Effects of ionizing radiation on the survival of bacterial spores in artificial martian regolith

Bacterial spores of Bacillus subtilis were used as a model system to study the effects of ionizing radiation on the survivability of spores uncovered and covered with artificial martian regolith. Spore survival after X-ray exposure was mainly depending on the role of non-homologous end-joining (NHEJ) as the major DNA double-strand break repair pathway during germination, the involvement of major small, acid-soluble spore proteins (SASP) as DNA radioprotectants and the coverage by martian regolith, whereas spores covered with martian regolith were significantly more sensitive to X-rays than uncovered spores, which is mainly due to the interaction of X-rays with artificial martian regolith resulting in the formation of secondary electrons and reactive oxygen species.     

Methane evolution from UV-irradiated spacecraft materials under simulated martian conditions: Implications for the Mars Science Laboratory (MSL) mission

Fifteen organic and three inorganic compounds were tested for methane (CH₄) evolution under simulated martian conditions of 6.9 mbar; UVC (200-280 nm) flux of 4 W m⁻²; 20 °C; simulated optical depth of 0.1; and a Mars gas composition of CO₂ (95.3%), N₂ (2.7%), Ar (1.7%), O₂ (0.13%), and water vapor (0.03%). All three inorganic compounds (i.e., NaCl, CaCO₃, graphite) failed to evolve methane at the minimum detection level 0.5 ppm, or above. In contrast, all organic compounds evolved methane when exposed to UV irradiation under simulated martian conditions. The polycyclic aromatic hydrocarbon, pyrene, released the most methane per unit of time at 0.175 nmol CH₄ g⁻¹ h⁻¹, and a spectral reflectance target material used for the MER rovers and Phoenix lander released the least methane at 0.00065 nmol CH₄ cm⁻² h⁻¹. Methane was also released from UV-killed bacterial endospores of Bacillus subtilis. Although all organic compounds evolved methane when irradiated with UV photons under martian conditions, the concentrations of residual organics, biogenic signature molecules, and dead microbial cells should be relatively low on the exterior surfaces of the MSL rover, and, thus, not significant sources of methane contamination. In contrast, kapton tape was found to evolve methane at the rate of 0.00165 nmol CH₄ cm⁻² h⁻¹ (16.5 nmol m⁻² h⁻¹) under the UV and martian conditions tested. Although the evolution of methane from kapton tape was found to decline over time, the large amount of kapton tape used on the MSL rover (lower bound estimated at 3 m²) is likely to create a significant source of terrestrial methane contamination during the early part of the mission.     

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.     

Production and detection of carbon dioxide on Iapetus

Cassini VIMS detected carbon dioxide on the surface of Iapetus during its insertion orbit. We evaluated the CO₂ distribution on Iapetus and determined that it is concentrated almost exclusively on Iapetus’ dark material. VIMS spectra show a 4.27-μm feature with an absorption depth of 24%, which, if it were in the form of free ice, requires a layer 31 nm thick. Extrapolating for all dark material on Iapetus, the total observable CO₂ would be 2.3 × 10⁸ kg.Previous studies note that free CO₂ is unstable at 10 AU over geologic timescales. Carbon dioxide could, however, be stable if trapped or complexed, such as in inclusions or clathrates. While complexed CO₂ has a lower thermal volatility, loss due to photodissociation by UV radiation and gravitational escape would occur at a rate of 2.6 × 10⁷ kg year⁻¹. Thus, Iapetus’ entire inventory of surface CO₂ could be lost within a few decades.The high loss/destruction rate of CO₂ requires an active source. We conducted experiments that generated CO₂ by UV radiation of simulated icy regolith under Iapetus-like conditions. The simulated regolith was created by flash-freezing degassed water, crushing it into sub-millimeter sized particles, and then mixing it with isotopically labeled amorphous carbon (¹³C) dust. These samples were placed in a vacuum chamber and cooled to temperatures between 50 K and 160 K. The samples were irradiated with UV light, and the products were measured using a mass spectrometer, from which we measured ¹³CO₂ production at a rate of 2.0 × 10¹² mol s⁻¹. Extrapolating to Iapetus and adjusting for the solar UV intensity and Iapetus’ surface area, we calculated that CO₂ production for the entire surface would be 1.1 × 10⁷ kg year⁻¹, which is only a factor of two less than the loss rate. As such, UV photochemical generation of CO₂ is a plausible source of the detected CO₂.     

