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.     

Adsorptive fractionation of HDO on JSC MARS-1 during sublimation with implications for the regolith of Mars

A chamber was constructed to simulate the boundary between the ice table, regolith and atmosphere of Mars and to examine fractionation between H₂O and HDO during sublimation under realistic martian conditions of temperature and pressure. Thirteen experimental runs were conducted with regolith overlying the ice. The thickness and characteristic grain size of the regolith layer as well as the temperature of the underlying ice was varied. From these runs, values for the effective diffusivity, taking into account the effects of adsorption, of the regolith were derived. These effective diffusivities ranged from 1.8 × 10⁻⁴ m² s⁻¹ to 2.2 × 10⁻³ m² s⁻¹ for bare ice and from 2.4 × 10⁻¹¹ m² s⁻¹ to 2.0 × 10⁻⁹ m² s⁻¹ with an adsorptive layer present. From these, latent heats of adsorption of 8.6 ± 2.6 kJ mol⁻¹ and 9.3 ± 2.8 kJ mol⁻¹ were derived at ice-surface temperatures above 223 ± 8 K and 96 ± 28 kJ mol⁻¹ and 104 ± 31 kJ mol⁻¹ respectively for H₂O and HDO were derived at colder temperatures. For temperatures below 223 K, the effective diffusivity of HDO was found to be lower than the diffusivity of H₂O by 40% on average, suggesting that the regolith was adsorptively fractionating the sublimating gas with a fractionation factor of 1.96 ± 0.74. Applying these values to Mars predicts that adsorbed water on the regolith is enriched in HDO compared to the atmosphere, particularly where the regolith is colder. Based on current observations, the D/H ratio of the regolith may be as high as 21 ± 8 times VSMOW at 12°S and L_S = 357° if the regolith is hydrated primarily by the atmosphere, neglecting any hydration from subsurface ice.     

Spectral unmixing for mineral identification in pancam images of soils in Gusev crater, Mars

The objective of this work is to propose an automated unmixing technique for the analysis of 11-channel Mars Exploration Rover Panoramic Camera (MER/Pancam) spectra. Our approach is to provide a screening tool for identifying unique/distinct reflectance spectra. We demonstrate the utility of this unmixing technique in a study of the mineralogy of the bright salty soils exposed by the rover wheels in images of Gusev crater regions known as Paso Robles (Sols 400,426), Arad (Sol 721), and Tyrone (Sol 790). The unmixing algorithm is based on a novel derivation of the Nonnegative Matrix Factorization technique and includes added features that preclude the adverse effects of low abundance materials that would otherwise skew the unmixing. In order to create a full 11-channel spectrum out of the left and right eye stereo pairs, we also developed a new registration procedure that includes rectification and disparity calculation of the images. We identified two classes of endmember spectra for the bright soils imaged on Sols 426 and 790. One of these endmember classes is also observed for soils imaged on Sols 400 and 721 and has a unique spectral shape that is distinct from most iron oxide, sulfate and silicate spectra and differs from typical martian surface spectra. Instead, its unique spectral character resembles the spectral shape of the ferric sulfate minerals fibroferrite (Fe³⁺(SO₄)(OH) · 5H₂O) and ferricopiapite and the phosphate mineral ferristrunzite . The other endmember class is less consistent with specific minerals and is likely a mixture of altered volcanic material and some bright salts. Further analyses of data from Sols 400 and 790 using an anomaly detection algorithm as a tool for detecting low abundance materials additionally suggests the identification of the sulfate mineral paracoquimbite (Fe₂(SO₄)₃ · 9H₂O). This spectral study of Pancam images of the bright S- and P-enriched soils of Gusev crater identifies specific ferric sulfate and ferric phosphate minerals that are consistent with the unique spectral properties observed here in the 0.4-1 μm range.     

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.     

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.     

