Photochemistry of the martian atmosphere: Seasonal, latitudinal, and diurnal variations

There is a significant progress in the observational data relevant to Mars photochemistry in the current decade. These data are not covered by and sometimes disagree with the published models. Therefore we consider three types of models for Mars photochemistry. A steady-state model for global-mean conditions is currently the only way to calculate the abundances of long living species (H₂, O₂, and CO). However, our model does not fit the observed CO abundance using gas-phase chemistry and reasonable values of heterogeneous loss of odd hydrogen on the water ice aerosol. The second type of the calculated models is steady-state models for local conditions. The MGS/TES data on temperature profiles, H₂O, and dust are input parameters for these models. The calculations have been made for nine seasonal points spread over the martian year and for twelve latitudes with a step of 10° for each season. The only adopted heterogeneous reaction is a weak loss of H₂O₂ on water ice with probability of 5×¹⁰⁻⁴. The results are in good agreement with the recent observations of the O₂ dayglow at 1.27 μm and the O₃ and H₂O₂ abundances. Global maps of the seasonal and latitudinal behavior of these species have been made. The third type of models is a time-dependent model for local conditions. These models show that odd hydrogen quickly converts to H₂O₂ at the nighttime and the chemistry is switched off while the association of O, the heterogeneous loss of H₂O₂, and eddy diffusion continue. This requires significant changes in the global-mean and local steady-state models discussed above, and these changes have been properly done. The calculated diurnal variations of Mars photochemistry are discussed. The martian photochemistry at low and middle latitudes is significantly different in the aphelion period at LS=10°-130° from that in the remaining part of the year.     

The formation and evolution of youthful gullies on Mars: Gullies as the late-stage phase of Mars’ most recent ice age

Gullies are extremely young erosional/depositional systems on Mars that have been carved by an agent that was likely to have been comprised in part by liquid water [Malin, M.C., Edgett, K.S., 2000. Evidence for recent groundwater seepage and surface runoff on Mars. Science 288, 2330-2335; McEwen, A.S. et al., 2007. A closer look at water-related geologic activity on Mars. Science 317, 1706-1709]. The strong latitude and orientation dependencies that have been documented for gullies require (1) a volatile near the surface, and (2) that insolation is an important factor for forming gullies. These constraints have led to two categories of interpretations for the source of the volatiles: (1) liquid water at depth beneath the melting isotherm that erupts suddenly (“groundwater”), and (2) ice at the surface or within the uppermost layer of soil that melts during optimal insolation conditions (“surface/near-surface melting”). In this contribution we synthesize global, hemispheric, regional and local studies of gullies across Mars and outline the criteria that must be met by any successful explanation for the formation of gullies. We further document trends in both hemispheres that emphasize the importance of top-down melting of recent ice-rich deposits and the cold-trapping of atmospherically-derived H₂O frost/snow as important components in the formation of gullies. This provides context for the incorporation of high-resolution multi-spectral and hyper-spectral data from the Mars Reconnaissance Orbiter that show that (1) cold-trapping of seasonal H₂O frost occurs at the alcove/channel-level on contemporary Mars; (2) gullies are episodically active systems; (3) gullies preferentially form in the presence of deposits plausibly interpreted as remnants of the Late Amazonian emplacement of ice-rich material; and (4) gully channels frequently emanate from the crest of alcoves instead of the base, showing that alcove generation is not necessarily a product of undermining and collapse at these locations, a prediction of the groundwater model. We interpret these various lines of evidence to mean that the majority of gullies on Mars are explained by the episodic melting of atmospherically emplaced snow/ice under spin-axis/orbital conditions characteristic of the last several Myr.     

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.     

