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.     

Residual south polar cap of Mars: Stratigraphy, history, and implications of recent changes

The residual south polar cap (RSPC) of Mars includes a group of different depositional units of CO₂ ice undergoing a variety of erosional processes. Complete summer coverage of the RSPC by ∼6-m/pixel data of the Context Imager (CTX) on Mars Reconnaissance Orbiter (MRO) has allowed mapping and inventory of the units in the RSPC. Unit maps and estimated thicknesses indicate the total volume of the RSPC is currently <380 km³, and represents less than 3% of the total mass of the current Mars atmosphere. Scarp retreat rates in the CO₂ ice derived from comparison of High Resolution Imaging Science Experiment (HiRISE) data with earlier images are comparable to those obtained for periods up to 3 Mars years earlier. These rates, combined with sizes of depressions suggest that the oldest materials were deposited more than 125 Mars years ago. Most current erosion is by backwasting of scarps 1-12 m in height. This backwasting is initiated by a series of scarp-parallel fractures. In the older, thicker unit these fractures form about every Mars year; in thinner, younger materials they form less frequently. Some areas of the older, thicker unit are lost by downwasting rather than by the scarp retreat. A surprising finding from the HiRISE data is the scarcity of visible layering of RSPC materials, a result quite distinct from previous interpretations of layers in lower resolution images. Layers ∼0.1 m thick are exposed on the upper surfaces of some areas, but their timescale of deposition is not known. Late summer albedo changes mapped by the CTX images indicate local recycling of ice, although the amounts may be morphologically insignificant. Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) data show that the primary material of all the different forms of the RSPC is CO₂ ice with only small admixtures of water ice and dust.     

Adsorptive fractionation of HDO on JSC MARS-1 during sublimation with implications for the regolith of Mars

A chamber was constructed to simulate the boundary between the ice table, regolith and atmosphere of Mars and to examine fractionation between H₂O and HDO during sublimation under realistic martian conditions of temperature and pressure. Thirteen experimental runs were conducted with regolith overlying the ice. The thickness and characteristic grain size of the regolith layer as well as the temperature of the underlying ice was varied. From these runs, values for the effective diffusivity, taking into account the effects of adsorption, of the regolith were derived. These effective diffusivities ranged from 1.8 × 10⁻⁴ m² s⁻¹ to 2.2 × 10⁻³ m² s⁻¹ for bare ice and from 2.4 × 10⁻¹¹ m² s⁻¹ to 2.0 × 10⁻⁹ m² s⁻¹ with an adsorptive layer present. From these, latent heats of adsorption of 8.6 ± 2.6 kJ mol⁻¹ and 9.3 ± 2.8 kJ mol⁻¹ were derived at ice-surface temperatures above 223 ± 8 K and 96 ± 28 kJ mol⁻¹ and 104 ± 31 kJ mol⁻¹ respectively for H₂O and HDO were derived at colder temperatures. For temperatures below 223 K, the effective diffusivity of HDO was found to be lower than the diffusivity of H₂O by 40% on average, suggesting that the regolith was adsorptively fractionating the sublimating gas with a fractionation factor of 1.96 ± 0.74. Applying these values to Mars predicts that adsorbed water on the regolith is enriched in HDO compared to the atmosphere, particularly where the regolith is colder. Based on current observations, the D/H ratio of the regolith may be as high as 21 ± 8 times VSMOW at 12°S and L_S = 357° if the regolith is hydrated primarily by the atmosphere, neglecting any hydration from subsurface ice.     

Evaluation of the possible presence of clathrate hydrates in Europa's icy shell or seafloor

