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.     

Penetration of solar uv radiation and photodissociation in the Jovian atmosphere

We present computations of the photodissociation coefficients for NH₃, N₂H₄, PH₃, and H₂S in the Jupiter atmosphere. The calculations take into account multiple scattering and absorption using the radiative-transfer method known as δ-Eddington approximation. The atmospheric models include two cloud layers of variable thickness and haze layers above the upper cloud and between the clouds. One of the results of the radiative computations deal with the reflectivity of the Jovian atmosphere as a function of wavelength. A comparison with available data on the albedo of the planet gives some important indications about mixing ratios and distributions of gases and aerosols. The results for the photolysis rates are compared with similar rates obtained by considering either the direct flux or the flux determined by the molecular gas absorption alone. The latter is usually the approximation used in aeronomic models. The results of this comparison show that a considerable difference exists with direct flux photodissociation but significant differences with molecular absorption flux exist only in atmospheric regions where photodissociation is relatively small.     

Chemical reactions in the Titan’s troposphere during lightning

In the lower troposphere of the Titan the temperature is about 90 K, therefore the chemical production of compounds in the CH₄/N₂ atmosphere is extremely slow. However, atmospheric electricity could provide conditions at which chemical reactions are fast. This paper is based on the assumption that there are lightning discharges in the Titan’s lower atmosphere. The temporal temperature profile of a gas parcel after lightning was calculated at the conditions of 10 km above the Titan’s surface. Using this temperature profile, composition of the after-lightning atmosphere was simulated using a detailed chemical kinetic mechanism consisting of 1829 reactions of 185 species. The main reaction paths leading to the products were investigated. The main products of lighting discharges in the Titan’s atmosphere are H₂, HCN, C₂N₂, C₂H₂, C₂H₄, C₂H₆, NH₃ and H₂CN. The annual production of these compounds was estimated in the Titan’s atmosphere.     

Detectability of minor constituents in the martian atmosphere by infrared and submillimeter spectroscopy

Spectroscopic remote sensing in the infrared and (sub)millimeter range is a powerful technique that is well suited for detecting minor species in planetary atmospheres (Planet Space Sci. 43(1995) 1485). Yet, only a handful of molecules in the Mars atmosphere (CO₂, CO and H₂O along with their isotopic species, O_3, and more recently H₂O₂ and CH₄) have been detected so far by this method. New high performance spectroscopic instruments will become available in the future in the infrared and (sub)millimeter range, for observations from the ground (infrared spectrometers on 8 m class telescopes, large millimeter and submillimeter interferometers) and from space, in particular the Planetary Fourier Spectrometer (PFS) aboard Mars Express (MEx), and the Heterodyne Instrument for the Far-Infrared (HIFI) aboard the Herschel Space Observatory (HSO). In this paper we will present results of a study that determines detectability of minor species in the atmosphere of Mars, taking into account the expected performance of the above spectroscopic instruments. In the near future, a new determination of the D/H value is expected with the PFS, especially during times of maximum H₂O abundance in the martian atmosphere. PFS is also expected to place constraints on the abundance of several minor species (H₂O₂,CH₄,CH₂O, SO₂, H₂S, OCS, HCl) above any local outgassing sources, the hot spots. It will be possible to obtain complementary information on some minor species (O₃,H₂O₂, CH₄) from ground-based infrared spectrometers on large telescopes. In the more distant future, HIFI will be ideally suited for measuring the isotopic ratios with unprecedented accuracy. Moreover, it should be able to observe O₂, which has not yet been detected spectroscopically in the IR/submm range, as well as H₂O₂. HIFI should also provide upper limits for several species that have not yet been detected (HCl, NH₃, PH₃) in the atmosphere of Mars. Some species (SO, SO₂,H₂S, OCS, CH₂O) that may be observable from the ground could be searched for with present single-dish antennae and arrays, and in the future with the Atacama Large Millimeter Array (ALMA) submillimeter interferometer.     

Absorption and photodissociation in the Schumann-Runge bands of molecular oxygen in the terrestrial atmosphere

The penetration in the terrestrial atmosphere of solar radiation corresponding to the spectral range of the Schumann-Runge bands of molecular oxygen is analyzed between 1750 and 2050 Å. The variation of the absorption cross section with temperature is taken into account and it is shown that average O₂ absorption cross sections cannot lead to correct photodissociation coefficients. Reduction factors are defined in order to simplify the computation of the molecular oxygen photodissociation and to permit a simple determination of the photodissociation coefficients of any minor constituent with smoothly varying absorption cross section. Examples are given for O₂, H₂O, CO₂, N₂O, HNO₃ and H₂O₂. Numerical approximations are developed for three types of spectral subdivisions: Schumann-Runge band intervals, 500 cm^?1 and 10 Å intervals. The approximations are valid from the lower thermosphere down to the stratosphere and they can be applied for a wide range of atmospheric models and solar zenith distances.     

