Spectroscopy of molecular oxygen in the Atmospheres of Venus and Mars

The abundances of molecular oxygen in the atmospheres of Venus and Mars are sensitive to fundamental photochemical processes. A new upper limit is reported for the molecular oxygen mixing ratio (O₂/CO₂ < × 10^?7) in the integrated column above the visible cloud tops of Venus, based on spectroscopic observations carried out in early spring, 1982. During the same observing period, an O₂ column abundance of 8.5 cm-am for the atmosphere of Mars was measured, slightly below the O₂ abundances measured a decade earlier.     

Effects of impacts on the atmospheric evolution: Comparison between Mars, Earth, and Venus

Classified as a terrestrial planet, Venus, Mars, and Earth are similar in several aspects such as bulk composition and density. Their atmospheres on the other hand have significant differences. Venus has the densest atmosphere, composed of CO₂ mainly, with atmospheric pressure at the planet's surface 92 times that of the Earth, while Mars has the thinnest atmosphere, composed also essentially of CO₂, with only several millibars of atmospheric surface pressure. In the past, both Mars and Venus could have possessed Earth-like climate permitting the presence of surface liquid water reservoirs. Impacts by asteroids and comets could have played a significant role in the evolution of the early atmospheres of the Earth, Mars, and Venus, not only by causing atmospheric erosion but also by delivering material and volatiles to the planets. Here we investigate the atmospheric loss and the delivery of volatiles for the three terrestrial planets using a parameterized model that takes into account the impact simulation results and the flux of impactors given in the literature. We show that the dimensions of the planets, the initial atmospheric surface pressures and the volatiles contents of the impactors are of high importance for the impact delivery and erosion, and that they might be responsible for the differences in the atmospheric evolution of Mars, Earth and Venus.     

Noble gases in planetary atmospheres: Implications for the origin and evolution of atmospheres

The radiogenic and primordial noble gas content of the atmospheres of Venus, Earth, and Mars are compared with one another and with the noble gas content of other extraterrestial samples, especially meteorites. The fourfold depletion of ⁴⁰Ar for Venus relative to the Earth is attributed to the outgassing rates and associated tectonics and volcanic styles for the two planets diverging significantly within the first billion or so years of their history, with the outgassing rate for Venus becoming much less than that for the Earth at subsequent times. This early divergence in the tectonic style of the two planets may be due to a corresponding early onset of the runaway greenhouse on Venus. The 16-fold depletion of ⁴⁰Ar for Mars relative to the Earth may be due to a combination of a mild K depletion for Mars, a smaller fraction of its interior being outgassed, and to an early reduction in its outgassing rate. Venus has lost virtually all of its primordial He and some of its radiogenic He. The escape flux of He may have been quite substantial in Venus' early history, but much diminished at later times, with this time variation being perhaps strongly influenced by massive losses of H₂ resulting from efficient H₂O loss processes.Key trends in the primordial noble gas content of terrestial planetary atmospheres include (1) a several orders of magnitude decrease in ²⁰Ne and ³⁶Ar from Venus to Earth to Mars; (2) a nearly constant ²⁰Ne/³⁶Ar ratio which is comparable to that found in the more primitive carbonaceous chondrites and which is two orders of magnitude smaller than the solar ratio; (3) a sizable fractionation of Ar, Kr, and Xe from their solar ratios, although the degree of fractionation, especially for ³⁶Ar/¹³²Xe, seems to decrease systematically from carbonaceous chondrites to Mars to Earth to Venus; and (4) large differences in Ne and Xe isotopic ratios among Earth, meteorites, and the Sun. Explaining trends (2), (2) and (4), and (1) pose the biggest problems for the solar-wind implantation, primitive atmosphere, and late veneer hypotheses, respectively. It is suggested that the grain-accretion hypothesis can explain all four trends, although the assumptions needed to achieve this agreement are far from proven. In particular, trends (1), (2), (3), and (4) are attributed to large pressure but small temperature differences in various regions of the inner solar system at the times of noble gas incorporation by host phases; similar proportions of the host phases that incorporated most of the He and Ne on the one hand (X) and Ar, Kr, and Xe on the other hand (Q); a decrease in the degree of fractionation with increasing noble-gas partial pressure; and the presence of interstellar carriers containing isotopically anomalous noble gases.Our analysis also suggests that primordial noble gases were incorporated throughout the interior of the outer terrestial planets, i.e., homogeneous accretion is favored over inhomogeneous accretion. In accord with meteorite data, we propose that carbonaceous materials were key hosts for the primordial noble gases incorporated into planets and that they provided a major source of the planets' CO₂ and N₂.     

