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.     

Role of H2O and CO2 Ices in Martian Climate Changes

In order to study the stability of martian climate, we constructed a two-dimensional (horizontal-vertical) energy balance model. The long-term CO₂ mass exchange process between the atmosphere and CO₂ ice caps is investigated with particular attention to the effect of planetary ice distribution on the climate stability. Our model calculation suggests that high atmospheric pressure presumed for past Mars would be unstabilized if H₂O ice widely prevailed. As a result, a cold climate state might have been achieved by the condensation of atmospheric CO₂ onto ice caps. On the other hand, the low atmospheric pressure, which is buffered by the CO₂ ice cap and likely close to the present pressure, would be unstabilized if the CO₂ ice albedo decreased. This may have led the climate into a warm state with high atmospheric pressure owing to complete evaporation of CO₂ ice cap. Through the albedo feedback mechanisms of H₂O and CO₂ ices in the atmosphere-ice cap system, Mars may have experienced warm and cold climates episodically in its history.     

A new estimate of volatile outgassing on Mars

The presence of 28% argon on Mars as calculated by Levine and Riegler and indirectly inferred from Soviet Mars-6 lander data has important implications for the outgassing history of H₂O, CO₂, and N₂ on Mars. Even if the terrestrial volatile outgassing ratio is only approximately valid for Mars, then large quantities of H₂O [of the order of 10⁵ gcm^?2 (about 10⁸ more H₂O than is currently present in the Martian atmosphere)] and about 10⁴ gcm^?2 of CO₂ (about 10³ times more CO₂ than found at present in the Martian atmosphere) and some 450 gcm^?2 of N₂ may have outgassed over the history of Mars.     

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.     

Martian volatiles: Their degassing history and geochemical fate

Observations of Mars and cosmochemical considerations imply that the total inventory of degassed volatiles on Mars is 10² to 10³ times that present in Mars' atmosphere and polar caps. The degassed volatiles have been physically and chemically incorporated into a layer of unconsolidated surface rubble (a “megaregolith”) up to 2km thick. Tentative lines of evidence suggest a high concentration (～5g/cm²) of ⁴⁰ Ar in the atmosphere of Mars. If correct, this would be consistent with a degassing model for Mars in which the Martian “surface” volatile inventory is presumed identical to that of Earth but scaled to Mars' smaller mass and surface area. The implied inventory would be: (⁴⁰Ar) = 4g/cm², (H₂O) = 1 × 10⁵g/cm², (CO₂) = 7 × 10³g/cm², (N₂) = 3 × 10²g/cm², (Cl) = 2 × 10³g/cm², and (S) = 2 × 10²g/cm². Such a model is useful for testing, but differences in composition and planetary energy history may be anticipated between Mars and Earth on theoretical grounds. Also, the model demands huge regolith sinks for the volatiles listed.If the regolith were in physical equilibrium with the atmosphere, as much as 2 × 10⁴g/cm² of H₂O could be stored in it as hard-frozen permafrost, or 5 × 10⁴g/cm² if equilibrium with the atmosphere were inhibited. Spectral measurements of Martian regolith material and laboratory measurement of weathering kinetics on simulated regolith material suggest large amounts of hydrated iron oxides and clay minerals exist in the regolith; the amount of chemically bound H₂O could be from 1 × 10⁴ to 4 × 10⁴g/cm². In an Earth-analogous model, a 2 km mixed regolith must contain the following concentrations of other volatile-containing compounds by weight: carbonates = 1.5%, nitrates = 0·3%, chlorides = 0.6%, and sulfates = 0.1%. Such concentrations would be undetectable by current Earth-based spectral reflectance measurements, and (except the nitrates) formation of the “required” amounts of these compounds could result from interaction of adsorbed H₂O and ice with primary silicates expected on Mars. Most of the CO₂ could be physically adsorbed on the regolith.Thus, maximum amounts of H₂O and other volatiles which could be stored in the Mars regolith are marginally compatible with those required by an Earth-analogous model, although a lower atmospheric ⁴⁰Ar concentration and regolith volatile inventory would be easier to reconcile with observational constraints. Differences in the ratios of H₂O and other volatiles to ⁴⁰Ar between surface volatiles on the real Mars and on an Earth-analogous Mars could result from and reflect differences in bulk composition and time history of degassing between Mars and Earth. Models relating Viking-observable parameters, e.g., (⁴⁰Ar) and (³⁶Ar), to the time history and overall intensity of Mars degassing are given.     

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.     

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.     

