Early Mars volcanic sulfur storage in the upper cryosphere and formation of transient SO2‐rich atmospheres during the Hesperian

In a previous paper (Chassefière et al. 2013 ), we have shown that most volcanic sulfur released to the early Mars atmosphere could have been trapped in the upper cryosphere under the form of CO₂‐SO₂ clathrates. Huge amounts of sulfur, up to the equivalent of an ~1 bar atmosphere of SO₂, would have been stored in the Noachian upper cryosphere, then massively released to the atmosphere during the Hesperian due to rapidly decreasing CO₂ pressure. It could have resulted in the formation of the large sulfate deposits observed mainly in Hesperian terrains, whereas no or little sulfates are found at the Noachian. In the present paper, we first clarify some aspects of our previous work. We discuss the possibility of a smaller cooling effect of sulfur particles, or even of a net warming effect. We point out the fact that CO₂‐SO₂ clathrates formed through a progressive enrichment of a pre‐existing reservoir of CO₂ clathrates and discuss processes potentially involved in the slow formation of a SO₂‐rich upper cryosphere. We show that episodes of sudden destabilization at the Hesperian may generate 1000 ppmv of SO₂ in the atmosphere and contribute to maintaining the surface temperature above the water freezing point.     

Methane release and the carbon cycle on Mars

It has been suggested that the present release rate of methane to the Martian atmosphere could be the result of serpentinization in the deep subsurface, followed by the conversion of H₂ to CH₄ in a CO₂-rich fluid. Making this assumption, we show that the cryosphere could act as a buffer storing, under the form of micron-size methane clathrate particles, the methane delivered from below by hydrothermal fluids and progressively releasing it to the atmosphere at the top. From an extrapolation of the present CH₄ release rate back to the past, we calculate that up to several hundred millibars (～200–2000 mbar) of CO₂, resulting from the oxidation of the released CH₄, in addition to the volcanic supply (～400 mbar), should have accumulated in the atmosphere in the absence of a CO₂ sink. We reassess the capability of escape to have removed CO₂ from the atmosphere by C non-thermal escape and show that it is not significant. We suggest that atmospheric carbon is recycled to the crust through an active subsurface hydrological system, and precipitates as carbonates within the crust. During episodic periods of magmatic activity, these carbonates are decomposed to CO₂ dissolved in running water, and CO₂ can react with H₂ formed by serpentinization to build CH₄. CH₄ is then buffered in the subsurface cryosphere, above the water table, and finally released to the atmosphere, before being recycled to the subsurface hydrological system, and converted back to carbonates. We propose a typical evolution curve of the CO₂ pressure since the late Noachian based on our hypothesis. Contrary to the steady state carbon cycle at work on Earth, a progressive damping of the carbon cycle occurs on Mars due to the absence of plate tectonics and the progressive cooling of the planet.     

The environment of early Mars and the missing carbonates

Abstract– A model is presented in which the aqueous conditions needed to generate phyllosilicate minerals in the absence of carbonates found in the ancient Noachian crust are maintained by an early CO₂‐rich atmosphere, that, together with iron (II) oxidation, would prevent carbonate formation at the surface. After cessation of the internal magnetic dynamo, a CO₂‐rich primordial atmosphere was stripped by interactions with the solar wind and surface conditions evolved from humid to arid, with ground waters partially dissolving subsurface carbonate and sulfide minerals to produce acid‐sulfate evaporitic deposits in areas with upwelling ground water. In a subsequent geochemical state (Late Noachian to Hesperian), surface and subsurface acidic solutions were neutralized in the subsurface through interaction with basaltic crust, allowing the precipitation of secondary carbonates. This model suggests that, in the early Noachian, the surface waters of Mars maintained acidity because of a drop in temperature. This would have favored increased dissolution of CO₂ and a reduction in atmospheric pressure. In this scenario, physicochemical conditions precluded the formation of surface carbonates, but induced the precipitation of carbonates in the subsurface.     

