Regolith-atmosphere exchange of water and carbon dioxide on Mars: Effects on atmospheric history and climate change

Exchange of CO₂ and H₂O between the Mars regolith and the atmosphere-cap system plays an important role in governing the evolution of the martian atmosphere and the martian climate. Most of the exchangeable CO₂ (perhaps one or two orders of magnitude more than the atmospheric inventory) is currently adsorbed on the deep regolith, and can be “cryopumped” to a large quasipermanent CO₂ cap (not now present) during lowest Mars obliquity (θ). During the obliquity driven regolith-cap CO₂ exchange cycle, the atmospheric pressure varies harmonically between ~0.1 mb (lowest Θ) and ? 20 mb (highest Θ). The regolith buffer plays only a small or negligible role in the seasonal CO₂ pressure variations caused by atmosphere-cap exchange because adsorption greatly inhibits diffusion of the seasonal “pressure wave” into the regolith. In contrast, thermally driven H₂O seasonal exchange between the atmosphere and regolith appears to be in large part responsible for observed seasonal variations in the small atmospheric H₂O inventory. Long term exchange of H₂O may be dominated by transfer between the polar caps and ice in the regolith. Available and potential tests of regolith-atmospheric-cap volatile exchange models using ground-based and spacecraft-based techniques are discussed.     

Carbon dioxide-water clathrate as a reservoir of CO2 on Mars

It has been suggested that the residual polar caps of Mars contain a reservoir of permanently frozen carbon dioxide which is controlling the atmospheric pressure. However, observational data and models of the polar heat balance suggest that the temperatures of the Martian poles are too high for solid CO₂ to survive permanently. On the other hand, the icelike compound carbon dioxide-water clathrate (CO₂ · 6H₂O) could function as a CO₂ reservoir instead of solid CO₂, because it is stable at higher temperatures. This paper shows that the permanent polar caps may contain several millibars of CO₂ in the form of clathrate, and discusses the implications of this permanent clathrate reservoir for the present and past atmospheric pressure on Mars.     

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.     

PFS-MEX observation of ices in the residual south polar cap of Mars

The Mars Express spacecraft has a highly inclined orbit around Mars and so has been able to observe the south pole of Mars in illuminated conditions at the end of the southern summer (L_s=330). Spectra from the planetary Fourier spectrometer (PFS) short wavelength (SW) channel were recorded over the permanent ice cap to study its composition in terms of CO₂ ice and H₂O ice. Models are fitted to the observed data, which include a spatial mixture of soil (not covered by ice) and CO₂ frost (with a specific grain size and a small amount of included dust and H₂O ice). Two different kinds of spectra were observed: those over the permanent polar cap with almost pure CO₂ ice, negligible water ice, no soil fraction required, and bright; and those over mixed terrain (at the edge of the cap or near troughs) containing a significant soil spatial fraction, more water ice and smaller CO₂ grain size. The amount of water ice given by fits to scaled albedo models is less than 10 ppm by weight. When using multi-stream reflectance models with the appropriate lighting geometry, the water amount must be 2-5 times greater than the albedo fit (less than 50 ppm). At the periphery of the residual polar cap, we found a region almost completely covered by water frost, modeled as a mixture of micron-sized and sub-mm sized grains. Our result using a granular mixture of micron-sized grains of water ice and dust with the CO₂ grains is different from the modeling of OMEGA polar cap observations using molecular mixtures.     

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.     

Martian Seasonal CO2 Ice in Polygonal Troughs in Southern Polar Region: Role of the Distribution of Subsurface H2O Ice

The Mars Orbiter Camera onboard the Mars Global Surveyor has obtained several images of polygonal features in the southern polar region. In images taken during the end of the southern spring, when the surrounding surface is free of the seasonal frost, CO₂ ice still appears to be present within the polygonal troughs. In Earth's polar regions, polygons such as these are indicative of water ice in the ground below. We analyzed the seasonal evolution of the thermal state and the CO₂ content of these features. Our 2-D model includes condensation and sublimation of the CO₂ ice, a self consistent treatment of the variations of the thermal properties of the regolith, and the seasonal variations of the local atmospheric pressure which we take from the results of a general circulation model. We find that the residence time of seasonal CO₂ ice in troughs depends not only on atmospheric opacity and albedo of the CO₂ ice, but also and most significantly on the distribution of water ice in the regolith. Optical properties of the atmosphere and surface CO₂ ice can be independently obtained from observations. To date this is not true about the distribution of water ice below the surface. Our analysis quantifies the dependence of the seasonal cycle of the CO₂ ice within the troughs on the assumed distribution of the water ice below the surface. We show that presence of water ice in the ground at a depth smaller than the depth of the troughs reduces winter condensation rate of CO₂ ice. This is due to higher heat flux conducted from the water ice rich regolith toward the facets of the troughs.     