The origin of water on Mars

This paper considers the origin of water on Mars, in the context of a dynamical model that accounts for most of the Earth's water as a product of collisions between the growing Earth and planet-sized “embryos” from the asteroid belt. Mars' history is found to be different; to explain the present mass of Mars requires that it suffer essentially no giant collisions and the bulk of its growth is through addition of smaller bodies. Asteroids and comets from beyond 2.5 AU provide the source of Mars' water, which totals 6-27% of the Earth's present ocean (1 Earth ocean≡1.5×10²¹ kg), equivalent to 600-2700-m depth on the martian surface. The D/H ratio of this material is 1.2-1.6 times Standard Mean Ocean Water, the smaller value obtaining for the larger amount of water accreted. The upper half of the range of total water accreted, while many times less than that acquired by the Earth, is consistent with geological data on Mars, and the D/H value is that derived for martian magmatic water from SNC meteorites. Both together are consistent with published interpretations of the high D/H in present-day martian atmospheric water in terms of water loss through atmospheric escape.     

Simultaneous mapping of H2O and H2O2 on Mars from infrared high-resolution imaging spectroscopy

New maps of martian water vapor and hydrogen peroxide have been obtained in November-December 2005, using the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infra Red Telescope facility (IRTF) at Mauna Kea Observatory. The solar longitude Ls was 332° (end of southern summer). Data have been obtained at 1235-1243 cm⁻¹, with a spectral resolution of 0.016 cm⁻¹ (R=8×¹⁰⁴). The mean water vapor mixing ratio in the region [0°-55° S; 345°-45° W], at the evening limb, is 150±50 ppm (corresponding to a column density of 8.3±2.8 pr-μm). The mean water vapor abundance derived from our measurements is in global overall agreement with the TES and Mars Express results, as well as the GCM models, however its spatial distribution looks different from the GCM predictions, with evidence for an enhancement at low latitudes toward the evening side. The inferred mean H₂O₂ abundance is 15±10 ppb, which is significantly lower than the June 2003 result [Encrenaz, T., Bézard, B., Greathouse, T.K., Richter, M.J., Lacy, J.H., Atreya, S.K., Wong, A.S., Lebonnois, S., Lefèvre, F., Forget, F., 2004. Icarus 170, 424-429] and lower than expected from the photochemical models, taking in account the change in season. Its spatial distribution shows some similarities with the map predicted by the GCM but the discrepancy in the H₂O₂ abundance remains to be understood and modeled.     

Rosetta-Alice observations of exospheric hydrogen and oxygen on Mars

The European Space Agency’s Rosetta spacecraft, en route to a 2014 encounter with comet 67P/Churyumov-Gerasimenko, made a gravity assist swing-by of Mars on 25 February 2007, closest approach being at 01:54 UT. The Alice instrument on board Rosetta, a lightweight far-ultraviolet imaging spectrograph optimized for in situ cometary spectroscopy in the 750-2000 Å spectral band, was used to study the daytime Mars upper atmosphere including emissions from exospheric hydrogen and oxygen. Offset pointing, obtained five hours before closest approach, enabled us to detect and map the H i Lyman-α and Lyman-β emissions from exospheric hydrogen out beyond 30,000 km from the planet’s center. These data are fit with a Chamberlain exospheric model from which we derive the hydrogen density at the 200 km exobase and the H escape flux. The results are comparable to those found from the Ultraviolet Spectrometer experiment on the Mariner 6 and 7 fly-bys of Mars in 1969. Atomic oxygen emission at 1304 Å is detected at altitudes of 400-1000 km above the limb during limb scans shortly after closest approach. However, the derived oxygen scale height is not consistent with recent models of oxygen escape based on the production of suprathermal oxygen atoms by the dissociative recombination of .     

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.     

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.     

