Excitation of the oxygen nightglow on the terrestrial planets

A scheme of excitation, quenching, and energy transfer processes in the oxygen nightglow on the Earth, Venus, and Mars has been developed based on the observed nightglow intensities and vertical profiles, measured reaction rate coefficients, and photochemical models of the nighttime atmospheres of the Venus and Mars. The scheme involves improved radiative lifetimes of some band systems, calculated yields of the seven electronic states of O₂ in termolecular association, and rate coefficients of seven processes of electronic quenching of the Herzberg states of O₂, which are evaluated by fitting to the nightglow observations. Electronic quenching of the vibrationally excited Herzberg states by O₂ and N₂ in the Earth's nightglow is a quarter of total collisional removal of the O₂(A, A′) states and a dominant branch for the O₂(c) state. The scheme supports the conclusion by Steadman and Thrush (1994) that the green line is excited by energy transfer from the O₂(A³Σ_u⁺, v≥6) molecules, and the inferred rate coefficient of this transfer is 1.5×10⁻¹¹ cm³ s⁻¹. The O₂ bands at 762 nm and 1.27 μm are excited directly, by quenching of the Herzberg states, and by energy transfer from the O₂(⁵Π_g) state. Quenching of the O₂ band at 762 nm excites the band at 1.27 μm as well. Effective yield of the O₂(a¹Δ_g) state in termolecular association on Venus and Mars is ∼0.7. Quantitative assessments of all these processes have been made. A possible reaction of O₂(c¹Σ_u⁻)+CO is a very minor branch of recombination of CO₂ on Venus and Mars. Night airglow on Mars is calculated for typical conditions of the nighttime atmosphere. The calculated vertical intensity of the O₂ band at 1.27 μm is 13 kR, far below the recently reported detections.     

Half-widths, their temperature dependence, and line shifts for the HDO-CO2 collision system for applications to CO2-rich planetary atmospheres

Measurements of water vapor in the atmospheres of Venus or Mars by spectroscopic techniques in the infrared range are being made routinely by instruments onboard the Venus Express and the Mars Reconnaissance Orbiter. The interpretation of these measurements in the 2250-4450 cm⁻¹ region is being complicated by the presence of HDO lines absorbing radiation in this region. These spectra cannot be modeled properly because line shape parameters for CO₂ broadening (principal gas in these atmospheres) of HDO are not available. Here semi-classical line shape calculations for the HDO-CO₂ collision system are made using the Robert-Bonamy formalism for some 2300 rotational band transitions of HDO. From these calculations, the half-width, its temperature dependence, and the line shift are determined to aid in the reduction of the measured spectra. These data will greatly reduce the uncertainty of the reduced profiles from the Venus and Mars measurements and will also allow better estimates of the D/H ratio on these planets.     

Ionospheric photoelectrons: Comparing Venus, Earth, Mars and Titan

The sunlit portion of planetary ionospheres is sustained by photoionization. This was first confirmed using measurements and modelling at Earth, but recently the Mars Express, Venus Express and Cassini-Huygens missions have revealed the importance of this process at Mars, Venus and Titan, respectively. The primary neutral atmospheric constituents involved (O and CO₂ in the case of Venus and Mars, O and N₂ in the case of Earth and N₂ in the case of Titan) are ionized at each object by EUV solar photons. This process produces photoelectrons with particular spectral characteristics. The electron spectrometers on Venus Express and Mars Express (part of ASPERA-3 and 4, respectively) were designed with excellent energy resolution (ΔE/E=8%) specifically in order to examine the photoelectron spectrum. In addition, the Cassini CAPS electron spectrometer at Saturn also has adequate resolution (ΔE/E=16.7%) to study this population at Titan. At Earth, photoelectrons are well established by in situ measurements, and are even seen in the magnetosphere at up to 7R_E. At Mars, photoelectrons are seen in situ in the ionosphere, but also in the tail at distances out to the Mars Express apoapsis (∼3R_M). At both Venus and Titan, photoelectrons are seen in situ in the ionosphere and in the tail (at up to 1.45R_V and 6.8R_T, respectively). Here, we compare photoelectron measurements at Earth, Venus, Mars and Titan, and in particular show examples of their observation at remote locations from their production point in the dayside ionosphere. This process is found to be common between magnetized and unmagnetized objects. We discuss the role of photoelectrons as tracers of the magnetic connection to the dayside ionosphere, and their possible role in enhancing ion escape.     