Minimum estimates of the amount and timing of gases released into the martian atmosphere from volcanic eruptions

Volcanism has been a major process during most of the geologic history of Mars. Based on data collected from terrestrial basaltic eruptions, we assume that the volatile content of martian lavas was typically ∼0.5 wt.% water, ∼0.7 wt.% carbon dioxide, ∼0.14 wt.% sulfur dioxide, and contained several other important volatile constituents. From the geologic record of volcanism on Mars we find that during the late Noachian and through the Amazonian volcanic degassing contributed ∼0.8 bar to the martian atmosphere. Because most of the outgassing consisted of greenhouse gases (i.e., CO₂ and SO₂) warmer surface temperatures resulting from volcanic eruptions may have been possible. Our estimates suggest that ∼1.1 × 10²¹ g (∼8 ± 1 m m⁻²) of juvenile water were released by volcanism; slightly more than half the amount contained in the north polar cap and atmosphere. Estimates for released CO₂ (1.6 × 10²¹ g) suggests that a large reservoir of carbon dioxide is adsorbed in the martian regolith or alternatively ∼300 cm cm⁻² of carbonates may have formed, although these materials would not occur readily in the presence of excess SO₂. Up to ∼120 cm cm⁻² (2.2 × 10²⁰ g) of acid rain (H₂SO₄) may have precipitated onto the martian surface as the result of SO₂ degassing. The hydrogen flux resulting from volcanic outgassing may help explain the martian atmospheric D/H ratio. The amount of outgassed nitrogen (∼1.3 mbar) may also be capable of explaining the martian atmospheric ¹⁵N/¹⁴N ratio. Minor gas constituents (HF, HCl, and H₂S) could have formed hydroxyl salts on the surface resulting in the physical weathering of geologic materials. The amount of hydrogen fluoride emitted (1.82 × 10¹⁸ g) could be capable of dissolving a global layer of quartz sand ∼5 mm thick, possibly explaining why this mineral has not been positively identified in spectral observations. The estimates of volcanic outgassing presented here will be useful in understanding how the martian atmosphere evolved over time.     

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.     

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.     

Slow degradation of ATP in simulated martian environments suggests long residence times for the biosignature molecule on spacecraft surfaces on Mars

Prelaunch planetary protection protocols on spacecraft are designed to reduce the numbers and diversity of viable bioloads on surfaces in order to mitigate the forward contamination of planetary surfaces. In addition, there is a growing appreciation that prelaunch spacecraft cleaning protocols will be required to reduce the levels of biogenic signature molecules on spacecraft to levels that will not compromise life-detection experiments on landers. The biogenic molecule, adenosine triphosphate (ATP) was tested for long-term stability under simulated Mars surface conditions of high UV flux, low temperature, low pressure, Mars atmosphere, and clear-sky dust loading conditions. Data on UV-induced ATP degradation rates were then extrapolated to a diversity of global conditions using a radiative transfer model for UV on Mars. The UV-induced degradation of ATP tested at 4.1 W m⁻² UVC (200-280 nm), −10 °C, 7.1 mb, 95% CO₂ gas composition, and an atmospheric opacity of τ=0.1 yielded a half-life for ATP of 1342 kJ m⁻²; or extrapolated to approximately 22 sols on equatorial Mars with an atmospheric opacity of τ=0.5. Temperature was found to moderately affect ATP degradation rates under martian conditions; tests at −80 or 20 °C yielded ATP half-lives of 2594 or 1183 kJ m⁻², respectively. The ATP degradation rates reported here are over 10 orders of magnitude slower than the UV-induced biocidal rates reported in the literature on the inactivation of strongly UV-resistant bacterial spores from Bacillus pumilus SAFR-032 [Schuerger, A.C., Richards, J.T., Newcombe, D.A., Venkateswaran, K.J., 2006. Icarus 181, 52-62]. Extrapolating results to global Mars conditions, residence times for a 99% reduction of ATP on spacecraft surfaces ranged from 158 sols on Sun-exposed surfaces to approximately 32,000 sols for the undersides of landers similar to Viking. However, spacecraft materials greatly affected the survival times of ATP under martian conditions. Stainless steel was found to enhance the UV degradation of ATP by over 2 orders of magnitude compared to ATP-doped iridited aluminum, graphite, and astroquartz coupons. Extrapolating these results to global conditions, ATP on stainless steel might be expected to persist between 2 and 320 sols for upper and lower surfaces of landers. Liquid chromatography-mass spectrometry data supported the conclusion that UV irradiation acted to remove the γ-phosphate group from ATP, and no evidence was observed for the UV-degradation of d-ribose or adenine moieties. Long residence times for ATP on spacecraft materials under martian conditions suggest that prelaunch cleaning protocols may need to be strengthened to mitigate against possible ATP contamination of life-detection experiments on Mars landers.     