Synthetic spectra of simulated terrestrial atmospheres containing possible biomarker gases.

NASA's proposed Terrestrial Planet Finder, a space-based interferometer, will eventually allow spectroscopic analyses of the atmospheres of extrasolar planets. Such analyses would provide information about the existence of life on these planets. One strategy in the search for life is to look for evidence of O3 (and hence O2) in a planet's atmosphere; another is to look for gases that might be present in an atmosphere analogous to that of the inhabited early Earth. In order to investigate these possibilities, we have calculated synthetic spectra for several hypothetical terrestrial-type atmospheres. The model atmospheres represent four different scenarios. The first two, representing inhabited terrestrial planets, are an Earth-like atmosphere containing variable amounts of oxygen and an early Earth-type atmosphere containing methane. In addition, two cases representing Mars-like and early Venus-like atmospheres were evaluated, to provide possible "false positive" spectra. The calculated spectra suggest that ozone could be detected by an instrument like Terrestrial Planet Finder if the O2 concentration in the planet's atmosphere is > or = 200 ppm, or 10(-3) times the present atmospheric level. Methane should be observable on an early-Earth type planet if it is present in concentrations of 100 ppm or more. Methane has both biogenic and abiogenic sources, but concentrations exceeding 1000 ppm, or 0.1% by volume, would be difficult to produce from abiogenic sources alone. High methane concentrations in a planet's atmosphere are therefore another potential indicator for extraterrestrial life.     

Loss of water from Venus. I. Hydrodynamic escape of hydrogen

A one-dimensional photochemical-dynamic model is used to study hydrodynamic loss of hydrogen from a primitive, water-rich atmosphere on Venus. The escape flux is calculated as a function of the H₂O mixing ratio at the atmospheric cold trap. The cold-trap mixing ratio is then related in an approximate fashion to the H₂O concentration in the lower atmosphere. Hydrodynamic escape should have been the dominant loss process for hydrogen when the H₂O mass mixing ratio in the lower atmosphere exceeded ～0.1. The escape rate would have depended upon the magnitude of the solar ultraviolet flux and the atmospheric euv heating efficiency and, to a lesser extent, on the O₂ content of the atmosphere. The time required for Venus to have lost the bulk of a terrestrial ocean of water is on the order of a billion years. Deutrium would have been swept away along with hydrogen if the escape rate was high enough, but some D/H enrichment should have occurred as the escape rate slowed down.     

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.     

Atmospheric chemistry on Venus, Earth, and Mars: Main features and comparison

This paper deals with two common problems and then considers major aspects of chemistry in the atmospheres of Mars and Venus. (1) The atmospheres of the terrestrial planets have similar origins but different evolutionary pathways because of the different masses and distances to the Sun. Venus lost its water by hydrodynamic escape, Earth lost CO₂ that formed carbonates and is strongly affected by life, Mars lost water in the reaction with iron and then most of the atmosphere by the intense meteorite impacts. (2) In spite of the higher solar radiation on Venus, its thermospheric temperatures are similar to those on Mars because of the greater gravity acceleration and the higher production of O by photolysis of CO₂. O stimulates cooling by the emission at 15 μm in the collisions with CO₂. (3) There is a great progress in the observations of photochemical tracers and minor constituents on Mars in the current decade. This progress is supported by progress in photochemical modeling, especially by photochemical GCMs. Main results in these areas are briefly discussed. The problem of methane presents the controversial aspects of its variations and origin. The reported variations of methane cannot be explained by the existing data on gas-phase and heterogeneous chemistry. The lack of current volcanism, SO₂, and warm spots on Mars favor the biological origin of methane. (4) Venus’ chemistry is rich and covers a wide range of temperatures and pressures and many species. Photochemical models for the middle atmosphere (58-112 km), for the nighttime atmosphere and night airglow at 80-130 km, and the kinetic model for the lower atmosphere are briefly discussed.     