Comparative analysis of Venus and Mars magnetotails

We have an unique opportunity to compare the magnetospheres of two non-magnetic planets as Mars and Venus with identical instrument sets Aspera-3 and Aspera-4 on board of the Mars Express and Venus Express missions. We have performed both statistical and case studies of properties of the magnetosheath ion flows and the flows of planetary ions behind both planets. We have shown that the general morphology of both magnetotails is generally identical. In both cases the energy of the light (H⁺) and the heavy (O⁺, etc.) ions decreases from the tail periphery (several keV) down to few eV in the tail center. At the same time the wake center of both planets is occupied by plasma sheet coincident with the current sheet of the tail. Both plasma sheets are filled by accelerated (500-1000 eV) heavy planetary ions. We report also the discovery of a new feature never observed before in the tails of non-magnetic planets: the plasma sheet is enveloped by consecutive layers of He⁺ and H⁺ with decreasing energies.     

Hydroxyl airglow on Venus in comparison with Earth

Hydroxyl nightglow is intensively studied in the Earth atmosphere, due to its coupling to the ozone cycle. Recently, it was detected for the first time also in the Venus atmosphere, thanks to the VIRTIS-Venus Express observations. The main Δν=1, 2 emissions in the infrared spectral range, centred, respectively, at 2.81 and 1.46 μm (which correspond to the (1-0) and (2-0) transitions, respectively), were observed in limb geometry (Piccioni et al., 2008) with a mean emission rate of 880±90 and 100±40 kR (1R=10⁶ photon cm⁻² s⁻¹ (4πster)⁻¹), respectively, integrated along the line of sight. In this investigation, the Bates-Nicolet chemical reaction is reported to be the most probable mechanism for OH production on Venus, as in the case of Earth, but HO₂ and O may still be not negligible as mechanism of production for OH, differently than Earth. The nightglow emission from OH provides a method to quantify O₃, HO₂, H and O, and to infer the mechanism of transport of the key species involved in the production. Very recently, an ozone layer was detected in the upper atmosphere of Venus by the SPICAV (Spectroscopy for Investigation of Characteristics of the Atmosphere of Venus) instrument onboard Venus Express (Montmessin et al., 2009); this discovery enhances the importance of ozone to the OH production in the upper atmosphere of Venus through the Bates-Nicolet mechanism. On Venus, OH airglow is observed only in the night side and no evidence has been found whether a similar emission exists also in the day side. On Mars it is expected to exist both on the day and night sides of the planet, because of the presence of ozone, though OH airglow has not yet been detected.In this paper, we review and compare the OH nightglow on Venus and Earth. The case of Mars is also briefly discussed for the sake of completeness. Similarities from a chemical and a dynamical point of view are listed, though visible OH emissions on Earth and IR OH emissions on Venus are compared.     

Transterminator ion flow in the Martian ionosphere

The upper ionospheres of Mars and Venus are permeated by the magnetic fields induced by the solar wind. It is a long-standing question whether these fields can put the dense ionospheric plasma into motion. If so, the transterminator flow of the upper ionosphere could explain a significant part of the ion escape from the planets atmospheres. But it has been technically very challenging to measure the ion flow at energies below 20 eV. The only such measurements have been made by the ORPA instrument of the Pioneer Venus Orbiter reporting speeds of 1-5 km/s for O⁺ ions at Venus above 300 km altitude at the terminator ( [Knudsen et al., 1980] and [Knudsen et al., 1982]). At Venus the transterminator flow is sufficient to sustain a permanent nightside ionosphere, at Mars a nightside ionosphere is observed only sporadically. We here report on new measurements of the transterminator ion flow at Mars by the ASPERA-3 experiment on board Mars Express with support from the MARSIS radar experiment for some orbits with fortunate observation geometry. We observe a transterminator flow of O⁺ and O₂⁺ ions with a super-sonic velocity of around 5 km/s and fluxes of 0.8×10⁹/cm² s. If we assume a symmetric flux around the terminator this corresponds to an ion flow of 3.1±0.5×10²⁵/s half of which is expected to escape from the planet. This escape flux is significantly higher than previously observed on the tailside of Mars. A possible mechanism to generate this flux can be the ionospheric pressure gradient between dayside and nightside or momentum transfer from the solar wind via the induced magnetic field since the flow velocity is in the Alfvénic regime. We discuss the implication of these new observations for ion escape and possible extensions of the analysis to dayside observations which may allow us to infer the flow structure imposed by the induced magnetic field.     

