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.     

Roles of methane and carbon dioxide in geological processes on Mars

We discuss in this paper possible roles of methane and carbon dioxide in geological processes on Mars. These volatiles in the martian crust may migrate upward from their sources either directly or via various traps (structural, sedimentary, ground ice, gas hydrates). They are then likely emitted to the atmosphere by seepage or through diverse vent structures. Though gas hydrates have never been directly detected on Mars, theoretical studies favor their presence in the crust and polar caps; they could have played an important role as significant gas reservoirs in the subsurface. The martian gas hydrates would possibly be a binary system of methane and carbon dioxide occupying clathrate cavities. Landforms such as mud volcanoes with well-known linkage to gas venting are extensively distributed on Earth, and methane is the primary gas involved. Thus, identification of these landforms on Mars could suggest that methane and possibly carbon dioxide have contributed to geological processes of the planet. For example, we present a newly identified field in Chryse Planitia where features closely resembling terrestrial mud volcanoes occur widely, though with no observable activity. We also present results of a preliminary search for possible recent or present-day, methane-emission zones in the regions over which enrichments of atmospheric methane have been reported.     

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.     

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.     

Methane adsorption on a martian soil analog: An abiogenic explanation for methane variability in the martian atmosphere

Recent observations suggest methane in the martian atmosphere is variable on short spatial and temporal scales. However, to explain the variability by loss reactions requires production rates much larger than expected. Here, we report results of laboratory studies of methane adsorption onto JSC-Mars-1, a martian soil simulant, and suggest that this process could explain the observations. Uptake coefficient (γ) values were measured as a function of temperature using a high-vacuum Knudsen cell able to simulate martian temperature and pressure conditions. Values of γ were measured from 115 to 135 K, and the data were extrapolated to higher temperatures with more relevance to Mars. Adsorptive uptake was found to increase at lower temperatures and larger methane partial pressures. Although only sub-monolayer methane surface coverage is likely to exist under martian conditions, a very large mineral surface area is available for adsorption as atmospheric methane can diffuse meters into the regolith. As a result, significant methane may be temporarily lost to the regolith on a seasonal time scale. As this weak adsorption is fully reversible, methane will be re-released into the atmosphere when surface and subsurface temperatures rise and so no net loss of methane occurs. Heterogeneous interaction of methane with martian soil grains is the only process proposed thus far which contains both rapid methane loss and rapid methane production mechanisms and is thus fully consistent with the reported variability of methane on Mars.     

Assessment of a 2016 mission concept: The search for trace gases in the atmosphere of Mars

The reported detection of methane in the atmosphere of Mars as well as its potentially large seasonal spatial variations challenge our understanding of both the sources and sinks of atmospheric trace gases. The presence of methane suggests ongoing exchange between the subsurface and the atmosphere of potentially biogenic trace gases, while the spatial and temporal variations cannot be accounted for with current knowledge of martian photochemistry. A Joint Instrument Definition Team (JIDT) was asked to assess concepts for a mission that might follow up on these discoveries within the framework of a series of joint missions being considered by ESA and NASA for possible future exploration of Mars. The following is based on the report of the JIDT to the space agencies (Zurek et al., 2009); a synopsis of the report was presented at the Workshop on Mars Methane held in Frascati, Italy, in November 2009. To summarize, the JIDT believed that a scientifically exciting and credible mission could be conducted within the evolving capabilities of the science/telecommunications orbiter being considered by ESA and NASA for possible launch in the 2016 opportunity for Mars.     

Metastable methane clathrate particles as a source of methane to the martian atmosphere

The observations of methane made by the PFS instrument onboard Mars Express exhibit a definite correlation between methane mixing ratio, water vapor mixing ratio, and cloud optical depth. The recent data obtained from ground-based telescopes seem to confirm the correlation between methane and water vapor. In order to explain this correlation, we suggest that the source of gaseous methane is atmospheric, rather than at the solid surface of the planet, and that this source may consist of metastable submicronic particles of methane clathrate hydrate continuously released to the atmosphere from one or several clathrate layers at depth, according to the phenomenon of “anomalous preservation” evidenced in the laboratory. These particles, lifted up to middle atmospheric levels due to their small size, and therefore filling the whole atmosphere, serve as condensation nuclei for water vapor. The observed correlation between methane and water vapor mixing ratios could be the signature of the decomposition of the clathrate crystals by condensation-sublimation processes related to cloud activity. Under the effect of water condensation on crystal walls, metastability could be broken and particles be eroded, resulting in a subsequent irreversible release of methane to the gas phase. Using PFS data, and according to our hypothesis, the lifetime of gaseous methane is estimated to be smaller than an upper limit of 6 ± 3 months, much smaller than the lifetime of 300 yr calculated from atmospheric chemical models. The reason why methane has a short lifetime might be the occurrence of heterogeneous chemical decomposition of methane in the subsurface, where it is known since Viking biology experiments that oxidants efficiently decompose organic matter. If true, it is shown by using existing models of H₂O₂ penetration in the regolith that methane could prevent H₂O₂ from penetrating in the subsurface, and further oxidizing the soil, at depths larger than a few millimeters. The present source of methane clathrate, acting over the last few hundred thousand or million years, could have given rise to the thin CO₂-ice layer covering the permanent water ice south polar cap. The hypothesis proposed in this paper requires, to be validated, a number of laboratory experiments studying the stability of methane clathrates in martian atmospheric conditions, and the kinetics and amplitude of clathrate particle erosion in presence of condensing water vapor. Detailed future observations of methane, and associated modeling, will allow to more accurately quantify the production rate of methane clathrate, its temporal variability at seasonal scale, and possibly to locate the source(s) of clathrates at the surface.     