Response of Earth's atmosphere to increases in solar flux and implications for loss of water from Venus

A one-dimensional radiative-convective model is used to compute temperature and water vapor profiles as functions of solar flux for an Earth-like atmosphere. The troposphere is assumed to be fully saturated, with a moist adiabatic lapse rate, and changes in cloudiness are neglected. Predicted surface temperatures increase monotonically from ?1 to 111°C as the solar flux increased from 0.81 to 1.45 times its present value. Surface temperatures corresponding to high solar fluxes may be underestimated, however, owing to neglect of H₂O continuum absorption outside of the 8- to 12-μm window region. These results imply that the surface temperature of a primitive water-rich Venus should have been at least 80–100°C and may have been much higher. The existence of liquid water at the surface depends on poorly known aspects of H₂O continuum absorption and on uncertainties concerning relative humidity and cloudiness. In any case, water vapor should have been a major atmospheric constituent at all altitudes, leading to the rapid hydrodynamic escape of hydrogen. The oxygen left behind by this process was presumably consumed by reactions with reduced minerals in the crust. Both the loss of oxygen and the presently observed enrichment of the deuterium-to-hydrogen ratio are most easily explained if oceans of liquid water were initially present.     

The origin and evolution of the atmospheres of the terrestrial planets

The chemical nature of the Earth's atmosphere is determined by its interaction with the biosphere, hydrosphere and lithosphere. Detailed balance is maintained over long time periods by a complex series of cyclical processes. The chemical differences between the atmosphere of the Earth, on the one hand, and the atmospheres of Venus and Mars, on the other, can be understood in terms of the greater complexity of the terrestrial interactions. When this has been taken into account, the origin of all three planetary atmospheres can be explained as resulting from degassing. Despite the similarity of the atmospheres of Venus and Mars, it seems necessary to invoke different mechanisms for the low amount of water vapour on each.     

Temperature effect on the photodissociation rates in the atmospheres of Mars and Venus

The available solar flux at a given altitude in the atmospheres of Mars and Venus is attenuated mainly by CO₂ (molecular absorption and Rayleigh scattering) with an extra contribution due to SO₂ on Venus. The dissociation cross section of CO₂ depends on temperature. At temperatures appropriate for these atmospheres (～250°K), the cross sections are about 15% lower than those at room conditions (Y.L. Yung and W.B. De More, 1982, Icarus, 51, 199). It is shown that this temperature effect cannot be neglected in the evaluation of photolysis rates. Calculations of the photodissociation coefficients of CO₂, SO₂, HCl, and H₂O are presented. For example, at the surface of Mars, the coefficient of H₂O is nearly multiplied by a factor of 10!     

On the small-scale turbulence parameters in the atmosphere of venus and their use in the global circulation models

Vertical profiles of the turbulence parameters calculated for the planet-averaged conditions from the experimental data on the turbulent fluctuations of temperature and wind velocity are presented. Improved formulas accounting for the difference between the atmospheric gas on Venus and an ideal one, and the large difference in its thermal capacity at different altitudes, are used. The commonly used formula for the potential temperature describing the atmospheres of the Earth and Mars is inapplicable to the atmosphere of Venus. It has been shown that the opinion on the absence of turbulence in the atmosphere of Venus is based on overestimated values of the dynamic Richardson number obtained from the smoothed profiles of wind velocity, while its actual values are below unity due to the large wind velocity gradients produced by buoyancy waves. To improve the global circulation models of the atmosphere of Venus, it is necessary to use the currently available turbulence parameters calculated from experimental data.     

Large-scale quasi-two-dimensional turbulence and a inverse spectral flux of energy in the atmosphere of Venus

The comparison of the theoretical inferences and the experimental data on large-scale turbulence in the atmospheres of the Earth and Venus, including those acquired with the Venus Express spacecraft, allows us to conclude that there is a inverse spectral flux of energy in the atmosphere of Venus, as in the terrestrial atmosphere, which participates in generating the superrotation of the atmosphere.     

