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1.
Density profiles for CO, O, and O2 in the Cytherean atmosphere above 90 km are plotted with eddy diffusion coefficient (K) as a parameter, subject to the constraint that the mixing ratios of CO and O2 approach their observed value or values under the observed upper limit at the lower boundary. It is then shown that the value of K puts upper limits on the amount of hydrogen (in the form of H2O, HCl, and H2) the atmosphere near 90km can contain. This value is a function of the density and temperature of hydrogen at the critical level and the magnitude of the total escape flux, where unspecified flux mechanisms other than thermal are postulated ad hoc. In general these constraints call for large values of K to accomodate the atomic hydrogen produced by measured mixing ratios of HCl and H2O. Hence they constrain thee amount of O in the upper atmosphere to values well under 1% at 130 km unless there are very large hydrogen escape fluxes, 107 cm?2sec?1 or larger. The freedom to assume arbitrary amounts of H2 in the atmosphere is also restricted. We suggest either very effective escape mechanisms—despite low exospheric hydrogen densities—or novel excitation mechanisms for O(33S) and O(35S) in the upper atmosphere.  相似文献   

2.
Models are presented for the height distribution of various photochemically active gases in Venus' upper atmosphere. Attention is directed to the chemistry and vertical transport of odd hydrogen (H, OH, HO2, H2O2), odd oxygen (O, O3), free chlorine (Cl, ClO, ClOO, Cl2), CO, O2, H2 and H2O. Supply of O2 may play a limiting role in the formation of a possible H2SO4 cloud on Venus. The supply rate is influenced by both chemical and dynamical processes in the stratosphere, and an analysis of recent spectroscopic data for O2 implies a lower limit to the appropriate eddy coefficient of about 3 × 105 cm2/sec. The abundances of thermospheric O and CO are determined largely by vertical mixing, and an analysis of Mariner 10 measurements of Venus' Lyman α airglow suggests that the eddy coefficient in the lower thermosphere may be as large as 5 × 107cm2sec. The corresponding values for the mixing ratios of O and CO at the ionospheric peak are approximately 1 per cent. The Lyman α data could be reconciled with larger values for thermospheric O, and smaller values for the vertical eddy coefficient, if non-thermal loss processes were to play a dominant role in hydrogen escape, and if the corresponding flux were to exceed 107 atoms/cm2/sec. A sink of this magnitude would imply major depletion of Venus' atmospheric water over geologic time, and would appear to require mixing ratios of H2O in the lower atmosphere in excess of 4 × 10?4. The extensive component to the Lyman α emission measured by Mariner 5 may be due to resonance scattering of sunlight by hot atoms formed by charge transfer with O+. The H scale height, therefore, may reflect the temperature of positive ions in Venus' topside ionosphere.  相似文献   

3.
Altitude profiles for the number densities of NO, NO2, NO3, N2O5, HNO2, CH3O, CH3O2, H2CO, OH, and HO2 are calculated as a function of time of day with a steady-state photochemical model in which the altitude profiles for the number densities of H2O, CH4, H2, CO, O3, and the sum of NO and NO2 are fixed at values appropriate to a summer latitude of 34°. Average daily profiles are calculated for the long-lived species, HNO3, H2O2, and CH3O2H.The major nitrogen compound HNO3 may have a number density approaching 5 × 1011 molecules cm?3 at the surface, although an effective loss path due to collisions with particulates could greatly reduce this value.The number density of OH remains relatively unchanged in the first 6 km and reaches 1 × 107 molecules cm?3 at noon, while the number density of HO2 decreases throughout the lower troposphere from its noontime value of 8 × 108 molecules cm?3 at the surface.H2O2 and H2CO both have number densities in the ppb range in the lower troposphere.Owing to decreasing temperature and water concentration, the production of radicals and their steady-state number densities decrease with altitude, reaching a noontime minimum of 1 × 108 molecules cm?3 for OH and 3 × 107 molecules cm?3 for HO2 at the tropopause. The related minor species show even sharper decreases with increasing altitude.The primary path for interconverting OH and HO2 serves as the major sink for CO and leads to a tropospheric lifetime for CO of ~0.1 yr.Another reaction cycle, the oxidation of CH4, is quite important in the lower troposphere and leads to the production of H2CO along with the destruction of CH4 for which a tropospheric lifetime of ~2 yr is estimated.The destruction of H2CO that was produced in the CH4 oxidation cycle provides the major source of CO and H2 in the atmosphere.  相似文献   

