Detectability of minor constituents in the martian atmosphere by infrared and submillimeter spectroscopy

Spectroscopic remote sensing in the infrared and (sub)millimeter range is a powerful technique that is well suited for detecting minor species in planetary atmospheres (Planet Space Sci. 43(1995) 1485). Yet, only a handful of molecules in the Mars atmosphere (CO₂, CO and H₂O along with their isotopic species, O_3, and more recently H₂O₂ and CH₄) have been detected so far by this method. New high performance spectroscopic instruments will become available in the future in the infrared and (sub)millimeter range, for observations from the ground (infrared spectrometers on 8 m class telescopes, large millimeter and submillimeter interferometers) and from space, in particular the Planetary Fourier Spectrometer (PFS) aboard Mars Express (MEx), and the Heterodyne Instrument for the Far-Infrared (HIFI) aboard the Herschel Space Observatory (HSO). In this paper we will present results of a study that determines detectability of minor species in the atmosphere of Mars, taking into account the expected performance of the above spectroscopic instruments. In the near future, a new determination of the D/H value is expected with the PFS, especially during times of maximum H₂O abundance in the martian atmosphere. PFS is also expected to place constraints on the abundance of several minor species (H₂O₂,CH₄,CH₂O, SO₂, H₂S, OCS, HCl) above any local outgassing sources, the hot spots. It will be possible to obtain complementary information on some minor species (O₃,H₂O₂, CH₄) from ground-based infrared spectrometers on large telescopes. In the more distant future, HIFI will be ideally suited for measuring the isotopic ratios with unprecedented accuracy. Moreover, it should be able to observe O₂, which has not yet been detected spectroscopically in the IR/submm range, as well as H₂O₂. HIFI should also provide upper limits for several species that have not yet been detected (HCl, NH₃, PH₃) in the atmosphere of Mars. Some species (SO, SO₂,H₂S, OCS, CH₂O) that may be observable from the ground could be searched for with present single-dish antennae and arrays, and in the future with the Atacama Large Millimeter Array (ALMA) submillimeter interferometer.     

AOST: Fourier spectrometer for studying mars and phobos

An AOST Fourier spectrometer of the Phobos-Soil project is intended for studying Mars and Phobos by means of measurements of IR radiation spectra of the Martian surface and atmosphere, the Phobos surface, and the spectrum of solar radiation passing through the Martian atmosphere on its limb. The main scientific problems to be solved with the spectrometer on Mars are measurements of methane content, search for minor constituents, and study of diurnal variations in the temperature and atmospheric aerosol. The spectrometer will also study the Martian and Phobos surface both remotely and after landing. The spectral range of the instrument is 2.5?C25 ??m, the best spectral resolution (without apodization) is 0.6 cm^?1, and the instantaneous field of view is 2.5°. The recording time of one spectrum is equal to 5 s in solar observations and 50 s in observations of Mars and Phobos. The instrument has self-thermal stabilization and two-axis pointing systems, as well as a built-in radiation source for flight calibration. The spectrometer mass is 4 kg, and power consumption is up to 13 W. Scientific problems, measurement modes, and, briefly, engineering implementation of the experiment are discussed in this work.     

Measurement of the isotopic signatures of water on Mars; Implications for studying methane

The recent discovery of methane on Mars has led to much discussion concerning its origin. On Earth, the isotopic signatures of methane vary with the nature of its production. Specifically, the ratios among ¹²CH₄, ¹³CH₄, and ¹²CH₃D differ for biotic and abiotic origins. On Mars, measuring these ratios would provide insights into the origins of methane and measurements of water isotopologues co-released with methane would assist in testing their chemical relationship. Since 1997, we have been measuring HDO and H₂O in Mars’ atmosphere and comparing their ratio to that in Earth’s oceans. We recently incorporated a line-by-line radiative transfer model (LBLRTM) into our analysis. Here, we present a map for [HDO]/[H₂O] along the central meridian (154°W) for L_s=50°. From these results, we constructed models to determine the observational conditions needed to quantify the isotopic ratios of methane in Mars’ atmosphere. Current ground-based instruments lack the spectral resolution and sensitivity needed to make these measurements. Measurements of the isotopologues of methane will likely require in situ sampling.     

