The texture of condensed CO2 on the martian polar caps

The widespread deposition of CO₂ ice on the martian polar caps in winter is readily visible from Earth and has been extensively studied from orbit. As the surface cools during polar night, CO₂ condenses directly out of the atmosphere at a rate that establishes equilibrium between radiative loss and latent heat of condensation. Since radiative loss is strongly geometry-dependent, the CO₂ frost will grow most rapidly on exposed surfaces and more slowly in depressions. Positive feedback will cause a dramatic enhancement of the relief of the underlying topography and a corresponding reduction in the average bulk density. The resulting surface will be highly textured and riddled with perforations.     

The martian mesosphere as revealed by CO2 cloud observations and General Circulation Modeling

Different missions have observed mesospheric clouds on Mars in the last years. The presence of these clouds implies, among other conditions, mesospheric temperatures below CO₂ condensation temperature. We use a General Circulation Model to study the mesospheric temperatures and compare the observed distribution of the mesospheric clouds and the predicted climatology of mesospheric temperatures. Although the model does not usually predict temperatures below condensation for daytime conditions, in some regions the predicted temperatures are close enough to condensation that perturbations caused by small scale processes could produce local excursions below condensation. The location and time of the lowest temperatures predicted by the GCM correspond to a first order with the two observed populations of mesospheric clouds: equatorial clouds observed before and after the Northern summer solstice, and mid-latitude clouds observed around the Northern winter solstice. For the equatorial clouds season, the model predicts temperatures close to condensation at the longitude, latitude, altitude and local time where they have been observed. We find that the diurnal migrating thermal tide and non-migrating tides are at the root of the spatial confinement of the equatorial clouds. For the mid-latitude clouds season, the temperatures predicted by the model at the location of the observed clouds is too high. Stereo observations by two different instruments allow for the determination of the zonal speed of these clouds producing a rare dataset of mesospheric winds. We compare the mesospheric zonal winds predicted by the model with these observations, finding a good agreement, although in some cases the observed variability exceeds that predicted by the model.     

Sublimation of the Martian CO2 Seasonal South Polar Cap

The polar condensation/sublimation of CO₂, that involve about one fourth of the atmosphere mass, is the major Martian climatic cycle. Early observations in visible and thermal infrared have shown that the sublimation of the Seasonal South Polar Cap (SSPC) is not symmetric around the geographic South Pole.Here we use observations by OMEGA/Mars Express in the near-infrared to detect unambiguously the presence of CO₂ at the surface, and to estimate albedo. Second, we estimate the sublimation of CO₂ released in the atmosphere and show that there is a two-step process. From Ls=180° to 220°, the sublimation is nearly symmetric with a slight advantage for the cryptic region. After Ls=220° the anti-cryptic region sublimation is stronger. Those two phases are not balanced such that there is 22% ± 9 more mass the anti-cryptic region, arguing for more snow precipitation. We compare those results with the MOLA height measurements. Finally we discuss implications for the Martian atmosphere about general circulation and gas tracers, e.g. Ar.     

The H2O and CO2 adsorption properties of phyllosilicate-poor palagonitic dust and smectites under martian environmental conditions

The recent detection of up to ∼10 wt% water-equivalent H heterogeneously distributed in the upper meter of the equatorial regions of the martian surface and the presence of the 3-μm hydrations feature across the entire planet raises the question whether martian surficial dust can account for this water-equivalent H. We have investigated the H₂O and CO₂ adsorption properties of palagonitic dust (<5 μm size fraction of phyllosilicate-poor palagonitic tephra HWMK919) as a martian dust analog and two smectites under simulated martian equatorial surface conditions. Our results show that the palagonitic dust, which contains hydrated and hydroxylated volcanic glass of basaltic composition, accommodates significantly more H₂O under comparable humidity and temperature conditions than do the smectites nontronite and montmorillonite.     

