A note on strong mass loss from early sun and warm and wet Mars

Recently, the possibility of strong mass loss from an early sun has been proposed in connection with the lithium depletion problem along with early solar system problems. However, the time scale for this enhanced mass loss is uncertain. Using an empirical relation for the dependence of the Martian surface temperature on solar luminosity and surface pressure, we find that the mass loss time scale for a 1.1 M sun should be about 1 × 10⁹ years or longer if Mars had liquid water on its surface 3.8 billion years ago. The minimum surface pressure on early Mars should be about 5 bars of CO₂.     

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.     

Mars: Chemical weathering as a massive volatile sink

Photostimulated oxidation weathering irreversibly removes both oxygen and hydrogen from the atmosphere at a rate of 10⁸ to 10¹¹ cm^?2sec^?1. This corresponds to a net loss of 10²⁵ to 10²⁸ molecules cm^?2 (10² to 10⁵ g cm^?2 of H₂O, assuming a uniform rate over geologic time. Additional H₂O is removed through hydration of Fe₂O₃ and clay minerals, but the loss is reversible and the extent of regolith storage is uncertain. CO₂ is irreversibly removed from the atmosphere through the formation of CaCO₃ at a rate of 10⁷?10¹⁰cm^?2sec^?1. Over geologic time this corresponds to a net loss of 10²⁴?10²⁷ molecules cm^?2 (10¹?10⁴g cm^?2) of CO₂. Previously, it was proposed that exospheric escape was the principal irreversible volatile sink, amounting to only 10²g cm^?2 of H₂O and 10⁰g cm^?2 of CO₂ over geologic time. A recent tentative identification of abundant argon on Mars suggests that the planet may have degassed up to 10⁵g cm^?2 of H₂O and 10⁴g cm^?2 of CO₂. If the amounts of H₂O and CO₂ removed by photostimulated oxidation are close to the upper limits proposed here, it is possible that chemical weathering may have had a major effect on limiting the supply of H₂O and CO₂ trapped in the regolith and polar caps.     

Impact processing of nitrogen on early Mars

An intense impact flux upon a planet having a CO₂ + N₂ atmosphere, such as Mars, provides energy to synthesize nitric oxide, NO, which is likely converted into nitrate minerals. The same impact flux can decompose nitrate minerals if present in the crust. We build a numerical model to study the effects of early impact processes on the evolution of nitrogen in a dominantly CO₂ atmosphere. We model the period of intense post-accretionary bombardment, the roughly 500 Myr period after crustal stabilization that locks in previously accreted volatiles. A best-guess, “fiducial” set of parameters is chosen, with a fixed “veneer” of post-accretionary impactors (δR=950 m thick), assumed to contain carbon at 1 wt% (fg=0.01), with a molar C/N ratio of 18, an initial atmospheric pressure of 1 bar (with CO₂/N₂ = 36), and a power law impactor mass distribution slope b=0.75. This model produces a nitrate reservoir RNO₃?0.5×¹⁰¹⁹ moles, equivalent to ∼30 mbars of N₂, during the intense impact phase. Starting with 1 bar, the atmosphere grows to 2.75 bars. Results of models with variations of parameter values show that RNO₃ responds sluggishly to changes in parameter values. To significantly limit the size of this reservoir, one is required to limit the initial total atmospheric pressure be less than about 0.5 bars, and the impactor volatile content fg to be less than 0.003. The value of fg substantially determines whether the atmosphere grows or not; when fg=0.01, the atmosphere gains about 1.7 bars, while for fg=0.003, the atmosphere gains less than 200 mbars, and for fg=0.001, it loses about 400 mbars. Impact erosion is a minor sink of N, constituting generally less than 10% of the total supply. The loss of impactor volatile plumes can take almost 50% of incoming N and C under fiducial parameters, when atmospheric pressures are low. This nitrogen does not significantly interact with Mars, and hence is not properly delivered. When the initial N is greater than the delivered N, most of the nitrogen ends up as nitrates; when delivered N is larger, most nitrogen ends up in the atmosphere. The reason for this dichotomy seems to be that initial nitrogen is present during the whole bombardment, while delivered N, on average, only experiences half the bombardment. The operating caveat here is that the above results are all conditioned on the assumption that impact processes dominate this period of Mars atmospheric evolution.     

