Martian isotopic ratios and upper limits for possible minor constituents as derived from Mariner 9 infrared spectrometer data

The Mariner 9 infrared spectrometer obtained data over a large part of Mars for almost a year beginning late in 1971. Mars' infrared emission spectrum was measured from 200 to 2000 cm^?1 with an apodized resolution of 2.4 cm^?1. No significant deviation from terrestrial ratios of carbon (¹²C/¹³C) or oxygen (¹⁶O/¹⁸O; ¹⁶O/¹⁷O) isotopes was observed on Mars. The ¹²C/¹³C isotopic ratio was found to be terrestrial with an uncertainty of 15%. Upper limits have been calculated for several minor constituents. With an effective noise equivalent radiance of 1.2 × 10^?9 W cm^?2 sr^?1/cm^?1, new upper limits in centimeter-atmospheres of 2 × 10^?5 for C₂H₂, 4 × 10^?3 for C₂H₄, 3 × 10^?3 for C₂H₆, 2 × 10^?4 for CH₄, 1 × 10^?3 for N₂O, 1 × 10^?4 for NO₂, 4 × 10^?5 for NH₃, 1 × 10^?3 for PH₃, 7 × 10^?4 for SO₂, and 1 × 10^?4 for OCS have been derived.     

Mars: Chemical weathering as a massive volatile sink

Photostimulated oxidation weathering irreversibly removes both oxygen and hydrogen from the atmosphere at a rate of 10⁸ to 10¹¹ cm^?2sec^?1. This corresponds to a net loss of 10²⁵ to 10²⁸ molecules cm^?2 (10² to 10⁵ g cm^?2 of H₂O, assuming a uniform rate over geologic time. Additional H₂O is removed through hydration of Fe₂O₃ and clay minerals, but the loss is reversible and the extent of regolith storage is uncertain. CO₂ is irreversibly removed from the atmosphere through the formation of CaCO₃ at a rate of 10⁷?10¹⁰cm^?2sec^?1. Over geologic time this corresponds to a net loss of 10²⁴?10²⁷ molecules cm^?2 (10¹?10⁴g cm^?2) of CO₂. Previously, it was proposed that exospheric escape was the principal irreversible volatile sink, amounting to only 10²g cm^?2 of H₂O and 10⁰g cm^?2 of CO₂ over geologic time. A recent tentative identification of abundant argon on Mars suggests that the planet may have degassed up to 10⁵g cm^?2 of H₂O and 10⁴g cm^?2 of CO₂. If the amounts of H₂O and CO₂ removed by photostimulated oxidation are close to the upper limits proposed here, it is possible that chemical weathering may have had a major effect on limiting the supply of H₂O and CO₂ trapped in the regolith and polar caps.     

Regolith-atmosphere exchange of water and carbon dioxide on Mars: Effects on atmospheric history and climate change

Exchange of CO₂ and H₂O between the Mars regolith and the atmosphere-cap system plays an important role in governing the evolution of the martian atmosphere and the martian climate. Most of the exchangeable CO₂ (perhaps one or two orders of magnitude more than the atmospheric inventory) is currently adsorbed on the deep regolith, and can be “cryopumped” to a large quasipermanent CO₂ cap (not now present) during lowest Mars obliquity (θ). During the obliquity driven regolith-cap CO₂ exchange cycle, the atmospheric pressure varies harmonically between ~0.1 mb (lowest Θ) and ? 20 mb (highest Θ). The regolith buffer plays only a small or negligible role in the seasonal CO₂ pressure variations caused by atmosphere-cap exchange because adsorption greatly inhibits diffusion of the seasonal “pressure wave” into the regolith. In contrast, thermally driven H₂O seasonal exchange between the atmosphere and regolith appears to be in large part responsible for observed seasonal variations in the small atmospheric H₂O inventory. Long term exchange of H₂O may be dominated by transfer between the polar caps and ice in the regolith. Available and potential tests of regolith-atmospheric-cap volatile exchange models using ground-based and spacecraft-based techniques are discussed.     