H-implantation in SO2 and CO2 ices

Ices in the solar system are observed on the surface of planets, satellites, comets and asteroids where they are continuously subordinate at particle fluxes (cosmic ions, solar wind and charged particles caught in the magnetosphere of the planets) that deeply modify their physical and structural properties. Each incoming ion destroys molecular bonds producing fragments that, by recombination, form new molecules also different from the original ones. Moreover, if the incoming ion is reactive (H⁺, Oⁿ⁺, Sⁿ⁺, etc.), it can concur to the formation of new molecules.Those effects can be studied by laboratory experiments where, with some limitation, it is possible to reproduce the astrophysical environments of planetary ices.In this work, we describe some experiments of 15-100 keV H⁺ and He⁺ implantation in pure sulfur dioxide (SO₂) at 16 and 80 K and carbon dioxide (CO₂) at 16 K ices aimed to search for the formation of new molecules. Among other results we confirm that carbonic acid (H₂CO₃) is formed after H-implantation in CO₂, vice versa H-implantation in SO₂ at both temperatures does not produce measurable quantity of sulfurous acid (H₂SO₃). The results are discussed in the light of their relevance to the chemistry of some solar system objects, particularly of Io, the innermost of Jupiter's Galilean satellites, that exhibits a surface very rich in frost SO₂ and it is continuously bombarded with H⁺ ions caught in Jupiter's magnetosphere.     

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.     

Release of N2, CH4, CO2, and H2O from surface ices on Enceladus

We vapor deposit at 20 K a mixture of gases with the specific Enceladus plume composition measured in situ by the Cassini INMS [Waite, J.H., Combi, M.R., Ip, W.H., Cravens, T.E., McNutt, R.L., Kasprzak, W., Yelle, R., Luhmann, J., Niemann, H., Gell, D., Magee, B., Fletcher, G., Lunine, J., Tseng, W.L., 2006. Science 311, 1419-1422] to form a mixed molecular ice. As the sample is slowly warmed, we monitor the escaping gas quantity and composition with a mass spectrometer. Pioneering studies [Schmitt, B., Klinger, J., 1987. Different trapping mechanisms of gases by water ice and their relevance for comet nuclei. In: Rolfe, E.J., Battrick, B. (Eds.), Diversity and Similarity of Comets. SP-278. ESA, Noordwijk, The Netherlands, pp. 613-619; Bar-Nun, A., Kleinfeld, I., Kochavi, E., 1988. Phys. Rev. B 38, 7749-7754; Bar-Nun, A., Kleinfeld, I., 1989. Icarus 80, 243-253] have shown that significant quantities of volatile gases can be trapped in a water ice matrix well above the temperature at which the pure volatile ice would sublime. For our Enceladus ice mixture, a composition of escaping gases similar to that detected by Cassini in the Enceladus plume can be generated by the sublimation of the H₂O:CO₂:CH₄:N₂ mixture at temperatures between 135 and 155 K, comparable to the high temperatures inferred from the CIRS measurements [Spencer, J.R., Pearl, J.C., Segura, M., Flasar, F.M., Mamoutkine, A., Romani, P., Buratti, B.J., Hendrix, A.R., Spilker, L.J., Lopes, R.M.C., 2006. Science 311, 1401-1405] of the Enceladus “tiger stripes.” This suggests that the gas escape phenomena that we measure in our experiments are an important process contributing to the gases emitted from Enceladus. A similar experiment for ice deposited at 70 K shows that both the processes of volatile trapping and release are temperature dependent over the temperature range relevant to Enceladus.     

CO2 distribution on Mars

Ground-based observations of the CO₂ distribution on Mars were made this past opposition from Cerro Tololo Interamerican Observatory. Almost complete coverage of the Martian surface from 40°N to 60°S was obtained. Agreement with previous Kitt Peak observations is good, and confirmation of a pressure anomaly in the Tharsis region has been obtained. The ridge whose eastern slope is Syrtis Major stops at about 15°S, in agreement with the 1971 radar data. The Noachis-Hellas region south of Syrtis Major appears at about average altitude, indicating that the dust storm of 1971 was already active in that region as early as the end of August.     

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.     

