Non-thermal water loss of the early Mars: 3D multi-ion hybrid simulations

In this study we analyze the non-thermal loss rates of O⁺, O₂⁺ and CO₂⁺ ions over the last 4.5 billion years (Gyr) in the Martian history by using a 3D hybrid model. For this reason we derived the past solar wind conditions in detail. We take into account the intensified particle flux of the early Sun as well as an Martian atmosphere, which was exposed to a sun's extreme ultraviolet (EUV) radiation flux 4.5 Gyr ago that was 100 times stronger than today. Furthermore, we model the evolution of the interplanetary magnetic field by a Weber & Davis solar wind model. The ‘external’ influences of the Sun's radiation flux and solar wind flux lead to the formation of an ionospheric obstacle by photoionization, charge exchange and electron impact. For the early Martian conditions we could show that charge exchange was the dominant ionization mechanism. Several hybrid simulations for different stages in the evolution of the Martian atmosphere, at 1, 2, 5, 10, 30 and 100 EUV, were performed to analyze the non-thermal escape processes by ion pick-up, momentum transfer from the solar wind to the ionosphere and detached ionospheric plasma clouds. Our results show a non-linear evolution of the loss rates. Using mean solar wind parameters the simulations result in an oxygen loss equivalent to the depth of a global Martian ocean of about 2.6 m over the last 4.5 Gyr. The induced magnetic field strength could be increased up to about 2000 nT. A simulation run with high solar wind density results in an oxygen loss of a Martian ocean up to 205 m depth during 150 million years after the sun reached the zero age mean sequence (ZAMS).     

Ionospheric plasma acceleration at Mars: ASPERA-3 results

The Analyzer of Space Plasma and Energetic Atoms (ASPERA) on-board the Mars Express spacecraft (MEX) measured penetrating solar wind plasma and escaping/accelerated ionospheric plasma at very low altitudes (250 km) in the dayside subsolar region. This implies a direct exposure of the martian topside atmosphere to solar wind plasma forcing leading to energization of ionospheric plasma. The ion and electron energization and the ion outflow from Mars is surprisingly similar to that over the magnetized Earth. Narrow “monoenergetic” cold ion beams, ion beams with broad energy distributions, sharply peaked electron energy spectra, and bidirectional streaming electrons are particle features also observed near Mars. Energized martian ionospheric ions (O⁺, O⁺₂, CO⁺₂, etc.) flow in essentially the same direction as the external sheath flow. This suggests that the planetary ion energization couples directly to processes in the magnetosheath/solar wind. On the other hand, the beam-like distribution of the energized plasma implies more indirect energization processes like those near the Earth, i.e., energization in a magnetized environment by waves and/or parallel (to B) electric fields. The general conditions for martian plasma energization are, however, different from those in the Earth's magnetosphere. Mars has a weak intrinsic magnetic field and solar wind plasma may therefore penetrate deep into the dense ionospheric plasma. Local crustal magnetization, discovered by Acuña et al. [Acuña, M.J., Connerey, J., Ness, N., Lin, R., Mitchell, D., Carlsson, C., McFadden, J., Anderson, K., Rème, H., Mazelle, C., Vignes, D., Wasilewski, P., Cloutier, P., 1999. Science 284, 790-793], provide some dayside shielding against the solar wind. On the other hand, multiple magnetic anomalies may also lead to “hot spots” facilitating ionospheric plasma energization. We discuss the ASPERA-3 findings of martian ionospheric ion energization and present evidences for two types of plasma energization processes responsible for the low- and mid-altitude plasma energization near Mars: magnetic field-aligned acceleration by parallel electric fields and plasma energization by low frequency waves.     