Seasonal variations of photochemical tracers at low and middle latitudes on Mars: Observations and models

Mars Express observations give ozone abundances that are smaller than those from the ground-based infrared heterodyne and HST observations at low and middle latitudes. Both ground-based and Mars Express observations of the O₂ dayglow at 1.27 μm, which originates from photolysis of ozone, are in mutual agreement after correction for the local time variability. Therefore a problem appears: whether the MEX ozone data are compatible with (1) the observed O₂ dayglow intensities and (2) the photochemical model by Krasnopolsky [Krasnopolsky, V.A., 2006. Icarus 185, 153-170] within uncertainties of its reaction rate coefficients. That model involves heterogeneous loss of H₂O₂ on water ice and agrees with the observations of the O₂ dayglow, H₂O₂, and the ground-based and HST ozone. The answers are ‘yes’ to both questions. A version of the model is given that fits the MEX ozone as well as the observed O₂ dayglow and H₂O₂. Laboratory studies of two reaction rate coefficients could indicate a preferable version of the model and a preferable set of the ozone data (MEX versus the ground-based and HST). The predicted seasonal behavior of H₂O₂ is different from that in the model by Lefevre et al. [Lefevre, F., Bertaux, J.L., Clancy, R.T., Encrenaz, T., Fast, K., Forget, F., Lebonnois, S., Montmessin, F., Perrier, S., 2008. Nature 454, 971-975], and future observations may help to choose between the models.     

Mars atmospheric water vapor abundance: 1991-1999, emphasis 1998-1999

Our ground-based measurements of martian atmospheric water vapor, made throughout Ls=34° to 249°, 24 September 1998 to 23 November 1999, during Mars year 24 (MY 24), show changes in Mars' humidity on hourly, daily, and seasonal timescales. We made concomitant measurement of nearby CO₂ bands, and when possible, results were corrected for aerosol extinction using aerosol optical depths derived from our own CO₂ analysis. Where there is spatial and temporal overlap, similar results are obtained for water vapor abundances and aerosol opacities as those observed from the Thermal Emission Spectrometer on Mars Global Surveyor. In addition some further discussion of our published earlier water vapor measurements (1991-1995) is included. Six results from this data set are: (1) the measured aerosol opacity in Mars atmosphere was variable but not greater than τ=1, with almost no clear atmosphere being observed, (2) measurements made with the slit crossing many hours of local time on Mars' Earth-facing disk show a diurnal pattern with highest abundances at mid-day and low abundance in very early morning and late afternoon for some but not all measurements, (3) water vapor abundance is patchy on hourly and daily time scales but follows the usual seasonal trends seen by instrumentation on the Mars Atmospheric Water Detector on the Viking Orbiters and by the Thermal Emission Spectrometer on Mars Global Surveyor, (4) there is a slight longitudinal correlation with the ground-ice observed by the Gamma Ray Spectrometer on Mars Odyssey, (5) there is evidence of the Low Southern Latitude Summer Minimum in our water vapor measurements but our data set for southern summer is limited, and (6) MY 24 appears to be wetter than MY 22 and MY 23.     

Hydrogen peroxide on Mars: evidence for spatial and seasonal variations

Hydrogen peroxide (H₂O₂) has been suggested as a possible oxidizer of the martian surface. Photochemical models predict a mean column density in the range of 10¹⁵-10¹⁶ cm⁻². However, a stringent upper limit of the H₂O₂ abundance on Mars (9×10¹⁴ cm⁻²) was derived in February 2001 from ground-based infrared spectroscopy, at a time corresponding to a maximum water vapor abundance in the northern summer (30 pr. μm, Ls=112°). Here we report the detection of H₂O₂ on Mars in June 2003, and its mapping over the martian disk using the same technique, during the southern spring (Ls=206°) when the global water vapor abundance was ∼10 pr. μm. The spatial distribution of H₂O₂ shows a maximum in the morning around the sub-solar latitude. The mean H₂O₂ column density (6×10¹⁵ cm⁻²) is significantly greater than our previous upper limit, pointing to seasonal variations. Our new result is globally consistent with the predictions of photochemical models, and also with submillimeter ground-based measurements obtained in September 2003 (Ls=254°), averaged over the martian disk (Clancy et al., 2004, Icarus 168, 116-121).     

