Photochemistry of minor constituents in the troposphere

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.     

The aeronomy of the upper atmosphere of Venus

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.     

Equatorial ozone profiles from the solar maximum mission—a comparison with theory

The u.v. spectrometer polarimeter on the Solar Maximum Mission has been utilized to measure mesospheric ozone vs altitude profiles by the technique of solar occultation. Sunset data are presented for 1980, during the fall equinoctal period within ± 20° of the geographic equator. Mean O₃, concentrations are 4.0 × 10¹⁰ cm^?3at 50 km, 1.6 × 10¹⁰ cm^?3 at 55 km. 5.5 × 10⁹ cm^?3 at 60 km and 1.5 × 10⁹ cm^?3 at 65 km. Som profiles exhibit altitude structure which is wavelike. The mean ozone profile is fit best with the results of a time-dependent model if the assumed water vapor mixing ratio employed varies from 6 ppm at 50 km to 2–4 ppm at 65 km.     

Some problems in Venus' aeronomy

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.     

The evolution and variability of atmospheric ozone over geological time

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 O_x(O₃, O, O(¹D)), N₂O, NO_x(NO, NO₂, HNO₃), H₂O, and HO_x(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 NO_x than it does in the present atmosphere.     

Solar radiation scattered in the Venus atmosphere: The Venera 11,12 data

Results of the scattered solar radiation spectrum measurements made deep in the Venus atmosphere by the Venera 11 and 12 descent probes are presented. The instrument had two channels: spectrometric (to measure downward radiation in the range 0.45 < γ < 1.17 μm) and photometric (four filters and circular angle scanning in an almost vertical plane). Spectra and angular scans were made in the height range from 63 km above the planet surface. The integral flux of solar radiation is 90 ± 12 W m^?2 measured on the surface at the subsolar point. The mean value of surface absorbed radiation flux per planetary unit area is 17.5 ± 2.3 W m^?2. For Venera 11 and 12 landing sites the atmospheric absorbed radiation flux is ～15 W m^?2 for H >; 43 km and ～45 W m^?2 for H < 48 km in the range 0.45 to 1.55 μm. At the landing sites of the two probes the investigated portion of the cloud layer has almost the same structure: it consists of three parts with boundaries between them at about 51 and 57 km. The base of clouds is near 48 km above the surface. The optical depth of the cloud layer (below 63 km) in the range 0.5 to 1 μm does not depend on the wavelength and is ～29 and ～38 for the Venera 11 and 12 landing sites, respectively. The single-scattering albedo, ω₀, in the clouds is very close to 1 outside the absorption bands. Below 58 km the parameter (1 ? ω₀) is <10^?3 for 0.49 and 0.7 μm. The parameter (1 ? ω₀) obviously increases above 60 km. Below 48 km some aerosol is present. The optical depth here is a strong function of wavelength. It varies from 1.5 to 3 at λ = 0.49 μm and from 0.13 to 0.4 at 1.0 μm. The mean size of particles below the cloud deck is about 0.1 μm. Below 35 km true absorption was found at λ < 0.55 μm with the (1 ? ω₀) maximum at H ≈ 15 km. The wavelength and height dependence of the absorption coefficient are compatible with the assumption that sulfur with a mixing ratio ～2 × 10^?8 normalized to S₂ molecules is the absorber. The upper limits of the mixing ratio for Cl₂, Br₂, and NO₂ are 4 × 10^?8, 2 × 10^?11, and 4 × 10^?10, respectively. The CO₂ and H₂O bands are confidently identified in the observed spectra. The mean value of the H₂O mixing ratio is 3 × 10^?5 < F_H2O < 10^?4 in the undercloud atmosphere. The H₂O mixing ratio evidently varies with height. The most probable profile is characterized by a gradual increase from F_H2O = 2 × 10^?5 near the surface to a 10 to 20 times higher value in the clouds.     

Mapping of Ozone and Water in the Atmosphere of Mars near the 1997 Aphelion

We present absolute abundances and latitudinal variations of ozone and water in the atmosphere of Mars during its late northern spring (L_s=67.3°) shortly before aphelion. Long-slit maps of the a¹Δ_g state of molecular oxygen (O₂) and HDO, an isotopic form of water, were acquired on UT January 21.6 1997 using a high-resolution infrared spectrometer (CSHELL) at the NASA Infrared Telescope Facility. O₂(a¹Δ_g) is produced by ozone photolysis, and the ensuing dayglow emission at 1.27 μm is used as a tracer for ozone. Retrieved vertical column densities for ozone above ∼20 km ranged between 1.5 and 2.8 μm-atm at mid- to low latitudes (30°S-60°N) and decreased outside that region. A significant decrease in ozone density is seen near 30°N (close to the subsolar latitude of 23.5°N). The rotational temperatures retrieved from O₂(a-X) emissions show a mean of 172±2.5 K, confirming that the sensed ozone lies in the middle atmosphere (∼24 km). The ν₁ fundamental band of HDO near 3.67 μm was used as a proxy for H₂O. The retrieved vertical column abundance of water varies from 3 precipitable microns (pr-μm) at ∼30°S to 24 pr-μm at ∼60°N. We compare these results with current photochemical models and with measurements obtained by other methods.     