The astronomical theory of climatic change on Mars

We examine the response of Martian climate to changes in solar energy deposition caused by variations of the Martian orbit and obliquity. We systematically investigate the seasonal cycles of carbon dioxide, water, and dust to provide a complete picture of the climate for various orbital configurations. We find that at low obliquity (15°) the atmospheric pressure will fall below 1 mbar; dust storms will cease; thick permanent CO₂ caps will form; the regolith will release CO₂; and H₂O polar ice sheets will develop as the permafrost boundaries move poleward. At high obliquity (35°) the annual average polar temperature will increase by about 10°K, slightly desorbing the polar regolith and causing the atmospheric pressure to increase by not more than 10 to 20 mbar. Summer polar ground temperatures as high as 273°K will occur. Water ice caps will be unstable and may disappear as the equilibrium permafrost boundary moves equatorward. However, at high eccentricity, polar ice sheets will be favored at one pole over the other. At high obliquity dust storms may occur during summers in both hemispheres, independent of the eccentricity cycle. Eccentricity and longitude of perihelion are most significant at modest obliquity (25°). At high eccentricity and when the longitude of perihelion is close to the location of solstice hemispherical asymmetry in dust-storm generation and in polar ice extent and albedo will occur.The systematic examination of the relation of climate and planetary orbit provides a new theory for the formation of the polar laminae. The terraced structure of the polar laminae originates when eccentricity and/or obliquity variations begin to drive water ice off the dusty permanent H₂O polar caps. Then a thin (meters) layer of consolidated dust forms on top of a dirty, slightly thicker (tens of meters) ice sheet and the composite is preserved as a layer of laminae composed predominately of water ice. Because of insolation variation on slopes, a series of poleward- and equatorward-facing scarps are formed where the edges of the laminae are exposed. Independently of orbital variations, these scarps propagate poleward both by erosion of the equatorward slopes and by deposition on the poleward slopes. Scarp propagation resurfaces and recycles the laminae forming the distinctive spiral bands of terraces observed and provides a supply of water to form new permanent ice caps. The polar laminae boundary marks the furthest eqautorward extension of the permanent H₂O caps as the orbit varies. The polar debris boundary marks the furthest equatorward extension of the annual CO₂ caps as the orbit varies.The Martian regolith is now a significant geochemical sink for carbon dioxide. CO₂ has been irreversibly removed from the atmosphere by carbonate formation. CO₂ has also benn removed by regolith adsorption. Polar temperature increases caused by orbital variations are not great enough     

Liquid water on Mars: An energy balance climate model for CO2/H2O atmospheres

Geologic evidence of the prior existence of liquid water on Mars suggests surface temperatures T_s were once considerably warmer than at present; and that such a condition may have arisen from a larger atmospheric greenhouse. Here we develop a simple climate model for a CO₂/H₂O Mars atmosphere including water vapor-longwave opacity feedback in the atmosphere and temperature-albedo feedback at surface icecaps, under the assumption that once the Martian surface pressure was p_s ≥ 1 atm CO₂. Longwave flux to space is computed as a function of T_s and p_s using band-absorption models for the effect of the 15-μm fundamental, and the 10- and 15-μm hot bands, of the CO₂ molecule; as well as the pure rotation bands and e continuum of H₂O. The derived global radiative balance predicts a global mean surface temperature of 283°K at 1 atm CO₂. When the emission model is coupled to a latitudinally resolved energy balance climate model, including the effect of poleward heat transfer by atmospheric baroclinic eddies, the solutions vary, depending on p_s. We considered two cases: (1) the present Mars (p_s ? 0.007 atm) with pressure-buffering by solid CO₂ icecaps, and limited poleward heat flux by the atmosphere; and (2) a hypothetical “hot Mars” (p_s ? 1.0 atm), whose much higher CO₂ amount augmented by H₂O evaporative feedback yields a theoretical T_s distribution with latitude admitting liquid water over 95% of the surface, water icecaps at the poles, and a diminished equator-to-pole temperature gradient relative to the present.     