The ultraviolet environment of Mars: biological implications past, present, and future.

A radiative transfer model is used to quantitatively investigate aspects of the martian ultraviolet radiation environment, past and present. Biological action spectra for DNA inactivation and chloroplast (photosystem) inhibition are used to estimate biologically effective irradiances for the martian surface under cloudless skies. Over time Mars has probably experienced an increasingly inhospitable photobiological environment, with present instantaneous DNA weighted irradiances 3.5-fold higher than they may have been on early Mars. This is in contrast to the surface of Earth, which experienced an ozone amelioration of the photobiological environment during the Proterozoic and now has DNA weighted irradiances almost three orders of magnitude lower than early Earth. Although the present-day martian UV flux is similar to that of early Earth and thus may not be a critical limitation to life in the evolutionary context, it is a constraint to an unadapted biota and will rapidly kill spacecraft-borne microbes not covered by a martian dust layer. Microbial strategies for protection against UV radiation are considered in the light of martian photobiological calculations, past and present. Data are also presented for the effects of hypothetical planetary atmospheric manipulations on the martian UV radiation environment with estimates of the biological consequences of such manipulations.     

A photohabitable zone in the martian snowpack? A laboratory and radiative-transfer study of dusty water-ice snow

Dusty water-ice snowpacks on Mars may provide a habitable zone for DNA based photosynthetic life. Previous work has over estimated the depths and thicknesses of such photohabitable zones by not considering the effect of red dust within the snowpack. For the summer solar solstice, at 80°N and a surface albedo of 0.45, there is a calculated photohabitable zone in the snowpack between depths of 5.5 and 7.5 cm. For an albedo of 0.62, there is a calculated photohabitable zone in the snowpack between depths of 8 and 11 cm. A coupled atmosphere-snow radiative-transfer model was set to model the Photosynthetic Active Radiation and DNA dose rates through water-ice snow at the north polar region of Mars. The optical properties of the polar caps were determined by creating a laboratory analogue to the Mars north polar deposits, and directly measuring light penetration and albedo. It is important for future exobiology missions to the polar regions of Mars to consider the implications of these findings, as drilling to depths of ∼11 cm should be sufficient to determine whether life exists within the martian snows, whether it is photosynthetic or otherwise, as at this depth the snow cover will provide a permanent protection from DNA damaging UV radiation.     

Evidence for Mg-rich carbonates on Mars from a 3.9 μm absorption feature

The origin and nature of the early atmosphere of Mars is still debated. The discovery of sulfate deposits on the surface, coupled with the evidence that there are not large abundances of carbonates detectable on Mars in the optically accessible part of the regolith, leaves open different paleoclimatic evolutionary pathways. Even if carbonates are responsible for the feature observed by TES and Mini-TES at 6.76 μm, alternative hypotheses suggest that it could be due to the presence of Hydrated Iron Sulfates (HIS). Carbonates can be discerned from HIS by investigating the spectral region in which a strong overtone carbonate band is present. The Planetary Fourier Spectrometer on board the Mars Express spacecraft has acquired several thousand martian spectra in the range 1.2-45 μm since January 2004, most of which show a weak absorption feature between 3.8 and 4 μm. A similar feature was observed previously from the Earth, but its origin could not be straightforwardly ascribed to surface materials, and specifically to carbonates. Here we show the surficial nature of this band that can be ascribed to carbonate mixed with the martian soil materials. The materials that best reproduce the detected feature are Mg-rich carbonates (huntite [CaMg₃(CO₃)₄] and/or magnesite [MgCO₃]). The presence of carbonates is demonstrated in both bright and dark martian regions. An evaluation of the likeliest abundance gives an upper limit of ∼10 wt%. The widespread distribution of carbonates supports scenarios that suggest carbonate formation occurred not by precipitation in a water-rich environment but by weathering processes.     