The role of photochemical processes in evolution of the isotopic composition of the atmosphere of Titan

Molecular nitrogen, the main component of the modern atmosphere of Titan, may have formed without significant changes in the nitrogen and hydrogen isotopic composition from the clathrate hydrate of ammonia NH₃ · H₂O_SLD, which is the main accreted form of nitrogen. The most preferable transformation mechanism of NH₃ · H₂O_SLD into atmospheric N₂ is its thermal decomposition in the interior of Titan rather than the photochemical decomposition of ammonia in the upper atmosphere of early Titan. The photolysis of ammonia does not lead to a change in the isotopic composition of nitrogen, as all the nitrogen remains in Titan’s atmosphere. The photolysis of NH does not lead to a change in the isotopic composition of nitrogen in Titan’s atmosphere. Fractionation of hydrogen and nitrogen isotopes during the impacts of comets with Titan does not seem to be significant either. It will be possible to determine the dissociative fractionation factor, the original ratio ¹⁴N/¹⁵N, and the mass of Titan’s original atmosphere when fractionation of nitrogen isotopes in Titan’s atmosphere is examined in additional theoretical and experimental studies that take into account processes occurring during the formation of a system of Saturn’s satellites.     

Ground-Based Observations of the Martian Atmosphere in Support of Space Missions

Although Mars is a favored target for planetary exploration, there is still a need for complementary ground-based observing programs of the Martian atmosphere, and this need will remain in the future. Indeed, as the atmosphere is very tenuous (less than 0.01 bar at the surface), the lines are very narrow and a high spectral resolving power (above 10⁴) is required over large spectral intervals. In addition, ground-based observations of Mars allow the instantaneous mapping of the whole planet, and thus the study of diurnal effects, which cannot be achieved from an orbiter. Recent ground-based achievements about the Martian atmospheric science include the first detection of H₂O₂ in the submillimeter range, the measurement of winds from CO millimetric transitions, the first detection of CH₄ and the O₃, H₂O₂, H₂O, and CH₄ mapping in the infrared. With an ELT, it will be possible to study at high spatial resolution transient atmospheric phenomena and to search for traces of minor constituents with unprecedented sensitivity. With ALMA, it will be also possible to search for minor species and to map the mesospheric winds for better constraining the climate models.     

The role of ion-molecule reactions in the conversion of N2O5 to HNO3 in the stratosphere

We have investigated the role of several ion-molecule reactions in the conversion of N₂O₅ to HNO₃. In the proposed conversion, an N₂O₅ molecule would react with an H₂O molecule clustered to an inert ion to produce two HNO₃ molecules. Subsequent clustering of an H₂O molecule to the inert ion would make the reaction catalytic. If such an ion-catalysed conversion of N₂O₅ to HNO₃ occurs, it would probably play a role in the stratospheric chemistry at high latitudes in winter. In this paper we present reaction rate constant measurements made in a flowing afterglow apparatus for hydrated H₃O⁺, H⁺(CH₃CN)_m (m = 1, 2, 3), and several negative ions reacting with N₂O₅. Slow rate constants were found for these ions for hydration levels that are predominant in the stratosphere. With the known stratospheric ion density, these slow rate constants preclude significant N₂O₅ conversion by ion-molecule reactions.     

Global atmospheric monitoring with SCIAMACHY

SCIAMACHY (SCanning Imaging Absorption spectrometer for Atmospheric CHartographY) is a space based spectrometer designed to measure sunlight transmitted, reflected and scattered by the Earth atmosphere or surface. It is a contribution to the Envisat-1 satellite to be launched in late 1999.SCIAMACHY measurements will provide amounts and distribution of 0₃, BrO, OCl0, ClO, S0₂, H₂CO, N0₂, CO, CO₂, CH₄, H₂O, N₂0, pressure, temperature, aerosol, radiation, cloud cover and cloud top height from atmospheric measurements in nadir, limb and occultation geometry.By the combination of the near simultaneous limb and nadir observations SCIAMACHY is one of a limited number of instruments which is able to detect tropospheric column amounts of 0₃, N0₂, CO, CH₄, H₂O, N₂0, S0₂, H₂CO, and BrO down to the planetary boundary layer under cloud free conditions.     

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.     

Atmospheric and cloud structures of the Jovian planets

Wet adiabatic atmospheric models are computed for the four Jovian planets. Possible cloud-forming condensates considered are H₂O ice, aqueous NH₃ solution, NH₄SH, and solid NH₃, CH₄, and Ar. Some techniques for computer calculation of condensation in a multiphase system of variable composition are discussed. Nominal models are computed for all four-planets, and the effects of variations in composition and different pressure-temperature regimes are investigated in detail for Jupiter. The meaning of the calculated cloud densities and their relation to the actual densities are discussed. The computed atmospheric profiles represent average conditions, subject to considerable local variations.     