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.     

Albedo models for the residual south polar cap on Mars: Implications for the stability of the cap under near-perihelion global dust storm conditions

It is uncertain whether the residual (perennial) south polar cap on Mars is a transitory or a permanent feature in the current Martian climate. While there is no firm evidence for complete disappearance of the cap in the past, clearly observable changes have been documented. Observations suggest that the perennial cap lost more CO₂ material in the spring/summer season prior to the Mariner 9 mission than in those same seasons monitored by Viking and Mars Global Surveyor. In this paper we examine one process that may contribute to these changes—the radiative effects of a planet encircling dust storm that starts during late Martian southern spring on the stability of the perennial south polar cap. To approach this, we model the radiative transfer through a dusty planetary atmosphere bounded by a sublimating CO₂ surface.A critical parameter for this modeling is the surface albedo spectrum from the near-UV to the thermal-IR, which was determined from both space-craft and Earth-based observations covering multiple wavelength regimes. Such a multi-wavelength approach is highly desirable since one spectral band by itself cannot tightly constrain the three-parameter space for polar surface albedo models, namely photon “scattering length” in the CO₂ ice and the amounts of intermixed water and dust.Our results suggest that a planet-encircling dust storm with onset near solstice can affect the perennial cap's stability, leading to advanced sublimation in a “dusty” year. Since the total amount of solid CO₂ removed by a single storm may be less than the total CO₂ thickness, a series of dust storms would be required to remove the entire residual CO₂ ice layer from the south perennial cap.     

Interannual and seasonal behavior of Martian residual ice-cap albedo

The Mars Orbiter Laser Altimeter (MOLA), functioning as a high-resolution radiometer, has observed several appearances of the Martian residual ice caps. We examine these data to quantify both seasonal behavior and interannual differences. The northern residual cap (NRC) was found to be mostly stable with the exception of one, previously identified, region of strong variability. Interannual change in the extent of the NRC appears to be small and reversible on timescales of 1 or 2 years. The NRC has an elaborate seasonal evolution of albedo. Annuli of fine-grained CO₂ and water frost, which track the inner and outer edges of the seasonal CO₂ cap, cause large temporary brightenings. The NRC albedo is stable from just after solstice to L_s 150°, after which albedo decreases steadily. This late-summer darkening can be explained by shadowing within the rough topography of the NRC, leading to a lower limit on topographic relief of 80 cm. The southern residual cap (SRC) appears stable in extent. As has been previously discovered, its seasonal frost albedo behavior appears to be correlated with insolation. However, residual CO₂ appears not to share this characteristic; we use this behavioral difference to infer net deposition of CO₂ ice on the SRC during 1 out of 3 years. Uncharacteristically, the SRC abruptly darkens at L_s 320° in 1 Martian year (year beginning April 2002). Circumstantial evidence suggests atmospheric scattering by dust is responsible. The 2001 global dust-storm appears, either, to have had no effect on the polar cap albedos, or, resulted in slightly brighter ice deposits.     

Constraints on the composition of the martian south polar cap from gravity and topography

The polar caps of Mars have long been acknowledged to be composed of unknown proportions of water ice, solid CO₂ (dry ice), and dust. Gravity and topography data are here analyzed over the southern cap to place constraints on its density, and hence composition. Using a localized spectral analysis combined with a lithospheric flexure model of ice cap loading, the best fit density of the volatile-rich south polar layered deposits is found to be 1271 kg m⁻³ with 1-σ limits of 1166 and 1391 kg m⁻³. The best fit elastic thickness of this geologically young deposit is 140 km, though any value greater than 102 km can fit the observations. The best fit density implies that about 55% dry ice by volume could be sequestered in these deposits if they were completely dust free. Alternatively, if these deposits were completely free of solid CO₂, the dust content would be constrained to lie between about 14 and 28% by volume. The bulk thermal conductivity of the polar cap is not significantly affected by these maximum allowable concentrations of dust. However, even if a moderate quantity of solid CO₂ were present as horizontal layers, the bulk thermal conductivity of the polar cap would be significantly reduced. Reasonable estimates of the present day heat flow of Mars predict that dry ice beneath the thicker portions of the south polar cap would have melted. Depending on the quantity of solid CO₂ in these deposits today, it is even possible that water ice could melt where the cap is thickest. If independent estimates for either the dust or CO₂ content of the south polar cap could be obtained, and if radar sounding data could determine whether this polar cap is presently experiencing basal melting or not, it would be possible to use these observations to place tight constraints on the present day heat flow of Mars.     