Protection of chemolithoautotrophic bacteria exposed to simulated Mars environmental conditions

Current surface conditions (strong oxidative atmosphere, UV radiation, low temperatures and xeric conditions) on Mars are considered extremely challenging for life. The question is whether there are any features on Mars that could exert a protective effect against the sterilizing conditions detected on its surface. Potential habitability in the subsurface would increase if the overlaying material played a protective role. With the aim of evaluating this possibility we studied the viability of two microorganisms under different conditions in a Mars simulation chamber. An acidophilic chemolithotroph isolated from Río Tinto belonging to the Acidithiobacillus genus and Deinococcus radiodurans, a radiation resistant microorganism, were exposed to simulated Mars conditions under the protection of a layer of ferric oxides and hydroxides, a Mars regolith analogue. Samples of these microorganisms were exposed to UV radiation in Mars atmospheric conditions at different time intervals under the protection of 2 and 5 mm layers of oxidized iron minerals. Viability was evaluated by inoculation on fresh media and characterization of their growth cultures. Here we report the survival capability of both bacteria to simulated Mars environmental conditions.     

Mapping the mesospheric CO2 clouds on Mars: MEx/OMEGA and MEx/HRSC observations and challenges for atmospheric models

This study presents the latest results on the mesospheric CO₂ clouds in the martian atmosphere based on observations by OMEGA and HRSC onboard Mars Express. We have mapped the mesospheric CO₂ clouds during nearly three martian years of OMEGA data yielding a cloud dataset of ∼60 occurrences. The global mapping shows that the equatorial clouds are mainly observed in a distinct longitudinal corridor, at seasons L_s = 0-60° and again at and after L_s = 90°. A recent observation shows that the equatorial CO₂ cloud season may start as early as at L_s = 330°. Three cases of mesospheric midlatitude autumn clouds have been observed. Two cloud shadow observations enabled the mapping of the cloud optical depth (τ = 0.01-0.6 with median values of 0.13-0.2 at λ = 1 μm) and the effective radii (mainly 1-3 μm with median values of 2.0-2.3 μm) of the cloud crystals. The HRSC dataset of 28 high-altitude cloud observations shows that the observed clouds reside mainly in the altitude range ∼60-85 km and their east-west speeds range from 15 to 107 m/s. Two clouds at southern midlatitudes were observed at an altitude range of 53-62 km. The speed of one of these southern midlatitude clouds was measured, and it exhibited west-east oriented speeds between 5 and 42 m/s. The seasonal and geographical distribution as well as the observed altitudes are mostly in line with previous work. The LMD Mars Global Climate Model shows that at the cloud altitude range (65-85 km) the temperatures exhibit significant daily variability (caused by the thermal tides) with the coldest temperatures towards the end of the afternoon. The GCM predicts the coldest temperatures of this altitude range and the season L_s = 0-30° in the longitudinal corridor where most of the cloud observations have been made. However, the model does not predict supersaturation, but the GCM-predicted winds are in fair agreement with the HRSC-measured cloud speeds. The clouds exhibit variable morphologies, but mainly cirrus-type, filamented clouds are observed (nearly all HRSC observations and most of OMEGA observations). In ∼15% of OMEGA observations, clumpy, round cloud structures are observed, but very few clouds in the HRSC dataset show similar morphology. These observations of clumpy, cumuliform-type clouds raise questions on the possibility of mesospheric convection on Mars, and we discuss this hypothesis based on Convective Available Potential Energy calculations.     

Extended survival of several organisms and amino acids under simulated martian surface conditions

Recent orbital and landed missions have provided substantial evidence for ancient liquid water on the martian surface as well as evidence of more recent sedimentary deposits formed by water and/or ice. These observations raise serious questions regarding an independent origin and evolution of life on Mars. Future missions seek to identify signs of extinct martian biota in the form of biomarkers or morphological characteristics, but the inherent danger of spacecraft-borne terrestrial life makes the possibility of forward contamination a serious threat not only to the life detection experiments, but also to any extant martian ecosystem. A variety of cold and desiccation-tolerant organisms were exposed to 40 days of simulated martian surface conditions while embedded within several centimeters of regolith simulant in order to ascertain the plausibility of such organisms’ survival as a function of environmental parameters and burial depth. Relevant amino acid biomarkers associated with terrestrial life were also analyzed in order to understand the feasibility of detecting chemical evidence for previous biological activity. Results indicate that stresses due to desiccation and oxidation were the primary deterrent to organism survival, and that the effects of UV-associated damage, diurnal temperature variations, and reactive atmospheric species were minimal. Organisms with resistance to desiccation and radiation environments showed increased levels of survival after the experiment compared to organisms characterized as psychrotolerant. Amino acid analysis indicated the presence of an oxidation mechanism that migrated downward through the samples during the course of the experiment and likely represents the formation of various oxidizing species at mineral surfaces as water vapor diffused through the regolith. Current sterilization protocols may specifically select for organisms best adapted to survival at the martian surface, namely species that show tolerance to radical-induced oxidative damage and low water activity environments. Additionally, any hypothetical martian ecosystems may have evolved similar physiological traits that allow sporadic metabolism during periods of increased water activity.     