The O2 nightglow in the martian atmosphere by SPICAM onboard of Mars-Express

We present observations of the O₂(a¹Δ_g) nightglow at 1.27 μm on Mars using the SPICAM IR spectrometer onboard of the Mars Express orbiter. In contrast to the O₂(a¹Δ_g) dayglow that results from the ozone photodissociation, the O₂(a¹Δ_g) nightglow is a product of the recombination of O atoms formed by CO₂ photolysis on the dayside at altitudes higher than 80 km and transported downward above the winter pole by the Hadley circulation. The first detections of the O₂(a¹Δ_g) nightglow in 2010 indicate that it is about two order of magnitude less intense than the dayglow (Bertaux, J.-L., Gondet, B., Bibring, J.-P., Montmessin, F., Lefèvre, F. [2010]. Bull. Am. Astron. Soc. 42, 1040; Clancy et al. [2010]. Bull. Am. Astron. Soc. 42, 1041). SPICAM IR sounds the martian atmosphere in the near-IR range (1–1.7 μm) with the spectral resolution of 3.5 cm^?1 in nadir, limb and solar occultation modes. In 2010 the vertical profiles of the O₂(a¹Δ_g) nightside emission have been obtained near the South Pole at latitudes of 82–83°S for two sequences of observations: L_s = 111–120° and L_s = 152–165°. The altitude of the emission maximum varied from 45 km on L_s = 111–120° to 38–49 km on L_s = 152–165°. Averaged vertically integrated intensity of the emission at these latitudes has shown an increase from 0.22 to 0.35 MR. Those values of total vertical emission rate are consistent with the OMEGA observations on Mars-Express in 2010. The estimated density of oxygen atoms at altitudes from 50 to 65 km varies from 1.5 × 10¹¹ to 2.5 × 10¹¹ cm^?3. Comparison with the LMD general circulation model with photochemistry (Lefèvre, F., Lebonnois, S., Montmessin, F., Forget, F. [2004]. J. Geophys. Res. 109, E07004; Lefèvre et al. [2008]. Nature 454, 971–975) shows that the model reproduces fairly well the O₂(a¹Δ_g) emission layer observed by SPICAM when the large field of view (>20 km on the limb) of the instrument is taken into account.     

Helium on Mars and Venus: EUVE observations and modeling

Long-exposure spectroscopy of Mars and Venus with the Extreme Ultraviolet Explorer (EUVE) has revealed emissions of He 584 Å on both planets and He 537 Å/O⁺ 539 Å and He⁺ 304 Å on Venus. Our knowledge of the solar emission at 584 Å, eddy diffusion in Mars' upper atmosphere, electron energy distributions above Mars' ionopause, and hot oxygen densities in Mars' exosphere has been significantly improved since our analysis of the first EUVE observation of Mars [Krasnopolsky, Gladstone, 1996, Helium on Mars: EUVE and Phobos data and implications for Mars' evolution, J. Geophys. Res. 101, 15,765-15,772]. These new results and a more recent EUVE observation of Mars are the motivation for us to revisit the problem in this paper. We find that the abundance of helium in the upper atmosphere, where the main loss processes occur, is similar to that in the previous paper, though the mixing ratio in the lower and middle atmosphere is now better estimated at 10±6 ppm. Our estimate of the total loss of helium is almost unchanged at 8×¹⁰²³ s⁻¹, because a significant decrease in the loss by electron impact ionization above the ionopause is compensated by a higher loss in collisions with hot oxygen. We neglect the outgassing of helium produced by radioactive decay of U and Th because of the absence of current volcanism and a very low upper limit to the seepage of volcanic gases. The capture of solar wind α-particles is currently the only substantial source of helium on Mars, and its efficiency remains at 0.3. A similar analysis of EUV emissions from Venus results in a helium abundance in the upper atmosphere which is equal to the mean of the abundances measured previously with two optical and two mass spectrometers, and a derived helium mixing ratio in the middle and lower atmosphere of 9±6 ppm. Helium escape by ionization and sweeping out of helium ions by the solar wind above the ionopause is smaller than that calculated by Prather and McElroy [1983, Helium on Venus: implications for uranium and thorium, Science 220, 410-411] by a factor of 3. However, charge exchange of He⁺ ions with CO₂ and N₂ between the exobase and ionopause and collisions with hot oxygen ignored previously add to the total loss which appears to be at the level of 10⁶ cm⁻² s⁻¹ predicted by Prather and McElroy [1983, Science 220, 410-411]. The loss of helium is compensated by outgassing of helium produced by radioactive decay of U and Th and by the capture of the solar wind α-particles with an efficiency of 0.1. We also compare our derived α-particle capture efficiencies for Mars and Venus with observed X-ray emissions resulting from the charge exchange of solar wind heavy ions with the extended atmospheres on both planets [Dennerl et al., 2002, Discovery of X-rays from Venus with Chandra, Astron. Astrophys. 386, 319-330; Dennerl, 2002, Discovery of X-rays from Mars with Chandra, Astron. Astrophys. 394, 1119-1128]. The emissions from both disk and halo on Mars agree with our calculated values; however, we do not see a reasonable explanation for the X-ray halo emission on Venus. The ratio of the charge exchange efficiencies derived from the disk X-ray emissions of Mars and Venus is similar to the ratio of the capture efficiencies for these planets. The surprisingly bright emission of He⁺ at 304 Å observed by EUVE and Venera 11 and 12 suggests that charge exchange in the flow of the solar wind α-particles around the ionopause is much stronger than in the flow of α-particles into the ionosphere.     

