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.     

Rapid inactivation of seven Bacillus spp. under simulated Mars UV irradiation

Seven Bacillus spp. were exposed to simulations of Mars-normal UV fluence rates in order to study the effects of UV irradiation on microbial survival. A UV illumination system was calibrated to deliver 9.78 W m⁻² (35.2 kJ m⁻² h⁻¹) of UVC + UVB irradiation (200-320 nm) to microbial samples, thus creating a clear-sky simulation (0.5 optical depth) of equatorial Mars. The Bacillus spp. studied were: B. licheniformis KL-196, B. megaterium KL-197, B. nealsonii FO-092, B. pumilus FO-36B, B. pumilus SAFR-032, B. subtilis 42HS1, and B. subtilis HA101. The bacteria were prepared as thin monolayers of endospores on aluminum coupons in order to simulate contaminated spacecraft surfaces. Bacterial monolayers were exposed to Mars UV irradiation for time-steps of 0, 0.25, 0.5, 1, 5, 15, 30, 60, 120, or 180 min. The surviving endospores were then assayed with a Most Probable Numbers (MPN) procedure and with a culture-based assay that utilized a bacillus spore germination medium. Results indicated that B. pumilus SAFR-032 was the most resistant, and B. subtilis 42HS-1 and B. megaterium were the most sensitive of the seven strains exposed to martian UV fluence rates. Bacillus subtilis 42HS1 and B. megaterium were inactivated after 30 min exposure to Mars UV, while B. pumilus SAFR-032 required 180 min for full inactivation in both assays. Spores of B. pumilus SAFR-032 exhibited significantly different inactivation kinetics suggesting that this wild type isolate also was more resistant than the standard dosimetric strain, B. subtilis HA101. Although the various Bacillus spp. exhibited diverse levels of UV resistance, none were immune to UV irradiation, and, thus, all species would be expected to be inactivated on Sun-exposed spacecraft surfaces within a few tens-of-minutes to a few hours on sol 1 under clear-sky conditions on equatorial Mars. The inactivation kinetics of all seven Bacillus spp. support the conclusion that significant levels of bioload reductions are possible on Sun-exposed spacecraft surfaces in very short time periods under clear-sky conditions on Mars. However, the presence of UV resistant microbes on spacecraft surfaces rapidly covered in dust during landing operations, and non-Sun-exposed surfaces of spacecraft remain concerns that must continue to be addressed through adequate spacecraft sanitizing procedures prior to launch.     

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.     

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.     

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.     

Alteration of five organic compounds by glow discharge plasma and UV light under simulated Mars conditions

The Viking missions to Mars failed to detect any organic material in regolith samples. Since then, several removal mechanisms of organic material have been proposed. Two of these proposed methods are removal due to exposure to plasmas created in dust devils and exposure to UV irradiation. The experiments presented here were performed to identify similarities between the two potential removal mechanisms and to identify any compounds produced from these mechanisms that would have been difficult for the Viking instruments to detect. Five organic compounds, phenanthrene, octadecane, octadecanoic acid, decanophenone and benzoic acid, were exposed to a glow discharge plasma created in simulated martian atmospheres as might be present in dust devils, and to UV irradiation similar to that found at the surface of Mars. Glow discharge exposure was carried out in a chamber with 6.9 mbar pressure of a Mars like gas composed mostly of carbon dioxide. The plasma was characterized using emission spectroscopy and found to contain cations and excited neutral species including carbon dioxide, carbon monoxide, and nitrogen. UV irradiation experiments were performed in a Mars chamber which simulates the temperature, pressure, atmospheric composition, and UV fluence rates of equatorial Mars. The non-volatile residues left after each exposure were characterized by mass loss, infrared spectroscopy and high resolution mass spectrometry. Oxidized, higher molecular weight versions of the parent compounds containing carbonyl, hydroxyl and alkenyl functional groups were identified. The presence of these oxidized compounds suggests that searches for organic material in soils on Mars use instrumentation suitable for detection of compounds which contain the above functional groups. Discussions of possible reaction mechanisms are given.     

Surface and near-surface atmospheric temperatures for the Mars Exploration Rover landing sites

Downward-looking spectra of the martian surface from the Miniature Thermal Emission spectrometer (Mini-TES), onboard each of the two Mars Exploration Rovers, are modeled in order to retrieve surface and near-surface atmospheric temperatures. By fitting the observed radiance in the vicinity of the 15-μm CO₂ absorption feature, the surface temperature and the near-surface atmospheric temperature, approximately 1.1 m above the surface, are determined. The temperatures from the first 180 sols (martian days) of each surface mission are used to characterize the diurnal dependence of temperatures. The near-surface atmospheric temperatures are consistently 20 K cooler than the surface temperatures in the warmest part of each sol, which is 1300-1400 LTST (local true solar time) depending on the location. Seasonal cooling trends are seen in the data by displaying the temperatures as a function of sol. Long ground stares, 8.5 min in duration, show as much as 8 K fluctuation in the near-surface atmospheric temperatures during the early afternoon hours when the near-surface atmosphere is unstable.     