Quantum chemical calculation on the potential energy surface of H2CO3 and its implication for martian chemistry

A detailed theoretical study of the potential energy surface of H₂CO₃ is explored at the CCSD(T)//B3LYP/aug-cc-pVTZ level. On the potential energy surface, 12 isomers of H₂CO₃ are located. Their molecular properties such as geometries, vibrational frequencies, rotational constants, dipole moments, gas-phase acidities, and relative energies are calculated. Various reaction pathways and decomposition products have also been discussed. Among these products, CO₂ and H₂O are definitely the most favorable products with predominant abundance. Large energy barriers are predicted for other dissociation channels leading to the formation of oxygen, formaldehyde, and so on. These high energy channels are not important thermodynamically and kinetically, but they might occur in the presence of cosmic rays in astronomic environments. From the present work we suggest that chemical reactions between CO₂ and H₂O at the polar ice caps could be a potential source of H₂CO and O₂, in addition to the previously proposed mechanisms, i.e., the oxidation of methane and cosmic-ray-mediated production through the intermediate H₂CO₃. The results of the present work may provide useful data to improve our understanding of icy chemistry at the polar caps on Mars.     

Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures

We present near-IR spectra of solid CO₂ in H₂O and CH₃OH, and find they are significantly different from that of pure solid CO₂. Peaks not present in either pure H₂O or pure CO₂ spectra become evident when the two are mixed. First, the putative theoretically forbidden CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹), that is absent from our spectrum of pure solid CO₂, is prominent in the spectra of H₂O/CO₂=5 and 25 mixtures. Second, a 2.74-μm (3650 cm⁻¹) dangling OH feature of H₂O (and a potentially related peak at 1.89 μm) appear in the spectra of CO₂-H₂O ice mixtures, but are probably not diagnostic of the presence of CO₂. Other CO₂ peaks display shifts in position and increased width because of intermolecular interactions with H₂O. Warming causes some peak positions and profiles in the spectrum of a H₂O/CO₂=5 mixture to take on the appearance of pure CO₂. Absolute strengths for absorptions of CO₂ in solid H₂O are estimated. Similar results are observed for CO₂ in solid CH₃OH. Since the CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹) is not present in pure CO₂ but prominent in mixtures, it may be a good observational (spectral) indicator of whether solid CO₂ is a pure material or intimately mixed with other molecules. These observations may be applicable to Mars polar caps as well as outer Solar System bodies.     

CO2 permafrost and Martian topography

The role of CO₂ permafrost as an erosive agent on Mars is considered. In the CO₂H₂O system, with a CO₂ triple point at 217°K and 5.1-bar pressure, carbon dioxide solid, liquid, or gas, CO₂ clathrate, and ice are possible stable phases in the range of temperatures and pressures likely to be encountered in the Martian regolith. It is argued that conditions may exist in which CO₂ permafrost is extensive on Mars, provided that adequate CO₂ is available: the maximum ratio of H₂O:CO₂ required in the subsurface pore space system is 17:3. Erosional processes likely to result from such permafrost are block slumping, leading to canyon development; pit chains along faults; chaotic terrain where massive permafrost destruction has occured; large-scale flows of slurry; and perhaps even the flash floods which create channels.     