Several substances besides water ice have been detected on the surface of Europa by spectroscopic sensors, including CO₂, SO₂, and H₂S. These substances might occur as pure crystalline ices, as vitreous mixtures, or as clathrate hydrate phases, depending on the system conditions and the history of the material. Clathrate hydrates are crystalline compounds in which an expanded water ice lattice forms cages that contain gas molecules. The molecular gases that may constitute Europan clathrate hydrates may have two possible ultimate origins: they might be primordial condensates from the interstellar medium, solar nebula, or jovian subnebula, or they might be secondary products generated as a consequence of the geological evolution and complex chemical processing of the satellite. Primordial ices and volatile-bearing compounds would be difficult to preserve in pristine form in Europa without further processing because of its active geological history. But dissociated volatiles derived from differentiation of a chondritic rock or cometary precursor may have produced secondary clathrates that may be present now. We have evaluated the current stability of several types of clathrate hydrates in the crust and the ocean of Europa. The depth at which the clathrates of SO₂, CO₂, H₂S, and CH₄ are stable have been obtained using both the temperatures observed in the surface [Spencer, J.R., Tamppari, L.K., Martin, T.Z., Travis, L.D., 1999. Temperatures on Europa from Galileo photopolarimeter-radiometer: Nighttime thermal anomalies. Science 284, 1514-1516] and thermal models for the crust. In addition, their densities have been calculated in order to determine their buoyancy in the ocean, obtaining different results depending upon the salinity of the ocean and type of clathrate. For instance, assuming a eutectic composition of the system MgSO₄H₂O for the ocean, CO₂, H₂S, and CH₄ clathrates would float but SO₂ clathrate would sink to the seafloor; an ocean of much lower salinity would allow all these clathrates to sink, except that CH₄ clathrate would still float. Many geological processes may be driven or affected by the formation, presence, and destruction of clathrates in Europa such as explosive cryomagmatic activity [Stevenson, D.J., 1982. Volcanism and igneous processes in small icy satellites. Nature 298, 142-144], partial differentiation of the crust driven by its clathration, or the local retention of heat within or beneath clathrate-rich layers because of the low thermal conductivity of clathrate hydrates [Ross, R.G., Kargel, J.S., 1998. Thermal conductivity of Solar System ices, with special reference to martian polar caps. In: Schmitt, B., De Berg, C., Festou, M. (Eds.), Solar System Ices. Kluwer Academic, Dordrecht, pp. 33-62]. On the surface, destabilization of these minerals and compounds, triggered by fracture decompression or heating could result in formation of chaotic terrain morphologies, a mechanism that also has been proposed for some martian chaotic terrains [Tanaka, K.L., Kargel, J.S., MacKinnon, D.J., Hare, T.M., Hoffman, N., 2002. Catastrophic erosion of Hellas basin rim on Mars induced by magmatic intrusion into volatile-rich rocks. Geophys. Res. Lett. 29 (8); Kargel, J.S., Prieto-Ballesteros, O., Tanaka K.L., 2003. Is clathrate hydrate dissociation responsible for chaotic terrains on Earth, Mars, Europa, and Triton? Geophys. Res. 5. Abstract 14252]. Models of the evolution of the ice shell of Europa might take into account the presence of clathrate hydrates because if gases are vented from the silicate interior to the water ocean, they first would dissolve in the ocean and then, if the gas concentrations are sufficient, may crystallize. If any methane releases occur in Europa by hydrothermal or biological activity, they also might form clathrates. Then, from both geological and astrobiological perspectives, future missions to Europa should carry instrumentation capable of clathrate hydrate detection.     

CO clathrate hydrate: Near to mid-IR spectroscopic signatures

Carbon monoxide is the second most abundant molecule after H₂ in the molecular universe, and as such an abundant constituent of interstellar and Solar System ices. To trace the possibility of this molecule to be found in a clathrate hydrate inclusion compound, its pure phase FTIR spectrum is investigated. We confirm the formation of a type I clathrate structure whereas simple guest size estimates would favour a type II clathrate hydrate, revealing interactions of this molecule with its water network during clathrate formation. The observed cage vibrational downshift with respect to pure CO ice is within 5 cm⁻¹. The temperature dependent wavenumber separation between the two enclathrated CO vibrational transitions in the two distinct type I clathrate cages is less than a wavenumber below 140 K, implying that the spectral simplification for detailed spectroscopic analysis of the individual profiles is a difficult task. The dynamics of the CO molecules in its cage change considerably from 5 K to 140 K. At temperatures above 30 K, the molecule is extremely mobile in the cages, as revealed by the infrared profile, significantly different from CO entrapped in water ice and different from observed profiles in astrophysical objects.     