Crustal recycling, mantle dehydration, and the thermal evolution of Mars

We have reinvestigated the coupled thermal and crustal evolution of Mars taking new laboratory data concerning the flow behavior of iron-rich olivine into account. The low mantle viscosities associated with the relatively higher iron content of the martian mantle as well as the observed high concentrations of heat producing elements in a crust with a reduced thermal conductivity were found to promote phases of crustal recycling in many models. As crustal recycling is incompatible with an early separation of geochemical reservoirs, models were required to show no episodes of crustal recycling. Furthermore, admissible models were required to reproduce the martian crust formation history, to allow for the formation of partial melt under present day mantle conditions and to reproduce the measured concentrations of potassium and thorium on the martian surface. Taking dehydration stiffening of the mantle viscosity by the extraction of water from the mantle into account, we found that admissible models have low initial upper mantle temperatures around 1650 K, preferably a primordial crustal thickness of 30 km, and an initially wet mantle rheology. The crust formation process on Mars would then be driven by the extraction of a primordial crust after core formation, cooling the mantle to temperatures close to the peridotite solidus. According to this scenario, the second stage of global crust formation took place over a more extended period of time, waning at around 3500 Myr b.p., and was driven by heat produced by the decay of radioactive elements. Present-day volcanism would then be driven by mantle plumes originating at the core-mantle boundary under regions of locally thickened, thermally insulating crust. Water extraction from the mantle was found to be relatively efficient and close to 40% of the total inventory was lost from the mantle in most models. Assuming an initial mantle water content of 100 ppm and that 10% of the extracted water is supplied to the surface, this amount is equivalent to a 14 m thick global surface layer, suggesting that volcanic outgassing of H₂O could have significantly influenced the early martian climate and increased the planet’s habitability.     

Infrared imaging spectroscopy of Mars: H2O mapping and determination of CO2 isotopic ratios

High-resolution infrared imaging spectroscopy of Mars has been achieved at the NASA Infrared Telescope Facility (IRTF) on June 19-21, 2003, using the Texas Echelon Cross Echelle Spectrograph (TEXES). The areocentric longitude was 206°. Following the detection and mapping of hydrogen peroxide H₂O₂ [Encrenaz et al., 2004. Icarus 170, 424-429], we have derived, using the same data set, a map of the water vapor abundance. The results appear in good overall agreement with the TES results and with the predictions of the Global Circulation Model (GCM) developed at the Laboratory of Dynamical Meteorology (LMD), with a maximum abundance of water vapor of 3±1.5×¹⁰⁻⁴(17±9 pr-μm). We have searched for CH₄ over the martian disk, but were unable to detect it. Our upper limits are consistent with earlier reports on the methane abundance on Mars. Finally, we have obtained new measurements of CO₂ isotopic ratios in Mars. As compared to the terrestrial values, these values are: (¹⁸O/¹⁷O)[M/E] = 1.03 ± 0.09; (¹³C/¹²C)[M/E] = 1.00 ± 0.11. In conclusion, in contrast with the analysis of Krasnopolsky et al. [1996. Icarus 124, 553-568], we conclude that the derived martian isotopic ratios do not show evidence for a departure from their terrestrial values.     

