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.     

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.     

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.     

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.     

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.     

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.     

The Martian hydrologic cycle: Effects of CO2 mass flux on global water distribution

The Martian CO₂ cycle, which includes the seasonal condensation and subsequent sublimation of up to 30% of the planet's atmosphere, produces meridional winds due to the consequent mass flux of CO₂. These winds currently display strong seasonal and hemispheric asymmetries due to the large asymmetries in the distribution of insolation on Mars. It is proposed that asymmetric meridional advection of water vapor on the planet due to these CO₂ condensation winds is capable of explaining the observed dessication of Mars' south polar region at the current time. A simple model for water vapor transport is used to verify this hypothesis and to speculate on the effects of changes in orbital parameters on the seasonal water cycle.     

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.     

On the abundance of NO2 in the Martian atmosphere

Spectrophotometric scans of Mars and the Moon in the region 4000–5000 Å were obtained and ratioed. No evidence of any absorption greater than 3% is visible in the Martian spectrum. Using our own laboratory spectra of NO₂ as well as the published work of Hall and Blacet (1952) we confirm Marshall's (1964) upper limit of 8 μm atmospheres (0.0008 cm amagat) for the abundance of NO₂ in the atmosphere of Mars.     

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.     

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.     

Concatenation of HRSC colour and OMEGA data for the determination and 3D-parameterization of high-altitude CO2 clouds in the Martian atmosphere

We used Mars Express HRSC and OMEGA data to investigate mesospheric cloud features observed in the equatorial belt of Mars from December 2007 until early March 2008. This period corresponds to early northern spring of Martian year 29. The reflection peak at 4.26 μm in OMEGA data identifies the clouds as CO₂ ice clouds. HRSC observed the clouds together with OMEGA in five orbits. Cloud features are most prominent in the shortwave HRSC colour channels with wavelength centers at 440 and 530 nm, but rarely visible in all other channels. In the period of Ls 0-36°, OMEGA and HRSC together detected mesospheric CO₂ ice clouds in 40 orbits. They occur in a latitude belt of ±20° around the equator and at longitudes between 240°E (Tharsis) in the West and 30°E (Sinus Meridiani) in the East. The clouds were observed between 3 and 5 p.m. local time with mainly ripple-like to filamentary cloud forms. The viewing angles of the HRSC blue and green colour channels differ by 6.6° and the resulting parallax can be used to directly measure cloud heights by means of ray intersection. 17 HRSC data takes were found to exhibit clouds with heights from 66 to 83 km with an accuracy of 1-2 km. The pushbroom imaging technique also yields a time delay for the two observations in the order of 5-15 s close to periapsis, and therefore time-related cloud movements can be detected. A method was developed to determine the across-track cloud displacements, which can directly be translated to wind velocities. Zonal cloud movements could be measured in 13 cases and were oriented from East to West. Related wind speeds range between 60 and 93 m/s with an accuracy of 10-13 m/s.     

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.     

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.     

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.     

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.     

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.     

Observations of the phase variation of Venus CO2 equivalent widths

We present equivalent widths of Venus CO₂ scans of the P branch (P8–P32) of the 5ν₃ band at 8689 Å, the P16 line of the 5ν₃ band, and the P14 line of the ν₁ + 5ν₃ band at 7820 Å covering phase angles between 5°.1 and 170°. The equivalent widths reach a minimum at 10°, in agreement with a phase function with a backward lobe at 160° which is caused by a single internal reflection within the cloud particles. This is evidence that Venus cloud particles are composed of liquid droplets. Maximum equivalent widths are observed at ～60°, a value which is closer to the maximum of single-layer Mie scattering models than to that of two-layer models. At high phase angles we observe equivalent widths greater than those computed from homogeneous scattering models, indicating that at high altitudes the mixing ratio of scattering particles to CO₂ increases with depth. At all phase angles, particularly at large phase angles, the temporal and spatial variations in the observed equivalent widths confuse the phase variation.     

On the HCN and CO2 abundance and distribution in Jupiter's stratosphere

Observations of Jupiter by Cassini/CIRS, acquired during the December 2000 flyby, provide the latitudinal distribution of HCN and CO₂ in Jupiter's stratosphere with unprecedented spatial resolution and coverage. Following up on a preliminary study by Kunde et al. [Kunde, V.G., and 41 colleagues, 2004. Science 305, 1582-1587], the analysis of these observations leads to two unexpected results (i) the total HCN mass in Jupiter's stratosphere in 2000 was (6.0±1.5)×¹⁰¹³ g, i.e., at least three times larger than measured immediately after the Shoemaker-Levy 9 (SL9) impacts in July 1994 and (ii) the latitudinal distributions of HCN and CO₂ are strikingly different: while HCN exhibits a maximum at 45° S and a sharp decrease towards high Southern latitudes, the CO₂ column densities peak over the South Pole. The total CO₂ mass is (2.9±1.2)×¹⁰¹³ g. A possible cause for the HCN mass increase is its production from the photolysis of NH₃, although a problem remains because, while millimeter-wave observations clearly indicate that HCN is currently restricted to submillibar (∼0.3 mbar) levels, immediate post-impact infrared observations have suggested that most of the ammonia was present in the lower stratosphere near 20 mbar. HCN appears to be a good atmospheric tracer, with negligible chemical losses. Based on 1-dimensional (latitude) transport models, the HCN distribution is best interpreted as resulting from the combination of a sharp decrease (over an order of magnitude in Kyy) of wave-induced eddy mixing poleward of 40° and an equatorward transport with velocity. The CO₂ distribution was investigated by coupling the transport model with an elementary chemical model, in which CO₂ is produced from the conversion of water originating either from SL9 or from auroral input. The auroral source does not appear adequate to reproduce the CO₂ peak over the South Pole, as required fluxes are unrealistically high and the shape of the CO₂ bulge is not properly matched. In contrast, the CO₂ distribution can be fit by invoking poleward transport with a velocity and vigorous eddy mixing (). While the vertical distribution of CO₂ is not measured, the combined HCN and CO₂ results imply that the two species reside at different stratospheric levels. Comparing with the circulation regimes predicted by earlier radiative-dynamical models of Jupiter's stratosphere, and with inferences from the ethane and acetylene stratospheric latitudinal distribution, we suggest that CO₂ lies in the middle stratosphere near or below the 5-mbar level.     

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.