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

Methane emissions from Earth’s degassing: Implications for Mars

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

Limits on the trapping of atmospheric CH4 in martian polar ice analogs

Recent detection of methane (CH₄) on Mars has generated interest in possible biological or geological sources, but the factors responsible for the reported variability are not understood. Here we explore one potential sink that might affect the seasonal cycling of CH₄ on Mars - trapping in ices deposited on the surface. Our apparatus consisted of a high-vacuum chamber in which three different Mars ice analogs (water, carbon dioxide, and carbon dioxide clathrate hydrates) were deposited in the presence of CH₄ gas. The ices were monitored for spectroscopic evidence of CH₄ trapping using transmission Fourier-Transform Infrared (FT-IR) spectroscopy, and during subsequent sublimation of the ice films the vapor composition was measured using mass spectrometry (MS). Trapping of CH₄ in water ice was confirmed at deposition temperatures <100 K which is consistent with previous work, thus validating the experimental methods. However, no trapping of CH₄ was observed in the ice analogs studied at warmer temperatures (140 K for H₂O and CO₂ clathrate, 90 K for CO₂ snow) with approximately 10 mTorr CH₄ in the chamber. From experimental detection limits these results provide an upper limit of 0.02 for the atmosphere/ice trapping ratio of CH₄. If it is assumed that the trapping mechanism is linear with CH₄ partial pressure and can be extrapolated to Mars, this upper limit would indicate that less than 1% is expected to be trapped from the largest reported CH₄ plume, and therefore does not represent a significant sink for CH₄.     

Early Mars climate near the Noachian–Hesperian boundary: Independent evidence for cold conditions from basal melting of the south polar ice sheet (Dorsa Argentea Formation) and implications for valley network formation

Currently, and throughout much of the Amazonian, the mean annual surface temperatures of Mars are so cold that basal melting does not occur in ice sheets and glaciers and they are cold-based. The documented evidence for extensive and well-developed eskers (sediment-filled former sub-glacial meltwater channels) in the south circumpolar Dorsa Argentea Formation is an indication that basal melting and wet-based glaciation occurred at the South Pole near the Noachian–Hesperian boundary. We employ glacial accumulation and ice-flow models to distinguish between basal melting from bottom-up heat sources (elevated geothermal fluxes) and top-down induced basal melting (elevated atmospheric temperatures warming the ice). We show that under mean annual south polar atmospheric temperatures (?100 °C) simulated in typical Amazonian climate experiments and typical Noachian–Hesperian geothermal heat fluxes (45–65 mW/m²), south polar ice accumulations remain cold-based. In order to produce significant basal melting with these typical geothermal heat fluxes, the mean annual south polar atmospheric temperatures must be raised from today’s temperature at the surface (?100 °C) to the range of ?50 to ?75 °C. This mean annual polar surface atmospheric temperature range implies lower latitude mean annual temperatures that are likely to be below the melting point of water, and thus does not favor a “warm and wet” early Mars. Seasonal temperatures at lower latitudes, however, could range above the melting point of water, perhaps explaining the concurrent development of valley networks and open basin lakes in these areas. This treatment provides an independent estimate of the polar (and non-polar) surface temperatures near the Noachian–Hesperian boundary of Mars history and implies a cold and relatively dry Mars climate, similar to the Antarctic Dry Valleys, where seasonal melting forms transient streams and permanent ice-covered lakes in an otherwise hyperarid, hypothermal climate.     

Variability of the methane trapping in martian subsurface clathrate hydrates

Recent observations have evidenced traces of methane (CH₄) heterogeneously distributed in the martian atmosphere. However, because the lifetime of CH₄ in the atmosphere of Mars is estimated to be around 300-600 years on the basis of photochemistry, its release from a subsurface reservoir or an active primary source of methane have been invoked in the recent literature. Among the existing scenarios, it has been proposed that clathrate hydrates located in the near subsurface of Mars could be at the origin of the small quantities of the detected CH₄. Here, we accurately determine the composition of these clathrate hydrates, as a function of temperature and gas phase composition, by using a hybrid statistical thermodynamic model based on experimental data. Compared to the other recent works, our model allows us to calculate the composition of clathrate hydrates formed from a more plausible composition of the martian atmosphere by considering its main compounds, i.e. carbon dioxide, nitrogen and argon, together with methane. Besides, because there is no low temperature restriction in our model, we are able to determine the composition of clathrate hydrates formed at temperatures corresponding to the extreme ones measured in the polar caps. Our results show that methane enriched clathrate hydrates could be stable in the subsurface of Mars only if a primitive CH₄-rich atmosphere has existed or if a subsurface source of CH₄ has been (or is still) present.     