Martian volatiles: Their degassing history and geochemical fate

Observations of Mars and cosmochemical considerations imply that the total inventory of degassed volatiles on Mars is 10² to 10³ times that present in Mars' atmosphere and polar caps. The degassed volatiles have been physically and chemically incorporated into a layer of unconsolidated surface rubble (a “megaregolith”) up to 2km thick. Tentative lines of evidence suggest a high concentration (～5g/cm²) of ⁴⁰ Ar in the atmosphere of Mars. If correct, this would be consistent with a degassing model for Mars in which the Martian “surface” volatile inventory is presumed identical to that of Earth but scaled to Mars' smaller mass and surface area. The implied inventory would be: (⁴⁰Ar) = 4g/cm², (H₂O) = 1 × 10⁵g/cm², (CO₂) = 7 × 10³g/cm², (N₂) = 3 × 10²g/cm², (Cl) = 2 × 10³g/cm², and (S) = 2 × 10²g/cm². Such a model is useful for testing, but differences in composition and planetary energy history may be anticipated between Mars and Earth on theoretical grounds. Also, the model demands huge regolith sinks for the volatiles listed.If the regolith were in physical equilibrium with the atmosphere, as much as 2 × 10⁴g/cm² of H₂O could be stored in it as hard-frozen permafrost, or 5 × 10⁴g/cm² if equilibrium with the atmosphere were inhibited. Spectral measurements of Martian regolith material and laboratory measurement of weathering kinetics on simulated regolith material suggest large amounts of hydrated iron oxides and clay minerals exist in the regolith; the amount of chemically bound H₂O could be from 1 × 10⁴ to 4 × 10⁴g/cm². In an Earth-analogous model, a 2 km mixed regolith must contain the following concentrations of other volatile-containing compounds by weight: carbonates = 1.5%, nitrates = 0·3%, chlorides = 0.6%, and sulfates = 0.1%. Such concentrations would be undetectable by current Earth-based spectral reflectance measurements, and (except the nitrates) formation of the “required” amounts of these compounds could result from interaction of adsorbed H₂O and ice with primary silicates expected on Mars. Most of the CO₂ could be physically adsorbed on the regolith.Thus, maximum amounts of H₂O and other volatiles which could be stored in the Mars regolith are marginally compatible with those required by an Earth-analogous model, although a lower atmospheric ⁴⁰Ar concentration and regolith volatile inventory would be easier to reconcile with observational constraints. Differences in the ratios of H₂O and other volatiles to ⁴⁰Ar between surface volatiles on the real Mars and on an Earth-analogous Mars could result from and reflect differences in bulk composition and time history of degassing between Mars and Earth. Models relating Viking-observable parameters, e.g., (⁴⁰Ar) and (³⁶Ar), to the time history and overall intensity of Mars degassing are given.     

The evolution of an impact-generated atmosphere

Shock wave and thermodynamic data for rock-forming and volatile-bearing minerals are used to determine minimum impact velocities (v_cr) and minimum impact pressures (p_cr) required to form a primary H₂O atmosphere during planetary accretion from chondritelike planetesimals. The escape of initially released water from an accreting planet is controlled by the dehydration efficiency. Since different planetary surface porosities will result from formation of a regolith, v_cr and p_cr can vary from 1.5 to 5.8 km/sec and from 90 to 600 kbar, respectively, for target porosities between 0 and ～45%. On the basis of experimental data, hydration rates for forsterite and enstatite are derived. For a global regolith layer on the Earth's surface, the maximum hydration rate equals 6 × 10¹⁰ g H₂O sec^?1 during accretion of the Earth. Attenuation of impact-induced shock pressure is modeled to the extent that the amount of released water as a function of projectile radius, impact velocity, weight fraction of water in the target, target porosity, and dehydration efficiency can be estimated. The two primary processes considered are the impact release of water bound in hydrous minerals (e.g., serpentine) and the subsequent reincorporation of free water by hydration of forsterite and enstatite. These processes are described in terms of model calculations for the accretion of the Earth. Parameters which lead to a primary atmosphere/hydrosphere are: an accretion time of ? 1.6 × 10⁸years, the use of an accretion model defined by Weidenschilling (1974, 1976), a mean planetesimal radius of 0.5 km, a hydration rate of 6 × 10¹⁰ g H₂O sec^?1 inferred from a mean porosity of ～ 10% for the upper 1 km of the accreting Earth, and values for the dehydration efficiency, DE, of 0.55 and 0.07 for the maximum and minimum pressure decay model, respectively. Conditions which prohibit the formation of a primary atmosphere include an accretion time much longer than 1.6 × 10⁸ years, a hydration rate for forsterite and enstatite well in excess of 6 × 10¹⁰ g H₂O sec^?1, and a dehydration efficiency DE < 0.07. We conclude that the concept of dehydration efficiency is of dominant importance in determining the degree to which an accreting planet acquires an atmosphere during its formation.     

