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1.
Michael B. McElroy 《Planetary and Space Science》1975,23(5):763-786
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
2.
A variety of models are explored to study the photochemistry of CO2 in the Martian atmosphere with emphasis on reactions involving compounds of carbon, hydrogen, and oxygen. Acceptable models are constrained to account for measured concentrations of CO and O above 90 km, with an additional requirement that they should be in accord with observations of CO, O2, and O3 in the lower atmosphere. Dynamical mixing must be exceedingly rapid at altitudes above 90 km, with effective eddy diffusion coefficients in excess of 107 cm2 sec?1. If recombination of CO2 is to occur mainly by gas phase chemistry, catalyzed by trace quantities of H, OH, and HO2, mixing must be rapid over the altitude interval 30 to 40 km. The value implied for the diffusion coefficient in this region is a function of assumptions made regarding the rates for reaction of OH with HO2 to form H2O and of the rate for reaction of HO2 with itself to form H2O2. If rates for these reactions are taken to have values similar to rates used in current models for the Earth's stratosphere, the eddy diffusion coefficient at 40 km on Mars should be about 5 × 107 cm2 sec?1, consistent with Zurek's (1976) estimate for this parameter inferred from tidal theory. Surface chemistry could have an influence on the abundances of atmospheric CO and O2, but a major effect would imply sluggish mixing at all altitudes below 50 km and in addition would carry implications for the magnitude of the rates for reaction of OH with HO2 and HO2 with itself. 相似文献
3.
H. Levy 《Planetary and Space Science》1973,21(4):575-591
Altitude profiles for the number densities of NO, NO2, NO3, N2O5, HNO2, CH3O, CH3O2, H2CO, 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 H2CO 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 H2CO along with the destruction of CH4 for which a tropospheric lifetime of ~2 yr is estimated.The destruction of H2CO that was produced in the CH4 oxidation cycle provides the major source of CO and H2 in the atmosphere. 相似文献
4.
The title reaction was studied by photolyzing mixtures of Cl2 and SO2 with and without O2 present in an atmosphere of N2, using Fourier transform infrared spectrophotometry to monitor reactants and products. In the absence of oxygen, sulfur dioxide is quantitatively converted to sulfuryl chloride. With 10 to 150 Torr O2 present H2SO4 is produced as well as SO2Cl2. When a number of speculative reactions inferred from these experiments are added to a published model for Venus stratospheric chemistry, it emerges that SO2Cl2 is a key reservoir species for chlorine and that the reaction between Cl and So2 provides an important cycle for destroying O2 and converting SO2 to H2So4. The modified model could provide a possible solution to the photochemistry of the Venus stratosphere if the mixing ratio of chlorine on Venus were as high as 8 ppm. 相似文献
5.
Vladimir A. Krasnopolsky 《Icarus》2012,218(1):230-246
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
6.
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
7.
Models are developed for the photochemistry of a CO2H2ON2 atmosphere on Mars and estimates are given for the concentrations of N, NO, NO2, NO3, N2O5, HNO2, HNO3, and N2O as a function of altitude. Nitric oxide is the most abundant form of odd nitrogen, present with a mixing ratio relative to CO2 of order 10?8. Deposition rates for nitrite and nitrate minerals could be as large as 3× 105 N equivalent atoms cm?2 sec?1 under present conditions and may have been higher in the past. 相似文献
8.