Submillimeter and millimeter observations of Uranus and Neptune

We have made narrowband photometric measurements of Uranus and Neptune covering the wavelength range from 0.35 to 3.3 mm. The observations provide accurate comparative radiometry of these planets. Absolute calibration was referenced to Mars, and to Jupiter as a secondary standard. The results establish Uranus and Neptune as reliable secondary calibrators in their own right. We have combined our observations with other measurements made in the period 1978 through 1984 in the spectral range of 17 μm through 3 mm to form models for atmospheric temperature structure in the vertical range from 100 mbar to 8 bar. The simplest models imply that the tropospheres of both planets are consistent with “frozen” equilibrium H₂ and a mixing ratio of CH₄ of about 2% by volume in the deep atmosphere. There is some evidence in the Uranus data which implies the presence of discrete spectral lines. These could be due to CH₄ pure rotational or dimer transitions or to minor constituents such as CO, which remain uncondensed even at the cold temperatures in the atmosphere of Uranus.     

Identification of a new band system of isotopic CO2 near 3.3 μm: Implications for remote sensing of biomarker gases on Mars

We present the discovery of a new vibrational band system of isotopic CO₂ (carbon dioxide) near 3.3 μm, with multiple strong P, Q and R lines in the prime spectral region used to search for Mars CH₄ (methane). The band system was discovered on Mars using high-resolution spectrometers (λ/δλ>40,000, CSHELL and NIRSPEC) at telescopes (NASA-IRTF and Keck-2) atop Mauna Kea, HI. The observed line intensities and frequencies agree very well with values predicted by a vibrational band model that we developed using known parameters for the molecular levels involved. Using this model, we synthesized spectra for different observing conditions (from Space and ground-based telescopes) and for different spectral resolving powers (5000 to 40,000). Although the total atmospheric burden on Mars is more than 150 times smaller than on Earth, the greater mixing ratio of CO₂ ensures that its column abundance on Mars is almost 20 times greater than on Earth. Thus, weak telluric CO₂ band systems appear much stronger on Mars. Many molecules of possible biological and geothermal interest have strong signatures at these wavelengths, in particular hydrocarbons owing to their strong ro-vibrational CH stretching modes. For example, the new isotopic CO₂ band-system encompasses lines of CH₄, C₂H₆ (ethane), CH₃OH (methanol) and H₂O (water). Implications for previous and future searches of biomarker gases are presented.     

The gas exchange experiment for life detection: The Viking Mars Lander

The Gas Exchange Experiment of the Viking mission accepts a sample of Martian soil, incubates this soil with nutrient medium, and periodically samples the enclosed atmosphere over this soil for the gases H₂, N₂, O₂, CH₄, Kr, and CO₂. These gases are analyzed by an automated gas chromatograph, and the data are transmitted to Earth. The design of the experiment and the qualitative and quantitative changes, if any, of gas composition should allow conclusions to be made on the presence of life on Mars. Data and theory substantiating this approach are presented.     

Determining the local abundance of Martian methane and its’ 13C/12C and D/H isotopic ratios for comparison with related gas and soil analysis on the 2011 Mars Science Laboratory (MSL) mission