Deep versus shallow origin of gravity anomalies, topography and volcanism on Earth, Venus and Mars

The relation between gravity anomalies, topography and volcanism can yield important insights about the internal dynamics of planets. From the power spectra of gravity and topography on Earth, Venus and Mars we infer that gravity anomalies have likely predominantly sources below the lithosphere up to about spherical harmonic degree l=30 for Earth, 40 for Venus and 5 for Mars. To interpret the low-degree part of the gravity spectrum in terms of possible sublithospheric density anomalies we derive radial mantle viscosity profiles consistent with mineral physics. For these viscosity profiles we then compute gravity and topography kernels, which indicate how much gravity anomaly and how much topography is caused by a density anomaly at a given depth. With these kernels, we firstly compute an expected gravity-topography ratio. Good agreement with the observed ratio indicates that for Venus, in contrast to Earth and Mars, long-wavelength topography is largely dynamically supported from the sublithospheric mantle. Secondly, we combine an empirical power spectrum of density anomalies inferred from seismic tomography in Earth’s mantle with gravity kernels to model the gravity power spectrum. We find a good match between modeled and observed gravity power spectrum for all three planets, except for 2?l?4 on Venus. Density anomalies in the Venusian mantle for these low degrees thus appear to be very small. We combine gravity kernels and the gravity field to derive radially averaged density anomaly models for the Martian and Venusian mantles. Gravity kernels for l?5 are very small on Venus below ≈800 km depth. Thus our inferences on Venusian mantle density are basically restricted to the upper 800 km. On Mars, gravity anomalies for 2?l?5 may originate from density anomalies anywhere within its mantle. For Mars as for Earth, inferred density anomalies are dominated by l=2 structure, but we cannot infer whether there are features in the lowermost mantle of Mars that correspond to Earth’s Large Low Shear Velocity Provinces (LLSVPs). We find that volcanism on Mars tends to occur primarily in regions above inferred low mantle density, but our model cannot distinguish whether or not there is a Martian analog for the finding that Earth’s Large Igneous Provinces mainly originate above the margins of LLSVPs.     

Helium on Mars and Venus: EUVE observations and modeling

Long-exposure spectroscopy of Mars and Venus with the Extreme Ultraviolet Explorer (EUVE) has revealed emissions of He 584 Å on both planets and He 537 Å/O⁺ 539 Å and He⁺ 304 Å on Venus. Our knowledge of the solar emission at 584 Å, eddy diffusion in Mars' upper atmosphere, electron energy distributions above Mars' ionopause, and hot oxygen densities in Mars' exosphere has been significantly improved since our analysis of the first EUVE observation of Mars [Krasnopolsky, Gladstone, 1996, Helium on Mars: EUVE and Phobos data and implications for Mars' evolution, J. Geophys. Res. 101, 15,765-15,772]. These new results and a more recent EUVE observation of Mars are the motivation for us to revisit the problem in this paper. We find that the abundance of helium in the upper atmosphere, where the main loss processes occur, is similar to that in the previous paper, though the mixing ratio in the lower and middle atmosphere is now better estimated at 10±6 ppm. Our estimate of the total loss of helium is almost unchanged at 8×¹⁰²³ s⁻¹, because a significant decrease in the loss by electron impact ionization above the ionopause is compensated by a higher loss in collisions with hot oxygen. We neglect the outgassing of helium produced by radioactive decay of U and Th because of the absence of current volcanism and a very low upper limit to the seepage of volcanic gases. The capture of solar wind α-particles is currently the only substantial source of helium on Mars, and its efficiency remains at 0.3. A similar analysis of EUV emissions from Venus results in a helium abundance in the upper atmosphere which is equal to the mean of the abundances measured previously with two optical and two mass spectrometers, and a derived helium mixing ratio in the middle and lower atmosphere of 9±6 ppm. Helium escape by ionization and sweeping out of helium ions by the solar wind above the ionopause is smaller than that calculated by Prather and McElroy [1983, Helium on Venus: implications for uranium and thorium, Science 220, 410-411] by a factor of 3. However, charge exchange of He⁺ ions with CO₂ and N₂ between the exobase and ionopause and collisions with hot oxygen ignored previously add to the total loss which appears to be at the level of 10⁶ cm⁻² s⁻¹ predicted by Prather and McElroy [1983, Science 220, 410-411]. The loss of helium is compensated by outgassing of helium produced by radioactive decay of U and Th and by the capture of the solar wind α-particles with an efficiency of 0.1. We also compare our derived α-particle capture efficiencies for Mars and Venus with observed X-ray emissions resulting from the charge exchange of solar wind heavy ions with the extended atmospheres on both planets [Dennerl et al., 2002, Discovery of X-rays from Venus with Chandra, Astron. Astrophys. 386, 319-330; Dennerl, 2002, Discovery of X-rays from Mars with Chandra, Astron. Astrophys. 394, 1119-1128]. The emissions from both disk and halo on Mars agree with our calculated values; however, we do not see a reasonable explanation for the X-ray halo emission on Venus. The ratio of the charge exchange efficiencies derived from the disk X-ray emissions of Mars and Venus is similar to the ratio of the capture efficiencies for these planets. The surprisingly bright emission of He⁺ at 304 Å observed by EUVE and Venera 11 and 12 suggests that charge exchange in the flow of the solar wind α-particles around the ionopause is much stronger than in the flow of α-particles into the ionosphere.     