Chemical kinetic model for the lower atmosphere of Venus 总被引：1，自引：0，他引：1
Vladimir A. Krasnopolsky 《Icarus》2007,191(1):25-37
A self-consistent chemical kinetic model of the Venus atmosphere at 0-47 km has been calculated for the first time. The model involves 82 reactions of 26 species. Chemical processes in the atmosphere below the clouds are initiated by photochemical products from the middle atmosphere (H2SO4, CO, Sx), thermochemistry in the lowest 10 km, and photolysis of S3. The sulfur bonds in OCS and Sx are weaker than the bonds of other elements in the basic atmospheric species on Venus; therefore the chemistry is mostly sulfur-driven. Sulfur chemistry activates some H and Cl atoms and radicals, though their effect on the chemical composition is weak. The lack of kinetic data for many reactions presents a problem that has been solved using some similar reactions and thermodynamic calculations of inverse processes. Column rates of some reactions in the lower atmosphere exceed the highest rates in the middle atmosphere by two orders of magnitude. However, many reactions are balanced by the inverse processes, and their net rates are comparable to those in the middle atmosphere. The calculated profile of CO is in excellent agreement with the Pioneer Venus and Venera 12 gas chromatographic measurements and slightly above the values from the nightside spectroscopy at 2.3 μm. The OCS profile also agrees with the nightside spectroscopy which is the only source of data for this species. The abundance and vertical profile of gaseous H2SO4 are similar to those observed by the Mariner 10 and Magellan radio occultations and ground-based microwave telescopes. While the calculated mean S3 abundance agrees with the Venera 11-14 observations, a steep decrease in S3 from the surface to 20 km is not expected from the observations. The ClSO2 and SO2Cl2 mixing ratios are ∼10−11 in the lowest scale height. The existing concept of the atmospheric sulfur cycles is incompatible with the observations of the OCS profile. A scheme suggested in the current work involves the basic photochemical cycle, that transforms CO2 and SO2 into SO3, CO, and Sx, and a minor photochemical cycle which forms CO and Sx from OCS. The net effect of thermochemistry in the lowest 10 km is formation of OCS from CO and Sx. Chemistry at 30-40 km removes the downward flux of SO3 and the upward flux of OCS and increases the downward fluxes of CO and Sx. The geological cycle of sulfur remains unchanged. 相似文献
9.
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
10.
For purified binary gas mixtures like NH3H2O or HClH2O, partial pressures appreciably greater than the two saturation partial pressures are needed to condense the gas mixture into small solution droplets (“homogeneous hetero-molecular nucleation”). Thus without foreign nuclei, clouds are not as easily formed as in the theories of Lewis; the latter should be valid only if large condensation nuclei are available. We calculate here from classical homogeneous heteromolecular nucleation theory the threshold partial pressures necessary to achieve droplet nucleation for the gas mixtures NH3H2O (Jupiter,…), HClH2O (Venus), H2SO4H2O (Venus), and C2H5OHH2O (laboratory). In the last case, theory and experiment agree satisfactorily. If no “dust” particles are available as condensation nuclei, then we expect in Jupiter's atmosphere the cloud base level to be around 40 km above the 400K level instead of 10–25 km in Lewis' models (1969) (similar upward shifts for the outer Jovian planets). For Venus, our corrections make the formation of HClH2O clouds less probable for the 60-km layer at 0°C. If H2SO4 is formed by (photo-)chemical oxidation of SO2 and if clouds are formed at that level where the H2SO4 production is largest, then the cloud base levels for H2SO4H2O mixture clouds will not be shifted by our nucleation effects. For more reliable predictions, one needs more accurate data on the water vapor content of the planetary atmospheres and laboratory experiments testing the theoretically predicted nucleation behavior of these gaseous mixtures. 相似文献
11.
A review is given of the stratospheric budgets of odd oxygen, odd nitrogen, nitrous oxide, methane and carbonyl sulfide. The stratospheric column production rate of NO by the reaction N2O + O(1D) → 2 NO is 1.1–1.9 × 108 molecules cm?2 s?1. The stratospheric loss rates for N2O, CH4 and COS are equal to 0.9–1.4 × 109, 1 × 1010 and 0.5 × 107 molecules cm?2 s?1, respectively. From currently available information on the global distributions of N2O and CH4 there are some indications of about two times smaller OH concentrations below 35 km than those which are calculated based on the latest compilation of kinetic data.Most significantly, however, it is shown that photochemical models and available ozone observations cannot be reconciled and that there may be particularly severe problems in the 25–35 km region. This issue is thoroughly discussed.Volcanic emissions of SO2 to the stratosphere may locally lead to much enhanced ozone concentrations and heating rates. These may influence the dynamic behaviour of volcanic plumes before their dispersion over large volumes of the stratosphere. 相似文献
12.