Comets,volcanism, the salt-rich regolith,and cycling of volatiles on Mars

Estimates of the total inventory of the volatile elements C, H, O, and N on Mars, based upon atmospheric gas tracers, vary by a factor of 25 among different authors. Accretion of comets as the source of volatiles can account for less than 5% of the actual inventory, assuming the chondritic S/Cl abundance ratio in comets and a Martian outgassing ratio for these two elements no lower than for the estimated excess volatile inventory on Earth. Sulfate salt formation with the igneous minerals in the regolith can be a major sink for H₂O, but first will recycle C and N incorporated in carbonate and nitrate minerals back to the atmosphere. Extrusive and shallow intrusive volcanism, at a persistent but decreasing rate, can interfere with this volatile recycling by irreversibly masking much of the incorporated inventory, resulting in the inevitable evolution to a relatively volatile-poor environment at the outermost, observable surface of Mars.     

The Monahans chondrite and halite: Argon‐39/argon‐40 age,solar gases,cosmic‐ray exposure ages,and parent body regolith neutron flux and thickness

Abstract— The Monahans H‐chondrite is a regolith breccia containing light and dark phases and the first reported presence of small grains of halite. We made detailed noble gas analyses of each of these phases. The ³⁹Ar‐⁴⁰Ar age of Monahans light is 4.533 ± 0.006 Ma. Monahans dark and halite samples show greater amounts of diffusive loss of ⁴⁰Ar and the maximum ages are 4.50 and 4.33 Ga, respectively. Monahans dark phase contains significant concentrations of He, Ne and Ar implanted by the solar wind when this material was extant in a parent body regolith. Monahans light contains no solar gases. From the cosmogenic ³He, ²¹Ne, and ³⁸Ar in Monahans light we calculate a probable cosmic‐ray, space exposure age of 6.0 ± 0.5 Ma. Monahans dark contains twice as much cosmogenic ²¹Ne and ³⁸Ar as does the light and indicates early near‐surface exposure of 13–18 Ma in a H‐chondrite regolith. The existence of fragile halite grains in H‐chondrites suggests that this regolith irradiation occurred very early. Large concentrations of ³⁶Ar in the halite were produced during regolith exposure by neutron capture on ³⁵Cl, followed by decay to ³⁶Ar. The thermal neutron fluence seen by the halite was (2–4) × 10¹⁴ n/cm². The thermal neutron flux during regolith exposure was ～0.4‐0.7 n/cm²/s. The Monahans neutron fluence is more than an order of magnitude less than that acquired during space exposure of several large meteorites and of lunar soils, but the neutron flux is lower by a factor of ≤5. Comparison of the ³⁶Ar_n/²¹Ne_cos ratio in Monahans halite and silicate with the theoretically calculated ratio as a function of shielding depth in an H‐chondrite regolith suggests that irradiation of Monahans dark occurred under low shielding in a regolith that may have been relatively shallow. Late addition of halite to the regolith can be ruled out. However, irradiation of halite and silicate for different times at different depths in an extensive regolith cannot be excluded.     

Postperihelion interference filter photometry of the “annual” comet P/Encke

Interference filter photometry was taken of Comet Encke on June 14, 1974 (1.07 AU heliocentric distance, postperihelion) at the CTIO (Cerro Tololo Interamerican Observatory) 150-cm reflector. Production rates were calculated of 4.1 × 10²³ mol sec^?1 of CN, 5.3 × 10²³ mol sec^?1 of C₃, and 4.3 × 10²⁴ mol sec^?1 of C₂. These are about three times smaller than at comparable heliocentric distance preperihelion, assuming a value of 100 for the ratio H₂O/ (C₂ + C₃ + CN). An upper limit was placed on the production of nonvolatiles at about one-third that of volatiles in mass by assuming a bulk density of 1 g cm^?3, a particle geometric albedo of 0.1, and a phase function of 0.2.     

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.     

Regolith history of lunar meteorites

Abstract— The regolith evolution of the lunar meteorites Dhofar (Dho) 081, Northwest Africa (NWA) 032, NWA 482, NWA 773, Sayh al Uhaymir (SaU) 169, and Yamato (Y‐) 981031 was investigated by measuring the light noble gases He, Ne, and Ar. The presence of trapped solar neon in Dho 081, NWA 773, and Y‐981031 indicates an exposure at the lunar surface. A neon three‐isotope diagram for lunar meteorites yields an average solar ²⁰Ne/²²Ne ratio of 12.48 ± 0.07 representing a mixture of solar energetic particles neon at a ratio of 11.2 and solar wind neon at a ratio of 13.8. Based on the production rate ratio of ²¹Ne and ³⁸Ar, the shielding depth in the lunar regolith of NWA 032, NWA 482, SaU 169, and Y‐981031 was obtained. The shielding depth of these samples was between 10.5 g/cm² and >500 g/cm². Based on spallogenic Kr and Xe, the shielding depth of Dho 081 was estimated to be most likely between 120 and 180 g/cm². Assuming a mean density of the lunar regolith of 1.8 g/cm³, 10.5 g/cm² corresponds to a depth of 5.8 cm and 500 g/cm² to 280 cm below the lunar surface. The range of regolith residence time observed in this study is 100 Ma up to 2070 Ma.     