Water sorption on martian regolith analogs: Thermodynamics and near-infrared reflectance spectroscopy

The near-infrared reflectance spectra of the martian surface present strong absorption features attributed to hydration water present in the regolith. In order to characterize the relationships between this water and atmospheric vapor and decipher the physical state of water molecules in martian regolith analogs, we designed and built an experimental setup to measure near-IR reflectance spectra under martian atmospheric conditions. Six samples were studied that cover part of the diversity of Mars surface mineralogy: a hydrated ferric oxide (ferrihydrite), two igneous samples (volcanic tuff, and dunite sand), and three potential water rich soil materials (Mg-sulfate, smectite powder and a palagonitic soil, the JSC Mars-1 regolith stimulant). Sorption and desorption isotherms were measured at 243 K for water vapor pressure varying from 10⁻⁵ to ∼0.3 mbar (relative humidity: 10⁻⁴ to 75%). These measurements reveal a large diversity of behavior among the sample suite in terms of absolute amount of water adsorbed, shape of the isotherm and hysteresis between the adsorption and desorption branches. Simultaneous in situ spectroscopic observations permit a detailed analysis of the spectral signature of adsorbed water and also point to clear differences between the samples. Ferric (oxy)hydroxides like ferrihydrite or other phases present in palagonitic soils are very strong water adsorbent and may play an important role in the current martian water cycle by allowing large exchange of water between dust-covered regions and atmosphere at diurnal and seasonal scales.     

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.     

Novel solvent systems for in situ extraterrestrial sample analysis

The life marker chip (LMC) is being designed to test for the chemical signature of life in the soil and rocks of Mars. It will use an antibody array as part of its detection and characterisation system and aims to detect both polar and non-polar molecules at the sub-ppm to tens of ppb level. It is necessary to use a solvent to transfer organic compounds from the Martian samples to the LMC itself, but organic solvents such as dichloromethane or hexane, commonly used to dissolve non-polar molecules, are incompatible with the LMC antibodies. Hence, an aqueous-based solvent capable of dissolving the biomarkers that might exist in the soil or rocks of Mars is required. Solvent extractions of a Martian soil analogue, JSC Mars-1, spiked with a range of standards show that a 20:80 (vol:vol) mixture of methanol and water is incapable of extracting compounds insoluble in water. However, addition of 1.5 mg ml⁻¹ of the surfactant polysorbate 80 produces extraction efficiencies of the aliphatic standards, hexadecane and phytane, equal to 25-30% of those produced by the common organic solvent mixture 93:7 (vol:vol) dichloromethane:methanol. Extraction of squalene and stigmasterol using the polysorbate solution is less efficient but still successful, at 5-10% of the efficiency of 93:7 dichloromethane:methanol. Such aliphatic compounds with occasional functional groups represent the compound classes to which most fossil organic biomarkers belong. The polysorbate solution did not extract the aromatic compounds pyrene and anthracene with great efficiency. A solvent of 20:80 methanol:water with 1.5 mg ml⁻¹ polysorbate 80 is therefore capable of selectively extracting aliphatic biomarkers from Martian samples and transferring them to the antibody sites on the life marker chip.     

Zero-valent iron on Mars: An alternative energy source for methanogens

Zero-valent iron, montmorillonite-like smectites, and CO₂ gas are known to exist on Mars, and work was performed to investigate the ability of methanogens to subsist on these materials. After 71 days of incubation at 55 °C, mean methane concentration as percent of headspace volume was 19.80 ± 1.76% (mean ± SE) for replicates containing elemental iron and 0.50 ± 0.15% for those lacking elemental iron.     

MARCI and MOC observations of the atmosphere and surface cap in the north polar region of Mars