Early Mars may have had a methanol ocean

The detection of gray crystalline hematite deposits on Mars by Thermal Emission Spectrometer (TES) has been used to argue for the presence of liquid water on Mars in the distant past. By methanol-thermal treatment of anhydrous FeCl₃ at low temperatures (70-160 °C), crystalline gray hematite with layered structure was synthesized, based on this result an alternative explanation for the origin of martian hematite deposits is suggested. Methane could be abundant in the early martian atmosphere; process such as photochemical oxidation of methane could result in the formation of ocean or pool of organic compounds such as methanol, which provides an environment for the formation of large-scale hematite deposits on Mars.     

Do ice caves exist on Mars?

We have developed a numerical model for assessing the lifetime of ice deposits in martian caves that are open to the atmosphere. Our model results and sensitivity tests indicate that cave ice would be stable over significant portions of the surface of Mars. Ice caves on Earth commonly occur in lava tubes, and Mars has been significantly resurfaced by volcanic activity during its history, including the two main volcanic provinces, the Tharsis and Elysium rises. These areas, known or suspected of having subsurface caves and related voids are among the most favorable regions for the occurrence of ice stability. The martian ice cave model predicts regions which, if caves occur, would potentially be areas of astrobiological importance as well as possible water sources for future human missions to Mars.     

Detection of methane in the martian atmosphere: evidence for life?

Using the Fourier Transform Spectrometer at the Canada-France-Hawaii Telescope, we observed a spectrum of Mars at the P-branch of the strongest CH₄ band at 3.3 μm with resolving power of 180,000 for the apodized spectrum. Summing up the spectral intervals at the expected positions of the 15 strongest Doppler-shifted martian lines, we detected the absorption by martian methane at a 3.7 sigma level which is exactly centered in the summed spectrum. The observed CH₄ mixing ratio is 10±3 ppb. Total photochemical loss of CH₄ in the martian atmosphere is equal to , the CH₄ lifetime is 340 years and methane should be uniformly mixed in the atmosphere. Heterogeneous loss of atmospheric methane is probably negligible, while the sink of CH₄ during its diffusion through the regolith may be significant. There are no processes of CH₄ formation in the atmosphere, so the photochemical loss must therefore be balanced by abiogenic and biogenic sources. Outgassing from Mars is weak, the latest volcanism is at least 10 million years old, and thermal emission imaging from the Mars Odyssey orbiter does not reveal any hot spots on Mars. Hydrothermal systems can hardly be warmer than the room temperature at which production of methane is very low in terrestrial waters. Therefore a significant production of hydrothermal and magmatic methane is not very likely on Mars. The calculated average production of CH₄ by cometary impacts is 2% of the methane loss. Production of methane by meteorites and interplanetary dust does not exceed 4% of the methane loss. Methane cannot originate from an extinct biosphere, as in the case of “natural gas” on Earth, given the exceedingly low limits on organic matter set by the Viking landers and the dry recent history which has been extremely hostile to the macroscopic life needed to generate the gas. Therefore, methanogenesis by living subterranean organisms is a plausible explanation for this discovery. Our estimates of the biomass and its production using the measured CH₄ abundance show that the martian biota may be extremely scarce and Mars may be generally sterile except for some oases.     

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.     

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.     

Comment on “Methane on Mars: A product of H2O photolysis in the presence of CO” by A. Bar-Nun and V. Dimitrov

Bar-Nun and Dimitrov [Bar-Nun, A., Dimitrov, V., 2006. Icarus 181, 320-322] suggested a sequence of reactions to form methane on Mars. These reactions are based on the study of products in the N₂-CO-H₂O mixture irradiated at 185 nm. The suggested scheme was not quantitatively justified by chemical kinetics. One of the key reactions is effectively blocked by O₂ in the martian atmosphere, and another key reaction does not exist. There are no pathways for effective formation of methane in the martian atmosphere.     