Kinetics of CO2 production on venus

Consideration of theoretical limits and experimental data for the kinetics of the reaction quartz + calcite → wollastonite + CO₂ supports the concept of a shortterm quasiequilibrium state for the atmosphere of Venus. These data indicate that the time scale of this reaction and of any competing CO₂ producing reaction may be as short as several hundred years or less at the inferred Venus surface temperatures.     

The natural latitudinal distribution of atmospheric CO2

Although poorly understood, the north–south distribution of the natural component of atmospheric CO₂ offers information essential to improving our understanding of the exchange of CO₂ between the atmosphere, oceans, and biosphere. The natural or unperturbed component is equivalent to that part of the atmospheric CO₂ distribution which is controlled by non-anthropogenic CO₂ fluxes from the ocean and terrestrial biosphere. Models should be able to reproduce the true north–south gradient in CO₂ due to the natural component before they can reliably estimate present-day CO₂ sources and sinks and predict future atmospheric CO₂. We have estimated the natural latitudinal distribution of atmospheric CO₂, relative to the South Pole, using measurements of atmospheric CO₂ during 1959–1991 and corresponding estimates of anthropogenic CO₂ emissions to the atmosphere. Key features of the natural latitudinal distribution include: (1) CO₂ concentrations in the northern hemisphere that are lower than those in the southern hemisphere; (2) CO₂ concentration differences that are higher in the tropics (associated with outgassing of the oceans) than those currently measured; and (3) CO₂ concentrations over the southern ocean that are relatively uniform. This natural latitudinal distribution and its sensitivity to increasing fossil fuel emissions both indicate that near-surface concentrations of atmospheric CO₂ in the northern hemisphere are naturally lower than those in the southern hemisphere. Models that find the contrary will also mismatch present-day CO₂ in the northern hemisphere and incorrectly ascribe that region as a large sink of anthropogenic CO₂.     

Sublimation kinetics of CO2 ice on Mars

Dynamic models of the martian polar caps are in abundance, but most rely on the assumption that the rate of sublimation of CO₂ ice can be calculated from heat transfer and lack experimental verification. We experimentally measured the sublimation rate of pure CO₂ ice under simulated martian conditions as a test of this assumption, developed a model based on our experimental results, and compared our model's predictions with observations from several martian missions (MRO, MGS, Viking). We show that sun irradiance is the primary control for the sublimation of CO₂ ice on the martian poles with the amount of radiation penetrating the surface being controlled by variations in the optical depth, ensuring the formation and sublimation of the seasonal cap. Our model confirmed by comparison of MGS-MOC and MRO-HiRISE images, separated by 2-3 martian years, shows that ∼0.4 m are currently being lost from the south perennial cap per martian year. At this rate, the ∼2.4-m-thick south CO₂ perennial cap will disappear in about 6-7 martian years, unless a short-scale climatic cycle alters this rate of retreat.     

Martian glaciation and the flow of solid CO2

The flow law determined experimentally for solid CO₂ establishes that a hypothesis of glacial flow of CO₂ at the Martian poles is not physically unrealistic. Compression experiments carried out under 1 atm pressure and constant strain rate demonstrate that the strength of CO₂ near its sublimation point is considerably less than the strength of water ice near its melting point. The data fit a power law “creep” equation of the form

$\text{?}\text{?}\text{= (4 × 10}{}^6\text{) σ}{}^{3.9}\text{exp}\text{(}\text{?12 200}\text{RT}\text{)}$

, where ? is compressive strain rate (sec^?1), σ is compressive stress (bars), R is the gas constant in calories per mole, and T is absolute temperature. The exponent of σ of 3.9 contrasts with a value near 3.1 for water ice, and indicates that the strain rate is somewhat more sensitive to stress for CO₂ than for water. Likewise, the low activation energy for creep, 12 200 cal mole^?1, illustrates that CO₂ is not highly sensitive to temperature and is thus likely to flow over a broad range of temperatures below its melting point. Strength values for CO₂ are of the order of one-tenth to one-third the strength of ice under equivalent conditions.A plausible glacial model for the Martian polar caps can be constructed and is helpful in explaining the unique character of the polar regions. CO₂-rich layers deposited near the pole would have flowed outward laterally to relieve high internal shear stresses. The topography of the polar caps, the uniform layering of the layered deposits, and the general extent of the polar “sediments” could all be explained using this model. Flow of CO₂ rather than water ice greatly reduces the problems with Martian glaciation. Nevertheless, problems do remain, in particular the large amounts of CO₂ necessary, the need to increase vapor pressure and temperature with depth in the polar deposits, and the lack of good observational evidence of flor features. Within the limits of the present knowledge of surface conditions of Mars, CO₂ glaciation appears to be a realistic alternate working hypothesis for the origin of the polar features.     