4.
It is argued that ozone measurements made by Weeks et al. (1972) can be interpreted in terms of the enhanced ionization present. The conversion of O2+ ions to oxonium, H3O+ · (H2O)n, ions plus the dissociative recombination of these ions provides for an increased OH and/or H formation rate. The resulting enhanced OH and HO2 concentrations reduce the ambient atomic oxygen and hence ozone populations. The net excess H + OH formation rate is found to lie between one and two times the ionization production rate at altitudes where oxonium ions are the dominant positive ion species.  相似文献   

5.
Darrell F. Strobel 《Icarus》1974,21(4):466-470
Detailed photochemical models are constructed for two model atmospheres: (1) 100% CH4 and (2) 50% H2, 50% CH4. Both models predict large column densities of C2H2 and C2H6 (~1 cm atm) for eddy mixing rates ~105 cm2 sec?, which are comparable to rates appropriate for Jupiter. These column densities vary inversely with the eddy diffusion coefficient. The models confirm the interpretation by Danielson et al. (1973) of the 12μ feature in the spectra of Gillet et al. (1973) as emission by C2H6 in a thermal inversion region. The C2H6C2H2 mixing ratio is sensitive to the net escape rate of H atoms from the exobase.  相似文献   

6.
A mechanism has been proposed for uv-accelerated desorption from Fe2+ sites on mineral surfaces that satisfies kinetic constraints determined in the laboratory by Huguenin. The process is an integral step of the photochemical weathering mechanism for producing dust on Mars, and it now appears that it may play primary roles in stabilizing CO2 against dissociation by sunlight and in controlling the oxidation state of the atmosphere. We propose that adsorption occurs at octahedrally coordinated Fe2+ surface sites to form seven-coordinate transition-state complexes. These complexes acquire 16–18 kcal mole?1 of ligand field stabilization energy. During illumination (λ ≤ 0.35 μm), electrons are photoemitted from the surfaced Fe2+, temporarily oxidizing them to Fe3+. Fe3+ has no ligand field stabilization energy, and the complexes lose 16–18 kcal mole?1 of stabilization energy. This is a large fraction of the 19- to 28-kcal mole?1 activation energy for dissociating the complexes, and desorption should proceed spontaneously. The gases that were observed to undergo adsorption-photodesorption include O2, CO2, CO, H2O, N2, and Ar. Photodesorption can drive several catalytic reactions, one of which is the oxidation of CO to CO2. The rate of this reaction should be limited by the supply of CO and O2 to the surface to ~2 × 1012 cm?2 sec?1 (column photodissociation rate of CO2). By including this surface reaction in models of Martian atmospheric CO2 chemistry, CO2 can be stabilized against photodissociation with eddy diffusion coefficients of only 3 × 105?1 × 107 cm2 sec?1 below 40 km, raising to ~ 109 cm2 sec?1 at 140 km. Odd hydrogen is not needed to catalyze the oxidation of CO below 40 km, and odd hydrogen mixing ratios need only to be fH ? 10?10 to depress ozone concentrations below the observed upper limit in equatorial regions. Another catalytic reaction that should be driven by photodesorption on Mars is 20H?(ads)H2O + 12O2(g) + 2e?crystal. This is an important source of atmospheric O2, amounting to 7 × 1013?2 × 1017 O2 molecules cm?2 yr?1, and it could have a significant effect on atmospheric oxidation state.  相似文献   