Limits on the trapping of atmospheric CH4 in martian polar ice analogs

Recent detection of methane (CH₄) on Mars has generated interest in possible biological or geological sources, but the factors responsible for the reported variability are not understood. Here we explore one potential sink that might affect the seasonal cycling of CH₄ on Mars - trapping in ices deposited on the surface. Our apparatus consisted of a high-vacuum chamber in which three different Mars ice analogs (water, carbon dioxide, and carbon dioxide clathrate hydrates) were deposited in the presence of CH₄ gas. The ices were monitored for spectroscopic evidence of CH₄ trapping using transmission Fourier-Transform Infrared (FT-IR) spectroscopy, and during subsequent sublimation of the ice films the vapor composition was measured using mass spectrometry (MS). Trapping of CH₄ in water ice was confirmed at deposition temperatures <100 K which is consistent with previous work, thus validating the experimental methods. However, no trapping of CH₄ was observed in the ice analogs studied at warmer temperatures (140 K for H₂O and CO₂ clathrate, 90 K for CO₂ snow) with approximately 10 mTorr CH₄ in the chamber. From experimental detection limits these results provide an upper limit of 0.02 for the atmosphere/ice trapping ratio of CH₄. If it is assumed that the trapping mechanism is linear with CH₄ partial pressure and can be extrapolated to Mars, this upper limit would indicate that less than 1% is expected to be trapped from the largest reported CH₄ plume, and therefore does not represent a significant sink for CH₄.     

Some problems related to the origin of methane on Mars

The following problems related to the origin of methane on Mars have been considered. (1) Laboratory simulations of the impact phenomena confirm effective heterogeneous chemistry between the products of the fireball. This chemistry lowers the fireball freezing temperature from 2000 to 750 K for methane and to 1100 K for CO/CO₂. Production of methane on Mars by cometary impacts is 0.8% of the total production. A probability that the observed methane on Mars came from impact of a single comet is 0.0011. (2) The PFS observations of variations of methane on Mars require a very effective heterogeneous loss of methane. Heterogeneous effect of dust is half that of the surface rocks. Thermochemical equilibrium requires production, not loss, of methane. Existing kinetic data show a very low efficiency of heterogeneous reactions of methane. Highly reactive superoxide ions generated by the solar UV photons on the martian rocks cannot remove methane. The required efficiency of heterogeneous loss of methane on Mars is higher than that on Earth by a factor of ?1000, although the expected efficiency on Earth is stronger than that on Mars because of the liquid ocean and the abundant oxygen. All these inconsistencies may be removed if variations of the rock reflectivity contribute to the PFS observations of methane on Mars. The PFS data on H₂CO, HCl, HF, and HBr also raise doubts. (3) Although geologic sources of methane are possible, the lack of current volcanism, hydrothermal activity, hot spots, and very low seepage of gases from the interior are not favorable for geologic methane. Any proposed geological source of methane on Mars should address these problems. Some weak points in the suggested geologic sources are discussed. (4) Measurements of ¹³C/¹²C and D/H in methane would be difficult because of the low methane abundance. These ratios are mostly sensitive to a temperature of methane formation and cannot distinguish between biogenic and low-temperature geologic sources. Their analysis requires the carbon isotope ratio in CO₂ on Mars, which is known with the insufficient accuracy, and D/H in water, which is different in the atmosphere, polar caps, regolith and interior. Therefore, the stable isotope ratios may not give a unique answer on the origin of methane. (5) Ethane and propane react with OH much faster than methane. If their production relative to methane is similar to that on Earth, then their expected abundances on Mars are of a few parts per trillion. (6) Loss of SO₂ in the reaction with peroxide on ice is smaller than its gas-phase loss by an order of magnitude. The overall results strengthen the biogenic origin of martian methane and its low variability.     