Understanding the origin of Martian methane will require numerous complementary measurements from both in situ and remote sensing investigations and laboratory work to correlate planetary surface geophysics with atmospheric dynamics and chemistry. Three instruments (Quadrupole Mass Spectrometer (QMS), Gas Chromatograph (GC) and Tunable Laser Spectrometer (TLS)) with sophisticated sample handling and processing capability make up the Sample Analysis at Mars (SAM) analytical chemistry suite on NASA’s 2011 Mars Science Laboratory (MSL) Mission. Leveraging off the SAM sample and gas processing capability that includes methane enrichment, TLS has unprecedented sensitivity for measuring absolute methane (parts-per-trillion), water, and carbon dioxide abundances in both the Martian atmosphere and evolved from heated soil samples. In concert with a wide variety of associated trace gases (e.g. SO₂, H₂S, NH₃, higher hydrocarbons, organics, etc.) and other isotope ratios measured by SAM, TLS will focus on determining the absolute abundances of methane, water and carbon dioxide, and their isotope ratios: ¹³C/¹²C and D/H in methane; ¹³C/¹²C and ¹⁸O/¹⁷O/¹⁶O in carbon dioxide; and ¹⁸O/¹⁷O/¹⁶O and D/H in water. Measurements near the MSL landing site will be correlated with satellite (Mars Express, Mars 2016) and ground-based observations.     

A new estimate of volatile outgassing on Mars

The presence of 28% argon on Mars as calculated by Levine and Riegler and indirectly inferred from Soviet Mars-6 lander data has important implications for the outgassing history of H₂O, CO₂, and N₂ on Mars. Even if the terrestrial volatile outgassing ratio is only approximately valid for Mars, then large quantities of H₂O [of the order of 10⁵ gcm^?2 (about 10⁸ more H₂O than is currently present in the Martian atmosphere)] and about 10⁴ gcm^?2 of CO₂ (about 10³ times more CO₂ than found at present in the Martian atmosphere) and some 450 gcm^?2 of N₂ may have outgassed over the history of Mars.     

Possibilities for the detection of hydrogen peroxide-water-based life on Mars by the Phoenix Lander

The Phoenix Lander landed on Mars on 25 May 2008. It has instruments on board to explore the geology and climate of subpolar Mars and to explore if life ever arose on Mars. Although the Phoenix mission is not a life detection mission per se, it will look for the presence of organic compounds and other evidence to support or discredit the notion of past or present life.The possibility of extant life on Mars has been raised by a reinterpretation of the Viking biology experiments [Houtkooper, J. M., Schulze-Makuch, D., 2007. A possible biogenic origin for hydrogen peroxide on Mars: the Viking results reinterpreted. International Journal of Astrobiology 6, 147-152]. The results of these experiments are in accordance with life based on a mixture of water and hydrogen peroxide instead of water. The near-surface conditions on Mars would give an evolutionary advantage to organisms employing a mixture of H₂O₂ and H₂O in their intracellular fluid: the mixture has a low freezing point, is hygroscopic and provides a source of oxygen. The H₂O₂-H₂O hypothesis also explains the Viking results in a logically consistent way. With regard to its compatibility with cellular contents, H₂O₂ is used for a variety of purposes in terran biochemistry. The ability of the anticipated organisms to withstand low temperatures and the relatively high water vapor content of the atmosphere in the Martian arctic, means that Phoenix will land in an area not inimical to H₂O₂-H₂O-based life. Phoenix has a suite of instruments which may be able to detect the signatures of such putative organisms.     

Early Mars serpentinization‐derived CH4 reservoirs,H2‐induced warming and paleopressure evolution

CH₄ has been observed on Mars both by remote sensing and in situ during the past 15 yr. It could have been produced by early Mars serpentinization processes that could also explain the observed Martian remanent magnetic field. Assuming a cold early Mars, a cryosphere could trap such CH₄ as clathrates in stable form at depth. The maximum storage capacity of such a clathrate cryosphere has been recently estimated to be 2 × 10¹⁹ to 2 × 10²⁰ moles of methane. We estimate how large amounts of serpentinization‐derived CH₄ stored in the cryosphere have been released into the atmosphere during the Noachian and the early Hesperian. Due to rapid clathrate dissociation and photochemical conversion of CH₄ to H₂, these episodes of massive CH₄ release may have resulted in transient H₂‐rich atmospheres, at typical levels of 10–20% in a background 1–2 bar CO₂ atmosphere. The collision‐induced heating effect of H₂ present in such an atmosphere has been shown to raise the surface temperature above the water freezing point. We show how local and rapid destabilization of the cryosphere can be induced by large events (such as the Hellas Basin or Tharsis bulge formation) and lead to such releases. Our results show that the early Mars cryosphere had a sufficient CH₄ storage capacity to have maintained H₂‐rich transient atmospheres during a total time period up to several million years or tens of million years, having potentially contributed to the formation of valley networks during the Noachian/early Hesperian.     

