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1.
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
2.
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
3.
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
4.
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
5.
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
6.
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 OO bond is broken mainly by S + O2 and SO + HO2. In the low-H2 models additional reactions for breaking the OO 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
7.
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
8.
Mikio Shimizu 《Astrophysics and Space Science》1975,36(2):353-361
Dirty ice of a second kind (major components, H2O, CO, and N2; minor components less than several percents, NH3, CH4, and other organic substances such as HCN, CH3CN etc.) is assumed for the composition of volatiles in the cometary nucleus. The consistency with the observations of molecular ions and daughter molecules in the cometary atmosphere is argued by taking into account various ion-molecular reactions and dissociative recombinations. There is a satisfactory agreement for the second kind of dirty-ice model, but the presence of large amounts of CH4 and NH3 is found to be rather in contradiction with observational evidence. A velocity of 8 km s?1 for the hydrogen atoms, derived from analysis of the hydrogen Lyman-alpha corona around comets, is found from the dissociative recombination of H3O+, the dominant constituent of cometary ionosphere, in accordance with H3O++e ?→OH+H+H. 相似文献
9.
The abundances of PH3, CH3D, and GeH4 are derived from the 2100- to 2250-cm?1 region of the Voyager 1 IRIS spectra. No evidence is seen for large-scale variations of the phosphine abundance over Jovian latitudes between ?30 and +30°. In the atmospheric regions corresponding to 170–200°K, the derived PH3/H2 value is (4.5 ± 1.5) × 10?7 or 0.75 ± 0.25 times the solar value. This result, compared with other PH3 determinations at 10 μm, suggests than the PH3/H2 ratio on Jupiter decreases with atmospheric pressure. In the 200–250°K region, we derive, within a factor of 2, CH3D/H2 and GeH4/H2 ratios of 2.0 × 10?7 and 1.0 × 10?9, respectively. Assuming a C/H value of 1.0 × 10?3, as derived from Voyager, our CH3D/H2 ratio implies a D/H ratio of 1.8 × 10?5, in reasonable agreement with the interstellar medium value. 相似文献
10.
Marcel Nicolet 《Planetary and Space Science》1984,32(7):871-880
The photodissociation of water vapour in the mesosphere depends on the absorption of solar radiation in the region (175–200 nm) of the O2 Schumann-Runge band system and also at H-Lyman alpha. The photodissociation products are OH + H, OH + H, O + 2H and H2 + O at Lyman alpha; the percentages for these four channels are 70, 8, 12 and 10%, respectively, but OH + H is the only channel between 175 and 200 nm. Such proportions lead to a production of H atoms corresponding to practically the total photodissociation of H2O, while the production of H2 molecules is only 10% of the H2O photodissociation by Lyman alpha.The photodissociation frequency (s?1) at Lyman alpha can be expressed by a simple formula where F10.7 cm is the solar radioflux at 10.7 cm and N the total number of O2 molecules (cm?2), and when the following conventional value is accepted for the Lyman alpha solar irradiance at the top of the Earth's atmosphere () qLyα,∞ = 3 × 1011 photons cm?2 s1?.The photodissociation frequency for the Schumann-Runge band region is also given for mesospheric conditions by a simple formula where JSRB,∞(H2O) = 1.2 × 10?6 and 1.4 × 10?6 s?1 for quiet and active sun conditions, respectively.The precision of both formulae is good, with an uncertainty less than 10%, but their accuracy depends on the accuracy of observational and experimental parameters such as the absolute solar irradiances, the variable transmittance of O2 and the H2O effective absorption cross sections. The various uncertainties are discussed. As an example, the absolute values deduced from the above formulae could be decreased by about 25-20% if the possible minimum values of the solar irradiances were used. 相似文献
11.
Jean-Paul Parisot 《Earth, Moon, and Planets》1986,34(3):273-279
The hydrogen radicals play an important role in the photochemistry of the troposphere of the Earth. The chemistry of OH, HO2 and H2O2 is linked directly to the photodissociation of O3 through the production of O(1D). Gaseous H2O2 (hydrogen peroxide may be removed by heterogeneous reactions involving aerosols and liquid water. During the day and the night the solubility of ambient H2O2 in water is estimated and the oxidant capacity of H2O2 may explain the bleaching properties of the dew used in the past. This phenomenon may also explain some old maxims concerning the properties of the Moon's light to corrupt colors. 相似文献
12.