7.
The Hadley mechanism is adopted to describe the axisymmetric four day superrotation in the Venus atmosphere, with solar driven meridional winds redistributing energy and momentum, and eddy diffusion describing the actions of three dimensional transient eddies. We address the question how the eddy diffusion coefficients are related to the properties of the circulation. For the atmosphere of a slowly rotating planet such as Venus, we show that a form of the non-linear closure is suggested by the mixing length hypothesis, which constrains the magnitude of the eddy diffusion coefficients. Combining this constraint with the concept of the Rossby radius of deformation yields zonal velocities on the order of 100 m sec–1. A steady state, non-linear, one-layer spectral model is used for a parametric study to find a relationship between heat source, meridional circulation and eddy diffusion coefficients, which yields the large zonal velocities observed. This analysis leads to the following conclusions: (1) Proportional changes in the heat source and eddy diffusion coefficients do not significantly change the zonal velocities. (2) The meridional velocity is virtually constant for large eddy diffusion coefficients. (3) Below a threshold in the diffusion rate, the meridional velocity decreases, commensurate with the mixing length hypothesis. Eddy heat conduction becomes important and shares with the Hadley cell advection in balancing the solar heating. The zonal velocities then reach large values near 100 m sec–1. (4) For large eddy diffusion and small heating rates, the zonal velocities decrease with decreasing planetary rotation rates. However, under condition (3), the zonal velocities are independent of the planetary rotation rate. Ramifications are discussed for related parameterizations in GCMs, emphasizing that eddy diffusion coefficients are governed by solar forcing and cannot be chosen independently.  相似文献   

8.
The calculation of number densities of CO2, H2O and N2 photolysis products was carried out for the Martian atmosphere at heights up to 60 km. The ozone distributed in the atmosphere as a layer of 10 km width with [O3] max = 2.5 × 109 cm3 at height of 35 km which agree well with the results of u.v. observations on the evening terminator from the Mars-5 satellite. The calculated densities of O2, CO and H2O are also in good agreement with the measured data. The eddy diffusion coefficient is equal to 3 × 106 in the troposphere (h ? 30 km) and 108 cm2 s?1 above 40 km. The dependence of the total ozone content on water vapour amount in the atmosphere is considered; the hypothesis about the influence of water ice aerosol on the ozone formation is proposed to explain the high concentrations of ozone in the morning.  相似文献   

9.
Altitude dependences of [CO2] and [CO2+] are deduced from Mariner 6 and 7 CO2+ airglow measurements. CO2 densities are also obtained from ne radio occultation measurements. Both [CO2] profiles are similar and correspond to the model atmosphere of Barth et al. (1972) at 120 km, but at higher altitudes they diverge and at 200–220 km the obtained [CO2] values are three times less the model. Both the airglow and radio occultation observations show that a correction factor of 2.5 should be included into the values for solar ionization flux given by Hinteregger (1970). The ratio of [CO2+]/ne is 0.15–0.2 and, hence, [O]/[CO2] is ~3% at 135 km. An atmospheric and ionospheric model is developed for 120–220 km. The calculated temperature profile is characterized by a value of T ≈ 370°K at h ? 220 km, a steep gradient (~2°/km) at 200-160 km, a bend in the profile at 160 km, a small gradient (~0.7°/km) below and a value of T ≈ 250°K at 120 km. The upper point agrees well with the results of the Lyman-α measurements; the steep gradient may be explained by molecular viscosity dissipation of gravity and acoustical waves (the corresponding energy flux is 4 × 10?2 erg cm?2sec?1 at 180 km). The bend at 160 km may be caused by a sharp decrease of the eddy diffusion coefficient and defines K ≈ 2 × 108cm2sec?1; and the low gradient gives an estimate of the efficiency of the atmosphere heating by the solar radiation as ? ≈ 0.1.  相似文献   