Polar warming in the middle atmosphere of Mars

We report ground-based laser heterodyne spectroscopy of non-thermal emission in the cores of the 10.33-μmR(8) and 10.72-μmP(32) lines of ¹²C¹⁶O₂, obtained at 23 locations on the disk of Mars during the 1984 opposition, at L_s = 130°. The data were obtained at a sub-Doppler spectral resolution, and the temperature of the middle Martian atmosphere (50–85 km) is derived from the frequency width and intensity of the R(8) emission, and from the total intensity of the P(32) emission. We find that the temperature of the middle Martian atmosphere varies with latitude. Near the subsolar latitude, the average 50- to 85-km temperature is close to the radiative equilibrium value for a CO₂ atmosphere. However, at high latitudes in both the northern (summer) and southern (winter) hemispheres the 50- to 85-km temperature exceeds the CO₂ radiative equilibrium value; a meridional gradient in the range of 0.4 – 0.9°K per degree of latitude is indicated by our data. The highest temperatures are seen at high latitudes in the winter hemisphere, reminiscent of the seasonal effects seen at the Earth's mesopause. As in the terrestrial case, this winter polar warming in the Martian middle atmosphere necessitates departures from radiative equilibrium; dynamical heating of order 4 × 10² ergs g⁻¹ sec⁻¹ is required at the edge of the winter polar night. A comparison with 2-D circulation models shows that the presence of atmospheric dust may enhance this dynamical heating at high winter latitudes, and may also account for heating at high latitudes in the summer hemisphere.     

Can rapid loss and high variability of Martian methane be explained by surface H2O2?

It has been reported by several groups that methane in the Martian atmosphere is both spatially and temporally variable. Gough et al. (2010) suggested that temperature dependent, reversible physical adsorption of methane onto Martian soils could explain this variability. However, it is also useful to consider if there might be chemical destruction of methane (and compensating sources) operating on seasonal time scales. The lifetime of Martian methane due to known chemical loss processes is long (on the order of hundreds of years). However, observations constrain the lifetime to be 4 years or less, and general circulation models suggest methane destruction must occur even faster (<1 year) to cause the reported variability and rapid disappearance. The Martian surface is known to be highly oxidizing based on the Viking Labeled Release experiments in which organic compounds were quickly oxidized by samples of the regolith. Here we test if simulated Martian soil is also oxidizing towards methane to determine if this is a relevant loss pathway for Martian methane. We find that although two of the analog surfaces studied, TiO₂·H₂O₂ and JSC-Mars-1 with H₂O₂, were able to oxidize the complex organic compounds (sugars and amino acids) used in the Viking Labeled Release experiments, these analogs were unable to oxidize methane to carbon dioxide within a 72 h experiment. Sodium and magnesium perchlorate, salts that were recently discovered at the Phoenix landing site and are potential strong oxidants, were not observed to directly oxidize either the organic solution or methane. The upper limit reaction coefficient, α, was found to be <4×10^?17 for methane loss on TiO₂·H₂O₂ and <2×10^?17 for methane loss on JSC-Mars-1 with H₂O₂. Unless the depth of soil on Mars that contains H₂O₂ is very deep (thicker than 500 m), the lifetime of methane with respect to heterogeneous oxidation by H₂O₂ is probably greater than 4 years. Therefore, reaction of methane with H₂O₂ on Martian soils does not appear to be a significant methane sink, and would not destroy methane rapidly enough to cause the reported atmospheric methane variability.     