Photochemistry of the Martian atmosphere

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.     

Vertical distribution of water vapor and mars model lower and middle atmosphere

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.     

Lightnings and nitric oxide on Venus

In an updating of energy characteristics of lightnings on Venus obtained from Venera-9 and -10 optical observations, the flash energy is given as 8 × 10⁸ J and the mean energy release of lightnings is 1 erg cm^?2 s which is 25 times as high as that on the Earth. Lightnings were observed in the cloud layer. The stroke rate in the near-surface atmosphere is less than 5 s^?1 over the entire planet if the light energy of the stroke exceeds 4 × 10⁵ J and less than 15 s^?1 for (1–4) × 10⁵ J.The average NO production due to lightnings equals 5 × 10⁸ cm^?2 s^?1, the atomic nitrogen production is equal to 7 × 10⁹ cm^?2s^?1,the N flux toward the nightside is 3.2 × 10⁹ cm^?2s^?1, the number densities [N] = 3 × 10⁷cm^?3 and [NO] = 1.8 × 10⁶cm^?3 at 135 km. Almost all NO molecules in the upper atmosphere vanish interacting with N and the resulting NO flux at 90-80 km equals 5 × 10⁵cm^?2s^?1, which is negligibly small as compared with lightning production. If the predissociation at 80–90 km is regarded as the single sink of NO, its mixing ratio, f_NO, is 4 × 10^?8, for the case of a surface sink f_NO = 0.8 × 10^?9 at 50 km. Excess amounts, $\text{f}{}_{\mathrm{<mtext>NO</mtext>}}\text{? 4 × 10}{}^{\mathrm{?8}}$, may exist in the thunderstorm region.     

Mars: Photodesorption from mineral surfaces and its effects on atmospheric stability

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 $\text{f}{}_{\mathrm{<mtext>H</mtext>}}\text{? 10}{}^{\mathrm{?10}}$ to depress ozone concentrations below the observed upper limit in equatorial regions. Another catalytic reaction that should be driven by photodesorption on Mars is $\text{20}\text{H}{}^{\mathrm{?}}{}_{\mathrm{<mtext>(</mtext><mtext>ads</mtext><mtext>)</mtext>}}\text{→}\text{H}{}_2\text{O}\text{+}\text{1}\text{2}\text{O}{}_{\mathrm{2(g)}}\text{+ 2e}{}^{\mathrm{?}}{}_{\mathrm{<mtext>crystal</mtext>}}$. 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.     

Solar infrared occultation observations by SPICAM experiment on Mars-Express: Simultaneous measurements of the vertical distributions of H2O, CO2 and aerosol

The infrared AOTF spectrometer is a part of the SPICAM experiment onboard the Mars-Express ESA mission. The instrument has a capability of solar occultations and operates in the spectral range of 1-1.7 μm with a spectral resolution of ∼3.5 cm⁻¹. We report results from 24 orbits obtained during MY28 at Ls 130°-160°, and the latitude range of 40°-55° N. For these orbits the atmospheric density from 1.43 μm CO₂ band, water vapor mixing ratio based on 1.38 μm absorption, and aerosol opacities were retrieved simultaneously. The vertical resolution of measurements is better than 3.5 km. Aerosol vertical extinction profiles were obtained at 10 wavelengths in the altitude range from 10 to 60 km. The interpretation using Mie scattering theory with adopted refraction indices of dust and H₂O ice allows to retrieve particle size (reff∼0.5-1 μm) and number density (∼1 cm⁻³ at 15-30 km) profiles. The haze top is generally below 40 km, except the longitude range of 320°-50° E, where high-altitude clouds at 50-60 km were detected. Optical properties of these clouds are compatible with ice particles (effective radius reff=0.1-0.3 μm, number density N∼10 cm−3) distributed with variance νeff=0.1-0.2 μm. The vertical optical depth of the clouds is below 0.001 at 1 μm. The atmospheric density profiles are retrieved from CO₂ band in the altitude range of 10-90 km, and H₂O mixing ratio is determined at 15-50 km. Unless a supersaturation of the water vapor occurs in the martian atmosphere, the H₂O mixing ratio indicates ∼5 K warmer atmosphere at 25-45 km than predicted by models.     