Nature of the Martian uplands: Effect on Martian meteorite age distribution and secondary cratering

Abstract— Martian meteorites (MMs) have been launched from an estimated 5–9 sites on Mars within the last 20 Myr. Some 80–89% of these launch sites sampled igneous rock formations from only the last 29% of Martian time. We hypothesize that this imbalance arises not merely from poor statistics, but because the launch processes are dominated by two main phenomena: first, much of the older Martian surface is inefficient in launching rocks during impacts, and second, the volumetrically enormous reservoir of original cumulate crust enhances launch probability for 4.5 Gyr old rocks. There are four lines of evidence for the first point, not all of equal strength. First, impact theory implies that MM launch is favored by surface exposures of near‐surface coherent rock (≤10² m deep), whereas Noachian surfaces generally should have ≥10² m of loose or weakly cemented regolith with high ice content, reducing efficiency of rock launch. Second, similarly, both Mars Exploration Rovers found sedimentary strata, 1–2 orders of magnitude weaker than Martian igneous rocks, favoring low launch efficiency among some fluvial‐derived Hesperian and Noachian rocks. Even if launched, such rocks may be unrecognized as meteorites on Earth. Third, statistics of MM formation age versus cosmic‐ray exposure (CRE) age weakly suggest that older surfaces may need larger, deeper craters to launch rocks. Fourth, in direct confirmation, one of us (N. G. B.) has found that older surfaces need larger craters to produce secondary impact crater fields (cf. Barlow and Block 2004). In a survey of 200 craters, the smallest Noachian, Hesperian, and Amazonian craters with prominent fields of secondaries have diameters of ?45 km, ?19 km, and ?10 km, respectively. Because 40% of Mars is Noachian, and 74% is either Noachian or Hesperian, the subsurface geologic characteristics of the older areas probably affect statistics of recognized MMs and production rates of secondary crater populations, and the MM and secondary crater statistics may give us clues to those properties.     

Measurement of the isotopic signatures of water on Mars; Implications for studying methane

The recent discovery of methane on Mars has led to much discussion concerning its origin. On Earth, the isotopic signatures of methane vary with the nature of its production. Specifically, the ratios among ¹²CH₄, ¹³CH₄, and ¹²CH₃D differ for biotic and abiotic origins. On Mars, measuring these ratios would provide insights into the origins of methane and measurements of water isotopologues co-released with methane would assist in testing their chemical relationship. Since 1997, we have been measuring HDO and H₂O in Mars’ atmosphere and comparing their ratio to that in Earth’s oceans. We recently incorporated a line-by-line radiative transfer model (LBLRTM) into our analysis. Here, we present a map for [HDO]/[H₂O] along the central meridian (154°W) for L_s=50°. From these results, we constructed models to determine the observational conditions needed to quantify the isotopic ratios of methane in Mars’ atmosphere. Current ground-based instruments lack the spectral resolution and sensitivity needed to make these measurements. Measurements of the isotopologues of methane will likely require in situ sampling.     