Chemical pathway analysis of the Martian atmosphere: CO2-formation pathways

The chemical composition of a planetary atmosphere plays an important role for atmospheric structure, stability, and evolution. Potentially complex interactions between chemical species do not often allow for an easy understanding of the underlying chemical mechanisms governing the atmospheric composition. In particular, trace species can affect the abundance of major species by acting in catalytic cycles. On Mars, such cycles even control the abundance of its main atmospheric constituent CO₂. The identification of catalytic cycles (or more generally chemical pathways) by hand is quite demanding. Hence, the application of computer algorithms is beneficial in order to analyze complex chemical reaction networks. Here, we have performed the first automated quantified chemical pathways analysis of the Martian atmosphere with respect to CO₂-production in a given reaction system. For this, we applied the Pathway Analysis Program (PAP) to output data from the Caltech/JPL photochemical Mars model. All dominant chemical pathways directly related to the global CO₂-production have been quantified as a function of height up to 86 km. We quantitatively show that CO₂-production is dominated by chemical pathways involving HO_x and O_x. In addition, we find that NO_x in combination with HO_x and O_x exhibits a non-negligible contribution to CO₂-production, especially in Mars’ lower atmosphere. This study reveals that only a small number of chemical pathways contribute significantly to the atmospheric abundance of CO₂ on Mars; their contributions to CO₂-production vary considerably with altitude. This analysis also endorses the importance of transport processes in governing CO₂-stability in the Martian atmosphere. Lastly, we identify a previously unknown chemical pathway involving HO_x, O_x, and HO₂-photodissociation, contributing 8% towards global CO₂-production by chemical pathways using recommended up-to-date values for reaction rate coefficients.     

The opacity of some local Martian dust storms observed by the Viking IRTM

In this paper we analyze some Viking infrared thermal mapping (IRTM) measurements of local Martian dust storms observed in the southern tropical region of the planet between L_s=225 and 262°. The derived opacities of these storms show that in the most opaque regions of the cloud, the optical thickness may be ≈6. Away from the individual clouds, the opacity is ≈2, which is still about four times the background level of dustiness in the Martian atmosphere. We find considerable structure in the derived opacity which will create corresponding variations in the atmospheric heating, which in turn may have an important feedback upon the local winds.     

Methane release and the carbon cycle on Mars

It has been suggested that the present release rate of methane to the Martian atmosphere could be the result of serpentinization in the deep subsurface, followed by the conversion of H₂ to CH₄ in a CO₂-rich fluid. Making this assumption, we show that the cryosphere could act as a buffer storing, under the form of micron-size methane clathrate particles, the methane delivered from below by hydrothermal fluids and progressively releasing it to the atmosphere at the top. From an extrapolation of the present CH₄ release rate back to the past, we calculate that up to several hundred millibars (～200–2000 mbar) of CO₂, resulting from the oxidation of the released CH₄, in addition to the volcanic supply (～400 mbar), should have accumulated in the atmosphere in the absence of a CO₂ sink. We reassess the capability of escape to have removed CO₂ from the atmosphere by C non-thermal escape and show that it is not significant. We suggest that atmospheric carbon is recycled to the crust through an active subsurface hydrological system, and precipitates as carbonates within the crust. During episodic periods of magmatic activity, these carbonates are decomposed to CO₂ dissolved in running water, and CO₂ can react with H₂ formed by serpentinization to build CH₄. CH₄ is then buffered in the subsurface cryosphere, above the water table, and finally released to the atmosphere, before being recycled to the subsurface hydrological system, and converted back to carbonates. We propose a typical evolution curve of the CO₂ pressure since the late Noachian based on our hypothesis. Contrary to the steady state carbon cycle at work on Earth, a progressive damping of the carbon cycle occurs on Mars due to the absence of plate tectonics and the progressive cooling of the planet.     