Mineral reaction buffering of Venus’ atmosphere: A thermochemical constraint and implications for Venus-like planets

The equilibrium suggested as a buffer for CO₂ in the Venus atmosphere, CaCO₃ + SiO₂ = CaSiO₃ + CO₂, cannot act as a buffer at the Venus surface/troposphere – the pressure–temperature slope of the equilibrium and that of the atmosphere (dry adiabat with significant greenhouse heating) do not provide buffering capacity (if indeed CaCO₃ were present). Instead, perturbations to T or P(CO₂) can produce catastrophic expansion or collapse of the atmosphere. This instability can be generalized to all devolatilization reactions that produce a radiatively active gas in a planetary atmosphere dominated by such gases, and gives a simple thermochemical criterion for whether a reaction could buffer such an atmosphere. Simple decarbonation reactions fail this criterion, suggesting that the abundance of CO₂ in a CO₂-dominated atmosphere cannot be buffered by chemical reactions with the surface; a similar conclusion holds for the abundance of H₂O in an H₂O-dominated (steam) atmosphere. Buffering of minor gases is more likely; a mineral buffer equilibrium for SO₂ proposed for Venus, FeS₂ + CO₂ = Fe₃O₄ + SO₂ + CO, passes the thermochemical criterion, as does a reaction involving Ca sulfate. These inferences can be generalized to atmospheres in ‘moist’ adiabatic equilibria, and to extrasolar Venus-like planets, and will help in interpreting the compositions of their atmospheres.     

The formation of the atmospheres of the terrestrial planets by impact

It is generally supposed that the atmospheres of the terrestrial planets were formed by secondary degassing processes. We propose, instead, that they are of primary origin, forming as an immediate and necessary consequence of the final stages of planetary accretion. Once the planetary embryo reached a critical size, the impacting material began to vaporize. The atmosphere, so created, then decelerated other impacting material, thus limiting the rate of atmospheric growth. We show that, given reasonable assumptions concerning the chemical composition of the impacting material, an acceptable model for the early atmosphere of the Earth, and the present atmospheres of Venus and Mars results.A discussion of the noble gas data for the terrestrial atmosphere indicates that these can be readily reconciled with an impact origin.     

Sulfuric acid aerosols in the atmospheres of the terrestrial planets

Clouds and hazes composed of sulfuric acid are observed to exist or postulated to have once existed on each of the terrestrial planets with atmospheres in our solar system. Venus today maintains a global cover of clouds composed of a sulfuric acid/water solution that extends in altitude from roughly 50 km to roughly 80 km. Terrestrial polar stratospheric clouds (PSCs) form on stratospheric sulfuric acid aerosols, and both PSCs and stratospheric aerosols play a critical role in the formation of the ozone hole. Stratospheric aerosols can modify the climate when they are enhanced following volcanic eruptions, and are a current focus for geoengineering studies. Rain is made more acidic by sulfuric acid originating from sulfur dioxide generated by industry on Earth. Analysis of the sulfur content of Martian rocks has led to the hypothesis that an early Martian atmosphere, rich in SO₂ and H₂O, could support a sulfur-infused hydrological cycle. Here we consider the plausibility of frozen sulfuric acid in the upper clouds of Venus, which could lead to lightning generation, with implications for observations by the European Space Agency's Venus Express and the Japan Aerospace Exploration Agency's Venus Climate Orbiter (also known as Akatsuki). We also present simulations of a sulfur-rich early Martian atmosphere. We find that about 40 cm/yr of precipitation having a pH of about 2.0 could fall in an early Martian atmosphere, assuming a surface temperature of 273 K, and SO₂ generation rates consistent with the formation of Tharsis. This modeled acid rain is a powerful sink for SO₂, quickly removing it and preventing it from having a significant greenhouse effect.     

Planetary atmospheres with ALMA

Thanks to its sensitivity, spatial resolution and instantaneous uv-coverage, ALMA will permit many new studies related to the general topic of the couplings between chemistry and dynamics in planetary atmospheres. It will include: (1) three-dimensional mapping of composition, temperatures and winds in the atmospheres of Mars, Venus and Titan; (2) several aspects of Giant Planet composition and dynamics, such as the origin of oxygen, the evolution of Shoemaker–Levy 9 products in Jupiter’s atmosphere, and the deep atmosphere structure and meteorology; (3) the study of tenuous and distant atmospheres (Io, Enceladus, Pluto, Triton and other Kuiper Belt objects).     