Near-infrared spectral monitoring of Triton with IRTF/SpeX II: Spatial distribution and evolution of ices

This report arises from an ongoing program to monitor Neptune’s largest moon Triton spectroscopically in the 0.8 to 2.4 μm range using IRTF/SpeX. Our objective is to search for changes on Triton’s surface as witnessed by changes in the infrared absorption bands of its surface ices N₂,CH₄,H₂O, CO, and CO₂. We have recorded infrared spectra of Triton on 53 nights over the ten apparitions from 2000 to 2009. The data generally confirm our previously reported diurnal spectral variations of the ice absorption bands (Grundy and Young, 2004). Nitrogen ice shows a large amplitude variation, with much stronger absorption on Triton’s Neptune-facing hemisphere. We present evidence for seasonal evolution of Triton’s N₂ ice: the 2.15 μm absorption band appears to be diminishing, especially on the Neptune-facing hemisphere. Although it is mostly dissolved in N₂ ice, Triton’s CH₄ ice shows a very different longitudinal variation from the N₂ ice, challenging assumptions of how the two ices behave. Unlike Triton’s CH₄ ice, the CO ice does exhibit longitudinal variation very similar to the N₂ ice, implying that CO and N₂ condense and sublimate together, maintaining a consistent mixing ratio. Absorptions by H₂O and CO₂ ices show negligible variation as Triton rotates, implying very uniform and/or high latitude spatial distributions for those two non-volatile ices.     

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.     

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.     

Mars CO2 cycle: Effects of airborne dust and polar cap ice emissivity

Mars General Circulation Model (GCM) simulations are presented to illustrate the importance of the ice emissivity of the seasonal CO₂ polar caps in regulating the effects of airborne dust on the martian CO₂ cycle. Simulated results show that atmospheric dust suppresses CO₂ condensation when the CO₂ ice emissivity is high but enhances it when the CO₂ ice emissivity is low. This raises the possibility that the reason for the repeatable nature of the CO₂ cycle in the presence of a highly variable dust cycle is that the CO₂ ice emissivity is “neutral” - the value that leads to no change in CO₂ condensation with changing atmospheric dust. For this GCM, the “neutral” emissivity is approximately 0.55, which is low compared to observed cap emissivities. This inconsistency poses a problem for this hypothesis. However, it is clear that the CO₂ ice emissivity is a critical physical parameter in determining how atmospheric dust affects the CO₂ cycle on 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.     

Infrared imaging spectroscopy of Mars: H2O mapping and determination of CO2 isotopic ratios

High-resolution infrared imaging spectroscopy of Mars has been achieved at the NASA Infrared Telescope Facility (IRTF) on June 19-21, 2003, using the Texas Echelon Cross Echelle Spectrograph (TEXES). The areocentric longitude was 206°. Following the detection and mapping of hydrogen peroxide H₂O₂ [Encrenaz et al., 2004. Icarus 170, 424-429], we have derived, using the same data set, a map of the water vapor abundance. The results appear in good overall agreement with the TES results and with the predictions of the Global Circulation Model (GCM) developed at the Laboratory of Dynamical Meteorology (LMD), with a maximum abundance of water vapor of 3±1.5×¹⁰⁻⁴(17±9 pr-μm). We have searched for CH₄ over the martian disk, but were unable to detect it. Our upper limits are consistent with earlier reports on the methane abundance on Mars. Finally, we have obtained new measurements of CO₂ isotopic ratios in Mars. As compared to the terrestrial values, these values are: (¹⁸O/¹⁷O)[M/E] = 1.03 ± 0.09; (¹³C/¹²C)[M/E] = 1.00 ± 0.11. In conclusion, in contrast with the analysis of Krasnopolsky et al. [1996. Icarus 124, 553-568], we conclude that the derived martian isotopic ratios do not show evidence for a departure from their terrestrial values.     

Identification of a new band system of isotopic CO2 near 3.3 μm: Implications for remote sensing of biomarker gases on Mars

We present the discovery of a new vibrational band system of isotopic CO₂ (carbon dioxide) near 3.3 μm, with multiple strong P, Q and R lines in the prime spectral region used to search for Mars CH₄ (methane). The band system was discovered on Mars using high-resolution spectrometers (λ/δλ>40,000, CSHELL and NIRSPEC) at telescopes (NASA-IRTF and Keck-2) atop Mauna Kea, HI. The observed line intensities and frequencies agree very well with values predicted by a vibrational band model that we developed using known parameters for the molecular levels involved. Using this model, we synthesized spectra for different observing conditions (from Space and ground-based telescopes) and for different spectral resolving powers (5000 to 40,000). Although the total atmospheric burden on Mars is more than 150 times smaller than on Earth, the greater mixing ratio of CO₂ ensures that its column abundance on Mars is almost 20 times greater than on Earth. Thus, weak telluric CO₂ band systems appear much stronger on Mars. Many molecules of possible biological and geothermal interest have strong signatures at these wavelengths, in particular hydrocarbons owing to their strong ro-vibrational CH stretching modes. For example, the new isotopic CO₂ band-system encompasses lines of CH₄, C₂H₆ (ethane), CH₃OH (methanol) and H₂O (water). Implications for previous and future searches of biomarker gases are presented.     