The composition of the Martian atmosphere: Minor constituents

The Mariner 6 and 7 infrared spectrometers provided data which, in principle, determine upper limits on the possible atmospheric abundance of every gaseous substance that was undetected but which has recognized absorptions in the accessible spectral region, 1.9 to 14.4 μ. Through supporting laboratory determinations of curves of growth under pressure broadening conditions appropriate to Mars, upper limits can be specified (expressed first in cm-atm, STP, for a vertical column and then in parts per million) for the following gases: NO₂ (<0.0016, 0.23); NH₃ (<0.0031, 0.44); C₃O₂ (<0.0032, 0.45); SO₂ (?0.0037, 0.52); OCS (<0.0040, 0.56); NO (<0.0050, 0.70); O₃ (<0.0061, 0.86); CH₄ (<0.026, 3.7); N₂O (<0.13, 18); HCl (<3.7, 520); HBr (?8.2, 1150); H₂S (<27, 3800). In addition, considerations of band contours, moments of inertia, and experimental absorption coefficients permit us to place useful upper limits on twenty-seven additional substances that were not detected and for which curves of growth have not been measured: less than 1.0ppm (or, <0.0071cm-atm); SF₆, NF₃, Cl₂CO, CF₄, CHF₃, Br₂CO, SiF₄; less than 6.0ppm (or, <0.035 cm-atm); C₂F₆, CO₃, F₂CO, C₂H₄, BF₃, CS₂, CHCl₃, C₂H₆, H₂CO, CH₃F, C₆H₆, CH₂I₂; less than 50ppm (or, <0.35 cm-atm): C₂H₂, HCN, CH₂Br₂, CH₂Cl₂, CH₃Br, PH₃, CH₃I, and CH₃Cl. These upper limits are compared to earlier limits based upon terrestrial measurements. The present limits placed upon the possible atmospheric content of the molecules C₃O₂ and CO₃ are of particular interest because of their relevance to the photochemistry of the Martian atmosphere.     

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.     

Martian volatiles: Their degassing history and geochemical fate

Observations of Mars and cosmochemical considerations imply that the total inventory of degassed volatiles on Mars is 10² to 10³ times that present in Mars' atmosphere and polar caps. The degassed volatiles have been physically and chemically incorporated into a layer of unconsolidated surface rubble (a “megaregolith”) up to 2km thick. Tentative lines of evidence suggest a high concentration (～5g/cm²) of ⁴⁰ Ar in the atmosphere of Mars. If correct, this would be consistent with a degassing model for Mars in which the Martian “surface” volatile inventory is presumed identical to that of Earth but scaled to Mars' smaller mass and surface area. The implied inventory would be: (⁴⁰Ar) = 4g/cm², (H₂O) = 1 × 10⁵g/cm², (CO₂) = 7 × 10³g/cm², (N₂) = 3 × 10²g/cm², (Cl) = 2 × 10³g/cm², and (S) = 2 × 10²g/cm². Such a model is useful for testing, but differences in composition and planetary energy history may be anticipated between Mars and Earth on theoretical grounds. Also, the model demands huge regolith sinks for the volatiles listed.If the regolith were in physical equilibrium with the atmosphere, as much as 2 × 10⁴g/cm² of H₂O could be stored in it as hard-frozen permafrost, or 5 × 10⁴g/cm² if equilibrium with the atmosphere were inhibited. Spectral measurements of Martian regolith material and laboratory measurement of weathering kinetics on simulated regolith material suggest large amounts of hydrated iron oxides and clay minerals exist in the regolith; the amount of chemically bound H₂O could be from 1 × 10⁴ to 4 × 10⁴g/cm². In an Earth-analogous model, a 2 km mixed regolith must contain the following concentrations of other volatile-containing compounds by weight: carbonates = 1.5%, nitrates = 0·3%, chlorides = 0.6%, and sulfates = 0.1%. Such concentrations would be undetectable by current Earth-based spectral reflectance measurements, and (except the nitrates) formation of the “required” amounts of these compounds could result from interaction of adsorbed H₂O and ice with primary silicates expected on Mars. Most of the CO₂ could be physically adsorbed on the regolith.Thus, maximum amounts of H₂O and other volatiles which could be stored in the Mars regolith are marginally compatible with those required by an Earth-analogous model, although a lower atmospheric ⁴⁰Ar concentration and regolith volatile inventory would be easier to reconcile with observational constraints. Differences in the ratios of H₂O and other volatiles to ⁴⁰Ar between surface volatiles on the real Mars and on an Earth-analogous Mars could result from and reflect differences in bulk composition and time history of degassing between Mars and Earth. Models relating Viking-observable parameters, e.g., (⁴⁰Ar) and (³⁶Ar), to the time history and overall intensity of Mars degassing are given.     