Electronic Sputtering Analysis of Astrophysical Ices

Experimental results on fast ion collision with icy surfaces having astrophysical interest are presented. ²⁵²Cf fission fragments projectiles were used to induce ejection of ionized material from H₂O, CO₂, CO, NH₃, N₂, O₂ and Ar ices; the secondary ions were identified by time-of-flight mass spectrometry. It is observed that all the bombarded frozen gas targets emit cluster ions which have the structure X_nR^±, where X is the neutral ice molecule and R^± is either an atomic or a molecular ion. The shape of the positive or negative ion mass spectra is characterized by a decreasing yield as the emitted ion mass increases and is generally described by the sum of two exponential functions. The positive ion water ice spectrum is dominated by the series (H₂O)_nH₃O⁺ and the negative ion spectrum by the series (H₂O)_nOH⁻ and (H₂O)_nO⁻. The positive ion CO₂ ice spectrum is characterized by R⁺ = C⁺, O⁺, CO⁺, O₂⁺ or CO₂⁺ and the negative one by R⁻ = CO₃⁻. The dominant series for ammonia ice correspond to R⁺ = NH₄⁺ and to R⁻ = NH₂⁻. The oxygen series are better described by (O₃)_nO_m⁺ secondary ions where m = 1, 2 or 3. Two positive ion series exist for N₂ ice: (N₂)_nN₂⁺ and (N₂)_nN⁺. For argon positive secondary ions, only the (Ar)_nAr⁺ series was observed. Most of the detected molecular ions were formed by one-step reactions. Ice temperature was varied from ∼20 K to complete sublimation.     

Ion chemistry in the cometary atmosphere

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.     

Surface-bounded atmosphere of Europa

A 1-D collisional Monte Carlo model of Europa's atmosphere is described in which the sublimation and sputtering sources of H₂O molecules and their molecular fragments are accounted for as well as the radiolytically produced O₂. Dissociation and ionization of H₂O and O₂ by magnetospheric electron, solar UV-photon and photo-electron impact, and collisional ejection from the atmosphere by the low-energy plasma are taken into account. Reactions with the surface are discussed, but only adsorption and atomic oxygen recombination are included in this model. The size of the surface-bounded oxygen atmosphere of Europa is primarily determined by a balance between atmospheric sources from irradiation of the satellite's icy surface by the high-energy magnetospheric charged particles and atmospheric losses from collisional ejection by the low-energy plasma, photo- and electron-impact dissociation, and ionization and pick-up from the surface-bounded atmosphere. A range of sources rates for O₂ to H₂O are used with a larger oxygen-to-water ratio than suggested by laboratory measurements in order to account for differences in adsorption onto grains in the regolith. These calculations show that the atmospheric composition is determined by both the water and oxygen photochemistry in the near-surface region, escape of suprathermal oxygen and water into the jovian system, and the exchange of radiolytic water products with the porous regolith. For the electron impact ionization rates used, pick-up ionization is the dominant oxygen loss process, whereas photo-dissociation and atmospheric sputtering are the dominant sources of neutral oxygen for Europa's neutral torus. Including desorption and loss of water enhances the supply of oxygen species to the neutral torus, but hydrogen produced by radiolysis is the dominant source of neutrals for Europa's torus in these models.     

Galactic cosmic rays and N2 dissociation on Titan

The electromagnetic and particle cascade resulting from the absorption of galactic cosmic rays in the atmosphere of Titan is shown to be an important mechanism for driving the photochemistry at pressures of 1 to 50 mbar in the atmosphere. In particular, the cosmic ray cascade dissociates N₂, a process necessary for the synthesis of nitrogen organics such as HCN. The important interactions of the cosmic ray cascade with the atmosphere are discussed. The N₂ excitation and dissociation rates and the ionization rates of the principal atmospheric constituents are computed for a Titan model atmosphere that is consistent with Voyager 1 observations. It is suggested that HCN may be formed efficiently in the lower atmosphere through the photodissociation of methylamine. It is also argued that models of nitrogen and hydrocarbon photochemistry in the lower atmosphere of Titan should include the absorption of galactic cosmic rays as an important energy source.     

Photochemistry of nitrogen in the Martian atmosphere

Models are developed for the photochemistry of a CO₂H₂ON₂ 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.     