HiRISE observations of gas sublimation-driven activity in Mars’ southern polar regions: II. Surficial deposits and their origins

The High Resolution Imaging Science Experiment (HiRISE) onboard Mars Reconnaissance Orbiter (MRO) has been used to monitor the seasonal evolution of several regions at high southern latitudes and, in particular, the jet-like activity which may result from the process described by Kieffer (JGR, 112, E08005, doi:10.1029/2006JE002816, 2007) involving translucent CO₂ ice. In this work, we mostly concentrate on observations of the Inca City (81°S, 296°E) and Manhattan (86°S, 99°E) regions in the southern spring of 2007. Two companion papers, [Hansen et al. this issue] and [Portyankina et al. this issue], discuss the surface features in these regions and specific models of the behaviour of CO₂ slab ice, respectively. The observations indicate rapid on-set of activity in late winter initiating before HiRISE can obtain adequately illuminated images (Ls < 174° at Inca City). Most sources become active within the subsequent 8 weeks. Activity is indicated by the production of dark deposits surrounded by brighter bluer deposits which probably arise from the freezing out of vented CO₂ [Titus et al., 2007. AGU (abstract P41A-0188)]. These deposits originate from araneiform structures (spiders), boulders on ridges, cracks on slopes, and along linear cracks in the slab ice on flatter surfaces. The type of activity observed can often be explained qualitatively by considering the local topography. Some dark fans are observed to shorten enormously in length on a timescale of 18 days. We consider this to be strong evidence that outgassing was in progress at the time of HiRISE image acquisition and estimate a total particulate emission rate of >30 g s⁻¹ from a single typical jet feature. Brighter deposits at Inca City become increasingly hard to detect after Ls = 210°. In the Inca City region, the orientations of surficial deposits are topographically controlled. The deposition of dark material also appears to be influenced by local topography suggesting that the ejection from the vents is at low velocity (<10 m s⁻¹) and that a ground-hugging flow process (a sort of “cryo-fumarole”) may be occurring. The failure up to this point to obtain a clear detection of outgassing though stereo imaging is consistent with low level transport. The downslope orientation of the deposits may result from the geometry of the vent or from catabatic winds. At many sites, more than one ejection event appears to have occurred suggesting re-charging of the sources. Around Ls = 230°, the brightness of the surface begins to drop rapidly on north-facing slopes and the contrast between the dark deposits and the surrounding surface reduces. This indicates that the CO₂ ice slab is being lost completely in some areas at around this time. By Ls = 280°, at Inca City, the ice slab has effectively gone. CRISM band ratios and THEMIS brightness temperature measurements are consistent with this interpretation.     

Water ice in the dark dune spots of Richardson crater on Mars

Interfacial liquid water has been hypothesized to form during the seasonal evolution of the dark dune spots observed in the high latitudes of Mars. In this study we assess the presence, nature and properties of ices - in particular water ice - that occur within these spots using HIRISE and CRISM observations, as well as the LMD Global Climate Model. Our studies focus on Richardson crater (72°S, 179°E) and cover southern spring and summer (L_S=175-341°). Three units have been identified of these spots: dark core, gray ring and bright halo. Each unit show characteristic changes as the season progress. In winter, the whole area is covered by CO₂ ice with H₂O ice contamination. Dark spots form during late winter and early spring. During spring, the dark spots are located in a 10 cm thick depression compared to the surrounding bright ice-rich layer. They are spectrally characterized by weak CO₂ ice signatures that probably result from spatial mixing of CO₂ ice-rich and ice-free regions within pixels, and from mixing of surface signatures due to aerosols scattering. The bright halo shaped by winds shows stronger CO₂ absorptions than the average ice-covered terrain, which is consistent with a formation process involving CO₂ re-condensation. According to spectral, morphological and modeling considerations, the gray ring is composed of a thin layer of a few tens of μm of water ice. Two sources/processes could participate to the enrichment of water ice in the gray ring unit: (i) water ice condensation at the surface in early fall (prior to the condensation of a CO₂-rich winter layer) or during wintertime (due to cold trapping of the CO₂ layer) and (ii) ejection of dust grains surrounded by water ice by the geyser activity responsible for the dark spot. In any case, water ice remains longer in the gray ring unit after the complete sublimation of the CO₂. Finally, we also looked for liquid water in the near-IR CRISM spectra using linear unmixing modeling but found no conclusive evidence for it.     