10.
The evolution and variability of atmospheric ozone over geological time   总被引:1,自引:0,他引:1  
The rise of atmospheric O3 as a function of the evolution of O2 has been investigated using a one-dimensional steady-state photochemical model based on the chemistry and photochemistry of Ox(O3, O, O(1D)), N2O, NOx(NO, NO2, HNO3), H2O, and HOx(H, OH, HO2, H2O2) including the effect of vertical eddy transport on the species distribution. The total O3 column density was found to maximize for an O2 level of 10?1 present atmospheric level (PAL) and exceeded the present total O3 column by about 40%. For that level of O2, surface and tropospheric O3 densities exceeded those of the present atmosphere by about an order of magnitude. Surface and tropospheric OH densities of the paleoatmosphere exceeded those of the present atmosphere by orders of magnitude. We also found that in the O2-deficient paleoatmosphere, N2O (even at present atmospheric levels) produces much less NOx than it does in the present atmosphere.  相似文献   

11.
Yuk L. Yung  W.B. Demore 《Icarus》1982,51(2):199-247
The photochemistry of the stratosphere of Venus was modeled using an updated and expanded chemical scheme, combined with the results of recent observations and laboratory studies. We examined three models, with H2 mixing ratio equal to 2 × 10?5, 5 × 10?7, and 1 × 10?13, respectively. All models satisfactorily account for the observations of CO, O2, O2(1Δ), and SO2 in the stratosphere, but only the last one may be able to account for the diurnal behavior of mesospheric CO and the uv albedo. Oxygen, derived from CO2 photolysis, is primarily consumed by CO2 recombination and oxidation of SO2 to H2SO4. Photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen and free chlorine radicals, essential for the catalytic oxidation of CO. Oxidation of SO2 by O occurs in the lower stratosphere. In the high-H2 model (model A) the OO bond is broken mainly by S + O2 and SO + HO2. In the low-H2 models additional reactions for breaking the OO bond must be invoked: NO + HO2 in model B and ClCO + O2 in model C. It is shown that lightning in the lower atmosphere could provide as much as 30 ppb of NOx in the stratosphere. Our modeling reveals a number of intriguing similarities, previously unsuspected, between the chemistry of the stratosphere of Venus and that of the Earth. Photochemistry may have played a major role in the evolution of the atmosphere. The current atmosphere, as described by our preferred model, is characterized by an extreme deficiency of hydrogen species, having probably lost the equivalent of 102–103 times the present hydrogen content.  相似文献   

12.
A model for the hydrogen coma of a comet on the basis of the Monte Carlo method is presented. In this model isotropic ejections of H atoms produced by photodissociation of H2O and OH, thermalization of the H atoms due to collisions with ambient H2O molecules, and the solar radiation pressure have been taken into account. A production spectrum of H atoms from OH is evaluated by using the predissociation rates and the level populations of OH, confirming that the spectrum has a sharp peak around 8.0 km sec?1 with the standard deviation of 0.1 km sec?1. Including the above effects, velocity distribution functions of the H atoms at various positions in the coma for the first time, as well as their density and outflow velocity profiles, have been calculated. It is pointed out that the collisional thermalization process in the inner coma is an important factor at small heliocentric distances in determining the density profiles and the velocity distributions. It is shown that thermalization leads to an increase in the H density in the inner coma larger than those expected from other models such as the vectorial model, in which collision is not taken into account. Lyman α isophotes and its line profiles in the optically thin region are computed by using the velocity distribution function.  相似文献   

13.
The radiative lifetimes of cometary OH are calculated as a function of the heliocentric velocity of the comet and the velocity distributions of the product atoms are determined. At a distance of 1 AU from the Sun, the lifetimes vary between 1.2×105 and 1.9×105 sec at solar minimum and between 1.0×105 and 1.4×105 sec at solar maximum, depending upon velocity. Continuous absorption into the repulsive 12Σ- state is major destruction path. The calculated lifetimes are generally consistent with the lifetimes inferred from observations, but suggest some elaboration of the models is necessary. Photodissociation of OH produces a low-velocity component of hydrogen atoms at 8 km sec?1 relative to the parent OH molecule and a high-velocity component between 17 and 27 km sec?1. Photodissociation of OH leads to metastable O(1D) and O(1S) and is an additional source of the red and green line emission of atomic oxygen. The lifetime of OD is estimated to be about 4.3× 105 sec at solar minimum and 2.6×105 sec at solar maximum so that the OD/OH ratio in comets is enhanced relative to the HDO/H2O production ratio by a factor between 2 and 3. Photodissociation of OD produces only high-velocity D atoms with a mean value of 17 km sec?1.  相似文献   