Temperature effect on the photodissociation rates in the atmospheres of Mars and Venus

The available solar flux at a given altitude in the atmospheres of Mars and Venus is attenuated mainly by CO₂ (molecular absorption and Rayleigh scattering) with an extra contribution due to SO₂ on Venus. The dissociation cross section of CO₂ depends on temperature. At temperatures appropriate for these atmospheres (～250°K), the cross sections are about 15% lower than those at room conditions (Y.L. Yung and W.B. De More, 1982, Icarus, 51, 199). It is shown that this temperature effect cannot be neglected in the evaluation of photolysis rates. Calculations of the photodissociation coefficients of CO₂, SO₂, HCl, and H₂O are presented. For example, at the surface of Mars, the coefficient of H₂O is nearly multiplied by a factor of 10!     

Loss of water from Mars:: Implications for the oxidation of the soil

The evolution of the martian atmosphere with regard to its H₂O inventory is influenced by thermal loss processes of H, H₂, nonthermal atmospheric loss processes of H⁺, H₂⁺, O, O⁺, CO₂, and O₂⁺ into space, as well as by chemical weathering of the surface soil. The evolution of thermal and nonthermal escape processes depend on the history of the intensity of the solar XUV radiation and the solar wind density. Thus, we use actual data from the observation of solar proxies with different ages from the Sun in Time program for reconstructing the Sun's radiation and particle environment from the present to 3.5 Gyr ago. The correlation between mass loss and X-ray surface flux of solar proxies follows a power law relationship, which indicates a solar wind density up to 1000 times higher at the beginning of the Sun's main sequence lifetime. For the study of various atmospheric escape processes we used a gas dynamic test particle model for the estimation of the pick up ion loss rates and considered pick up ion sputtering, as well as dissociative recombination. The loss of H₂O from Mars over the last 3.5 Gyr was estimated to be equivalent to a global martian H₂O ocean with a depth of about 12 m, which is smaller than the values reported by previous studies. If ion momentum transport, a process studied in detail by Mars Express is significant on Mars, the water loss may be enhanced by a factor of about 2. In our investigation we found that the sum of thermal and nonthermal atmospheric loss rates of H and all nonthermal escape processes of O to space are not compatible with a ratio of 2:1, and is currently close to about 20:1. Escape to space cannot therefore be the only sink for oxygen on Mars. Our results suggest that the missing oxygen (needed for the validation of the 2:1 ratio between H and O) can be explained by the incorporation into the martian surface by chemical weathering processes since the onset of intense oxidation about 2 Gyr ago. Based on the evolution of the atmosphere-surface-interaction on Mars, an overall global surface sink of about 2×10⁴² oxygen particles in the regolith can be expected. Because of the intense oxidation of inorganic matter, this process may have led to the formation of considerable amounts of sulfates and ferric oxides on Mars. To model this effect we consider several factors: (1) the amount of incorporated oxygen, (2) the inorganic composition of the martian soil and (3) meteoritic gardening. We show that the oxygen incorporation has also implications for the oxidant extinction depth, which is an important parameter to determine required sampling depths on Mars aimed at finding putative organic material. We found that the oxidant extinction depth is expected to lie in a range between 2 and 5 m for global mean values.     

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.     

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.     

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.     

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.     

Volatiles on Earth and Mars: A comparison

Based on our new and previous determinations of halogens in SNC meteorites, the bulk concentrations of halogens in the SPB, which is thought to be Mars, are estimated. The two-component model for the formation of terrestrial planets as proposed byA. E. Ringwood (Geochem. J. 11, 111–135 (1977) andOn the Origin of the Earth and Moon, Springer-Verlag, New York, 1979) andH. Wa¨nke (Philos. Trans. Roy. Soc. London, Ser. A 303, 287–302 (1981) is further substantiated. It is argued that almost all of the H₂O added to Mars during its homogeneous accretion was converted on reaction with metallic Fe to H₂, which escaped. By comparing the solubilities of H₂O and HCl in molten silicates, the amount of H₂O left in the mantle of Mars at the end of accretion can be related to the abundance of Cl. In this way an H₂O content in the Martian mantle of 36 ppm is obtained, corresponding to an ocean covering the whole planet to a depth of about 130 m.The huge quantities of H₂ produced by the reaction of H₂O with metallic iron should also have removed other volatile species by hydrodynamic escape. Thus it is postulated that the present atmospheres of Venus, Earth, and Mars were formed by degassing the interiors of the planets, after the production of H₂ had ceased, i.e., after metallic iron was no longer available. It is also postulated that the large differences in the amounts of primordial rare gases in the atmospheres of Venus, Earth, and Mars are due mainly to different loss factors.Except for gaseous species, Mars is found to be richer in volatile (halogens) and moderately volatile elements than the Earth. The resulting low release factor of⁴⁰Ar for Mars is attributed to a low degree of fractionation, leading to a relatively small crustal enrichment of even the most incompatible elements like K.     