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.     

Regolith-atmosphere exchange of water and carbon dioxide on Mars: Effects on atmospheric history and climate change

Exchange of CO₂ and H₂O between the Mars regolith and the atmosphere-cap system plays an important role in governing the evolution of the martian atmosphere and the martian climate. Most of the exchangeable CO₂ (perhaps one or two orders of magnitude more than the atmospheric inventory) is currently adsorbed on the deep regolith, and can be “cryopumped” to a large quasipermanent CO₂ cap (not now present) during lowest Mars obliquity (θ). During the obliquity driven regolith-cap CO₂ exchange cycle, the atmospheric pressure varies harmonically between ~0.1 mb (lowest Θ) and ? 20 mb (highest Θ). The regolith buffer plays only a small or negligible role in the seasonal CO₂ pressure variations caused by atmosphere-cap exchange because adsorption greatly inhibits diffusion of the seasonal “pressure wave” into the regolith. In contrast, thermally driven H₂O seasonal exchange between the atmosphere and regolith appears to be in large part responsible for observed seasonal variations in the small atmospheric H₂O inventory. Long term exchange of H₂O may be dominated by transfer between the polar caps and ice in the regolith. Available and potential tests of regolith-atmospheric-cap volatile exchange models using ground-based and spacecraft-based techniques are discussed.     

Methane emissions from Earth’s degassing: Implications for Mars

The presence of methane on Mars is of great interest, since one possibility for its origin is that it derives from living microbes. However, CH₄ in the martian atmosphere also could be attributable to geologic emissions released through pathways similar to those occurring on Earth. Using recent data on methane degassing of the Earth, we have estimated the relative terrestrial contributions of fossil geologic methane vs. modern methane from living methanogens, and have examined the significance that various geologic sources might have for Mars.Geologic degassing includes microbial methane (produced by ancient methanogens), thermogenic methane (from maturation of sedimentary organic matter), and subordinately geothermal and volcanic methane (mainly produced abiogenically). Our analysis suggests that ～80% of the “natural” emission to the terrestrial atmosphere originates from modern microbial activity and ～20% originates from geologic degassing, for a total CH₄ emission of ～28.0×10⁷ tonnes year^?1.Estimates of methane emission on Mars range from 12.6×10¹ to 57.0×10⁴ tonnes year^?1 and are 3–6 orders of magnitude lower than that estimated for Earth. Nevertheless, the recently detected martian, Northern-Summer-2003 CH₄ plume could be compared with methane expulsion from large mud volcanoes or from the integrated emission of a few hundred gas seeps, such as many of those located in Europe, USA, Mid-East or Asia. Methane could also be released by diffuse microseepage from martian soil, even if macro-seeps or mud volcanoes were lacking or inactive. We calculated that a weak microseepage spread over a few tens of km², as frequently occurs on Earth, may be sufficient to generate the lower estimate of methane emission in the martian atmosphere.At least 65% of Earth’s degassing is provided by kerogen thermogenesis. A similar process may exist on Mars, where kerogen might include abiogenic organics (delivered by meteorites and comets) and remnants of possible, past martian life. The remainder of terrestrial degassed methane is attributed to fossil microbial gas (～25%) and geothermal-volcanic emissions (～10%). Global abiogenic emissions from serpentinization are negligible on Earth, but, on Mars, individual seeps from serpentinization could be significant. Gas discharge from clathrate-permafrost destabilization should also be considered.Finally, we have shown examples of potential degassing pathways on Mars, including mud volcano-like structures, fault and fracture systems, and major volcanic edifices. All these types of structures could provide avenues for extensive gas expulsion, as on Earth. Future investigations of martian methane should be focused on such potential pathways.     