The effect of radiative transfer on shear-flow instability in the atmospheres on mars and venus

The results of two theoretical investigations concerning the destabilizing effects of radiative transfer on stably stratified shear flows are applied to the CO₂ atmospheres Mars and Venus. It is found that radiatively modified critical Richardson numbers remain below plausible atmospheric values throughout the stratospheres of both planets. Above certain altitudes, however, in the upper stratospheres of these planets (≈50 km on Mars and ≈100 km on Venus), critical Richardson numbers begin to increase significantly above the nonradiating critical value. This trend continues until, in the lower thermosphere, critical Richardson numbers eventually surpass atmospheric values. This effect could lead to observably greater turbulent mixing in the upper atmospheres of Mars and Venus than might be expected from terrestrial observation and from nonradiating theoretical calculations.     

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.     

Oxidation of CO on surface hematite in high CO2 atmospheres

We propose a mechanism for the oxidation of gaseous CO into CO₂ occurring on the surface mineral hematite (Fe₂O₃(s)) in hot, CO₂-rich planetary atmospheres, such as Venus. This mechanism is likely to constitute an important source of tropospheric CO₂ on Venus and could at least partly address the CO₂ stability problem in Venus’ stratosphere, since our results suggest that atmospheric CO₂ is produced from CO oxidation via surface hematite at a rate of 0.4 petagrammes (Pg) CO₂ per (Earth) year on Venus which is about 45% of the mass loss of CO₂ via photolysis in the Venusian stratosphere. We also investigated CO oxidation via the hematite mechanism for a range of planetary scenarios and found that modern Earth and Mars are probably too cold for the mechanism to be important because the rate-limiting step, involving CO(g) reacting onto the hematite surface, proceeds much slower at lower temperatures. The mechanism may feature on extrasolar planets such as Gliese 581c or CoRoT-7b assuming they can maintain solid surface hematite which, e.g. starts to melt above about 1200 K. The mechanism may also be important for hot Hadean-type environments and for the emerging class of hot Super-Earths with planetary surface temperatures between about 600 and 900 K.     

Modelling the atmospheric CO2 10-μm non-thermal emission in Mars and Venus at high spectral resolution

A study of the CO₂ atmospheric emissions at 10-μm in the upper atmospheres of Mars and Venus is performed in order to explain a number of ground-based measurements of these emissions recently taken at very high spectral resolution in both planets. The measurements are normally used to derive atmospheric temperatures and winds, but uncertainties on the actual emission layers were so far a serious drawback for their correct interpretation. The non-LTE models used for Mars and Venus in the present analysis are entirely similar in order to perform consistent comparisons between the two planets. In particular, the same scheme of CO₂ states and ro-vibrational bands are used, with similar assumptions on collisional routes and rate coef?cients, and also the same radiative transfer approximations. The emissions at 10-μm are produced in both atmospheres by the same excitation mechanism: radiative pumping of the CO₂(00⁰1) vibrational state by direct solar absorption(at 4.3 μm) and indirect absorption (at 2.7 μm, followed by collisional quenching). The computed radiances are specially strong in the upper mesosphere and lower thermosphere of the two planets during maximum solar illumination, producing a population inversion in such conditions with the lower states of the bands, the CO₂ (10⁰0) and CO₂(02⁰0). We obtained that other population inversions are also possible, involving higher energy CO₂ states. The larger solar ?ux available on Venus is found to produce larger vibrational populations and stronger emissions than equivalent atmospheric layers on Mars, in agreement with the observations. A number of perturbation studies were used to determine the exact emission altitudes, or weighting function peaks, for usual nadir sounding. The sensitivity of the emission to non-LTE model uncertainties and to atmospheric variations in temperature and CO₂ density is also presented. The dependence with the solar zenith angle and with the emission angle, as obtained with this model, could also be useful for guiding future observations.     