A thermodynamical analysis of the multicomponent system SiTiAlFeMnMgCaNaKPCHO open with respect to CO2, CO, H2O was carried out. Hydration and carbonatization processes are proposed to be geochemical consequences of the hypothesis of quasi-equilibrium conditions between the troposphere and crustal surface rocks. The probable rock-forming hydrated mineral phases are represented by epidote, glaucophane, tremolite, phlogopite, and annite; the carbonatization results in existence of calcite and dolomite as rock-forming minerals of weathered alkaline lavas. The surface rocks are assumed to have high ferric/ferrous iron ratios. The wollastonite equilibrium is rejected as a buffering chemical reaction. Hydrated minerals could be stable at least up to 5-km depths and contribute about 0.1 × 1024 g of H2O whereas about (0.7–0.8) × 1024 g of H2O would be consumed in ferrous iron oxidation with concomitant hydrogen dissipation. The distribution of H2O in the outer planetary shells is possibly a function of their temperatures. 相似文献
13.
Hydroxyl nightglow is intensively studied in the Earth atmosphere, due to its coupling to the ozone cycle. Recently, it was detected for the first time also in the Venus atmosphere, thanks to the VIRTIS-Venus Express observations. The main Δν=1, 2 emissions in the infrared spectral range, centred, respectively, at 2.81 and 1.46 μm (which correspond to the (1-0) and (2-0) transitions, respectively), were observed in limb geometry (Piccioni et al., 2008) with a mean emission rate of 880±90 and 100±40 kR (1R=106 photon cm−2 s−1 (4πster)−1), respectively, integrated along the line of sight. In this investigation, the Bates-Nicolet chemical reaction is reported to be the most probable mechanism for OH production on Venus, as in the case of Earth, but HO2 and O may still be not negligible as mechanism of production for OH, differently than Earth. The nightglow emission from OH provides a method to quantify O3, HO2, H and O, and to infer the mechanism of transport of the key species involved in the production. Very recently, an ozone layer was detected in the upper atmosphere of Venus by the SPICAV (Spectroscopy for Investigation of Characteristics of the Atmosphere of Venus) instrument onboard Venus Express (Montmessin et al., 2009); this discovery enhances the importance of ozone to the OH production in the upper atmosphere of Venus through the Bates-Nicolet mechanism. On Venus, OH airglow is observed only in the night side and no evidence has been found whether a similar emission exists also in the day side. On Mars it is expected to exist both on the day and night sides of the planet, because of the presence of ozone, though OH airglow has not yet been detected.In this paper, we review and compare the OH nightglow on Venus and Earth. The case of Mars is also briefly discussed for the sake of completeness. Similarities from a chemical and a dynamical point of view are listed, though visible OH emissions on Earth and IR OH emissions on Venus are compared. 相似文献
14.
Nonthermal escape processes responsible for the escape of hydrogen and deuterium from Venus are examined for present and past atmospheres. Three mechanisms are important for the escape of hydrogen from the present atmosphere: (a) charge exchange of plasmaspheric H+ with exospheric H, (b) impact of exospheric hot O atoms on H, and (c) ion molecule reactions involving O+ and H2. However, in the past when the H abundance was higher, the charge-exchange mechanism would be the strongest. The H escape flux increases rapidly with increasing hydrogen abundance in the upper atmosphere and saturates at a value of 1 × 1010 cm?2 sec?1 emerging primarily from the day side when the H mixing ratio at the homopause is 2 × 10?3. This corresponds to an H2O mixing ratio of 1 × 10?3 at the cold trap and ～15% at the surface. Deuterium would also escape by the charge-exchange mechanism and a D/H enrichment by a factor of ～1000 over the nonthermal escape regime is expected, which could have lasted over the last 3 billion years. Coincidentally, the onset of hydrodynamic flow leading to efficient H escape occurs just at the H2O mixing ratio at which the charge-exchange escape flux saturates. Thus it is possible that Venus has lost an Earth-equivalent ocean of water over geologic time. If so, either the D/H enrichment has been kept low by modest outgassing of juvenile water or Venus started out with a D/H ratio of ～4.0 × 10?6. 相似文献
15.
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
16.
