AE-E measure the abundance of ozone up to 70 km. The photochemical model accurately reproduces the observed relationship between BUV intensity and local solar zenith angle, although the absolute calibration on AE-E appears to be in error. The AE-E observations and the model both exhibit a morning-afternoon asymmetry, with more ozone in the morning owing to the build up of HOx species in the afternoon. Seasonal changes in atmospheric temperature produce an annual maximum in tropical mesospheric ozone during June-July-August. The amplitude of the observed effect is somewhat larger than calculated by the model. Some problems appear to remain with the presently accepted kinetic rates for HOx species in the atmosphere.

Prather, J. J.↗

Photochemistry of acetylene at 1470 A

The considered study was conducted to assess the importance of the major primary photochemical process of acetylene at 1470 A, to clarify the role of the metastable excited state, and to obtain information on the rates of C2H reactions with H2 and CH4. Concerning the photodissociation process of acetylene, it was found that at acetylene pressures below 0.8 Torr the direct dissociation process (C2H2 yields C2H + H) is the most important primary photochemical process with a quantum yield of 0.3. Another primary process may be the production of H2 with a quantum yield of approximately 0.1 (C2H2 yields C2 + H2). At acetylene pressures above 0.8 Torr diacetylene is formed by the direct dissociation process followed by the reaction: C2H + C2H2 yields C4H2 + H. At pressures above 20 Torr benzene becomes an important product with a concomitant decrease of diacetylene. The role of acetylene in the photochemistry of the Jovian atmosphere is also considered

Okabe, H.↗

Effects of multiple scattering and surface albedo on the photochemistry of the troposphere

The effect of treatment of incoming solar radiation on the photochemistry of the troposphere is discussed. A one dimensional photochemical model of the troposphere containing the species of the nitrogen, oxygen, carbon, hydrogen, and sulfur families was developed. The vertical flux is simulated by use of the parameterized eddy diffusion coefficients. The photochemical model is coupled to a radiative transfer model that calculates the radiation field due to the incoming solar radiation which initiates much of the photochemistry of the troposphere. Vertical profiles of tropospheric species were compared with the Leighton approximation, radiative transfer, matrix inversion model. The radiative transfer code includes the effects of multiple scattering due to molecules and aerosols, pure absorption, and surface albedo on the transfer of incoming solar radiation. It is indicated that significant differences exist for several key photolysis frequencies and species number density profiles between the Leighton approximation and the profiles generated with, radiative transfer, matrix inversion technique. Most species show enhanced vertical profiles when the more realistic treatment of the incoming solar radiation field is included

Augustsson, T. R.↗

The possible effect of 11 year solar cycle on the thermal structure of the stratosphere and ozone distribution investigated in a 2-D model

A two-dimensional time dependent radiative-photochemical-dynamical model of the stratosphere which takes into account the feedback effect of temperature on ozone concentration is used to investigate the possible changes in the seasonal and latitudinal variations of temperature, ozone, and other minor constituents associated with the UV flux variations from the solar minimum to the solar maximum. The transport model determines the zonal wind, non-zonal eddy transports, and eddy momentum fluxes, while the photochemical system includes the important reactions affecting the concentrations of ozone and other relevant trace constituents in the stratosphere. Experiments are carried out by changing the position of the sun every day and evaluating the daily average photodissociation integrals for the relevant minor constituents and ozone heating. Values are found for the ambient stratosphere and a stratosphere perturbed by solar cycle variations, and a rough comparison is made with observed ozone and temperature trends.

Vupputuri, R. K. R.↗

An analysis of the physical, chemical, optical, and historical impacts of the 1908 Tunguska meteor fall

An analysis is presented of the physical characteristics and photochemical aftereffects of the 1908 Tunguska explosive cometary meteor, whose physical manifestations are consistent with a five million ton object's entry into the earth's atmosphere at 40 km/sec. Aerodynamic calculations indicate that the shock waves emanating from the falling meteor could have generated up to 30 million tons of nitric oxide in the stratosphere and mesosphere. A fully interactive one-dimensional chemical-kinetics model of atmospheric trace constituents is used to estimate the photochemical consequences of such a large NO injection. The 35-45% hemispherical ozone depletion predicted by the model is in keeping with the 30 + or - 15% ozone variation reported for the first year after the Tunguska fall. Attention is also given to the optical anomalies which followed the event for indications of NO(x)-O(x) chemiluminescent emissions, NO2 solar absorption, and meteoric dust turbidity, along with possible climate changes due to the nearly one million tons of pulverized dust deposited in the mesosphere and stratosphere by the meteor.