Oxygen and carbon isotope ratios in the martian atmosphere

Oxygen and carbon isotope ratios in the martian CO₂ are key values to study evolution of volatiles on Mars. The major problems in spectroscopic determinations of these ratios on Mars are uncertainties associated with: (1) equivalent widths of the observed absorption lines, (2) line strengths in spectroscopic databases, and (3) thermal structure of the martian atmosphere during the observation. We have made special efforts to reduce all these uncertainties. We observed Mars using the Fourier Transform Spectrometer at the Canada–France–Hawaii Telescope. While the oxygen and carbon isotope ratios on Mars were byproducts in the previous observations, our observation was specifically aimed at these isotope ratios. We covered a range of 6022 to 6308 cm⁻¹ with the highest resolving power of ν/δν=3.5×10⁵ and a signal-to-noise ratio of 180 in the middle of the spectrum. The chosen spectral range involves 475 lines of the main isotope, 184 lines of ¹³CO₂, 181 lines of CO¹⁸O, and 119 lines of CO¹⁷O. (Lines with strengths exceeding 10⁻²⁷ cm at 218 K are considered here.) Due to the high spectral resolution, most of the lines are not blended. Uncertainties of retrieved isotope abundances are in inverse proportion to resolving power, signal-to-noise ratio, and square root of the number of lines. Laboratory studies of the CO₂ isotope spectra in the range of our observation achieved an accuracy of 1% in the line strengths. Detailed observations of temperature profiles using MGS/TES and data on temperature variations with local time from two GCMs are used to simulate each absorption line at various heights in each part of the instrument field of view and then sum up the results. Thermal radiation of Mars' surface and atmosphere is negligible in the chosen spectral range, and this reduces errors associated with uncertainties in the thermal structure on Mars. Using a combination of all these factors, the highest accuracy has been achieved in measuring the CO₂ isotope ratios: ¹³C/¹²C = 0.978 ± 0.020 and ¹⁸O/¹⁶O = 1.018 ± 0.018 times the terrestrial standards. Heavy isotopes in the atmosphere are enriched by nonthermal escape and sputtering, and depleted by fractionation with solid-phase reservoirs. The retrieved ratios show that isotope fractionation between CO₂ and oxygen and carbon reservoirs in the solid phase is almost balanced by nonthermal escape and sputtering of O and C from Mars.     

Comment on the papers “Production of hot nitrogen atoms in the martian thermosphere” by F. Bakalian and “Monte Carlo computations of the escape of atomic nitrogen from Mars” by F. Bakalian and R.E. Hartle

In recent articles published in Icarus, Bakalian [2006. Icarus 183, 69-78] discusses and computes the production rates of hot nitrogen atoms in the martian thermosphere due to N₂ photodissociation and N⁺₂ dissociative recombination, and Bakalian and Hartle [2006. Icarus 183, 55-68] use a Monte Carlo code to compute the escape rates of nitrogen atoms from Mars due to photodissociation of N₂, dissociative recombination of N⁺₂, and pickup ion escape due to photoionization of N atoms above the ionopause. Bakalian concludes that “photodissociation of N₂ is the dominant escape mechanism in the martian atmosphere.” We will show that this conclusion is not supportable. In addition, both papers contain scientific errors, misrepresentations, inaccurate referencing, lack of proper attribution, and they fail to place these investigations into the existing extensive body of work on this subject.     

Photochemistry of the martian atmosphere: Seasonal, latitudinal, and diurnal variations