Constraints on bulk composition,seasonal variation,and global dynamics of Pluto's atmosphere

Cosmic abundance, vapor pressure, and molecular weight considerations restrict the likely gas candidates for Pluto's atmosphere to Ne, N₂, CO, O₂, and Ar, in addition to the already detected CH₄. The vapor pressures and cosmic abundances of these gases indicate that all except Ne should be saturated in Pluto's atmosphere. The vapor pressure of Ne is so high that the existence of solid or liquid Ne on Pluto's surface is very unlikely; cosmic abundance arguments imply that Ne cannot attain saturation in Pluto's atmosphere. At both perihelion, N₂ should dominate the saturated gases. CO₂ should have the next highest mixing ratio, followed by O₂ and Ar. CH₄ should have the smallest mixing ratio. Because vapor pressures of these gases vary with temperature at diverse rates, the bulk and constituent mixing ratios of Pluto's atmosphere should vary with season. Between perihelion and aphelion, the column abundance of CH₄ may change by a factor of 260 while that of N₂ changes by only a factor of 52. The potential seasonal variation of Pluto's atmosphere was investigated by considering the behavior of these gases when individually mixed with CH₄. The effects of diurnal and latitudinal variation of insolation and eclipses on the atmosphere also were investigated. Seasonal effects are shown to dominate. It was shown that the atmospheric bulk may not be a minimum near aphelion but rather at intermediate distances from the Sun during summer/winter inadequate ice deposits may allow the atmosphere to collapse by freezing out over winter latitudes. If the atmosphere does not collapse, its weight is sufficient to keep it distributed uniformly around Pluto's surface. In this case, the atmosphere tends to regulate the surface temperature to a seasonally dependent value which is uniform over the globe.Finally, the likely global circulation regimes for each model atmosphere as a function of temperature were investigated and it was concluded that if CH₄, O₂, or CO dominates the atmosphere, Pluto will exhibit cyclic variations between an axially symmetric circulation system at perihelion and a baroclinic wave regime at aphelion. However, if N₂ dominates, as is likely, the wave regime should hold continuously. If the atmosphere collapses to a thin halo during summer/winter seasons, only a weak, symmetric circulation should occur.     

Loss of water from Mars:: Implications for the oxidation of the soil

The evolution of the martian atmosphere with regard to its H₂O inventory is influenced by thermal loss processes of H, H₂, nonthermal atmospheric loss processes of H⁺, H₂⁺, O, O⁺, CO₂, and O₂⁺ into space, as well as by chemical weathering of the surface soil. The evolution of thermal and nonthermal escape processes depend on the history of the intensity of the solar XUV radiation and the solar wind density. Thus, we use actual data from the observation of solar proxies with different ages from the Sun in Time program for reconstructing the Sun's radiation and particle environment from the present to 3.5 Gyr ago. The correlation between mass loss and X-ray surface flux of solar proxies follows a power law relationship, which indicates a solar wind density up to 1000 times higher at the beginning of the Sun's main sequence lifetime. For the study of various atmospheric escape processes we used a gas dynamic test particle model for the estimation of the pick up ion loss rates and considered pick up ion sputtering, as well as dissociative recombination. The loss of H₂O from Mars over the last 3.5 Gyr was estimated to be equivalent to a global martian H₂O ocean with a depth of about 12 m, which is smaller than the values reported by previous studies. If ion momentum transport, a process studied in detail by Mars Express is significant on Mars, the water loss may be enhanced by a factor of about 2. In our investigation we found that the sum of thermal and nonthermal atmospheric loss rates of H and all nonthermal escape processes of O to space are not compatible with a ratio of 2:1, and is currently close to about 20:1. Escape to space cannot therefore be the only sink for oxygen on Mars. Our results suggest that the missing oxygen (needed for the validation of the 2:1 ratio between H and O) can be explained by the incorporation into the martian surface by chemical weathering processes since the onset of intense oxidation about 2 Gyr ago. Based on the evolution of the atmosphere-surface-interaction on Mars, an overall global surface sink of about 2×10⁴² oxygen particles in the regolith can be expected. Because of the intense oxidation of inorganic matter, this process may have led to the formation of considerable amounts of sulfates and ferric oxides on Mars. To model this effect we consider several factors: (1) the amount of incorporated oxygen, (2) the inorganic composition of the martian soil and (3) meteoritic gardening. We show that the oxygen incorporation has also implications for the oxidant extinction depth, which is an important parameter to determine required sampling depths on Mars aimed at finding putative organic material. We found that the oxidant extinction depth is expected to lie in a range between 2 and 5 m for global mean values.     

The gas exchange experiment for life detection: The Viking Mars Lander

The Gas Exchange Experiment of the Viking mission accepts a sample of Martian soil, incubates this soil with nutrient medium, and periodically samples the enclosed atmosphere over this soil for the gases H₂, N₂, O₂, CH₄, Kr, and CO₂. These gases are analyzed by an automated gas chromatograph, and the data are transmitted to Earth. The design of the experiment and the qualitative and quantitative changes, if any, of gas composition should allow conclusions to be made on the presence of life on Mars. Data and theory substantiating this approach are presented.