We present an updated model for the photochemistry of Io's atmosphere and ionosphere and use this model to investigate the sensitivity of the chemical structure to vertical transport rates. SO2is assumed to be the dominant atmospheric gas, with minor molecular sodium species such as Na2S or Na2O released by sputtering or venting from the surface. Photochemical products include SO, O2, S, O, Na, NaO, NaS, and Na2. We consider both “thick” and “thin” SO2atmospheres that encompass the range allowed by recent HST and millimeter-wave observations, and evaluate the possibility that O2and/or SO may be significant minor dayside constituents and therefore likely dominant nightside gases. The fast reaction between S and O2limits the column abundance of O2to ∼104less than that calculated by Kumar (J. Geophys. Res.87, 1677–1684, 1982; 89(A9), 7399–7406, 1984) for a pure sulfur/oxygen atmosphere. If a significant source of NaO2or Na2O were supplied by the surface and mixed rapidly upward, then oxygen liberated in the chemical reactions which also liberate free Na would provide an additional source of O2. Fast eddy mixing will enhance the transport of molecular sodium species to the exobase, in addition to increasing the vertical transport rate of ions. Ions produced in the atmosphere will be accelerated by the reduced corotation electric field penetrating the atmosphere. These ions experience collisions with the neutral gas, leading to enhanced vertical ion diffusion. The dominant ion, Na+, is lost primarily by charge exchange with Na2O and/or Na2S in the lower atmosphere and by diffusion through the ionopause in the upper atmosphere. The atmospheric column abundance of SO, O2, and the upper atmosphere escape rates of Na, S, O, and molecular sodium species are all strong functions of the eddy mixing rate. Most atmospheric escape, including that of molecular sodium species, probably occurs from the low density “background” SO2atmosphere, while a localized high density “volcanic” SO2atmosphere can yield an ionosphere consistent with that detected by the Pioneer 10 spacecraft. 相似文献
17.
18.
Recent spacecraft observations of Venus permit a detailed model of sulfur chemistry in the atmosphere-lithosphere system. Pioneer Venus experiments confirm that, as predicted, COS and H2S are dominant over SO2 in the lower atmosphere, and that the equilibrium concentrations of S2 and S3 are significant. Many criteria serve to bracket the oxidation state of the crust: it is nearly certain that the S22?/SO42? buffer regulates the oxygen fucagity, and that FeO is at least as abundant as Fe2O3 in crustal silicates. A highly oxidized crust (as, for example, would result from O2 absorption complementary to escape of vast amounts of H2) is incompatible with the gas-phase sulfur chemistry. If the Pioneer Venus mass spectrometer estimates of the abundance of sulfur gases are correct, Earth-like models for the bulk composition of Venus are seriously in error, and a far lower FeO content is required for Venus. 相似文献
19.
A. Bar-nun 《Icarus》1980,42(3):338-342
The effects of the newly discovered thunderstorms on Venus upon the nitrogen and carbon species in its atmosphere were calculated. An Earth-like lightning frequency of 100 sec?1 was used for Venus, in accord with recent optical measurements by Pioneer-Venus (W. J. Borucki, J. W. Dyer, G. Z. Thomas, J. C. Jordon, and D. A. Comstock, submitted for publication). The rate of NO production by thunder shock waves, 2.5 × 1011 g year?1, is about an order of magnitude smaller than on the Earth. But on Venus, in the absence of precipitation, which is the major removal mechanism of odd nitrogen from the Earth's atmosphere, the mixing ratios of odd nitrogen species might be considerably higher. The global CO production is governed by CO2 photolysis rather than by CO2 pyrolysis by lightning. However, thunderstorms produce about 2.5 × 1011 g year?1 of CO in the cloud layer, far from the high altitude CO2 photolysis region. 相似文献
20.
The abundances of molecular oxygen in the atmospheres of Venus and Mars are sensitive to fundamental photochemical processes. A new upper limit is reported for the molecular oxygen mixing ratio (O2/CO2 < × 10?7) in the integrated column above the visible cloud tops of Venus, based on spectroscopic observations carried out in early spring, 1982. During the same observing period, an O2 column abundance of 8.5 cm-am for the atmosphere of Mars was measured, slightly below the O2 abundances measured a decade earlier. 相似文献