Thermal alteration of nontronite and montmorillonite: Implications for the martian surface

To test the effects of meteorite impacts on martian phyllosilicate deposits, we heated two smectites (nontronite and montmorillonite) to temperatures ranging from 350 °C to 1150 °C for durations of 4-24 h in two different atmospheres, under air and a steady flow of CO₂. Samples were analyzed using X-ray diffraction (XRD) and near-infrared (NIR) and mid-infrared (MIR) reflectance spectroscopy. Interlayer water was lost after heating to temperatures of ∼400 °C. Between 400 °C and 700 °C, nontronite converted to an intermediary phase which conserved the XRD pattern of untreated nontronite with the exception of the 0 0 1 peak. Nanocrystalline high-temperature phases formed for both smectites at temperatures between 700 °C and 1000 °C. Finally, after being heated to temperatures above ∼1100 °C, the samples melted and recrystallized into secondary phases. Secondary high-temperature phases included sillimanite and cristobalite for both smectites plus hematite for nontronite. NIR and MIR reflectance spectra significantly evolved with increasing temperature. NIR spectra of smectites showed that 1.4 and 1.9 μm bands decrease in intensity and disappear above 700 °C. Similarly, the 2.2-2.3 μm metal-OH band showed a decrease in intensity as well as an overall shift towards lower wavelengths (for nontronite) due to the thermal resistance of the Al-OH bond compared to the Fe-OH bond. NIR spectra of montmorillonite showed a gradual increase in band depth up to temperatures between 500 °C and 600 °C, then decreased with increasing temperature. In the MIR spectra of samples heated to temperatures above ∼1100 °C, newly formed bands confirmed the secondary phases identified by XRD. Similarities between the NIR spectra of our heated samples and the phyllosilicates in some martian craters imply that these phyllosilicates were altered by the impact-generated heat and thus were not formed post-impact. In addition, NIR reflectance spectra provide a proxy for shock temperatures of smectites up to 700 °C while MIR is optimum for identification of high-temperature phases of smectites above 700 °C.     

Incorporation of argon, krypton and xenon into clathrates on Mars

Calculations of the trapping of heavy noble gases within multiple guest clathrates under Mars-like conditions show that a substantial fraction of the martian Xe, perhaps even the vast majority, could be in clathrates. In addition, the Xe/Kr ratio in the clathrates would probably be much higher than in the atmosphere, so the formation or dissociation of a relatively small amount of clathrate could measurably change the atmospheric ratio. Relatively crude (factor of 2) measurements of the seasonal variability in that ratio by in situ spacecraft would be sensitive to ∼10% of the seasonal atmospheric CO₂ variability being a result of clathrates, rather than pure CO₂ frost. In addition, sequestration of Xe in clathrates remains a viable mechanism for explaining the variable Xe/Kr ratios seen in different suites of martian meteorites.     

Comparison of PFS and TES observations of temperature and water vapor in the martian atmosphere

The interval from L_s = 330° in Mars Year (MY) 26 until L_s = 84° in MY 27 has been used to compare and validate measurements from the Mars Global Surveyor Thermal Emission Spectrometer (TES) and the Mars Express Planetary Fourier Spectrometer (PFS). We studied differences between atmospheric temperatures observed by the two instruments. The best agreement between atmospheric temperatures was found at 50 Pa between 40°S and 40°N latitude, where differences were within ±5 K. For other atmospheric levels, differences as large as ∼25 K were observed between the two instruments at some locations. The largest temperature differences occurred mainly over the Hellas Planitia, Argyre Planitia, Tharsis and Valles Marineris regions.On this basis we report on the variability of the martian atmosphere during the 5.5 martian years of Mars climatology obtained by combining the two data sets from TES and PFS. Atmospheric temperatures at 50 Pa responded to the global-scale dust storms of MY 25 and in MY 28 raising temperatures from ∼220 K to ∼250 K during the daytime. An atmospheric temperature of ∼140 K at 50 Pa was observed poleward of 70°N during northern winter and poleward of 60°S during southern winter each year in both the PFS and TES results. Water vapor observed by the two spectrometers showed consistent seasonal and latitudinal variations.     

The density of the upper martian atmosphere measured by Lyman-α absorption with Mars Express SPICAM

Absorption of interplanetary Lyman-α emission by Mars’ nightside lower thermosphere was observed by Mars Express Spectrometer for Investigation of Characteristics of the Atmosphere of Mars (SPICAM), and is analyzed to derive the CO₂ density at 110 km during a martian year. The observed density seasonal variability is consistent with recent observations obtained by stellar occultations, proving that this method, though not as accurate as stellar occultations could be used complementary to them to characterize large variations of thermospheric density on Mars and provide a better spatial coverage by Lyman-α imagery.