Melting in the martian mantle: Shergottite formation and implications for present‐day mantle convection on Mars

Abstract— Radiometric age dating of the shergottite meteorites and cratering studies of lava flows in Tharsis and Elysium both demonstrate that volcanic activity has occurred on Mars in the geologically recent past. This implies that adiabatic decompression melting and upwelling convective flow in the mantle remains important on Mars at present. I present a series of numerical simulations of mantle convection and magma generation on Mars. These models test the effects of the total radioactive heating budget and of the partitioning of radioactivity between crust and mantle on the production of magma. In these models, melting is restricted to the heads of hot mantle plumes that rise from the core‐mantle boundary, consistent with the spatially localized distribution of recent volcanism on Mars. For magma production to occur on present‐day Mars, the minimum average radioactive heating rate in the martian mantle is 1.6 times 10^?12 W/kg, which corresponds to 39% of the Wanke and Dreibus (1994) radioactivity abundance. If the mantle heating rate is lower than this, the mean mantle temperature is low, and the mantle plumes experience large amounts of cooling as they rise from the base of the mantle to the surface and are, thus, unable to melt. Models with mantle radioactive heating rates of 1.8 to 2.1 times 10 ^?12 W/kg can satisfy both the present‐day volcanic resurfacing rate on Mars and the typical melt fraction observed in the shergottites. This corresponds to 43–50% of the Wanke and Dreibus radioactivity remaining in the mantle, which is geochemically reasonable for a 50 km thick crust formed by about 10% partial melting. Plausible changes to either the assumed solidus temperature or to the assumed core‐mantle boundary temperature would require a larger amount of mantle radioactivity to permit present‐day magmatism. These heating rates are slightly higher than inferred for the nakhlite source region and significantly higher than inferred from depleted shergottites such as QUE 94201. The geophysical estimate of mantle radioactivity inferred here is a global average value, while values inferred from the martian meteorites are for particular points in the martian mantle. Evidently, the martian mantle has several isotopically distinct compositions, possibly including a radioactively enriched source that has not yet been sampled by the martian meteorites. The minimum mantle heating rate corresponds to a minimum thermal Rayleigh number of 2 times 10⁶, implying that mantle convection remains moderately vigorous on present‐day Mars. The basic convective pattern on Mars appears to have been stable for most of martian history, which has prevented the mantle flow from destroying the isotopic heterogeneity.     

Natural transfer of viable microbes in space.

The possibility and probability of natural transfer of viable microbes from Mars to Earth and Earth to Mars traveling in meteoroids during the first 0.5 Ga and the following 4 Ga are investigated, including: --radiation protection against the galactic cosmic ray nuclei and the solar rays, dose rates as a function of the meteorite's radial column mass (radius x density), combined with dose rates generated by natural radioactivity within the meteorite; and survival curves for some bacterial species using NASA's HZETRN transport code --other factors affecting microbe survival: vacuum; central meteorite temperatures at launch, orbiting, and arrival; pressure and acceleration at launch; spontaneous DNA decay; metal ion migration --mean sizes and numbers of unshocked meteorites ejected and percentage falling on Earth, using current semiempirical results --viable flight times for the microbe species Bacillus subtilis and Deinococcus radiodurans R1 --the approximate fraction of microbes (with properties like the two species studied) viably arriving on Earth out of those ejected from Mars during the period 4 Ga BP to the present time, and during the 700 Ma from 4.5 to 3.8 Ga. Similarly, from Earth to Mars. The conclusion is that if microbes existed or exist on Mars, viable transfer to Earth is not only possible but also highly probable, due to microbes' impressive resistance to the dangers of space transfer and to the dense traffic of billions of martian meteorites which have fallen on Earth since the dawn of our planetary system. Earth-to-Mars transfer is also possible but at a much lower frequency.     

Investigation of the water sorption properties of Mars-relevant micro- and mesoporous minerals

Encouraged by recent results of the Mars Odyssey spacecraft mission and the OMEGA team (Mars Express) concerning water in equatorial latitudes between ±45° on Mars and the possible existence of hydrated minerals, we have investigated the water sorption properties of natural zeolites and clay minerals close to martian atmospheric surface conditions as well as the properties of Mg-sulfates and gypsum. To quantify the stability of hydrous minerals on the martian surface and their interaction with the martian atmosphere, the water adsorption and desorption properties of nontronite, montmorillonite, chabazite and clinoptilolite have been investigated using adsorption isotherms at low equilibrium water vapor pressures and temperatures, modeling of the adsorption equilibrium data, thermogravimetry (TG), differential scanning calorimetry (DSC), and proton magic angle spinning nuclear magnetic resonance measurements (¹H MAS NMR). Mg-sulfate hydrates were also analyzed using TG/DSC methods to compare with clay mineral and zeolites. Our data show that these microporous minerals can remain hydrated under present martian atmospheric conditions and hold up to 2.5-25 wt% of water in their void volumes at a partial water vapor pressure of 0.001 mbar in a temperature range of 333-193 K. Results of the ¹H MAS NMR measurements suggest that parts of the adsorbed water are liquid-like water and that the mobility of the adsorbed water might be of importance for adsorption-water-triggered chemistry and hypothetical exobiological activity on Mars.     