There is a significant progress in the observational data relevant to Mars photochemistry in the current decade. These data are not covered by and sometimes disagree with the published models. Therefore we consider three types of models for Mars photochemistry. A steady-state model for global-mean conditions is currently the only way to calculate the abundances of long living species (H₂, O₂, and CO). However, our model does not fit the observed CO abundance using gas-phase chemistry and reasonable values of heterogeneous loss of odd hydrogen on the water ice aerosol. The second type of the calculated models is steady-state models for local conditions. The MGS/TES data on temperature profiles, H₂O, and dust are input parameters for these models. The calculations have been made for nine seasonal points spread over the martian year and for twelve latitudes with a step of 10° for each season. The only adopted heterogeneous reaction is a weak loss of H₂O₂ on water ice with probability of 5×¹⁰⁻⁴. The results are in good agreement with the recent observations of the O₂ dayglow at 1.27 μm and the O₃ and H₂O₂ abundances. Global maps of the seasonal and latitudinal behavior of these species have been made. The third type of models is a time-dependent model for local conditions. These models show that odd hydrogen quickly converts to H₂O₂ at the nighttime and the chemistry is switched off while the association of O, the heterogeneous loss of H₂O₂, and eddy diffusion continue. This requires significant changes in the global-mean and local steady-state models discussed above, and these changes have been properly done. The calculated diurnal variations of Mars photochemistry are discussed. The martian photochemistry at low and middle latitudes is significantly different in the aphelion period at LS=10°-130° from that in the remaining part of the year.     

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.     

Modeling of global variations and ring shadowing in Saturn's ionosphere

A time-dependent one-dimensional model of Saturn's ionosphere has been developed as an intermediate step towards a fully coupled Saturn Thermosphere-Ionosphere Model (STIM). A global circulation model (GCM) of the thermosphere provides the latitude and local time dependent neutral atmosphere, from which a globally varying ionosphere is calculated. Four ion species are used (H⁺, H⁺₂, H⁺₃, and He⁺) with current cross-sections and reaction rates, and the SOLAR2000 model for the Sun's irradiance. Occultation data from the Voyager photopolarimeter system (PPS) are adapted to model the radial profile of the ultraviolet (UV) optical depth of the rings. Diurnal electron density peak values and heights are generated for all latitudes and two seasons under solar minimum and solar maximum conditions, both with and without shadowing from the rings. Saturn's lower ionosphere is shown to be in photochemical equilibrium, whereas diffusive processes are important in the topside. In agreement with previous 1-D models, the ionosphere is dominated by H⁺ and H⁺₃, with a peak electron density of ∼¹⁰⁴ electrons cm⁻³. At low- and mid-latitudes, H⁺ is the dominant ion, and the electron density exhibits a diurnal maximum during the mid-afternoon. At higher latitudes and shadowed latitudes (smaller ionizing fluxes), the diurnal maximum retreats towards noon, and the ratio of [H⁺]/[H⁺₃] decreases, with H⁺₃ becoming the dominant ion at altitudes near the peak (∼1200-1600 km) for noon-time hours. Shadowing from the rings leads to attenuation of solar flux, the magnitude and latitudinal structure of which is seasonal. During solstice, the season for the Cassini spacecraft's encounter with Saturn, attenuation has a maximum of two orders of magnitude, causing a reduction in modeled peak electron densities and total electron column contents by as much as a factor of three. Calculations are performed that explore the parameter space for charge-exchange reactions of H⁺ with vibrationally excited H₂, and for different influxes of H₂O, resulting in a maximum diurnal variation in electron density much weaker than the diurnal variations inferred from Voyager's Saturn Electrostatic Discharge (SED) measurements. Peak values of height-integrated Pedersen conductivities at high latitudes during solar maximum are modeled to be ∼42 mho in the summer hemisphere during solstice and ∼18 mho during equinox, indicating that even without ionization produced by auroral processes, magnetosphere-ionosphere coupling can be highly variable.     

Stochastic models of hot planetary and satellite coronas: A hot oxygen corona of Mars

The processes of the kinetics and transport of hot oxygen atoms in the transition (between thermosphere and exosphere) region of the upper atmosphere of Mars are studied. The reaction of dissociative recombination of the main ionospheric ion O ₂ ⁺ with thermal electrons in the ionosphere of Mars is considered as a source of hot oxygen atoms. The distribution of suprathermal oxygen atoms by kinetic energy is calculated. It is shown that the exosphere is populated by a considerable number of suprathermal oxygen atoms with kinetic energies just below the escape energy of 2 eV; that is, a hot oxygen corona of Mars is formed.     