14.
Models are developed to describe the photochemistry of ozone on Mars. Catalytic reactions involving H, OH and HO2 play a major role at low latitudes where they ensure a vertical column density for O3 of less than 2 × 10?4 cm atm. The source for odd hydrogen (H + OH + HO2) is relatively smaller at high latitudes in winter due to the small concentrations of H2O present there at that time. Odd hydrogen is also efficiently removed from the high-latitude winter atmosphere by condensation of H2O2. The role of catalytic chemistry is reduced accordingly and the vertical column density of O3 may be as large as 5.7 × 10?3 cm atm in accord with earlier observations carried out by Barth and co-workers with instruments on Mariner 9.  相似文献   

15.
Results of analysis of about 150 autocorrelation functions are presented for the period from about 2300 hr on 5 October to about 1200 hr on 7 October 1967. A large percentage concentration of helium ions are observed. It reaches a value as high as 50 per cent with a maximum at around 800 km. Downward heat fluxes deduced from the temperature variations yield a value of about 2–2.5 × 109 eV cm?2 sec?1 during the period 1200–1600 hr and a value of about 1.5 × 108 eV cm?2 sec?1 during the period 0100–0400 hr at night. These agree well with other measurements. The O+ ions are found not to be in diffusive equilibrium, and from the O+ fluxes and the electron density profiles, the O+ drift velocity has been estimated. It is found that the speed can be as high as 1–5 × 103 cm sec?1 even at altitudes as high as 700 km.  相似文献   

16.
The rates of photodissociation of the OH and OD molecules from absorption of solar radiation in he X2Π-A2Σ+ electronic transition are calculated to lie between 3.5 and 6.7 × 10?6 sec?1 for OH for heliocentric velocities between -60 and +60 km sec?1 and to be about 4.7 × 10?7 sec?1 for OD at 1 AU from the Sun. The corresponding lifetimes, which are upper bounds to the actual lifetimes, are generally consistent with the observational cometary data.  相似文献   

17.
The model is intended to respond to the recent findings in the Venus atmosphere from the Venus Express and ground-based submillimeter and infrared observations. It extends down to 47 km for comparison with the kinetic model for the lower atmosphere (Krasnopolsky, V.A. [2007]. Icarus 191, 25–37) and to use its results as the boundary conditions. The model numerical accuracy is significantly improved by reduction of the altitude step from 2 km in the previous models to 0.5 km. Effects of the NUV absorber are approximated using the detailed photometric observations at 365 nm from Venera 14. The H2O profile is not fixed but calculated in the model. The model involves odd nitrogen and OCS chemistries based on the detected NO and OCS abundances. The number of the reactions is significantly reduced by removing of unimportant processes. Column rates for all reactions are given, and balances of production and loss may be analyzed in detail for each species.The calculated vertical profiles of CO, H2O, HCl, SO2, SO, OCS and of the O2 dayglow at 1.27 μm generally agree with the existing observational data; some differences are briefly discussed. The OH dayglow is ~30 kR, brighter than the OH nightglow by a factor of 4. The H + O3 process dominates in the nightglow excitation and O + HO2 in the dayglow, because of the reduction of ozone by photolysis. A key feature of Venus’ photochemistry is the formation of sulfuric acid in a narrow layer near the cloud tops that greatly reduces abundances of SO2 and H2O above the clouds. Delivery of SO2 and H2O through this bottleneck determines the chemistry and its variations above the clouds. Small variations of eddy diffusion near 60 km result in variations of SO2, SO, and OCS at and above 70 km within a factor of ~30. Variations of the SO2/H2O ratio at the lower boundary have similar but weaker effect: the variations within a factor of ~4 are induced by changes of SO2/H2O by ±5%. Therefore the observed variations of the mesospheric composition originate from minor variations of the atmospheric dynamics near the cloud layer and do not require volcanism. NO cycles are responsible for production of a quarter of O2, SO2, and Cl2 in the atmosphere. A net effect of photochemistry in the middle atmosphere is the consumption of CO2, SO2, and HCl from and return of CO, H2SO4, and SO2Cl2 to the lower atmosphere. These processes may be balanced by thermochemistry in the lower atmosphere even without outgassing from the interior, though the latter is not ruled out by our models. Some differences between the model and observations and the previous models are briefly discussed.  相似文献   