Venus: A perspective at the beginning of planetary exploration

In situ measurements of the Venus atmosphere, made by the entry probes Venera 4, 5, 6, and 7, and data from the Mariner 5 flyby, have provided essentially new and reliable information and have powerfully contributed to our understanding of the nearest planet. The abundances of the principal atmospheric constituents and the temperature and pressure profiles down to the Venus surface were obtained for the first time. It was shown that the atmosphere is composed primarily of CO₂ and that N₂ (if any) and H₂O are relatively minor admixtures. In the region of the Venera 7 landing, the temperature and pressure at the Venus surface were established as equal to 747 ± 20°K and 90 ± 15 kgcm⁻². Space vehicles have also provided limited but quite important information on the physical properties of the Venus upper atmosphere and ionosphere, and on the interaction of the planet with the interplanetary environment. The main characteristics of the Venus atmosphere are discussed here with emphasis on the Venera results, including instrumentation, data processing, and altitude profiles.     

Atmospheric Chemistry in Giant Planets, Brown Dwarfs, and Low-Mass Dwarf Stars: I. Carbon, Nitrogen, and Oxygen

The chemical species containing carbon, nitrogen, and oxygen in atmospheres of giant planets, brown dwarfs (T and L dwarfs), and low-mass stars (M dwarfs) are identified as part of a comprehensive set of thermochemical equilibrium and kinetic calculations for all elements. The calculations cover a wide temperature and pressure range in the upper portions of giant planetary and T-, L-, and M-dwarf atmospheres. Emphasis is placed on the major gases CH₄, CO, NH₃, N₂, and H₂O but other less abundant gases are included. The results presented are independent of particular model atmospheres, and can be used to constrain model atmosphere temperatures and pressures from observations of different gases. The influence of metallicity on the speciation of these key elements under pressure-temperature (P-T) conditions relevant to low-mass object atmospheres is discussed. The results of the thermochemical equilibrium computations indicate that several compounds may be useful to establish temperature or pressure scales for giant planet, brown dwarf, or dwarf star atmospheres. We find that ethane and methanol abundance are useful temperature probes in giant planets and methane dwarfs such as Gl 229B, and that CO₂ can serve as a temperature probe in more massive objects. Imidogen (NH) abundances are a unique pressure-independent temperature probe for all objects. Total pressure probes for warmer brown dwarfs and M dwarfs are HCN, HCNO, and CH₂O. No temperature-independent probes for the total pressure in giant planets or T-dwarf atmospheres are identified among the more abundant C, N, and O bearing gases investigated here.     

Cloud base levels for Jupiter and Venus and the heteromolecular nucleation theory

For purified binary gas mixtures like NH₃H₂O or HClH₂O, partial pressures appreciably greater than the two saturation partial pressures are needed to condense the gas mixture into small solution droplets (“homogeneous hetero-molecular nucleation”). Thus without foreign nuclei, clouds are not as easily formed as in the theories of Lewis; the latter should be valid only if large condensation nuclei are available. We calculate here from classical homogeneous heteromolecular nucleation theory the threshold partial pressures necessary to achieve droplet nucleation for the gas mixtures NH₃H₂O (Jupiter,…), HClH₂O (Venus), H₂SO₄H₂O (Venus), and C₂H₅OHH₂O (laboratory). In the last case, theory and experiment agree satisfactorily. If no “dust” particles are available as condensation nuclei, then we expect in Jupiter's atmosphere the cloud base level to be around 40 km above the 400K level instead of 10–25 km in Lewis' models (1969) (similar upward shifts for the outer Jovian planets). For Venus, our corrections make the formation of HClH₂O clouds less probable for the 60-km layer at 0°C. If H₂SO₄ is formed by (photo-)chemical oxidation of SO₂ and if clouds are formed at that level where the H₂SO₄ production is largest, then the cloud base levels for H₂SO₄H₂O mixture clouds will not be shifted by our nucleation effects. For more reliable predictions, one needs more accurate data on the water vapor content of the planetary atmospheres and laboratory experiments testing the theoretically predicted nucleation behavior of these gaseous mixtures.     

Multidimensional radiative transfer: Applications to planetary coronae

A numerical solution to the integral equation for radiative transfer by resonance reradiation in an isothermal spherical atmosphere is described. The method presented is 100 times more efficient than earlier spherical radiative transfer models. The new model can accommodate density variations in the full three dimensional space and includes effects due to the presence of pure absorbers. Complete frequency redistribution is assumed for photon scattering. Applications of this model to the problem of solar photons scattered by atomic hydrogen in the atmospheres of Venus, Earth and Mars are described, and limb and disk profiles, as well as equivalent mean disk intensities for Venus, Earth and Mars, are presented.