Stochastic models of hot planetary and satellite coronas: A photochemical source of hot oxygen in the upper atmosphere of Mars

The processes of the kinetics and transport of hot oxygen atoms in the upper atmosphere of Mars are studied. A reaction of dissociative recombination of the main ionospheric ion O ₂ ⁺ with thermal electrons is considered as a photochemical source of suprathermal oxygen atoms. Oxygen atoms are formed in the dissociative recombination reaction with an excess of kinetic energy of about 0.4–4 eV and lose that energy in elastic and inelastic collisions with the ambient thermal atmospheric gas. The altitude distributions of the concentrations of neutral and ionized components, as well as their temperatures, were taken from Krasnopolsky (2002). Unlike the models published earlier, detailed calculations of the formation, collisional kinetics, and transport of suprathermal oxygen atoms in the thermosphere-exosphere transition region of the upper atmosphere of Mars have been made for the first time. For this, we used a stochastic model of the formation of a hot planetary corona (Shematovich, 2004). It has been shown that the considered photochemical source of suprathermal oxygen leads to the formation of the hot corona and to higher nonthermal losses of oxygen from the upper atmosphere of Mars due to escape fluxes. The detailed energy spectra of the fluxes of suprathermal atomic oxygen were calculated for the thermosphere-exosphere transition region of the Martian atmosphere.Translated from Astronomicheskii Vestnik, Vol. 39, No. 1, 2005, pp. 26–37.Original Russian Text Copyright © 2005 by Krestyanikova, Shematovich.     

Suprathermal oxygen and hydrogen atoms in the upper Martian atmosphere

The processes of kinetics and transport of hot oxygen and hydrogen atoms in the transition (from the thermosphere to the exosphere) region of the upper Martian atmosphere are studied. The reaction of dissociative recombination of the principal ionospheric ion O ₂ ⁺ with thermal electrons in the ionosphere of Mars served as the source of hot oxygen atoms. The process of momentum and energy transfer in elastic collisions between hot oxygen atoms and atmospheric hydrogen atoms with thermal energies was regarded as the source of hot hydrogen atoms. The kinetic energy distribution functions are determined for suprathermal oxygen and hydrogen atoms. It is shown that the exosphere is populated with a significant number of suprathermal oxygen atoms with kinetic energies ranging up to the escape energy of 2 eV (i.e., the hot oxygen Martian corona is formed). The transfer of energy from hot oxygen atoms to thermal hydrogen atoms creates an additional nonthermal flux of atomic hydrogen escaping from the Martian atmosphere.     

Production of hot nitrogen atoms in the martian thermosphere

The energy and altitude distributions for nitrogen atoms produced from photodissociation of N₂ and dissociative recombination of N⁺₂ have been computed for the low and high solar activity martian thermospheres. We find that the fraction of nitrogen atoms with E>Eesc at the exobase is ∼2.5% for photodissociation as compared to ∼22.6% for dissociative recombination. However, the peak magnitudes of the production rate profiles for dissociative recombination are a factor of ∼1000 and ∼200 times smaller than those of photodissociation at low and high solar activities, respectively. Thus, our findings suggest that photodissociation of N₂ is the dominant escape mechanism for atomic nitrogen for both the low and high solar activity martian thermospheres. The general consensus in the field prior to these research results was that dissociative recombination of N⁺₂ was the main escape mechanism. We find that it is the dissociation of N₂ along repulsive states that results in the production of very energetic nitrogen atoms.     