The chemistry and spectroscopy of proton-irradiated H2O + O2 ices have been investigated in relation to the production of oxidants in icy satellite surfaces. Hydrogen peroxide (H2O2), ozone (O3), and the hydroperoxy (HO2) and hydrogen trioxide (HO3) radicals have all been observed, and their temperature and dose dependent production trends have been measured. We find that O2 aggregates form during the growth of H2O + O2 ice films, and the presence of these aggregates greatly affects the HO2 and H2O2 yields. In addition, we have found that the position of the spectral maximum of the ν3 vibration of O3 shifts with ice composition, giving an indication of the degree of dispersion of O3 molecules within the ice. We discuss the relevance of these measurements to icy satellite surfaces. 相似文献
13.
Analyses of ultraviolet, visible, and near-infrared spectra of Saturn lead to an inhomogeneous atmospheric model, having a clear gas layer which lies above an absorbing particle layer which lies above an ammonia haze layer. The boundary between the clear layer and the absorbing particle layer is at a pressure of 0.2 atm in the equatorial region and 0.3 atm in the temperate region. The boundary between the absorbing particle layer and the haze layer is at the radiative-convective boundary. Observations of ammonia absorption lines indicate that sunlight penetrates the haze to the ammonia sublimation level at a depth of 1.1 atm. Absorbing particles cause the observed decrease in reflectivity from visible to ultraviolet wavelengths. Consideration of the wavelength variation of Mie scattering parameters leads to an upper limit of about 0.2 μm for the particle radii and a particle number density of 103 cm?3. Some possible particle compositions are discussed. Comparison of computed 3-0 and 4-0 band hydrogen quadropole line equivalent widths with observed values leads to a haze layer optical thickness above the ammonia sublimation level of approximately 10. Equivalent widths computed for an equilibrium distribution of states agree better with observed values than those computed for a normal distribution. Methane 3ν3 band manifold equivalent widths are in best agreement with measured equivalent widths for a CH4/H2 abundance ratio of 2 × 10?3, which is 4.5 times the solar C/H ratio. 相似文献
14.
The exosphere of an atmosphereless icy moon is the result of different surface release processes and subsequent modification of the released particles. At Europa icy moon, water molecules are directly released, but photolysis and radiolysis due to solar UV and Jupiter’s magnetospheric plasma, respectively, can result in OH, H, O and (possibly) H2 production. These molecules can recombine to reform water and/or new chemical species. As a consequence, Europa’s neutral environment becomes a mixture of different molecules, among which, H2O dominates in the highest altitudes and O2, formed mainly by radiolysis of ice and subsequent release of the produced molecules, prevails at lower altitudes. In this work, starting from a previously developed Monte Carlo model for the generation of Europa’s exosphere, where the only considered species was water, we make a first attempt to simulate also the H2 and O2 components of the neutral environment around Europa, already observed by the Hubble Space Telescope and the Ultraviolet Imaging Spectrograph on board Cassini, during its flyby of Jupiter. Considering a specific configuration where the leading hemisphere coincides with the sunlit hemisphere, we estimate along the Europa–Sun line an O2 column density of about 1.5 × 1019 m?2 at the dayside and 3 × 1018 m?2 at the nightside. In this work we also improve our previous estimation of the sputtered H2O exosphere of this moon, taking into consideration the trailing–leading asymmetry in the magnetospheric ion bombardment and the energy and temperature dependences of the process yields. We find that a density of 1.5 × 1012 H2O/m3 is expected at altitudes ～0.1RE above the surface of the trailing hemisphere. Additionally, we calculate the escape of H2O, O2 and H2. The total number of neutral atoms in Europa’s neutral torus, is estimated to be in the range 7.8 × 1032–3.3 × 1033. 相似文献
15.
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 to depress ozone concentrations below the observed upper limit in equatorial regions. Another catalytic reaction that should be driven by photodesorption on Mars is . 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
16.
A non-thermal, or “hot”, Venus corona of H atoms has been observed by Mariners 5 and 10 and Venera 9. Of the sources investigated, reaction of H2 with ionospheric O+is still the strongest. It can explain the smaller densities but falls somewhat short of the largest (from Mariner 5). The subsequent recombination of OH+, supplemented by solar-wind processes, may give an escape flux of 107 atoms cm?2 s?1. The low density of thermal H atoms on the day side has previously been attributed to either a large eddy diffusion coefficient or an escape flux tenfold greater than this. We support an alternative mechanism, suggested by Hartle and Mayr: the hydrogen is swept to the night side by strong thermospheric winds. This process is analogous to the “Johnson pump” for the terrestrial winter helium bulge. Large nightside bulges of H and H2 are predicted; the night/day density ratio is estimated to be as large as 100 for each. 相似文献
17.