We used MGS-MOC and MRO-MARCI daily mapping images of the North Polar Region of Mars from 16 August 2005 (L_s = 270°) to 21 May 2009 (L_s = 270°), covering portions of three consecutive martian years (MY 27-MY 29), to observe the seasonal behavior of the polar ice cap and atmospheric phenomena. The rate of cap regression was similar in MY 28 and MY 29, but was advanced by 3.5° of L_s (∼7-8 sols) in MY 29. The spatial and temporal behaviors of dust and condensate clouds were similar in the two years and generally in accord with prior years. Dust storms (>100 km²) were observed in all seasons, with peak activity occurring at L_s = 10-20° from 50°N to 70°N and at L_s = 135-140° from 70°N to 90°N. The most active quadrant was 0-90°W in MY 28, shifting to 180-270°W in MY 29. The majority of regional storms in both years developed in longitudes from 10°W to 60°W. During late summer the larger storms obscure the North Polar Region in a cloud of dust that transitions to north polar hood condensate clouds around autumnal equinox.Changes in the distribution of perennial ice deposits, especially in Olympia Planum, were observed between the 2 years, with the MY 29 ice distribution being the most extensive observed to date. Modeling suggests that the small, bright ice patches on the residual cap are not the result of slope or elevation effects. Rather we suggest that they are the result of local meteorological effects on ice deposition. The annual darkening and brightening of peripheral areas of the residual cap around summer solstice can be explained by the sublimation of a brighter frost layer revealing an underlying darker, ice rich layer that itself either sublimes to reveal brighter material below or acts as a cold trap, attracting condensation of water vapor that brightens the surface. An alternative explanation invokes transport and deposition of dust on the surface from the cap interior, and later removal of that dust. The decrease in cap albedo and accompanying increase in near surface atmospheric stability may be related to the annual minimum of polar storm activity near northern summer solstice.     

Estimation of the escape of photoelectrons from Mars in 2004 liberated by the ionization of carbon dioxide and atomic oxygen

Photoelectron peaks in the atmosphere of Mars caused by the ionization of carbon dioxide and atomic oxygen by solar 30.4 nm photons have been observed by the Electron Spectrometer (ELS), a component of the Mars Express (MEx) Analyzer of Space Plasmas and Energetic Atoms (ASPERA-3) experiment. Ionization mostly occurs at the Mars exobase with the majority of the photoionized electron flux trapped in the remanent and induced magnetic field, with a portion of that flux escaping the planet down its tail. Since Mars is overall charge neutral, the number of electrons must be identical to the number of ion charges which escape the planet. An estimate of the fraction of the total number of escaping electrons is obtained for the year 2004, specifically those produced by the ionization of carbon dioxide and atomic oxygen by solar 30.4 nm photons. In achieving this process, an illustrative example pass is used to show how the electron spectrum is adjusted for the potential on the spacecraft; then the region of the electron spectrum which shows photoelectron peaks is integrated over energy, yielding a flux of 5.74 × 10⁶ electrons/(cm² s sr). This technique is then applied to a subset of 22 sample averaged spectra from the 2004 data (5 January 2004 through 25 January 2005), yielding an average result of 4.15 × 10⁶ electrons/(cm² s sr) for the 22 cases. The observation cone of 33.75° is used to integrate over solid angle (assuming the flux is constant), giving 4.39 × 10⁶ electrons/(cm² s). This average value was taken as representative of the full data interval. Frequency of occurrence statistics showing about a 6.2% occurrence rate for the 2004 data is applied to give an average escape flux from Mars of 2.72 × 10⁵ electrons/(cm² s) during 2004. By estimating the outflow area as 1.16 × 10¹⁸ cm² at X = −1.5 R_Mars the electron escape rate of 3.14 × 10²³ electrons/s is obtained. Thus about 9.92 × 10³⁰ electrons or 16.5 Mmole of electrons escaped Mars during 2004 due to the ionization of carbon dioxide and atomic oxygen by the He 30.4 nm line. Due to the caveats of the analysis, these derived escape rates should be considered lower limits on the total electron escape rate from Mars.     

Solar activity variations of thermospheric temperatures on Mars and a problem of CO in the lower atmosphere