Radial distribution of production rates, loss rates and densities corresponding to ion masses ?40 amu in the inner coma of Comet Halley: Composition and chemistry

In this paper we have studied the chemistry of C, H, N, O, and S compounds corresponding to ions of masses ?40 amu in the inner coma of the Comet 1P/Halley. The production rates, loss rates, and ion mass densities are calculated using the Analytical Yield Spectrum approach and solving coupled continuity equation controlled by the steady state photochemical equilibrium condition. The primary ionization sources in the model are solar EUV photons, photoelectrons, and auroral electrons of the solar wind origin. The chemical model couples ion-neutral, electron-neutral, photon-neutral and electron-ion reactions among ions, neutrals, electrons, and photons through over 600 chemical reactions. Of the 46 ions considered in the model the chemistry of 24 important ions (viz., CH₃OH⁺₂, H₃CO⁺, NH⁺₄, H₃S⁺, H₂CN⁺, H₂O⁺, NH⁺₃, CO⁺, C₃H⁺₃, OH⁺, H₃O⁺, CH₃OH⁺, C₃H⁺₄, C₂H⁺₂, C₂H⁺, HCO⁺, S⁺, CH⁺₃, H₂S⁺, O⁺, C⁺, CH⁺₄, C⁺₂, and O⁺₂) are discussed in this paper. At radial distances <1000 km, the electron density is mainly controlled by 6 ions, viz., NH⁺₄, H₃O⁺, CH₃OH⁺₂, H₃S⁺, H₂CN⁺, and H₂O⁺, in the decreasing order of their relative contribution. However, at distances >1000 km, the 6 major ions are H₃O⁺, CH₃OH⁺₂, H₂O⁺, H₃CO⁺, C₂H⁺₂, and NH⁺₄; along with ions CO⁺, OH⁺, and HCO⁺, whose importance increases with further increase in the radial distance. It is found that at radial distances greater than ∼1000 km (±500 km) the major chemical processes that govern the production and loss of several of the important ions in the inner coma are different from those that dominate at distances below this value. The importance of photoelectron impact ionization, and the relative contributions of solar EUV, and auroral and photoelectron ionization sources in the inner coma are clearly revealed by the present study. The calculated ion mass densities are compared with the Giotto Ion Mass Spectrometer (IMS) and Neutral Mass Spectrometer (NMS) data at radial distances 1500, 3500, and 6000 km. There is a reasonable agreement between the model calculation and the Giotto measurements. The nine major peaks in the IMS spectra between masses 10 and 40 amu are reproduced fairly well by the model within a factor of two inside the ionopause. We have presented simple formulae for calculating densities of the nine major ions, which contribute to the nine major peaks in the IMS spectra, throughout the inner coma that will be useful in estimating their densities without running the complex chemical models.     

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.     

“Methane on Mars: A product of H2O photolysis in the presence of CO”: Response to V.A. Krasnopolsky

The detection of CH₄ in the martian atmosphere, at a mixing ratio of about 10 ppb, prompted Krasnopolsky et al. [Krasnopolsky, V.A., Maillard, J.P., Owen, T.C., 2004. Icarus 172, 537-547] and Krasnopolsky [Krasnopolsky, V.A., 2006. Icarus 180, 359-367] to propose that the CH₄ is of biogenic origin. Bar-Nun and Dimitrov [Bar-Nun, A., Dimitrov, V., 2006. Icarus 181, 320-322] proposed that CH₄ can be formed in the martian atmosphere by photolysis of H₂O in the presence of CO. We based our arguments on a clear demonstration that CH₄ is formed in our experiments, and on thermodynamic equilibrium calculations, which show that CH₄ formation is favored even in the presence of oxygen at a mixing ratio 1.3×¹⁰⁻³, as observed on Mars. In the present comment, Krasnopolsky [Krasnopolsky, V.A., 2007. Icarus, in press (this issue)] presents his arguments against the suggestion of Bar-Nun and Dimitrov [Bar-Nun, A., Dimitrov, V., 2006. Icarus 181, 320-322], based on the effect of O₂ on CH₄ formation, the absence of kinetic pathways for CH₄ formation and on the inadequacy of thermodynamic equilibrium calculations to describe the martian atmosphere. In this rebuttal we demonstrate that experiments with molecular oxygen at a ratio of O₂/CO₂=(8.9-17)×¹⁰⁻³, exceeding the martian ratio, still form CH₄. Thermodynamic equilibrium calculations replicate the experimental CH₄ mixing ratio to within a factor of 1.9 and demonstrate that CH₄ production is favored in the martian atmosphere, which is obviously not in thermodynamic equilibrium. Consequently, we do not find the presence of methane to be a sign of biological activity on Mars.     