18.
V.A. Krasnopolsky 《Icarus》1979,37(1):182-189
Observations and model calculations of water vapor diffusion suggest that about half the amount of water vapor is distributed with constant mixing ratio in the Martian atmosphere, the other half is the excess water vapor in the lower troposphere. During 24 hr the total content of water vapor may vary by a factor of two. The eddy diffusion coefficient providing agreement between calculations and observations is K = (3–10) × 106 cm2 sec?1 in the troposphere. An analytical expression is derived for condensate density in the stratosphere in terms of the temperature profile, the particle radius r, and K. The calculations agree with the Mars 5 measurements for r = 1.5 μm, condensate density 5 × 10?12 g/cm3 in the layer maximum at 30 to 35 km, condensate column density 7 × 10?6 cm?2, K = (1?3) × 106 cm2 sec?1, and the temperature profile T = 185 ? 0.05z ? 0.01z2 at 20 to 40 km. Condensation conditions yield a temperature of 160°K at 60 km in the evening; the scale height for scattered radiation yields T = 110°k at 80 to 90 km. The Mars model atmosphere has been developed up to 125 km.  相似文献   

19.
A global-mean model of coupled neutral and ion chemistry on Titan has been developed. Unlike the previous coupled models, the model involves ambipolar diffusion and escape of ions, hydrodynamic escape of light species, and calculates the H2 and CO densities near the surface that were assigned in some previous models. We tried to reduce the numbers of species and reactions in the model and remove all species and reactions that weakly affect the observed species. Hydrocarbon chemistry is extended to C12H10 for neutrals and C10H+11 for ions but does not include PAHs. The model involves 415 reactions of 83 neutrals and 33 ions, effects of magnetospheric electrons, protons, and cosmic rays. UV absorption by Titan's haze was calculated using the Huygens observations and a code for the aggregate particles. Hydrocarbon, nitrile, and ion chemistries are strongly coupled on Titan, and attempt to calculate them separately (e.g., in models of ionospheric composition) may result in significant error. The model densities of various species are typically in good agreement with the observations except vertical profiles in the stratosphere that are steeper than the CIRS limb data. (A model with eddy diffusion that facilitates fitting to the CIRS limb data is considered as well.) The CO densities are supported by the O+ flux from Saturn's magnetosphere. The ionosphere includes a peak at 80 km formed by the cosmic rays, steplike layers at 500-700 and 700-900 km and a peak at 1060 km (SZA = 60°). Nighttime densities of major ions agree with the INMS data. Ion chemistry dominates in the production of bicyclic aromatic hydrocarbons above 600 km. The model estimates of heavy positive and negative ions are in reasonable agreement with the Cassini results. The major haze production is in the reactions C6H + C4H2, C3N + C4H2, and condensation of hydrocarbons below 100 km. Overall, precipitation rate of the photochemical products is equal to 4-7 kg cm−2 Byr−1 (50-90 m Byr−1 while the global-mean depth of the organic sediments is ∼3 m). Escape rates of methane and hydrogen are 2.9 and 1.4 kg cm−2 Byr−1, respectively. The model does not support the low C/N ratio observed by the Huygens ACP in Titan's haze.  相似文献   

20.
A one dimensional time-dependent model of the neutral and ion chemistry of the middle atmosphere has been used to examine the production of odd hydrogen (H, OH, and HO2) during charged particle precipitation. At altitudes above about 65 km, odd hydrogen production depends on the ionization rate, and the atomic oxygen and water vapor densities. Odd hydrogen production is shown to exhibit diurnal and other time dependent variations during such an event at these altitudes, and the assumption that two odd hydrogen particles are always produced per ionization is reexamined.  相似文献   

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