South polar residual cap of Mars: Features, stratigraphy, and changes

The south residual polar cap of Mars, rich in CO₂ ice, is compositionally distinct from the north residual cap which is dominantly H₂O ice. The south cap is also morphologically distinct, displaying a bewildering variety of depressions formed in thin layered deposits, which have been observed to change by scarp retreat over an interval of one Mars year (Malin et al., 2001, Science 294, 2146-2148). The climatically sensitive locale of the residual caps suggests that their behavior may help in the interpretation of recent fluctuations or repeatability of the Mars climate. We have used Mars Global Surveyor Mars Orbiter Camera (MOC) images obtained in three southern summers to map the variety of features in the south residual cap and to evaluate changes over two Mars years (Mars y). The images show that there are two distinct layered units which were deposited at different times separated by a period of degradation. The older unit, ∼10 m thick, has layers approximately 2 m thick. The younger unit has variable numbers of layers, each ∼1 m thick. The older unit is eroding by scarp retreat averaging 3.6 m/Mars y, a rate greater than the retreat of 2.2 m/Mars y observed for the younger unit. The rates of scarp retreat and sizes of the different types of depressions indicate that the history of the residual cap has been short periods of deposition interspersed with longer erosional periods. Erosion of the older unit probably occupied ∼100-150 Mars y. One layer may have been deposited after the Mariner 9 observations in 1972. Residual cap layers appear to differ from normal annual winter deposits by having a higher albedo and perhaps by having higher porosities. These properties might be produced by differences in the depositional meteorology that affect the fraction of high porosity snow included in the winter deposition.     

Albedo control of seasonal South Polar cap recession on Mars

Over the last few decades, General Circulation Models (GCM) have been used to simulate the current martian climate. The calibration of these GCMs with the current seasonal cycle is a crucial step in understanding the climate history of Mars. One of the main climatic signals currently used to validate GCMs is the annual atmospheric pressure cycle. It is difficult to use changes in seasonal deposits on the surface of Mars to calibrate the GCMs given the spectral ambiguities between CO₂ and H₂O ice in the visible range. With the OMEGA imaging spectrometer covering the near infra-red range, it is now possible to monitor both types of ice at a spatial resolution of about 1 km. At global scale, we determine the change with time of the Seasonal South Polar Cap (SSPC) crocus line, defining the edge of CO₂ deposits. This crocus line is not symmetric around the geographic South Pole. At local scale, we introduce the snowdrop distance, describing the local structure of the SSPC edge. Crocus line and snowdrop distance changes can now be used to calibrate GCMs. The albedo of the seasonal deposits is usually assumed to be a uniform and constant parameter of the GCMs. In this study, albedo is found to be the main parameter controlling the SSPC recession at both global and local scale. Using a defrost mass balance model (referred to as D-frost) that incorporates the effect of shadowing induced by topography, we show that the global SSPC asymmetry in the crocus line is controlled by albedo variations. At local scale, we show that the snowdrop distance is correlated with the albedo variability. Further GCM improvements should take into account these two results. We propose several possibilities for the origin of the asymmetric albedo control. The next step will be to identify and model the physical processes that create the albedo differences.     

PFS/MEX observations of the condensing CO2 south polar cap of Mars

The condensing CO₂ south polar cap of Mars and the mechanisms of the CO₂ ice accumulation have been studied through the analysis of spectra acquired by the Planetary Fourier Spectrometer (PFS) during the first two years of ESA's Mars Express (MEX) mission. This dataset spans more than half a martian year, from Ls∼330° to Ls∼194°, and includes the southern fall season which is found to be extremely important for the study of the residual south polar cap asymmetry. The cap expands symmetrically and with constant speed during the fall season. The maximum extension occurs sometime in the 80°-90° Ls range, when the cap edges are as low as −40° latitude. Inside Hellas and Argyre basins, frost can be stable at lower latitudes due to the higher pressure values, causing the seasonal cap to be asymmetric. Within the seasonal range considered in this paper, the cap edge recession rate is approximately half the rate at which the cap edge expanded. The longitudinal asymmetries reduce during the cap retreat, and disappear around Ls∼145°. Two different mechanisms are responsible for CO₂ ice accumulation during the fall season, especially in the 50°-70° Ls range. Here, CO₂ condensation in the atmosphere, and thus precipitation, is allowed exclusively in the western hemisphere, and particularly in the longitudinal corridor of the perennial cap. In the eastern hemisphere, the cap consists mainly of CO₂ frost deposits, as a consequence of direct vapor deposition. The differences in the nature of the surface ice deposits are the main cause for the residual south polar cap asymmetry. Results from selected PFS orbits have also been compared with the results provided by the martian general circulation model (GCM) of the Laboratoire de Météorologie dynamique (LMD) in Paris, with the aim of putting the observations in the context of the global circulation. This first attempt of cross-validation between PFS measurements and the LMD GCM on the one hand confirms the interpretation of the observations, and on the other hand shows that the climate modeling during the southern polar night on Mars is extremely sensitive to the dynamical forcing.     