Stability of hydrous minerals on the martian surface

The presence of water-bearing minerals on Mars has long been discussed, but little or no data exist showing that minerals such as smectites and zeolites may be present on the surface in a hydrated state (i.e., that they could contain H₂O molecules in their interlayer or extra-framework sites, respectively). We have analyzed experimental thermodynamic and X-ray powder diffraction data for smectite and the most common terrestrial zeolite, clinoptilolite, to evaluate the state of hydration of these minerals under martian surface conditions. Thermodynamic data for clinoptilolite show that water molecules in its extra-framework sites are held very strongly, with enthalpies of dehydration for Ca-clinoptilolite up to three times greater than that for liquid water. Using these data, we calculated the Gibbs free energy of hydration of clinoptilolite and smectite as a function of temperature and pressure. The calculations demonstrate that these minerals would indeed be hydrated under the very low-P (H₂O) conditions existing on Mars, a reflection of their high affinities for H₂O. These calculations assuming the partial pressure of H₂O and the temperature range expected on Mars suggest that, if present on the surface, zeolites and Ca-smectites could also play a role in affecting the diurnal variations in martian atmospheric H₂O because their calculated water contents vary considerably over daily martian temperature ranges. The open crystal structure of clinoptilolite and existing hydration and kinetic data suggest that hydration/dehydration are not kinetically limited. Based on these calculations, it is possible that hydrated zeolites and clay minerals may explain some of the recent observations of significant amounts of hydrogen not attributable to water ice at martian mid-latitudes.     

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.     

Oxygen ion escape at Mars in a hybrid model: High energy and low energy ions

We have studied the escape and energization of several O⁺ populations and an population at Mars by using a hybrid model. The quasi-neutral hybrid model, HYB-Mars model, included five oxygen ion populations making it possible to distinguish photoions from oxygen ions originating from charge exchange processes and from the ionosphere.We have identified two high-energy ion components and one low-energy ion component of oxygen. They have different spatial and energy distributions near Mars. The two high-energy oxygen ion components, consisting of a high-energy “beam” and a high-energy “halo”, have different origins. (1) The high-energy (>∼100 eV) “beam” of O⁺ and ions are originating from the ionosphere. These ions form a highly asymmetric spatial distribution of escaping oxygen ions with respect to the direction of the convective electric field in the solar wind. (2) The high-energy (>∼100 eV) “halo” component contains O⁺ ions which are formed from the oxygen neutral exosphere by extreme ultraviolet radiation (EUV) and by charge exchange processes. These energetic halo ions can be found all around Mars. (3) The low energy O⁺ and ions (<∼100 eV) form a relatively symmetric spatial distribution around the Mars-Sun line. They originate from the ionosphere and from charge exchange processes between protons and exospheric oxygen atoms.The existence of the low- and the high-energy oxygen components is in agreement with recent in situ plasma measurements made by the ASPERA-3 instrument on the Mars Express mission. The analysis of the escaping oxygen ions suggests that the global energization of escaping planetary ions in the martian tail is controlled by the convective electric field.     