Production and condensation of organic gases in the atmosphere of Titan

The rates and altitudes for the dissociation of atmospheric constituents of Titan are calculated for solar UV, solar wind protons, interplanetary electrons, Saturn magnetospheric particles, and cosmic rays. The resulting integrated synthesis rates of organic products range from 10²–10³ g cm^?2 over 4.5 × 10⁹ years for high-energy particle sources to 1.3 × 10⁴ g cm^?2 for UV at $\text{λ < 1550}\text{A}\text{?}$, and to 5.0 × 10⁵ g cm^?2 if $\text{λ > 1550}\text{A}\text{?}$ (acting primarily on C₂H₂, C₂H₄, and C₄H₂) is included. The production rate curves show no localized maxima corresponding to observed altitudes of Titan's hazes and clouds. For simple to moderately complex organic gases in the Titanian atmosphere, condensation occurs below the top of the main cloud deck at 2825 km. Such condensates comprise the principal cloud mass, with molecules of greater complexity condensing at higher altitudes. The scattering optical depths of the condensates of molecules produced in the Titanian mesosphere are as great as ～ 10²/(particulate radius, μm) if column densities of condensed and gas phases are comparable. Visible condensation hazes of more complex organic compounds may occur at altitudes up to ～ 3060 km provided only that the abundance of organic products declines with molecular mass no faster than laboratory experiments indicate. Typical organics condensing at 2900 km have molecular masses = 100–150 Da. At current rates of production the integrated depth of precipitated organic liquids, ices, and tholins produced over 4.5 × 10⁹ years ranges from a minimum ～ 100 m to kilometers if UV at $\text{λ > 1550}\text{A}\text{?}$ is important. The organic nitrogen content of this layer is expected to be ～ 10^?1?10^?3 by mass.     

The global distribution of O3 on mars

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.     

Nonthermal escape of hydrogen and deuterium from Venus and implications for loss of water

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.     

Europa's atmosphere, gas tori, and magnetospheric implications

A two-dimensional kinetic model calculation for the water group species (H₂O, H₂, O₂, OH, O, H) in Europa's atmosphere is undertaken to determine its basic compositional structure, gas escape rates, and velocity distribution information to initialize neutral cloud model calculations for the most important gas tori. The dominant atmospheric species is O₂ at low altitudes and H₂ at higher altitudes with average day-night column densities of 4.5×¹⁰¹⁴ and 7.7×¹⁰¹³ cm⁻², respectively. H₂ forms the most important gas torus with an escape rate of ∼2×¹⁰²⁷ s⁻¹ followed by O with an escape rate of ∼5×¹⁰²⁶ s⁻¹, created primarily as exothermic O products from O₂ dissociation by magnetospheric electrons. The circumplanetary distributions of H₂ and O are highly peaked about the satellite location and asymmetrically distributed near Europa's orbit about Jupiter, have substantial forward clouds extending radially inward to Io's orbit, and have spatially integrated cloud populations of 4.2×¹⁰³³ molecules for H₂ and 4.0×¹⁰³² atoms for O that are larger than their corresponding populations in Europa's local atmosphere by a factor of ∼200 and ∼1000, respectively. The cloud population for H₂ is a factor of ∼3 times larger than that for the combined cloud population of Io's O and S neutral clouds and provides the dominant neutral population beyond the so-called ramp region at 7.4-7.8 RJ in the plasma torus. The calculated brightness of Europa's O cloud on the sky plane is very dim at the sub-Rayleigh level. The H₂ and O tori provide a new source of europagenic molecular and atomic pickup ions for the thermal plasma and introduce a neutral barrier in which new plasma sinks are created for the cooler iogenic plasma as it is transported radially outward and in which new sinks are created to alter the population and pitch angle distribution of the energetic plasma as it is transported radially inward. The europagenic instantaneous pickup ion rates are peaked at Europa's orbit, dominate the iogenic pickup ion rates beyond the ramp region, and introduce new secondary plasma source peaks in the solution of the plasma transport problem. The H₂ torus is identified as the unknown Europa gas torus that creates both the observed loss of energetic H⁺ ions at Europa's orbit and the corresponding measured ENA production rate for H.     

Chemical budgets of the stratosphere

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.