Minimum estimates of the amount and timing of gases released into the martian atmosphere from volcanic eruptions

Volcanism has been a major process during most of the geologic history of Mars. Based on data collected from terrestrial basaltic eruptions, we assume that the volatile content of martian lavas was typically ∼0.5 wt.% water, ∼0.7 wt.% carbon dioxide, ∼0.14 wt.% sulfur dioxide, and contained several other important volatile constituents. From the geologic record of volcanism on Mars we find that during the late Noachian and through the Amazonian volcanic degassing contributed ∼0.8 bar to the martian atmosphere. Because most of the outgassing consisted of greenhouse gases (i.e., CO₂ and SO₂) warmer surface temperatures resulting from volcanic eruptions may have been possible. Our estimates suggest that ∼1.1 × 10²¹ g (∼8 ± 1 m m⁻²) of juvenile water were released by volcanism; slightly more than half the amount contained in the north polar cap and atmosphere. Estimates for released CO₂ (1.6 × 10²¹ g) suggests that a large reservoir of carbon dioxide is adsorbed in the martian regolith or alternatively ∼300 cm cm⁻² of carbonates may have formed, although these materials would not occur readily in the presence of excess SO₂. Up to ∼120 cm cm⁻² (2.2 × 10²⁰ g) of acid rain (H₂SO₄) may have precipitated onto the martian surface as the result of SO₂ degassing. The hydrogen flux resulting from volcanic outgassing may help explain the martian atmospheric D/H ratio. The amount of outgassed nitrogen (∼1.3 mbar) may also be capable of explaining the martian atmospheric ¹⁵N/¹⁴N ratio. Minor gas constituents (HF, HCl, and H₂S) could have formed hydroxyl salts on the surface resulting in the physical weathering of geologic materials. The amount of hydrogen fluoride emitted (1.82 × 10¹⁸ g) could be capable of dissolving a global layer of quartz sand ∼5 mm thick, possibly explaining why this mineral has not been positively identified in spectral observations. The estimates of volcanic outgassing presented here will be useful in understanding how the martian atmosphere evolved over time.     

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.     

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.     

39Ar‐40Ar dating of the Zagami Martian shergottite and implications for magma origin of excess 40Ar

Abstract— The Zagami shergottite experienced a complex, petrogenetic formation history (McCoy et al. 1992, 1999). Like several shergottites, Zagami contains excess ⁴⁰Ar relative to its formation age. To understand the origin of this excess ⁴⁰Ar, we made ³⁹Ar‐⁴⁰Ar analyses on plagioclase and pyroxene minerals from two phases representing different stages in the magma evolution. Surprisingly, all these separates show similar concentrations of excess ⁴⁰Ar, ?1 × 10^?6 cm³/g. We present arguments against this excess ⁴⁰Ar having been introduced from the Martian atmosphere as impact glass. We also present evidence against excess ⁴⁰Ar being a partially degassed residue from a basalt that actually formed ?4 Gyr ago. We utilize our experimental data on Ar diffusion in Zagami and evidence that it was shock‐heated to only ?70 °C, and we assume this heating occurred during an ejection from Mars ?3 Myr ago. With these constraints, thermal considerations necessitates either that its ejected mass was impossibly large, or that its shock‐heating temperature was an order of magnitude higher than that measured. We suggest that this excess ⁴⁰Ar was inherited from the Zagami magma, and that it was introduced into the magma either by degassing of a larger volume of material or by early assimilation of old, K‐rich crustal material. Similar concentrations of excess ⁴⁰Ar in the analyzed separates imply that this magma maintained a relatively constant ⁴⁰Ar concentration throughout its crystallization. This likely occurred through volatile degassing as the magma rose toward the surface and lithostatic pressure was released. These concepts have implications for excess ⁴⁰Ar in other shergottites.     