History of Martian volatiles: Implications for organic synthesis

A theoretical reconstruction of the history of Martian volatiles indicates that Mars probably possessed a substantial reducing atmosphere at the outset of its history and that its present tenous and more oxidized atmosphere is the result of extensive chemical evolution. As a consequence, it is probable that Martian atmospheric chemical conditions, now hostile with respect to abiotic organic synthesis in the gas phase, were initially favorable. Evidence indicating the chronology and degradational history of Martian surface features, surface mineralogy, bulk volatile content, internal mass distribution, and thermal history suggests that Mars catastrophically developed a substantial reducing atmosphere as the result of rapid accretion. This atmosphere probably persisted—despite the direct and indirect effects of hydrogen escape—for a geologically short time interval during, and immediately following, Martian accretion. That was the only portion of Martian history when the atmospheric environment could have been chemically suited for organic synthesis in the gas phase. Subsequent gradual degrassing of the Martian interior throughout Martian history could not sustain a reducing atmosphere due to the low intensity of planet-wide orogenic activity and the short atmospheric mean residence time of hydrogen on Mars. During the post-accretion history of Mars, the combined effects of planetary hydrogen escape, solar-wind sweeping, and reincorporation of volatiles into the Martian surface produced and maintained the present atmosphere.     

Chemical weathering on Mars thermodynamic stabilities of primary minerals (and their alteration products) from mafic igneous rocks

Chemical weathering on Mars is examined theoretically from the standpoint of heterogeneous equilibrium between solid mineral phases and gaseous O₂, H₂O, and CO₂ in the Martian atmosphere. Thermochemical calculations are performed in order to identify important gas-solid decomposition reactions involving the major mineral constituents of mafic igneous rocks. Where unavailable in the thermochemical literature, Gibbs free energy and enthalpy of formation are estimated for certain minerals and details of these estimation procedures are given. Partial pressure stability diagrams are presented to show pertinent mineral reaction boundaries at 298 and at 240°K. In the present Martian environment, the thermodynamically stable products of gas-solid weathering of individual minerals at 240°K should be Fe₂O₃, as hematite or maghemite (from fayalite, magnetite, and Fe-bearing pyroxenes), quartz (from all silicates), calcite (from Ca-bearing pyroxenes and plagioclase), magnesite (from forsterite and Mg-bearing pyroxenes), corundum (from all Al-bearing silicates), Ca-beidellite (from anorthite), and szomolnokite, FeSO₄ or FeSO₄·H₂O (from iron sulfides). Albite, microcline, and apatite should be stable with respect to gas-solid decomposition, suggesting that gas-solid weathering products on Mars may be depleted in Na, K, and P (and, possibly, Cl and F). Certain montmorillonite-type clay minerals are thermodynamically favorable intermediate gas-solid decomposition products of Al-bearing pyroxenes and may be metastable intermediate products of special mineral surface reaction mechanisms. However, the predicted high thermodynamic susceptibility of these clay minerals to subsequent gas-solid decomposition implies that they should ultimately decompose in the present Martian surface environment. Kaolinite is apparently the only clay mineral which should be thermodynamically stable over all ranges of temperature and water vapor abundance in the present environment at the Martian surface. Considering thermodynamic criteria, including possible gas-solid decomposition reactions, it is doubtful that significant amounts of goethite and clay minerals can be currently forming on Mars by mechanisms known to operate to Earth. If major amounts of goethite and clay minerals occur on Mars, they probably owe their existence to formation in an environment characterized by the presence of liquid water or by mechanism possibly unique to Mars. In any case, any goethite or montmorillonite-type clay mineral on Mars must ultimately decompose.