HiRISE observations of gas sublimation-driven activity in Mars’ southern polar regions: III. Models of processes involving translucent ice

Enigmatic surface features, known as ‘spiders’, found at high southern martian latitudes, are probably caused by sublimation-driven erosion under the seasonal carbon dioxide ice cap. The Mars Reconnaissance Orbiter (MRO) High Resolution Imaging Science Experiment (HiRISE) has imaged this terrain in unprecedented details throughout southern spring. It has been postulated [Kieffer, H.H., Titus, T.N., Mullins, K.F., Christensen, P.R., 2000. J. Geophys. Res. 105, 9653-9700] that translucent CO₂ slab ice traps gas sublimating at the ice surface boundary. Wherever the pressure is released the escaping gas jet entrains loose surface material and carries it to the top of the ice where it is carried downslope and/or downwind and deposited in a fan shape. Here we model two stages of this scenario: first, the cleaning of CO₂ slab ice from dust, and then, the breaking of the slab ice plate under the pressure built below it by subliming ice. Our modeling results and analysis of HiRISE images support the gas jet hypothesis and show that outbursts happen very early in spring.     

The effect of ground ice on the Martian seasonal CO2 cycle

The mostly carbon dioxide (CO₂) atmosphere of Mars condenses and sublimes in the polar regions, giving rise to the familiar waxing and waning of its polar caps. The signature of this seasonal CO₂ cycle has been detected in surface pressure measurements from the Viking and Pathfinder landers. The amount of CO₂ that condenses during fall and winter is controlled by the net polar energy loss, which is dominated by emitted infrared radiation from the cap itself. However, models of the CO₂ cycle match the surface pressure data only if the emitted radiation is artificially suppressed suggesting that they are missing a heat source. Here we show that the missing heat source is the conducted energy coming from soil that contains water ice very close to the surface. The presence of ice significantly increases the thermal conductivity of the ground such that more of the solar energy absorbed at the surface during summer is conducted downward into the ground where it is stored and released back to the surface during fall and winter thereby retarding the CO₂ condensation rate. The reduction in the condensation rate is very sensitive to the depth of the soil/ice interface, which our models suggest is about 8 cm in the Northern Hemisphere and 11 cm in the Southern Hemisphere. This is consistent with the detection of significant amounts of polar ground ice by the Mars Odyssey Gamma Ray Spectrometer and provides an independent means for assessing how close to the surface the ice must be. Our results also provide an accurate determination of the global annual mean size of the atmosphere and cap CO₂ reservoirs, which are, respectively, 6.1 and 0.9 hPa. They also indicate that general circulation models will need to account for the effect of ground ice in their simulations of the seasonal CO₂ cycle.     

Trapping and release of gases by water ice and implications for icy bodies

The trapping and release of H₂, CO, CO₂, CH₄, Ar, Ne, and N₂ by amorphous water ice was studied experimentally under dynamic conditions, at low temperatures starting at 16°K, with gas pressure of 5 × 10^?8?10^?6 Torr. CO, CH₄, Ar, and N₂ were found to be released in three or four distinct temperature ranges, each resulting from a different trapping mechanism: (a) 30–55°K, where the gas frozen on the water ice evaporates; (b) 135–155°K, where gas is squeezed out of the water ice during the transformation of amorphous ice to cubic ice; (c) 165–190°K, where gas and water are released simultaneously, probably by the evaporation of a clathrate hydrate, and, occasionally (d) 160–175°K, where deeply buried gas is released during the transformation of cubic ice to hexagonal ice. If the third range is indeed due to clathrate formation, CO was found to form this compound. CO₂ did not form a clathrate under the experimental conditions. Excess hydrogen did not affect the occlusion of other gases. Hydrogen itself was trapped only at 16°K. Neon was not trapped at 25°K. With cubic ice, the only trapping mechanism is freezing of gas on the ice surface. No fractionation between the gas phase and the ice was observed with a mixture of CO and Ar. Massive ejection of ice grains was observed during the evaporation of the gas in three (a,c,d) out of the four ranges. The experimental results are used to explain several cometary phenomena, especially those occurring at large heliocentric distances, and are applied also to Titan's atmospheric composition and to the possible ejection of ice grains from Enceladus.     