Long-term MGS drag density observations at 390 km reveal variations of the density with season L_S (by a factor of 2) and solar activity index F_10.7 (by a factor of 3 for F_10.7 = 40-100). According to Forbes et al. (Forbes, J.M., Lemoine, F.G., Bruinsma, S.L., Smith, M.D., Zhang, X. [2008]. Geophys. Res. Lett. 35, L01201, doi:10.1029/2007GL031904), the variation with F_10.7 reflects variations of the exospheric temperature from 192 to 284 K. However, the derived temperature range corresponds to variation of the density at 390 km by a factor of 8, far above the observed factor of 3. The recent thermospheric GCMs agree with the derived temperatures but do not prove their adequacy to the MGS densities at 390 km. A model used by Forbes et al. neglects effects of eddy diffusion, chemistry and escape on species densities above 138 km. We have made a 1D-model of neutral and ion composition at 80-400 km that treats selfconsistently chemistry and transport of species with F_10.7, T_∞, and [CO₂]_80 km as input parameters. Applying this model to the MGS densities at 390 km, we find variation of T_∞ from 240 to 280 K for F_10.7 = 40 and 100, respectively. The results are compared with other observations and models. Temperatures from some observations and the latest models disagree with the MGS densities at low and mean solar activity. Linear fits to the exospheric temperatures are T_∞ = 122 + 2.17F_10.7 for the observations, T_∞ = 131 + 1.46F_10.7 for the latest models, and T_∞ = 233 + 0.54F_10.7 for the MGS densities at 390 km. Maybe the observed MGS densities are overestimated near solar minimum when they are low and difficult to measure. Seasonal variations of Mars’ thermosphere corrected for the varying heliocentric distance are mostly due to the density variations in the lower and middle atmosphere and weakly affect thermospheric temperature. Nonthermal escape processes for H, D, H₂, HD, and He are calculated for the solar minimum and maximum conditions.Another problem considered here refers to Mars global photochemistry in the lower and middle atmosphere. The models gave too low abundances of CO, smaller by an order of magnitude than those observed. Our current work shows that modifications in the boundary conditions proposed by Zahnle et al. (Zahnle, K., Haberle, R.M., Catling, D.C., Kasting, J.F. [2008]. J. Geophys. Res. 113, E11004, doi:10.1029/2008JE003160) are reasonable but do not help to solve the problem.     

O2 1.27 μm emission maps as derived from OMEGA/MEx data

We present a method to derive the 2D maps of the O₂ (a¹Δ_g) airglow emission at 1.27 μm from the OMEGA/MEx nadir observations. The OMEGA imaging capabilities allow monitoring the 2D distribution, daily and seasonal variation of the O₂ emission intensities with a detection limit of 4 MR. The highest values, of the order of ∼31 MR, are found on the south pole for 11 h < LT < 13 h, during the early spring (186° < Ls < 192°) of martian year (MY) 27, according to the Mars Year numbering scheme of Clancy et al. [Clancy, R.T., Wolff, M.J., Christensen, P.R., 2003. Mars aerosol studies with the MGS TES emission phase function observations: Optical depths, particle sizes, and ice cloud types versus latitude and solar longitude. J. Geophys. Res. 108. doi: 10.1029/2003JE002058]. In the polar regions the day-by-day variability, associated with polar vortex turbulences, is obtained of the order of 30-50% as predicted by the model [Lefévre, F., Lebonnois, S., Montmessin, F., Forget, F., 2004. Three-dimensional modeling of ozone on Mars. J. Geophys. Res. 109, E07004. doi: 10.1029/2004JE002268] and found by SPICAM [Perrier, S., Bertaux, J.-L., Lebonnois, S., Korablev, O., Fedorova, A., 2006. Global distribution of total ozone on Mars from SPICAM/MEX UV measurements. J. Geophys. Res. 111, E09S06. doi: 10.1029/2006JE002681]. In the considered set of data a maximum of the O₂ emission is observed between 11 h and 15 h LT in the latitude range 70-85° during early spring on both hemispheres, while for the southern autumn-winter season a maximum is found between 50° and 60° in the southern hemisphere for MY28. Increase of intensity of the O₂ emission observed from Ls 130° to 160° at southern high latitudes may be explained by increase of solar illumination conditions in the maps acquired during the considered period.Atmospheric waves crossing the terminator on the southern polar regions are observed for the first time during the MY28 early spring. The spatial scale of the waves ranges from 100 to 130 km, and the intensity fluctuations are of the order of 4MR.This study confirms the high potentiality of O₂ (a¹Δ_g) day glow as a passive tracer of the martian atmosphere dynamics at high latitudes.     