Volatile transport on inhomogeneous surfaces: I – Analytic expressions,with application to Pluto’s day

The two orders of magnitude drop between the measured atmospheric abundances of non-radiogenic argon, krypton and xenon in Earth versus Mars is striking. Here, in order to account for this difference, we explore the hypothesis that clathrate deposits incorporated into the current martian cryosphere have sequestered significant amounts of these noble gases assuming they were initially present in the paleoatmosphere in quantities similar to those measured on Earth (in mass of noble gas per unit mass of the planet). To do so, we use a statistical-thermodynamic model that predicts the clathrate composition formed from a carbon dioxide-dominated paleoatmosphere whose surface pressure ranges up to 3 bars. The influence of the presence of atmospheric sulfur dioxide on clathrate composition is investigated and we find that it does not alter the trapping efficiencies of other minor species. Assuming nominal structural parameters for the clathrate cages, we find that a carbon dioxide equivalent pressure of 0.03 and 0.9 bar is sufficient to trap masses of xenon and krypton, respectively, equivalent to those found on Earth in the clathrate deposits of the cryosphere. In this case, the amount of trapped argon is not sufficient to explain the measured Earth/Mars argon abundance ratio in the considered pressure range. In contrast, with a 2% contraction of the clathrate cages, masses of xenon, krypton and argon at least equivalent to those found on Earth can be incorporated into clathrates if one assumes the trapping of carbon dioxide at equivalent atmospheric pressures of ～2.3 bar. The proposed clathrate trapping mechanism could have then played an important role in the shaping of the current martian atmosphere.     

Trapped Ar isotopes in meteorite ALH 84001 indicate Mars did not have a thick ancient atmosphere

Water is not currently stable in liquid form on the martian surface due to the present mean atmospheric pressure of ～7 mbar and mean global temperature of ～220 K. However, geomorphic features and hydrated mineral assemblages suggest that Mars’ climate was once warmer and liquid water flowed on the surface. These observations may indicate a substantially more massive atmosphere in the past, but there have been few observational constraints on paleoatmospheric pressures. Here we show how the ⁴⁰Ar/³⁶Ar ratios of trapped gases within martian meteorite ALH 84001 constrain paleoatmospheric pressure on Mars during the Noachian era [～4.56–3.8 billion years (Ga)]. Our model indicates that atmospheric pressures did not exceed ～1.5 bar during the first 400 million years (Ma) of the Noachian era, and were <400 mbar by 4.16 Ga. Such pressures of CO₂ are only sufficient to stabilize liquid water on Mars’ surface at low latitudes during seasonally warm periods. Other greenhouse gases like SO₂ and water vapor may have played an important role in intermittently stabilizing liquid water at higher latitudes following major volcanic eruptions or impact events.     

“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.     

Enhanced CO2 trapping in water ice via atmospheric deposition with relevance to Mars

It has been suggested that inclusions of CO₂ or CO₂ clathrate hydrates may comprise a portion of the polar deposits on Mars. Here we present results from an experimental study in which CO₂ molecules were trapped in water ice deposited from CO₂/H₂O atmospheres at temperatures relevant for the polar regions of Mars. Fourier-Transform Infrared spectroscopy was used to monitor the phase of the condensed ice, and temperature programmed desorption was used to quantify the ratio of species in the generated ice films. Our results show that when H₂O ice is deposited at 140-165 K, CO₂ is trapped in large quantities, greater than expected based on lower temperature studies in amorphous ice. The trapping occurs at pressures well below the condensation point for pure CO₂ ice, and therefore this mechanism may allow for CO₂ deposition at the poles during warmer periods. The amount of trapped CO₂ varied from 3% to 16% by mass at 160 K, depending on the substrate studied. Substrates studied were a tetrahydrofuran (C₄H₈O) base clathrate and Fe-montmorillonite clay, an analog for Mars soil. Experimental evidence indicates that the ice structures are likely CO₂ clathrate hydrates. These results have implications for the CO₂ content, overall composition, and density of the polar deposits on Mars.     

Is there methane on Mars?