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.     

Semiperiodic variations in CO2 abundance on Venus

Photoelectric spectral scans of the P branch of the 8689 Å CO₂ band on Venus were made using the 107-inch coude scanner during seven observing periods in the past 2 years. The relative CO₂ line strength was determined for each scan, then normalized to remove the spatial variations leaving only temporal variations.The 4-day periodicity in the relative CO₂ line strength noted by Young et al. (1973) is not unique; we do confirm their 4-day periodicity in August 1973. Four other observing periods rule out a 4-day periodicity.A definite North-South asymmetry in the relative CO₂ line strength is noted during 1973, in most cases with the same periodicity present in both hemispheres. When the slit positions are referred to the equator of Venus, particularly near inferior conjunction, the large asymmetrics between the slit positions can be explained by a greater CO₂ line strength over the polar regions and weaker over the equatorial latitudes. The amplitude of variation of each position on the crescent is much greater near inferior conjunction either because we are sampling a smaller area on the planet or because the upper atmospheric abundance is more sensitive to the mechanism causing the variation in the smaller regions sampled at inferior conjunction.Simultaneous H₂O measurementsduring several of the observing runs indicate a lack of correlation in the relative CO₂ line strengths and the H₂O abundance.     

Warming the early earth—CO2 reconsidered

Despite a fainter Sun, the surface of the early Earth was mostly ice-free. Proposed solutions to this so-called “faint young Sun problem” have usually involved higher amounts of greenhouse gases than present in the modern-day atmosphere. However, geological evidence seemed to indicate that the atmospheric CO₂ concentrations during the Archaean and Proterozoic were far too low to keep the surface from freezing. With a radiative-convective model including new, updated thermal absorption coefficients, we found that the amount of CO₂ necessary to obtain 273 K at the surface is reduced up to an order of magnitude compared to previous studies. For the late Archaean and early Proterozoic period of the Earth, we calculate that CO₂ partial pressures of only about 2.9 mb are required to keep its surface from freezing which is compatible with the amount inferred from sediment studies. This conclusion was not significantly changed when we varied model parameters such as relative humidity or surface albedo, obtaining CO₂ partial pressures for the late Archaean between 1.5 and 5.5 mb. Thus, the contradiction between sediment data and model results disappears for the late Archaean and early proterozoic.     

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.     

Phytochemical changes in leaves of subtropical grasses and fynbos shrubs at elevated atmospheric CO2 concentrations

The effects of elevated atmospheric CO₂ concentrations on plant polyphenolic, tannin, nitrogen, phosphorus and total nonstructural carbohydrate concentrations were investigated in leaves of subtropical grass and fynbos shrub species. The hypothesis tested was that carbon-based secondary compounds would increase when carbon gain is in excess of growth requirements. This premise was tested in two ecosystems involving plants with different photosynthetic mechanisms and growth strategies. The first ecosystem comprised grasses from a C₄-dominated, subtropical grassland, where three plots were subjected to three different free air CO₂ enrichment treatments, i.e., elevated (600 to 800 μmol mol⁻¹), intermediate (400 μmol mol⁻¹) and ambient atmospheric CO₂. One of the seven grass species, Alloteropsis semialata, had a C₃ photosynthetic pathway while the other grasses were all C₄. The second ecosystem was simulated in a microcosm experiment where three fynbos species were grown in open-top chambers at ambient and 700 μmol mol⁻¹ atmospheric CO₂ in low nutrient acid sands typical of south western coastal and mountain fynbos ecosystems. Results showed that polyphenolics and tannins did not increase in the grass species under elevated CO₂ and only in Leucadendron laureolum among the fynbos species. Similarly, foliar nitrogen content of grasses was largely unaffected by elevated CO₂, and among the fynbos species, only L. laureolum and Leucadendron xanthoconus showed changes in foliar nitrogen content under elevated CO₂, but these were of different magnitude. The overall decrease in nitrogen and phosphorus and consequent increase in C:N and C:P ratio in both ecosystems, along with the increase in polyphenolics and tannins in L. laureolum in the fynbos ecosystem, may negatively affect forage quality and decomposition rates. It is concluded that fast growing grasses do not experience sink limitation and invest extra carbon into growth rather than polyphenolics and tannins and show small species-specific chemical changes at elevated atmospheric CO₂ concentrations. Responses of fynbos species are varied and were species-specific.     