HiRISE observations of gas sublimation-driven activity in Mars’ southern polar regions: II. Surficial deposits and their origins

The High Resolution Imaging Science Experiment (HiRISE) onboard Mars Reconnaissance Orbiter (MRO) has been used to monitor the seasonal evolution of several regions at high southern latitudes and, in particular, the jet-like activity which may result from the process described by Kieffer (JGR, 112, E08005, doi:10.1029/2006JE002816, 2007) involving translucent CO₂ ice. In this work, we mostly concentrate on observations of the Inca City (81°S, 296°E) and Manhattan (86°S, 99°E) regions in the southern spring of 2007. Two companion papers, [Hansen et al. this issue] and [Portyankina et al. this issue], discuss the surface features in these regions and specific models of the behaviour of CO₂ slab ice, respectively. The observations indicate rapid on-set of activity in late winter initiating before HiRISE can obtain adequately illuminated images (Ls < 174° at Inca City). Most sources become active within the subsequent 8 weeks. Activity is indicated by the production of dark deposits surrounded by brighter bluer deposits which probably arise from the freezing out of vented CO₂ [Titus et al., 2007. AGU (abstract P41A-0188)]. These deposits originate from araneiform structures (spiders), boulders on ridges, cracks on slopes, and along linear cracks in the slab ice on flatter surfaces. The type of activity observed can often be explained qualitatively by considering the local topography. Some dark fans are observed to shorten enormously in length on a timescale of 18 days. We consider this to be strong evidence that outgassing was in progress at the time of HiRISE image acquisition and estimate a total particulate emission rate of >30 g s⁻¹ from a single typical jet feature. Brighter deposits at Inca City become increasingly hard to detect after Ls = 210°. In the Inca City region, the orientations of surficial deposits are topographically controlled. The deposition of dark material also appears to be influenced by local topography suggesting that the ejection from the vents is at low velocity (<10 m s⁻¹) and that a ground-hugging flow process (a sort of “cryo-fumarole”) may be occurring. The failure up to this point to obtain a clear detection of outgassing though stereo imaging is consistent with low level transport. The downslope orientation of the deposits may result from the geometry of the vent or from catabatic winds. At many sites, more than one ejection event appears to have occurred suggesting re-charging of the sources. Around Ls = 230°, the brightness of the surface begins to drop rapidly on north-facing slopes and the contrast between the dark deposits and the surrounding surface reduces. This indicates that the CO₂ ice slab is being lost completely in some areas at around this time. By Ls = 280°, at Inca City, the ice slab has effectively gone. CRISM band ratios and THEMIS brightness temperature measurements are consistent with this interpretation.     

Impact of two DNA repair pathways, homologous recombination and non-homologous end joining, on bacterial spore inactivation under simulated martian environmental conditions

Spores of Bacillus subtilis were used as a model system to study the impact of the two major DNA double-strand break (DSB) repair mechanisms [homologous recombination (HR) and non-homologous end-joining (NHEJ)] on the survivability of air-dried mono- and multilayers of bacterial spores under a simulated martian environment; i.e., an environment with low temperature (−10 °C), pure CO₂ atmosphere (99.99% CO₂), 200-1100 nm UV-VIS-NIR radiation, and 0.69 kPa pressure. Spores in multilayers exhibited low inactivation rates compared to monolayers, mainly due to shadowing effects of overlying spores. Simulated martian UV irradiation reduced dramatically spore viability, whereas when shielded from martian UV radiation, spores deficient in NHEJ- and HR-mediated DNA repair were significantly more sensitive to simulated martian environmental conditions than were wild-type spores. In addition, NHEJ-deficient spores were consistently more sensitive than HR-deficient spores to simulated Mars environmental conditions, suggesting that DSBs were an important type of DNA damage. The results indicated that both HR and NHEJ provide an efficient set of DNA repair pathways ensuring spore survival after exposure to simulated martian environmental conditions.     

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.     