A model for the evolution of CO2 on Mars

We have constructed a model that predicts the evolution of CO2 on Mars from the end of the heavy bombardment period to the present. The model draws on published estimates of the main processes believed to affect the fate of CO2 during this period: chemical weathering, regolith uptake, polar cap formation, and atmospheric escape. Except for escape, the rate at which these processes act is controlled by surface temperatures which we calculate using a modified version of the Gierasch and Toon energy balance model (1973, J. Atmos. Sci. 30, 1502-1508). The modifications account for the change in solar luminosity with time, the greenhouse effect, and a polar and solar equatorial energy budget. Using published estimates for the main parameters, we find no evolutionary scenario in which CO2 is capable of producing a warm (global mean temperatures>250 K) and wet (surface pressures>30 mbar) early climate, and then evolves to present conditions with approximately 7 mbar in the atmosphere, <300 mbar in the regolith, and <5 mbar in the caps. Such scenarios would only exist if the early sun were brighter than standard solar models suggest, if greenhouse gases other than CO2 were present in the early atmosphere, or if the polar albedo were significantly lower than 0.75. However, these scenarios generally require the storage of large amounts of CO2 (>1 bar) in the carbonate reservoir. If the warm and wet early Mars constraint is relaxed, then we find best overall agreement with present day reservoirs for initial CO2 inventories of 0.5-1.0 bar. We also find that the polar caps can a profound effect on how the system evolves. If the initial amount of CO2 is less than some critical value, then there is not enough heating of the poles to prevent permanent caps from forming. Once formed, these caps control how the system evolves, because they set the surface pressure and, hence, the thermal environment. If the initial amount of CO2 is greater than this critical value, then caps do not form initially, but can form later on, when weathering and escape lower the surface pressure to a point at which polar heating is no longer sufficient to prevent cap formation and the collapse of the climate system. Our modeling suggests this critical initial amount of CO2 is between 1 and 2 bar, but its true value will depend on all factors affecting the polar heat budget.     

Tracking the edge of the south seasonal polar cap of Mars

The advance and retreat of the polar caps were one of the first observations that indicated Mars had seasons. Because a large portion of the atmosphere is cycled in and out of the seasonal caps during the year, the frost deposits play a significant role in regional and global atmospheric circulation. Understanding the nature of the seasonal polar caps is imperative if we are to understand the current Martian climate. In this study, we track the seasonal cap edges as a function of season and longitude for the fall and winter seasons (MY27), using data from the Planetary Fourier Spectrometer (PFS) onboard the Mars Express (MEX) ESA mission. Making use of the rapid rise (decrease) in surface temperature that occurs when CO₂ ice is removed (deposited), in a first approach, we defined the advancing cap edge to be where the surface temperature drops below 150 K, and the retreating cap edge where the surface temperature rises above 160 K. In this case, starting from Ls∼50°, the edge progression speed start to be longitude dependent. In the hemisphere that extends form the eastern limit of the Hellas basin to the western limit of the Argyrae basin (and containing the two) the edges progression speed is about a half than that of the other hemisphere; the cap is thus asymmetric and, unexpectedly, no CO₂ ice seems to be present inside the basins. This is because the above mentioned surface temperatures used in this approach to detect the cap edges are not adequate (too low) for the high-pressure regions inside the basins where, following the Clausius–Clapeyron's law, the CO₂ condensation temperature can be several degrees higher than that of the adjacent lower-pressure regions. In the second, final approach, special attention has been given to this aspect and the advancing and retreating cap edges are defined where, respectively, the surface temperatures drop below and rise above the CO₂ condensation temperature for the actual surface pressure values. Now, the results show an opposite situation than the previous one, with the progression speed being higher and the cap more extended (up to −30° latitude) in the hemisphere containing the two major Martian basins. During the fall season, up to Ls∼50° the South Martian polar cap consists of CO₂ frost deposits that advance towards lower latitudes at a constant speed of 10° of latitude per 15 degrees of Ls. The maximum extension (−40° latitude) of the South polar cap occurs somewhere in the 80°–90° Ls range. At the winter solstice, when the edges of the polar night start moving poleward, the cap recession has already started, in response to seasonal changes in insolation. The CO₂ ice South polar cap will recede with a constant speed of ∼5° of latitude every 25° degrees of Ls during the whole winter. The longitudinal asymmetries reduce during the cap retreat and completely disappear around Ls=145°.