Dust devil sediment flux on Earth and Mars: Laboratory simulations

Laboratory simulations using the Arizona State University Vortex Generator (ASUVG) were run to simulate sediment flux in dust devils in terrestrial ambient and Mars-analog conditions. The objective of this study was to measure vortex sediment flux in the laboratory to yield estimations of natural dust devils on Earth and Mars, where all parameters may not be measured. These tests used particles ranging from 2 to 2000 μm in diameter and 1300 to 4800 kg m⁻³ in density, and the results were compared with data from natural dust devils on Earth and Mars. Typically, the cores of dust devils (regardless of planetary environment) have a pressure decrease of ∼0.1-1.5% of ambient atmospheric pressure, which enhances the lifting of particles from the surface. Core pressure decreases in our experiments ranged from ∼0.01% to 5.00% of ambient pressure (10 mbar Mars cases and 1000 mbar for Earth cases) corresponding to a few tenths of a millibar for Mars cases and a few millibars for Earth cases. Sediment flux experiments were run at vortex tangential wind velocities of 1-45 m s⁻¹, which typically correspond to ∼30-70% above vortex threshold values for the test particle sizes and densities. Sediment flux was determined by time-averaged measurements of mass loss for a given vortex size. Sediment fluxes of ∼10⁻⁶-10⁰ kg m⁻² s⁻¹ were obtained, similar to estimates and measurements for fluxes in dust devils on Earth and Mars. Sediment flux is closely related to the vortex intensity, which depends on the strength of the pressure decrease in the core (ΔP). This study found vortex size is less important for lifting materials because many different diameters can have the same ΔP. This finding is critical in scaling the laboratory results to natural dust devils that can be several orders of magnitude larger than the laboratory counterparts.     

Stability of hydrous minerals on the martian surface

The presence of water-bearing minerals on Mars has long been discussed, but little or no data exist showing that minerals such as smectites and zeolites may be present on the surface in a hydrated state (i.e., that they could contain H₂O molecules in their interlayer or extra-framework sites, respectively). We have analyzed experimental thermodynamic and X-ray powder diffraction data for smectite and the most common terrestrial zeolite, clinoptilolite, to evaluate the state of hydration of these minerals under martian surface conditions. Thermodynamic data for clinoptilolite show that water molecules in its extra-framework sites are held very strongly, with enthalpies of dehydration for Ca-clinoptilolite up to three times greater than that for liquid water. Using these data, we calculated the Gibbs free energy of hydration of clinoptilolite and smectite as a function of temperature and pressure. The calculations demonstrate that these minerals would indeed be hydrated under the very low-P (H₂O) conditions existing on Mars, a reflection of their high affinities for H₂O. These calculations assuming the partial pressure of H₂O and the temperature range expected on Mars suggest that, if present on the surface, zeolites and Ca-smectites could also play a role in affecting the diurnal variations in martian atmospheric H₂O because their calculated water contents vary considerably over daily martian temperature ranges. The open crystal structure of clinoptilolite and existing hydration and kinetic data suggest that hydration/dehydration are not kinetically limited. Based on these calculations, it is possible that hydrated zeolites and clay minerals may explain some of the recent observations of significant amounts of hydrogen not attributable to water ice at martian mid-latitudes.     