Response of peak electron densities in the martian ionosphere to day-to-day changes in solar flux due to solar rotation

Photochemical Chapman theory predicts that the square of peak electron density, N_m, in the dayside ionosphere of Mars is proportional to the cosine of solar zenith angle. We use Mars Global Surveyor Radio Science profiles of electron density to demonstrate that this relationship is generally satisfied and that positive or negative residuals between observed and predicted values of are caused by periods of relatively high or low solar flux, respectively.Understanding the response of the martian ionosphere to changes in solar flux requires simultaneous observations of the martian ionosphere and of solar flux at Mars, but solar flux measurements are only available at Earth. Since the Sun's output varies both in time and with solar latitude and longitude, solar flux at Mars is not simply related to solar flux at Earth by an inverse-square law. We hypothesize that, when corrected for differing distances from the Sun, solar fluxes at Mars and Earth are identical when shifted in time by the interval necessary for the Sun to rotate through the Earth–Sun–Mars angle.We perform four case studies that quantitatively compare time series of N_m at Mars to time series of solar flux at Earth and find that our hypothesis is satisfied in the three of them that used ionospheric data from the northern hemisphere. We define a solar flux proxy at Mars based upon the E_10.7 proxy for solar flux at Earth and use our best case study to derive an equation that relates N_m to this proxy. We discuss how the ionosphere of Mars can be used to infer the presence of solar active regions not facing the Earth.Our fourth case study uses ionospheric observations from the southern hemisphere at latitudes where there are strong crustal magnetic anomalies. These profiles do not have Chapman-like shapes, unlike those of the other three case studies. We split this set of measurements into two subsets, corresponding to whether or not they were made at longitudes with strong crustal magnetic anomalies. Neither subset shows N_m responding to changes in solar flux in the manner that we observe in the three other case studies.We find many similarities in ionospheric responses to short-term and long-term changes in solar flux for Venus, Earth, and Mars. We consider the implications of our results for different parametric equations that have been published describing this response.     

Some problems related to the origin of methane on Mars

The following problems related to the origin of methane on Mars have been considered. (1) Laboratory simulations of the impact phenomena confirm effective heterogeneous chemistry between the products of the fireball. This chemistry lowers the fireball freezing temperature from 2000 to 750 K for methane and to 1100 K for CO/CO₂. Production of methane on Mars by cometary impacts is 0.8% of the total production. A probability that the observed methane on Mars came from impact of a single comet is 0.0011. (2) The PFS observations of variations of methane on Mars require a very effective heterogeneous loss of methane. Heterogeneous effect of dust is half that of the surface rocks. Thermochemical equilibrium requires production, not loss, of methane. Existing kinetic data show a very low efficiency of heterogeneous reactions of methane. Highly reactive superoxide ions generated by the solar UV photons on the martian rocks cannot remove methane. The required efficiency of heterogeneous loss of methane on Mars is higher than that on Earth by a factor of ?1000, although the expected efficiency on Earth is stronger than that on Mars because of the liquid ocean and the abundant oxygen. All these inconsistencies may be removed if variations of the rock reflectivity contribute to the PFS observations of methane on Mars. The PFS data on H₂CO, HCl, HF, and HBr also raise doubts. (3) Although geologic sources of methane are possible, the lack of current volcanism, hydrothermal activity, hot spots, and very low seepage of gases from the interior are not favorable for geologic methane. Any proposed geological source of methane on Mars should address these problems. Some weak points in the suggested geologic sources are discussed. (4) Measurements of ¹³C/¹²C and D/H in methane would be difficult because of the low methane abundance. These ratios are mostly sensitive to a temperature of methane formation and cannot distinguish between biogenic and low-temperature geologic sources. Their analysis requires the carbon isotope ratio in CO₂ on Mars, which is known with the insufficient accuracy, and D/H in water, which is different in the atmosphere, polar caps, regolith and interior. Therefore, the stable isotope ratios may not give a unique answer on the origin of methane. (5) Ethane and propane react with OH much faster than methane. If their production relative to methane is similar to that on Earth, then their expected abundances on Mars are of a few parts per trillion. (6) Loss of SO₂ in the reaction with peroxide on ice is smaller than its gas-phase loss by an order of magnitude. The overall results strengthen the biogenic origin of martian methane and its low variability.