Seasonal melting of surface water ice condensing in martian gullies

In this work we consider when and how much liquid water during present climate is possible within the gullies observed on the surface of Mars. These features are usually found on poleward directed slopes. We analyse the conditions for melting of H₂O ice, which seasonally condenses within the gullies. We follow full annual cycle of condensation and sublimation of atmospheric CO₂ and H₂O, accounting for the heat and mass transport in the soil. During the summer, once the facets of the gullies are exposed to the Sun the water ice can melt and evaporate. Two mid latitude locations in both hemispheres are considered. The model includes both the rough geometry of the gullies as well as the slope of the surface where the gullies appear. It is an extension of the model developed to calculate condensation of CO₂ ice in troughs of different sizes, including polygonal features on Mars (Kossacki and Markiewicz, 2002, Icarus 160, 73; Kossacki et al., 2003, Planet. Space Sci. 51, 569). We have found, that water ice accumulated during winter can undergo transition to the liquid phase after complete sublimation of CO₂ ice. The amount of liquid water depends on water content in the atmosphere and on the local wind speed. It is probably not enough to destabilise the slope and cause flow of the surface material. However, even the small amounts of liquid water predicted, can play an important role in surface chemistry, in increasing the cohesive strength of the soil's surface layer and possibly may have some exobiological implications.     

Possibilities for the detection of hydrogen peroxide-water-based life on Mars by the Phoenix Lander

The Phoenix Lander landed on Mars on 25 May 2008. It has instruments on board to explore the geology and climate of subpolar Mars and to explore if life ever arose on Mars. Although the Phoenix mission is not a life detection mission per se, it will look for the presence of organic compounds and other evidence to support or discredit the notion of past or present life.The possibility of extant life on Mars has been raised by a reinterpretation of the Viking biology experiments [Houtkooper, J. M., Schulze-Makuch, D., 2007. A possible biogenic origin for hydrogen peroxide on Mars: the Viking results reinterpreted. International Journal of Astrobiology 6, 147-152]. The results of these experiments are in accordance with life based on a mixture of water and hydrogen peroxide instead of water. The near-surface conditions on Mars would give an evolutionary advantage to organisms employing a mixture of H₂O₂ and H₂O in their intracellular fluid: the mixture has a low freezing point, is hygroscopic and provides a source of oxygen. The H₂O₂-H₂O hypothesis also explains the Viking results in a logically consistent way. With regard to its compatibility with cellular contents, H₂O₂ is used for a variety of purposes in terran biochemistry. The ability of the anticipated organisms to withstand low temperatures and the relatively high water vapor content of the atmosphere in the Martian arctic, means that Phoenix will land in an area not inimical to H₂O₂-H₂O-based life. Phoenix has a suite of instruments which may be able to detect the signatures of such putative organisms.     

Modelling of atmospheric dust extinction and surface reflectance of Mars applying a radiative transfer simulation in the 2.0 and 2.7 μm CO2 bands

Infrared radiation spectra of Mars which can be measured by an orbiting Planetary Fourier Spectrometer (PFS) have been simulated in the spectral region from 1 to 50 μm. The radiative transfer simulation technique considers absorption, emission and multiple scattering by molecular (CO₂, H₂O, CO) and particulate (palagonite) species. It is shown that the contribution from atmospheric dust extinction and surface reflectance can be separated in the region of the CO₂ bands at 2.0 and 2.7 μm. Quantitative results of simultaneous surface pressure, reflectance and aerosol optical depth retrievals are discussed.     

Comparison between polar regions of Mars from HEND/Odyssey data

In this paper, we have analyzed neutron spectroscopy data gathered by the High Energy Neutron Detector (HEND) instrument onboard Mars Odyssey for comparison of polar regions. It is known that observation of the neutron albedo of Mars provides important information about the distribution of water-ice in subsurface layers and about peculiarities of the CO₂ seasonal cycle. It was found that there are large water-rich permafrost areas with contents of up to ∼50% water by mass fraction at both the north and south Mars polar regions. The water-ice layers at high northern latitudes are placed close to the surface, but in the south they are covered by a dry and relatively thick (10-20 cm) layer of soil. Analysis of temporal variations of neutron flux between summer and winter seasons allowed the estimation of the masses of the CO₂ deposits which seasonally condense at the polar regions. The total mass of the southern seasonal deposition was estimated as 6.3×¹⁰¹⁵ kg, which is larger than the total mass of the seasonal deposition at the north by 40-50%. These results are in good agreement with predictions from the NASA Ames Research Center General Circulation Model (GCM). But, the dynamics of the condensation and sublimation processes are not quite as consistent with these models: the peak accumulation of the condensed mass of CO₂ occurred 10-15 degrees of Ls later than is predicted by the GCM.     