Interannual variability in TES atmospheric observations of Mars during 1999-2003

We use infrared spectra returned by the Mars Global Surveyor Thermal Emission Spectrometer (TES) to retrieve atmospheric and surface temperature, dust and water ice aerosol optical depth, and water vapor column abundance. The data presented here span more than two martian years (Mars Year 24, L_s=104°, 1 March 1999 to Mars Year 26, L_s=180°, 4 May 2003). We present an overview of the seasonal (L_s), latitudinal, and longitudinal dependence of atmospheric quantities during this period, as well as an initial assessment of the interannual variability in the current martian climate. We find that the perihelion season (L_s=180°-360°) is relatively warm, dusty, free of water ice clouds, and shows a relatively high degree of interannual variability in dust optical depth and atmospheric temperature. On the other hand, the aphelion season (L_s=0°-180°) is relatively cool, cloudy, free of dust, and shows a low degree of interannual variability. Water vapor abundance shows a moderate amount of interannual variability at all seasons, but the most in the perihelion season. Much of the small amount of interannual variability that is observed in the aphelion season appears to be caused by perihelion-season planet-encircling dust storms. These dust storms increase albedo through deposition of bright dust on the surface causing cooler daytime surface and atmospheric temperatures well after dust optical depth returns to prestorm values.     

Temporary liquid water in upper snow/ice sub-surfaces on Mars?

It is investigated whether conditions for melting can be temporarily created in the upper sub-surface parts of snow/ice-packs on Mars at subzero surface temperatures by means of the solid-state greenhouse effect, as occurs in snow- and ice-covered regions on Earth. The conditions for this possible temporary melting are quantitatively described for bolometric albedo values A = 0.8 and A = 0.2, and with model parameters typical for the thermo-physical conditions at snow/ice sites on the surface of present Mars. It is demonstrated by numerical modelling that there are several sets of parameters which will lead to development of layers of liquid water just below the top surface of snow- and ice-packs on Mars. This at least partial liquefaction occurs repetitively (e.g. diurnally, seasonally), and can in some cases lead to liquid water persisting through the night-time in the summer season. This liquid water can form in sufficient amounts to be relevant for macroscopic physical (rheology, erosion), for chemical, and eventually also for biological processes. The creation of temporary pockets of sub-surface water by this effect requires pre-existing snow or ice cover, and thus is more likely to take place at high latitudes, since the present deposits of snow/ice can mainly be found there. Possible rheologic and related erosion consequences of the appearance of liquid sub-surface water in martian snow/ice-packs are discussed in view of current observations of recent rheologic processes.     

Investigation of water vapor on Mars with PFS/SW of Mars Express

New insight into the seasonal, diurnal and spatial distribution of water vapor on Mars has been obtained from analyzing the spectra of the short-wavelength channel (SW) of the Planetary Fourier Spectrometer (PFS) onboard Mars Express. The processed dataset, recorded between January 2004 and April 2005, covers the seasons from LS=331° of Mars Year 26 to LS=196° of the following year. In this period the mean column density around vernal equinox was 8.2 pr. μm. The maximum values during northern summer were about 65 pr. μm, located around 75° N latitude with a longitudinally inhomogeneous distribution. Regarding the atmospheric transport, the majority of polar water vapor remains in the north polar region while only about a quarter is transported southward. Geographically there are two water vapor maxima visible, over Arabia Terra and the Tharsis plateau, that are most likely caused both by atmosphere-ground interaction and by atmospheric circulation. A comparison with other instruments generally shows a good agreement, only the SPICAM results are systematically lower. Compared to the results from the PFS long-wavelength channel the results of this work are slightly higher. A strong discrepancy is visible northward of about 50° N during the northern summer that is possibly explained by a non-uniform vertical H₂O mixing. In particular, a confinement of the water to the lower few kilometers yields a much better agreement between the retrieved column densities of the two PFS channels.