There have been several reports of methane on Mars at the 10-60 ppbv level. Most suggest that methane is both seasonally and latitudinally variable. Here we review why variable methane on Mars is physically and chemically implausible, and then we critically review the published reports. There is no known mechanism for destroying methane chemically on Mars. But if there is one, methane oxidation would deplete the O₂ in Mars’s atmosphere in less than 10,000 years unless balanced by an equally large unknown source of oxidizing power. Physical sequestration does not raise these questions, but adsorption in the regolith or condensation in clathrates ignore competition for adsorption sites or are inconsistent with clathrate stability, respectively. Furthermore, any mechanism that relies on methane’s van der Waals’ attraction is inconsistent with the continued presence of Xe in the atmosphere at the 60 ppbv level. We then use the HITRAN database and transmission calculations to identify and characterize the absorption lines that would be present on Earth or Mars at the wavelengths of the published observations. These reveal strong competing telluric absorption that is most problematic at just those wavelengths where methane’s signature seems most clearly seen from Earth. The competing telluric lines must be removed with models. The best case for martian methane was made for the ¹²CH₄ν₃ R0 and R1 lines seen in blueshift when Mars was approaching Earth in early 2003 (Mumma, M.J., Villanueva, G.L., Novak, R.E., Hewagama, T., Bonev, B.P., DiSanti, M.A., Mandell, A.M., Smith, M.D. [2009]. Science 323, 1041-1045). For these the Doppler shift moves the two martian lines into near coincidence with telluric ¹³CH₄ν₃ R1 and R2 lines that are 10-50× stronger than the inferred martian lines. By contrast, the ¹²CH₄ν₃ R0 and R1 lines when observed in redshift do not contend with telluric ¹³CH₄. For these lines, Mumma et al.’s observations and analyses are consistent with an upper limit on the order of 3 ppbv.     

The combined effects of escape and magnetic field histories at Mars

Mars is thought to have hosted large amounts of water and carbon dioxide at primitive epochs. The morphological analysis of the surface of Mars shows that large bodies of water were probably present in the North hemisphere at late Noachian (3.7–4 Gyr ago). Was this water solid or liquid? For maintaining liquid water at this time, when the Sun was (likely) less bright than now, a CO₂ atmosphere of typically 2 bars is required. Can sputtering, still presently acting at the top of the Martian atmosphere, have removed such a dense atmosphere over the last 3.5–4 Gyr? What was the fate of the 100–200 m global equivalent layer of water present at late Noachian? When did Martian magnetic dynamo vanish, initiating a long period of intense escape by sputtering? Because sputtering efficiency is highly non-linear with solar EUV flux, with a logarithmic slope of ≈7:Φ_sput≈Φ_EUV⁷, resulting in enhanced levels of escape at primitive epochs, when the sun was several times more luminous than now in the EUV, there is a large uncertainty on the cumulated amount of volatiles removed to space. This amount depends primarily on two factors: (i) the exact value of the non-linearity exponent (≈7 from existing models, but this value is rather uncertain), (ii) the exact time when the dynamo collapsed, activating sputtering at epochs when intense EUV flux and solar wind activity prevailed in the solar system. Both parameters are only crudely known at the present time, due the lack of direct observation of sputtering from Martian orbit, and to the incomplete and insufficiently spatially resolved map of the crustal magnetic field. Precise timing of the past Martian dynamo can be investigated through the demagnetisation signature associated with impact craters. A designated mission to Mars would help in answering this crucial question: was water liquid at the surface of Mars at late Noachian? Such a mission would consist of a low periapsis (≈100 km) orbiter, equipped with a boom-mounted magnetometer, for mapping the magnetic field, as well as adequate in situ mass and energy spectrometers, for a full characterization of escape and of its response to solar activity variations. Surface based observations of atmospheric noble gas isotopic ratios, which keep the signatures of past escape processes, including sputtering for the lightest of them (Ne, Ar), would bring a key constraint for escape models extrapolated back to the past.     