Evaporation effects on the formation of martian gullies

In order to investigate the formation of martian gullies and the stability of fluids on Mars, we examined about 120 gully images. Twelve HiRISE images contained a sufficient number of Transverse Aeolian Ridges (TARs) associated with the gullies to make the following measurements: overall gully length, length of the alcove, channel and apron, and we also measured the frequency of nearby TARs. Six of the 12 images examined showed a statistically significant negative correlation between overall gully length (alcove, channel and apron length) and TAR frequency. Previous experimental work from our group has shown that at temperatures below ∼200 K, evaporation rate increases by about an order of magnitude as wind speed increases from 0 to ∼15 m/s. Thus the negative correlations we observe between gully length and dune frequency can be explained by formation at temperatures below ∼200 K where wind speed/evaporation is a factor governing gully length. In these cases evaporation of the fluid carving the gully was a constraint on their dimensions. Cases where there is no correlation between gully length and TAR frequency, can be explained by formation at temperatures >200 K. The temperatures are consistent with Global Circulation Model and Thermal Emission Spectrometer (TES) data for these latitudes. The temperatures suggested by these trends are consistent with the fluid responsible for gully formation being a strong brine, such as Fe₂(SO₄)₃ which has a eutectic temperature of ∼200 K. We also find that formation timescales for gullies are 10⁵-10⁶ years.     

Discovery of jarosite within the Mawrth Vallis region of Mars: Implications for the geologic history of the region

Analysis of visible to near infrared reflectance data from the MRO CRISM hyperspectral imager has revealed the presence of an ovoid-shaped landform, approximately 3 by 5 km in size, within the layered terrains surrounding the Mawrth Vallis outflow channel. This feature has spectral absorption features consistent with the presence of the ferric sulfate mineral jarosite, specifically a K-bearing jarosite (KFe₃(SO₄)₂(OH)₆). Terrestrial jarosite is formed through the oxidation of iron sulfides in acidic environments or from basaltic precursor minerals with the addition of sulfur. Previously identified phyllosilicates in the Mawrth Vallis layered terrains include a basal sequence of layers containing Fe-Mg smectites and an upper set of layers of hydrated silica and aluminous phyllosilicates. In terms of its fine scale morphology revealed by MRO HiRISE imagery, the jarosite-bearing unit has fracture patterns very similar to that observed in Fe-Mg smectite-bearing layers, but unlike that observed in the Al-bearing phyllosilicate unit. The ovoid-shaped landform is situated in an east-west bowl-shaped depression superposed on a north sloping surface. Spectra of the ovoid-shaped jarosite-bearing landform also display an anomalously high 600 nm shoulder, which may be consistent with the presence of goethite and a 1.92 μm absorption which could indicate the presence of ferrihydrite. Goethite, jarosite, and ferrihydrite can be co-precipitated and/or form through transformation of schwertmannite, both processes generally occurring under low pH conditions (pH 2-4). To date, this location appears to be unique in the Mawrth Vallis region and could represent precipitation of jarosite in acidic, sulfur-rich ponded water during the waning stages of drying.     

A geomorphic analysis of Hale crater, Mars: The effects of impact into ice-rich crust

Hale crater, a 125 × 150 km impact crater located near the intersection of Uzboi Vallis and the northern rim of Argyre basin at 35.7°S, 323.6°E, is surrounded by channels that radiate from, incise, and transport material within Hale’s ejecta. The spatial and temporal relationship between the channels and Hale’s ejecta strongly suggests the impact event created or modified the channels and emplaced fluidized debris flow lobes over an extensive area (>200,000 km²). We estimate ∼10¹⁰ m³ of liquid water was required to form some of Hale’s smaller channels, a volume we propose was supplied by subsurface ice melted and mobilized by the Hale-forming impact. If 10% of the subsurface volume was ice, based on a conservative porosity estimate for the upper martian crust, 10¹² m³ of liquid water could have been present in the ejecta. We determine a crater-retention age of 1 Ga inside the primary cavity, providing a minimum age for Hale and a time at which we propose the subsurface was volatile-rich. Hale crater demonstrates the important role impacts may play in supplying liquid water to the martian surface: they are capable of producing fluvially-modified terrains that may be analogous to some landforms of Noachian Mars.     

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.