Laboratory simulations of Mars aqueous geochemistry

We report on laboratory experiments in which we allowed an SNC-derived mineral mix to react with pure water under a simulated Mars atmosphere for 7 months. These experiments were performed at one bar and at three different temperatures in order to simulate the subsurface conditions that most likely exist where liquid water and rock interact on Mars today. The dominant cations dissolved in the solutions we produced, which may be characterized as dilute brines, are Ca²⁺, Mg²⁺, Al³⁺, and Na⁺, while the major anions are dissolved C, F⁻, SO²⁻₄ and Cl⁻. Typical solution pH was in the range of 4.2-6.0. Abundance patterns of elements in our synthetic sulfate-chloride brines are distinctly unlike those of terrestrial ocean water or continental waters, however, they are quite similar to those measured in the martian fines at the Mars Pathfinder and Viking 1 and 2 Landing sites. This suggests that salts present in the martian regolith may have formed over time as a result of the interaction of surface or subsurface liquid water with basalts in the presence of a martian atmosphere similar in composition to that of today. If most of the mobile surface layer was formed during the Noachian when erosion rates were much higher than at present, and if this layer is homogeneous in salt composition, the total amount of salt in the martian fines is approximately the same as in the Earth's oceans. The minimum quantity of circulating water necessary to deposit this amount of salt is approximately equivalent to a global layer 625 m deep.     

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.     

How rapidly did Mars accrete? Uncertainties in the Hf-W timing of core formation

Estimates for the martian core formation timescale based on the hafnium-tungsten (Hf-W) isotopic system have varied by almost an order of magnitude, because of uncertainties in the martian mantle Hf/W ratio. Here we argue that the Hf/W ratio is ∼4 but is uncertain by ∼25%, resulting in (instantaneous) martian core formation timescales ranging from 0 to 10 Myr; accordingly, Hf-W isotope observations currently have limited utility in distinguishing between scenarios in which Mars formed as a stranded embryo and scenarios in which Mars suffered a prolonged accretion history.     

Roles of methane and carbon dioxide in geological processes on Mars

We discuss in this paper possible roles of methane and carbon dioxide in geological processes on Mars. These volatiles in the martian crust may migrate upward from their sources either directly or via various traps (structural, sedimentary, ground ice, gas hydrates). They are then likely emitted to the atmosphere by seepage or through diverse vent structures. Though gas hydrates have never been directly detected on Mars, theoretical studies favor their presence in the crust and polar caps; they could have played an important role as significant gas reservoirs in the subsurface. The martian gas hydrates would possibly be a binary system of methane and carbon dioxide occupying clathrate cavities. Landforms such as mud volcanoes with well-known linkage to gas venting are extensively distributed on Earth, and methane is the primary gas involved. Thus, identification of these landforms on Mars could suggest that methane and possibly carbon dioxide have contributed to geological processes of the planet. For example, we present a newly identified field in Chryse Planitia where features closely resembling terrestrial mud volcanoes occur widely, though with no observable activity. We also present results of a preliminary search for possible recent or present-day, methane-emission zones in the regions over which enrichments of atmospheric methane have been reported.     

Radiative habitable zones in martian polar environments

The biologically damaging solar ultraviolet (UV) radiation (quantified by the DNA-weighted dose) reaches the martian surface in extremely high levels. Searching for potentially habitable UV-protected environments on Mars, we considered the polar ice caps that consist of a seasonally varying CO2 ice cover and a permanent H2O ice layer. It was found that, though the CO2 ice is insufficient by itself to screen the UV radiation, at approximately 1 m depth within the perennial H2O ice the DNA-weighted dose is reduced to terrestrial levels. This depth depends strongly on the optical properties of the H2O ice layers (for instance snow-like layers). The Earth-like DNA-weighted dose and Photosynthetically Active Radiation (PAR) requirements were used to define the upper and lower limits of the northern and southern polar Radiative Habitable Zone (RHZ) for which a temporal and spatial mapping was performed. Based on these studies we conclude that photosynthetic life might be possible within the ice layers of the polar regions. The thickness varies along each martian polar spring and summer between approximately 1.5 and 2.4 m for H2O ice-like layers, and a few centimeters for snow-like covers. These martian Earth-like radiative habitable environments may be primary targets for future martian astrobiological missions. Special attention should be paid to planetary protection, since the polar RHZ may also be subject to terrestrial contamination by probes.     

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.     

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.