Volatiles on Earth and Mars: A comparison

Based on our new and previous determinations of halogens in SNC meteorites, the bulk concentrations of halogens in the SPB, which is thought to be Mars, are estimated. The two-component model for the formation of terrestrial planets as proposed byA. E. Ringwood (Geochem. J. 11, 111–135 (1977) andOn the Origin of the Earth and Moon, Springer-Verlag, New York, 1979) andH. Wa¨nke (Philos. Trans. Roy. Soc. London, Ser. A 303, 287–302 (1981) is further substantiated. It is argued that almost all of the H₂O added to Mars during its homogeneous accretion was converted on reaction with metallic Fe to H₂, which escaped. By comparing the solubilities of H₂O and HCl in molten silicates, the amount of H₂O left in the mantle of Mars at the end of accretion can be related to the abundance of Cl. In this way an H₂O content in the Martian mantle of 36 ppm is obtained, corresponding to an ocean covering the whole planet to a depth of about 130 m.The huge quantities of H₂ produced by the reaction of H₂O with metallic iron should also have removed other volatile species by hydrodynamic escape. Thus it is postulated that the present atmospheres of Venus, Earth, and Mars were formed by degassing the interiors of the planets, after the production of H₂ had ceased, i.e., after metallic iron was no longer available. It is also postulated that the large differences in the amounts of primordial rare gases in the atmospheres of Venus, Earth, and Mars are due mainly to different loss factors.Except for gaseous species, Mars is found to be richer in volatile (halogens) and moderately volatile elements than the Earth. The resulting low release factor of⁴⁰Ar for Mars is attributed to a low degree of fractionation, leading to a relatively small crustal enrichment of even the most incompatible elements like K.     

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.     

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.     

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.     

Ozone and photochemistry of the Martian lower atmosphere

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.     

Methane emissions from Earth’s degassing: Implications for Mars

The presence of methane on Mars is of great interest, since one possibility for its origin is that it derives from living microbes. However, CH₄ in the martian atmosphere also could be attributable to geologic emissions released through pathways similar to those occurring on Earth. Using recent data on methane degassing of the Earth, we have estimated the relative terrestrial contributions of fossil geologic methane vs. modern methane from living methanogens, and have examined the significance that various geologic sources might have for Mars.Geologic degassing includes microbial methane (produced by ancient methanogens), thermogenic methane (from maturation of sedimentary organic matter), and subordinately geothermal and volcanic methane (mainly produced abiogenically). Our analysis suggests that ～80% of the “natural” emission to the terrestrial atmosphere originates from modern microbial activity and ～20% originates from geologic degassing, for a total CH₄ emission of ～28.0×10⁷ tonnes year^?1.Estimates of methane emission on Mars range from 12.6×10¹ to 57.0×10⁴ tonnes year^?1 and are 3–6 orders of magnitude lower than that estimated for Earth. Nevertheless, the recently detected martian, Northern-Summer-2003 CH₄ plume could be compared with methane expulsion from large mud volcanoes or from the integrated emission of a few hundred gas seeps, such as many of those located in Europe, USA, Mid-East or Asia. Methane could also be released by diffuse microseepage from martian soil, even if macro-seeps or mud volcanoes were lacking or inactive. We calculated that a weak microseepage spread over a few tens of km², as frequently occurs on Earth, may be sufficient to generate the lower estimate of methane emission in the martian atmosphere.At least 65% of Earth’s degassing is provided by kerogen thermogenesis. A similar process may exist on Mars, where kerogen might include abiogenic organics (delivered by meteorites and comets) and remnants of possible, past martian life. The remainder of terrestrial degassed methane is attributed to fossil microbial gas (～25%) and geothermal-volcanic emissions (～10%). Global abiogenic emissions from serpentinization are negligible on Earth, but, on Mars, individual seeps from serpentinization could be significant. Gas discharge from clathrate-permafrost destabilization should also be considered.Finally, we have shown examples of potential degassing pathways on Mars, including mud volcano-like structures, fault and fracture systems, and major volcanic edifices. All these types of structures could provide avenues for extensive gas expulsion, as on Earth. Future investigations of martian methane should be focused on such potential pathways.     

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.     

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.