A model is presented for the formation of HCN in the upper troposphere and lower stratosphere of Jupiter by ultraviolet photolysis of the C2H5N isomer aziridine, a product of the recombination of NH2 and C2H3 radicals, which originate, respectively, from ammonia photolysis and addition of H atoms to acetylene. An HCN column density of ～ 2 × 1017 cm?2 in the tropopause region, which is comparable to that observed by A. T. Tokunaga, S. C. Beck, T. R. Geballe, J. H. Lacy, and E. Serabyn (Icarus48, 283–289, 1981), is predicted when vertical mixing is slow above the ammonia cloudtops. Sensitivity of the HCN column density to the individual rate constants and the eddy diffusion coefficient profile is discussed, as is the possibility of the existence of additional HCN-yielding pathways. Ammonia, which is saturated in the upper troposphere, is strongly depleted by photolysis in the lower stratosphere. Phosphine is also strongly depleted by photolysis and its abundance in the upper troposphere is shown to depend strongly on vertical mixing in the tropopause region. The possibility of the formation of phosphirane, the P-containing analog of aziridine, is considered but found to be substantially less probable than aziridine. 相似文献
18.
The temporal response of ion and neutral densities to a geomagnetic storm has been investigated on a global scale with data from consecutive orbits of OGO-6 (>400km) for 4 days covering both magnetically quiet and disturbed conditions. The first response of the neutral atmosphere to the storm takes place in the H and He densities which start to decrease near the time of the storm sudden commencement. The maximum decreases in H and He were more than 40% of the normal density at high latitudes. A subsequent increase in O and N2 densities occurs about 8 hours later than the change in H and He densities, while the relative O and N2 density changes indicate a depletion of atomic oxygen in the lower thermosphere by more than a factor of two. The overall features of the change in the neutral atmosphere, especially the patterns of change for individual species, strongly support the physical picture that energy is deposited primarily at high latitudes during the storm, and the thermosphere structure changes through (1) heating of the lower thermosphere and (2) generation of large scale circulation in the atmosphere with upwelling at high latitudes and subsidence at the equator. The storm-time response of H+ occurs in two distinct regions separated by the low latitude boundary of the light ion trough. While on the poleward side of the boundary the H+ density decreases in a similar manner to the decrease in H density, on the equatorward side of the boundary the H+ decrease occurs about half a day later. It is shown that the decrease of H+ density is principally caused by the decrease in H density for both regions. The difference in H+ response between the two regions is interpreted as the difference in H+ dynamics outside and inside the plasmasphere. The O+ density shows an increase, the pattern of which is rather similar to that for O. Two possibilities for explaining the observed change in O+ density are suggested. One attributes the observed increase in O+ density to an increase in the plasma temperature during the storm. The other possibility is that the increase in the production rate of O+ due to an increase in O density exceeds the increase in the loss rate of O+ due to an increase in N2 density, especially around the time of sunrise. Hence the change in O+ density in the F-region may actually be controlled by the change in O density. 相似文献
19.
A model is presented for the photochemistry of PH3 in the upper troposphere and lower stratosphere of Saturn that includes the effects of coupling with NH3 and hydrocarbon photochemistry, specifically the C2H2 catalyzed photodissociation of CH4. PH3 is rapidly depleted with altitude (scale height ～35 km) in the upper troposphere when K～104cm2sec?1; an upper limit for K at the tropopause is estimated at ～105cm2sec?1. If there is no gas phase P2H4 because of sublimation, P2 and P4 formation is unlikely unless the rate of the spin-forbidden recombination reaction PH + H2 + M → PH3 + M is exceedingly slow. An upper limit P4 column density of ～2×1015cm?2 is estimated in the limit of no recombination. If sublimation does not remove all gas phase P2H4, P2 and P4 may be produced in potentially larger quantities, although they would be restricted almost entirely to the lowest levels of our model, where T?100°K. Potentially observable amounts of the organophosphorus compounds CH3P2H2 and HCP are predicted, with column densities of >1017 cm?2 and production rates of ～2×108cm?2sec?1. The possible importance of electronically excited states of PHx and additional PH3/hydrocarbon photochemical coupling paths are also considered. 相似文献
20.
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