Martian dust particles as condensation nuclei: A preliminary assessment of mineralogical factors

Condensation of frosts on Mars should depend not only on temperature and degree of vapor supersaturation but also on the nature of dust particles that would act as condensation nuclei. For a given particle size, the favorability of a condensate nucleator is determined by (1) degree of crystallographic misfit, or disregistry (δ), between substrate and condensate, (2) chemical-bond compatibility between substrate and condensate, and (3) abundance of substrate surface defects that would encourage assembly of condensate atoms or molecules. New data on ice-forming characteristics of candidate Martian materials, obtained by differential scanning calorimetry, confirmed previous evidence for systematic variations in ice-nucleation temperature, T_in, among geologic materials. By considering individual types of minerals separately, factors (2) and (3) can be held relatively constant and differences in nucleation effectiveness can be estimated by computation of (1). Both calorimetry data and cloud-chamber (literature) data indicate that T_in varies inversely with minimum absolute value of disregistry, /δ/. On Mars, H₂OIc might be an important form of water ice whereas H₂OIh is the common form on Earth. Phase H₂OIc offers the lowest overall /δ/ values for heterogeneous nucleation of other condensates, including H₂OIh, solid CO₂, and CO₂ hydrate, suggesting that the best overall mineral nuclei might be those that most effectively nucleate H₂OIc. Based on /δ/ values, good nucleators of H₂OIc should include nonexpandable clay minerals (e.g., kaolinite, chlorite), certain zeolites (e.g., clinoptilolite), goethite, and bassanite. Although goethite might preferentially nucleate H₂OIc, hematite should preferentially nucleate H₂OIh. Cryptocrystalline mineraloids (e.g., palagonite) should be generally poor nucleators and nucleating abilities of expandable clay minerals (e.g., nontronite, montmorillonite) should vary significantly with degree of c-axis expansion, as controlled by degree of interlayer hydration.     

Climatology and first-order composition estimates of mesospheric clouds from Mars Climate Sounder limb spectra

Mesospheric clouds have been previously observed on Mars in a variety of datasets. However, because the clouds are optically thin and most missions have performed surface-focussed nadir sounding, geographic and seasonal coverage is sparse. We present new detections of mesospheric clouds using a limb spectra dataset with global coverage acquired by NASA’s Mars Climate Sounder (MCS) aboard Mars Reconnaissance Orbiter. Mesospheric aerosol layers, which can be CO₂ ice, water ice or dust clouds, cause high radiances in limb spectra, either by thermal emission or scattering of sunlight. We employ an object recognition and classification algorithm to identify and map aerosol layers in limb spectra acquired between December 2006 and April 2011, covering more than two Mars years. We use data from MCS band A4, to show thermal signatures of day and nightside features, and A6, which is sensitive to short wave IR and visible daytime features only. This large dataset provides several thousand detections of mesospheric clouds, more than an order of magnitude more than in previous studies.Our results show that aerosol layers tend to occur in two distinct regimes. They form in equatorial regions (30°S–30°N) during the aphelion season/northern hemisphere summer (L_s < 150°), which is in agreement with previous published observations of mesospheric clouds. During perihelion/dust storm season (L_s > 150°) a greater number of features are observed and are distributed in two mid-latitude bands, with a southern hemisphere bias. We observe temporal and longitudinal clustering of cloud occurrence, which we suggest is consistent with a formation mechanism dictated by interaction of broad temperature regimes imposed by global circulation and the propagation to the mesosphere of small-scale dynamics such as gravity waves and thermal tides.Using calculated frost point temperatures and a parameterization based on synthetic spectra we find that aphelion clouds are present in generally cooler conditions and are spectrally more consistent with H₂O or CO₂ ice. A significant fraction has nearby temperature retrievals that are within a few degrees of the CO₂ frost point, indicating a CO₂ composition for those clouds. Perihelion season clouds are spectrally most similar to H₂O ice and dust aerosols, consistent with temperature retrievals near to the clouds that are 30–80 K above the CO₂ frost point.