Antarctic Dry Valleys and indigenous weathering in Mars meteorites: Implications for water and life on Mars

The Dry Valleys of Antarctica are an excellent analog of the environment at the surface of Mars. Soil formation histories involving slow processes of sublimation and migration of water-soluble ions in polar desert environments are characteristic of both Mars and the Dry Valleys. At the present time, the environment in the Dry Valleys is probably the most similar to that in the mid-latitudes on Mars although similar conditions may be found in areas of the polar regions during their respective Mars summers. It is thought that Mars is currently in an interglacial period, and that subsurface water ice is sublimating poleward. Because the Mars sublimation zones seem to be the most similar to the Antarctic Dry Valleys, the Dry Valleys-type Mars climate is migrating towards the poles. Mars has likely undergone drastic obliquity changes, which means that the Dry Valleys analog to Mars may be valid for large parts of Mars, including the polar regions, at different times in geologic history. Dry Valleys soils contain traces of silicate alteration products and secondary salts much like those found in Mars meteorites. A martian origin for some of the meteorite secondary phases has been verified previously; it can be based on the presence of shock effects and other features which could not have formed after the rocks were ejected from Mars, or demonstrable modification of a feature by the passage of the meteorite through Earth's atmosphere (proving the feature to be pre-terrestrial). The martian weathering products provide critical information for deciphering the near-surface history of Mars. Definite martian secondary phases include Ca-carbonate, Ca-sulfate, and Mg-sulfate. These salts are also found in soils from the Dry Valleys of Antarctica. Results of earlier Wright Valley work are consistent with what is now known about Mars based on meteorite and orbital data. Results from recent and current Mars missions support this inference. Aqueous processes are active even in permanently frozen Antarctic Dry Valleys soils, and similar processes are probably also occurring on Mars today, especially at the mid-latitudes. Both weathering products and life in Dry Valleys soils are distributed heterogeneously. Such variations should be taken into account in future studies of martian soils and also in the search for possible life on Mars.     

Laboratory simulations of Mars aqueous geochemistry

We report on laboratory experiments in which we allowed an SNC-derived mineral mix to react with pure water under a simulated Mars atmosphere for 7 months. These experiments were performed at one bar and at three different temperatures in order to simulate the subsurface conditions that most likely exist where liquid water and rock interact on Mars today. The dominant cations dissolved in the solutions we produced, which may be characterized as dilute brines, are Ca²⁺, Mg²⁺, Al³⁺, and Na⁺, while the major anions are dissolved C, F⁻, SO²⁻₄ and Cl⁻. Typical solution pH was in the range of 4.2-6.0. Abundance patterns of elements in our synthetic sulfate-chloride brines are distinctly unlike those of terrestrial ocean water or continental waters, however, they are quite similar to those measured in the martian fines at the Mars Pathfinder and Viking 1 and 2 Landing sites. This suggests that salts present in the martian regolith may have formed over time as a result of the interaction of surface or subsurface liquid water with basalts in the presence of a martian atmosphere similar in composition to that of today. If most of the mobile surface layer was formed during the Noachian when erosion rates were much higher than at present, and if this layer is homogeneous in salt composition, the total amount of salt in the martian fines is approximately the same as in the Earth's oceans. The minimum quantity of circulating water necessary to deposit this amount of salt is approximately equivalent to a global layer 625 m deep.     

Reduced sulfur–carbon–water systems on Mars may yield shallow methane hydrate reservoirs

Methane clathrate hydrate reservoirs capped by overlying permafrost have been proposed as potential sources of atmospheric methane plumes on Mars. However, the surface flux of methane from hydrate dissociation is limited by the diffusion rate of methane through the overlying ice. Assuming hydrates underlay the entire plume footprint, the maximum diffusion path length is expected to be less than 15 m, depths too shallow to stabilize pure methane hydrates under Mars geothermal and lithostatic conditions at low to mid latitudes. Therefore, pure methane hydrates confined within permafrost could not produce methane surface fluxes of the magnitude observed near the equator. However, the addition of 10% H₂S, a secondary gas commonly associated with methane production on Earth, expands the hydrate stability field, with clathrates expected within 10 m of the surface at the equator and at depths less than 1 m at higher latitudes. This indicates that H₂S would also be expected to be released as well as methane if the plumes have a confined hydrate reservoir source.     