Interactive effects of hypobaria, low temperature, and CO2 atmospheres inhibit the growth of mesophilic Bacillus spp. under simulated martian conditions

Robotic spacecraft are launched with finite levels of terrestrial microorganisms that are similar to the microbial communities within facilities in which spacecraft are assembled. In particular, spores of mesophilic aerobic Bacillus species are common spacecraft contaminants considered most likely to survive interplanetary transfer to Mars. During the cruise phase to Mars, and then again during surface operations, microbial bioloads are exposed to a diversity of biocidal factors that are likely to render the microbial species either dead or significantly inhibited from active metabolic activity and replication. We report here, for the first time, that interactive effects of low pressure, low temperature, and high CO₂ atmospheres approaching conditions likely to be encountered on the martian surface strongly inhibit the growth and replication of seven common Bacillus spp. isolated from spacecraft. Tests were conducted within a small glass bell-jar system maintained in a low-temperature microbial incubator. Atmospheric pressures were controlled at 1013 (Earth-normal), 100, 50, 35, 25, or 15 mb, and temperatures were maintained at 30, 20, 15, 10, or 5 °C. Experiments were carried out for 48 h or 7 days under either Earth-normal O₂/N₂ or pure CO₂ atmospheres. Results indicated that low pressure, low temperature, and high CO₂ atmospheres, applied separately or in combination, were capable of inhibiting the growth and replication of B. pumilus SAFR-032, B. pumilus FO-36B, B. subtilis HA-101, B. subtilis 42HS-1, B. megaterium KL-197, B. licheniformis KL-196, and B. nealsonii FO-092 under simulated martian conditions. Endospores of all seven Bacillus spp. strains failed to germinate and grow at 25 mb at 30 °C. Although, vegetative cells of these strains exhibited a slightly greater ability to replicate at lower pressures than did endospores, vegetative cells of these species failed to grow at pressures below 25 mb. Interactive effects of these environmental parameters acted to generally increase the inhibitory nature of the low-pressure conditions on growth and replication of the seven Bacillus spp. tested.     

Distributions of H2O and CO2 ices on Ariel, Umbriel, Titania, and Oberon from IRTF/SpeX observations

We present 0.8-2.4 μm spectral observations of uranian satellites, obtained at IRTF/SpeX on 17 nights during 2001-2005. The spectra reveal for the first time the presence of CO₂ ice on the surfaces of Umbriel and Titania, by means of 3 narrow absorption bands near 2 μm. Several additional, weaker CO₂ ice absorptions have also been detected. No CO₂ absorption is seen in Oberon spectra, and the strengths of the CO₂ ice bands decline with planetocentric distance from Ariel through Titania. We use the CO₂ absorptions to map the longitudinal distribution of CO₂ ice on Ariel, Umbriel, and Titania, showing that it is most abundant on their trailing hemispheres. We also examine H₂O ice absorptions in the spectra, finding deeper H₂O bands on the leading hemispheres of Ariel, Umbriel, and Titania, but the opposite pattern on Oberon. Potential mechanisms to produce the observed longitudinal and planetocentric distributions of the two ices are considered.