Indications of brine related local seepage phenomena on the northern hemisphere of Mars

Springtime low albedo features, called Dark Dune Spots, on the seasonal frost covered dunes on Mars between 77°N and 84°N latitude have been analyzed. Two groups of these spots have been identified: “small” and “large” ones, where large spots have diameters above 4 m, and complex internal structure. From these “large” spots branching seepage-like features emanate and grow on the steep slopes. They show a characteristic sequence of changes: first only wind-blown features emanate from them, while later a bright circular and elevated ring forms, and dark seepage-features start from the spots. These streaks grow with a speed between 0.3 m/day and 7 m/day respectively, first only from the spots, later from all along the dune crest.During this “seepage period” the temperature is between 150 K and 180 K at a 3-9 km spatial resolution scale, indicating that CO₂ ice-free parts must be present at the observed dark spots. Around the receding northern seasonal CO₂ cap, an annulus of water ice lags behind, which is probably present in the spots too where the CO₂ frost has sublimated. Our model estimates show in the present work and in Kereszturi et al. (Kereszturi, A., Möhlmann, D., Berczi, Sz., Ganti, T., Kuti, A., Sik, A., Horvath, A. [2009b]. Icarus 201, 492-503) that the warming driven by solar insolation may produce not only interfacial water, but also bulk brines around the dune grains. The brine can support the movement of liquids and dune grains, enhances the sublimation of CO₂ frost, and produce the dark features, as well as liquid modifies the optical properties of the surface.Signs of movement of dune material after the total defrosting of the terrain is also visible but it is uncertain because of the limit of resolution. In our previous work (Kereszturi et al., 2009b) we showed that resembling seepage-like streaks at the southern hemisphere might have been formed by ephemeral interfacial water, as well as these northern features. Such wet environments may have astrobiological importance too.     

Comparison of PFS and TES observations of temperature and water vapor in the martian atmosphere

The interval from L_s = 330° in Mars Year (MY) 26 until L_s = 84° in MY 27 has been used to compare and validate measurements from the Mars Global Surveyor Thermal Emission Spectrometer (TES) and the Mars Express Planetary Fourier Spectrometer (PFS). We studied differences between atmospheric temperatures observed by the two instruments. The best agreement between atmospheric temperatures was found at 50 Pa between 40°S and 40°N latitude, where differences were within ±5 K. For other atmospheric levels, differences as large as ∼25 K were observed between the two instruments at some locations. The largest temperature differences occurred mainly over the Hellas Planitia, Argyre Planitia, Tharsis and Valles Marineris regions.On this basis we report on the variability of the martian atmosphere during the 5.5 martian years of Mars climatology obtained by combining the two data sets from TES and PFS. Atmospheric temperatures at 50 Pa responded to the global-scale dust storms of MY 25 and in MY 28 raising temperatures from ∼220 K to ∼250 K during the daytime. An atmospheric temperature of ∼140 K at 50 Pa was observed poleward of 70°N during northern winter and poleward of 60°S during southern winter each year in both the PFS and TES results. Water vapor observed by the two spectrometers showed consistent seasonal and latitudinal variations.     

Evidence for Mg-rich carbonates on Mars from a 3.9 μm absorption feature

The origin and nature of the early atmosphere of Mars is still debated. The discovery of sulfate deposits on the surface, coupled with the evidence that there are not large abundances of carbonates detectable on Mars in the optically accessible part of the regolith, leaves open different paleoclimatic evolutionary pathways. Even if carbonates are responsible for the feature observed by TES and Mini-TES at 6.76 μm, alternative hypotheses suggest that it could be due to the presence of Hydrated Iron Sulfates (HIS). Carbonates can be discerned from HIS by investigating the spectral region in which a strong overtone carbonate band is present. The Planetary Fourier Spectrometer on board the Mars Express spacecraft has acquired several thousand martian spectra in the range 1.2-45 μm since January 2004, most of which show a weak absorption feature between 3.8 and 4 μm. A similar feature was observed previously from the Earth, but its origin could not be straightforwardly ascribed to surface materials, and specifically to carbonates. Here we show the surficial nature of this band that can be ascribed to carbonate mixed with the martian soil materials. The materials that best reproduce the detected feature are Mg-rich carbonates (huntite [CaMg₃(CO₃)₄] and/or magnesite [MgCO₃]). The presence of carbonates is demonstrated in both bright and dark martian regions. An evaluation of the likeliest abundance gives an upper limit of ∼10 wt%. The widespread distribution of carbonates supports scenarios that suggest carbonate formation occurred not by precipitation in a water-rich environment but by weathering processes.