Geological features indicative of processes related to the hematite formation in Meridiani Planum and Aram Chaos, Mars: a comparison with diagenetic hematite deposits in southern Utah, USA

In order to understand the formation of the few but large, hematite deposits on Mars, comparisons are often made with terrestrial hematite occurrences. In southern Utah, hematite concretions have formed within continental sandstones and are exposed as extensive weathered-out beds. The hematite deposits are linked to geological and geomorphological features such as knobs, buttes, bleached beds, fractures and rings. These terrestrial features are visible in aerial and satellite images, which enables a comparison with similar features occurring extensively in the martian hematite-rich areas. The combination of processes involved in the movement and precipitation of iron in southern Utah can provide new insights in the context of the hematite formation on Mars. Here we present a mapping of the analogue geological and geomorphological features in parts of Meridiani Planum and Aram Chaos. Based on mapping comparisons with the Utah occurrences, we present models for the formation of the martian analogues, as well as a model for iron transport and precipitation on Mars. Following the Utah model, high albedo layers and rings in the mapped area on Mars are due to removal or lack of iron, and precipitation of secondary diagenetic minerals as fluids moved up along fractures and permeable materials. Hematite was precipitated intraformationally where the fluid transporting the reduced iron met oxidizing conditions. Our study shows that certain geological/geomorphological features can be linked to the hematite formation on Mars and that pH differences could suffice for the transport of the iron from an orthopyroxene volcanoclastic source rock. The presence of organic compounds can enhance the iron mobilization and precipitation processes. Continued studies will focus on possible influence of biological activity and/or methane in the formation of the hematite concretions in Utah and on Mars.     

A cold and wet Mars

Water on Mars has been explained by invoking controversial and mutually exclusive solutions based on warming the atmosphere with greenhouse gases (the “warm and wet” Mars) or on local thermal energy sources acting in a global freezing climate (the “cold and dry” Mars). Both have critical limitations and none has been definitively accepted as a compelling explanation for the presence of liquid water on Mars. Here is considered the hypothesis that cold, saline and acidic liquid solutions have been stable on the sub-zero surface of Mars for relatively extended periods of time, completing a hydrogeological cycle in a water-enriched but cold planet. Computer simulations have been developed to analyze the evaporation processes of a hypothetical martian fluid with a composition resulting from the acid weathering of basalt. This model is based on orbiter- and lander-observed surface mineralogy of Mars, and is consistent with the sequence and time of deposition of the different mineralogical units. The hydrological cycle would have been active only in periods of dense atmosphere, as having a minimum atmospheric pressure is essential for water to flow, and relatively high temperatures (over ∼245 K) are required to trigger evaporation and snowfall; minor episodes of limited liquid water on the surface could have occurred at lower temperatures (over ∼225 K). During times with a thin atmosphere and even lesser temperatures (under ∼225 K), only transient liquid water can potentially exist on most of the martian surface. Assuming that surface temperatures have always been maintained below 273 K, Mars can be considered a “cold and wet” planet for a substantial part of its geological history.     

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.     

Methane and related trace species on Mars: Origin,loss, implications for life,and habitability

One of the most puzzling aspects of Mars is that organics have not yet been found on the surface. The simplest of organic molecules, methane, was detected in the Martian atmosphere for the first time in 2003. The existence and behavior of methane on Mars is of great significance, as methane is a potential biomarker. In this paper we review our current understanding of possible sources and sinks of methane on Mars. We also investigate the role of other trace species in the maintenance and removal of methane from the atmosphere, as well as of other organic material from the surface. In particular, we examine the exogenous, hydrogeochemical—especially serpentinization—and biological sources, for supplying methane to Mars. We suggest that comets and meteorites are the least likely, whereas low-temperature serpentinization is the most plausible of all candidates to explain the methane observations. Nevertheless, it is premature to rule out the role of biology in producing methane on Mars, in view of available data. It is important to note that the loss of methane to surface must also be factored into any “source” scenarios for methane. Ordinary heterogeneous loss process to surface tends to be very slow. On the other hand, a reactive surface could potentially accelerate the destruction of methane. If correct, it would imply that a larger source of methane is present than currently estimated on the basis of photochemical loss alone. A reactive surface can also explain why no organic material has ever been detected on the Martian surface. The surface could become reactive if some oxidizer were present. We suggest that vast quantities of a powerful oxidant, hydrogen peroxide, can be produced in electrochemistry triggered by electrostatic fields generated in the Martian dust devils and dust storms, and in normal saltation process close to the surface. Finally, current observations are inadequate to prove or disprove the existence of life on Mars, now or in the past. The question of extraterrestrial life is a fundamental one, and it should be addressed meticulously on future missions to Mars. Measurements planned on the Mars Science Laboratory (MSL), especially carbon isotopes and chirality, will go a long way in meeting this goal. A brief overview of the MSL Mission and measurements relevant to the question of life and habitability of Mars is also presented in this paper.