Turco, R. P.↗

Chemistry and evolution of Titan's atmosphere

The chemistry and evolution of Titan's atmosphere are reviewed, in light of the scientific findings from the Voyager mission. It is argued that the present N2 atmosphere may be Titan's initial atmosphere, rather than one photochemically derived from an original NH3 atmosphere. The escape rate of hydrogen from Titan is controlled by photochemical production from hydrocarbons. CH4 is irreversibly converted to less hydrogen-rich hydrocarbons, which over geologic time accumulate on the surface to a layer thickness of about 0.5 km. Magnetospheric electrons interacting with Titan's exosphere may dissociate enough N2 into hot, escaping N atoms to remove about 0.2 of Titan's present atmosphere over geologic time. The energy dissipation of magnetospheric electrons exceeds solar EUV energy deposition in Titan's atmosphere by an order of magnitude, and is the principal driver of nitrogen photochemistry. The environmental conditions in Titan's upper atmosphere are favorable to building up complex molecules, particularly in the north polar cap region.

Strobel, D. F.↗

Cumulus cloud transport of transient tracers

A theoretical framework is developed for including cumulus cloud transport, rainout of water soluble gases, and aqueous phase chemistry into gas phase photochemical models. Cloud populations are represented as ensemble distributions of individual clouds of various heights. An individual cloud is represented as a one-dimensional, steady state plume with height-independent radius entraining air from the boundary of the cloud. The model is applied to several hypothetical atmospheric tracers to show how clouds may affect the tropospheric distributions of ozone, NO(y), SO2, peroxyacetylnitrate, hydrocarbons, and other gases. Although the numerical experiments were based on cloud mass fluxes from diagnostic studies in the tropics and thus are not representative of the entire globe, it was found that an increasing mixing ratio with height in the free troposphere can be produced for some gases with only a surface source when clouds are present. This suggests that some reactive tropospheric species with primarily surface sources may play a somewhat more important role in tropospheric chemistry than is presently believed depending on the global distribution of cloud mass fluxes. Deficiencies in existing photochemical models due to the way clouds are typically treated are discussed.

Gidel, L. T.↗

The effect of clouds on photolysis rates and ozone formation in the unpolluted troposphere

The photochemistry of the lower atmosphere is sensitive to short- and long-term meteorological effects; accurate modeling therefore requires photolysis rates for trace gases which reflect this variability. As an example, the influence of clouds on the production of tropospheric ozone has been investigated, using a modification of Luther's two-stream radiation scheme to calculate cloud-perturbed photolysis rates in a one-dimensional photochemical transport model. In the unpolluted troposphere, where stratospheric inputs of odd nitrogen appear to represent the photochemical source of O3, strong cloud reflectance increases the concentration of NO in the upper troposphere, leading to greatly enhanced rates of ozone formation. Although the rate of these processes is too slow to verify by observation, the calculation is useful in distinguishing some features of the chemistry of regions of differing mean cloudiness.

Thompson, A. M.↗

The evolution of the prebiotic atmosphere

One-dimensional radiative-convective and photochemical models are used to estimate the vertical temperature structure and composition of the earth's prebiotic atmosphere. Greatly enhanced CO2 levels (100-1000 times present) are required to keep the mean surface temperature above freezing in the face of decreased solar luminosity during the earth's early history. Such high CO2 partial pressures would have affected the atmospheric oxidation state by facilitating the photochemical production of soluble species including H2O2 and H2CO. Oxidation of ferrous iron in the oceans by H2O2 dissolved in rainwater should have kept the atmospheric H2 mixing ratio above 0.0002, and the ground-level O2 mixing ratio below 10 to the -11th, regardless of the magnitude of the rate of volcanic release of reduced gases.

Kasting, J. F.↗

Nonyellowing Polycarbonate for Outdoor Use

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.

Gupta, A.↗

The nitrogen cycle: Atmosphere interactions

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.

Levine, J. S.↗

Cometary atmospheres: Modeling the spatial distribution of observed neutral radicals

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.

Combi, M. R.↗

Interpretation of ozone temperature correlations. I - Theory

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.

Rood, R. B.↗

Noctilucent cloud formation and the effects of water vapor variability on temperatures in the middle atmosphere

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.

Mckay, C. P.↗

Assessment models

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.

Pyle, J. A.↗