Explaining the redox imbalance between the H and O escape fluxes at Mars by the oxidation of methane

From a comparison between the different observations of Martian methane existing today, including the new TES methane maps (Fonti and Marzo, 2010), we show that all sets of data are globally consistent with each other, and that a well definite seasonal cycle of methane has been at work for at least 10 yr. With a simple model of the balance between the loss fluxes of H and O, using up-to-date values of the escape fluxes, we show that the long-standing enigma of the imbalance between H and O escape fluxes may be solved by assuming that the missing sink of oxygen is the oxidation of methane. If no H₂ is released together with CH₄, a good agreement is found between the present CH₄ flux and the value imposed by the balance between H and O escape fluxes, an average over the last ≈10³ yr. If H₂ is released together with CH₄, as expected if CH₄ originates in serpentinization, the average level of CH₄ during the last 10³ yr should have been at least ten times lower than the present one. The lack of present H₂ release could suggest a long-term storage of methane in the subsurface under the form of clathrates, whereas H₂ has been lost to the atmosphere shortly after being produced. We suggest that the thin layer of CO₂ ice covering the permanent southern polar cap could result from the release of methane since the end of the last obliquity transition (time scale: 1 Myr), at an average rate of 0.1 Mt yr^?1, consistent with the values derived from: (i) the present observations of methane (time scale: 10 yr), (ii) the estimate from the observed imbalance between the H and O escape fluxes (time scale: 1 kyr). If so, the present release of methane from subsurface clathrates would have acted at a similar rate since at least 3 Myr.     

The upper ionosphere of Titan

Photoionization of the upper atmosphere of Titan by sunlight is expected to produce a substantial ionospheric layer. We have solved one-dimensional forms of the mass, momentum, and energy conservation equations for ions and electrons and have obtained electron number densities of about 10³ cm^?3, using various model atmospheres. The significant ions in a CH₄H₂ atmosphere are H⁺, H₃⁺, CH₅⁺, CH₅⁺, CH₃⁺, and C₂H₅⁺. Electron temperatures may be as high as 1000°K, depending on the abundance of hydrogen in the high atmosphere. Interaction of the solar wind with the ionosphere is also discussed.     

Formation of methane in comet impacts: implications for Earth, Mars, and Titan

We calculate the amount of methane that may form via reactions catalyzed by metal-rich dust that condenses in the wake of large cometary impacts. Previous models of the gas-phase chemistry of impacts predicted that the terrestrial planets' atmospheres should be initially dominated by CO/CO₂, N₂, and H₂O. CH₄ was not predicted to form in impacts because gas-phase reactions in the explosion quench at temperatures ∼2000 K, at which point all of the carbon is locked in CO. We argue that the dust that condenses out in the wake of a large comet impact is likely to have very effective catalytic properties, opening up reaction pathways to convert CO and H₂ to CH₄ and CO₂, at temperatures of a few hundred K. Together with CO₂, CH₄ is an important greenhouse gas that has been invoked to compensate for the lower luminosity of the Sun ∼4 Gyr ago. Here, we show that heterogeneous (gas-solid) reactions on freshly-recondensed dust in the impact cloud may provide a plausible nonbiological mechanism for reducing CO to CH₄ before and during the emergence of life on Earth, and perhaps Mars as well. These encouraging results emphasize the importance of future research into the kinetics and catalytic properties of astrophysical condensates or “smokes” and also more detailed models to determine the conditions in impact-generated dust clouds.     

Detection of new hydrocarbons in Uranus' atmosphere by infrared spectroscopy

Ethane (C₂H₆), methylacetylene (CH₃C₂H or C₃H₄) and diacetylene (C₄H₂) have been discovered in Spitzer 10-20 μm spectra of Uranus, with 0.1-mbar volume mixing ratios of (1.0±0.1)×¹⁰⁻⁸, (2.5±0.3)×¹⁰⁻¹⁰, and (1.6±0.2)×¹⁰⁻¹⁰, respectively. These hydrocarbons complement previously detected methane (CH₄) and acetylene (C₂H₂). Carbon dioxide (CO₂) was also detected at the 7-σ level with a 0.1-mbar volume mixing ratio of (4±0.5)×¹⁰⁻¹¹. Although the reactions producing hydrocarbons in the atmospheres of giant planets start from radicals, the methyl radical (CH₃) was not found in the spectra, implying much lower abundances than in the atmospheres of Saturn or Neptune where it has been detected. This finding underlines the fact that Uranus' atmosphere occupies a special position among the giant planets, and our results shed light on the chemical reactions happening in the absence of a substantial internal energy source.