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.     

Modeling the atmospheric limb emission of CO2 at 4.3 μm in the terrestrial planets

The MIPAS instrument on board Envisat, in Earth orbit, the PFS and OMEGA instruments on Mars Express, and VIRTIS on board Venus Express are currently providing a dataset of limb measurements of the CO₂ atmospheric fluorescence emission at 4.3‐μm from the upper atmosphere of the three planets. These measurements represent an excellent dataset to perform comparative studies between the terrestrial planets’ upper atmospheres, and also to test our theoretical understanding of these emissions. In order to exploit these datasets, we apply a set of non-local thermodynamic equilibrium (non-LTE) models developed at the IAA/CSIC, in Granada, Spain, to a selection of data. In general, the models can explain the main spectral features of the measurements, and also the altitude and solar zenith angle variations. However, the simulations for Mars and Venus give an incorrect ratio of the emissions at two wavelengths, 4.4 and . In order to explain this deficiency, a revision of the most uncertain non-LTE energy transfer parameters has been performed. The quenching rate of ν₃ quanta of high-energy CO₂ states by CO₂ itself could reduce the model-data discrepancy if increased by a factor 2-4, still within its current uncertainty range. This factor, however, is subject to the uncertainty in the thermal structure. A number of simulations with the non-LTE models were also used to study and compare the role of radiative transfer in this spectral region in the three terrestrial planets. Sensitivity studies of density and temperature are also presented, and they permit an analysis of how the differences between the planets and between the three instruments affect their sounding capabilities.     

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.     

Atmospheric angular momentum variations of Earth, Mars and Venus at seasonal time scales

Atmospheric angular momentum variations of a planet are associated with the global atmospheric mass redistribution and the wind variability. The exchange of angular momentum between the fluid layers and the solid planet is the main cause for the variations of the planetary rotation at seasonal time scales. In the present study, we investigate the angular momentum variations of the Earth, Mars and Venus, using geodetic observations, output of state-of-the-art global circulation models as well as assimilated data. We discuss the similarities and differences in angular momentum variations, planetary rotation and angular momentum exchange for the three terrestrial planets. We show that the atmospheric angular momentum variations for Mars and Earth are mainly annual and semi-annual whereas they are expected to be “diurnal” on Venus. The wind terms have the largest contributions to the LOD changes of the Earth and Venus whereas the matter term is dominant on Mars due to the CO₂ sublimation/condensation. The corresponding LOD variations (ΔLOD) have similar amplitudes on Mars and Earth but are much larger on Venus, though more difficult to observe.     

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.     

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.     

Evidence for high-altitude haze thickening on the dark side of Venus from 10-micron heterodyne spectroscopy of CO2

The 10.86-μm P(44) and 10.33-μm R(8) lines of ¹²C¹⁶O₂ were observed on Venus with an infrared heterodyne spectrometer. The spectral resolution equals the Doppler half-width and the line profiles are fully resolved. The P(44) line was observed in June 1979 on the day side of the planet. The P(44) line core appears in absorption; the nonthermal core emission, which is present at low J values, is negligible at J = 44. Modeling of the line profile indicates that a discrete, optically thick, cloud deck occurs at 45 mbar pressure, in essential agreement with current understanding of the Venusian cloud structure. The 10.33-μm R(8) line was observed in April 1980 at a variety of positions on the day side, and at a single position on the night side. The strong nonthermal core emission which appears on the day side for this line is not present on the night side, where the line core appears in absorption. This behavior is consistent with a solar radiative pump as an excitation mechanism for the nonthermal emission. Modeling of the R(8) night-side profile indicates that substantial high-altitude haze occurs above the cloud tops, in the region from 15 to 35 mbar pressure. Comparing the modeling for the R(8) line to the P(44) line we find that the variation in the mass of the high-altitude haze was greater than a factor of 2.     

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.