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.     

Amino acid photostability on the Martian surface

Abstract— In the framework of international planetary exploration programs, several space missions are planned to search for organics and bio‐signatures on Mars. Previous attempts have not detected any organic compounds in the Martian regolith. It is therefore critical to investigate the processes that may affect organic molecules on and below the planet's surface. Laboratory simulations can provide useful data about the reaction pathways of organic material at Mars' surface. We have studied the stability of amino acid thin films against ultraviolet (UV) irradiation and use those data to predict the survival time of these compounds on and in the Martian regolith. We show that thin films of glycine and D‐alanine are expected to have half‐lives of 22 ± 5 hr and of 3 ± 1 hr, respectively, when irradiated with Mars‐like UV flux levels. Modelling shows that the half‐lives of the amino acids are extended to the order of 10⁷ years when embedded in regolith. These data suggest that subsurface sampling must be a key component of future missions to Mars dedicated to organic detection.     

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

Global distribution and migration of subsurface ice on mars

A thermal/diffusive model of H₂O kinetics and equilibrium was developed to investigate the long-term evolution and depth distribution of subsurface ice on Mars. The model quantitatively takes into account (1) obliquity variations; (2) eccentricity variations; (3) long-term changes in the solar luminosity; (4) variations in the argument of subsolar meridian (in planetocentric equatorial coordinates); (5) albedo changes at higher latitudes due to seasonal phase changes of CO₂ and the varying extent of CO₂ ice cover; (6) planetary internal heat flow; (7) temperature variations in the regolith as a function of depth, time, and latitude due to the above factors; (8) atmospheric pressure variations over a 10⁴-year time scale; (9) the effects of factors (1) through (5) on seasonal polar cap temperatures; and (10) Knudsen and molecular diffusion of H₂O through the regolith. The migration of H₂O into or out of the regolith is determined by two boundary conditions, the H₂O vapor pressure at the subsurface ice boundary and the annual average H₂O concentration at the base of the atmosphere. These are controlled respectively by the annual average regolith temperature at the given depth and seasonal temperatures at the polar cap. Starting from an arbitrary initial uniform depth distribution of subsurface ice, H₂O fluxes into or out of the regolith are calculated for 100 selected obliquity cycles, each representing a different epoch in Mars' history. The H₂O fluxes are translated into ice thicknesses and extrapolated over time to give the subsurface ice depth as a function of latitude and time. The results show that obliquity variations influence annual average regolith temperatures in varying degrees, depending on latitude, with the greatest effect at the poles and almost no effect at 40° lat. Insolation changes at the pole, due to obliquity, argument of subsolar meridian, and eccentricity variations can produce enormous atmospheric H₂O concentration variations of ≈6 orders of magnitude over an obliquity cycle. Superimposed on these cyclic variations is a slow, monotonic change due to the increasing solar luminosity. Albedo changes at the polar cap due to seasonal phase changes of CO₂ and the varying thickness of the CO₂ ice cover are critically important in determining annual average atmospheric H₂O concentrations. Despite the strongly oscillating character of the boundary conditions, only small amounts of H₂O are exchanged between the regolith and the atmosphere per obliquity cycle (<10 g/cm²). The net result of H₂O migration is that the regolith below 30–40° lat is depleted of subsurface ice, while the regolith above 30–40° lat contains permanent ice due to the depth of penetration of the annual thermal wave. This result is supported by recent morphological studies. The rate of migration of H₂O is strongly dependent on average pore/capillary radius for which we have assumed values of 1 and 10 μm. We estimate that the H₂O ice removed from the regolith would produce a permanent ice cap with a volume between 2 × 10⁶ and 6 × 10⁶ km³. This generally agrees with estimates deduced from deflationary features at lower latitudes, depositional features at higher latitudes, and the mass of the polar caps.     

Spectroscopy of molecular oxygen in the Atmospheres of Venus and Mars

The abundances of molecular oxygen in the atmospheres of Venus and Mars are sensitive to fundamental photochemical processes. A new upper limit is reported for the molecular oxygen mixing ratio (O₂/CO₂ < × 10^?7) in the integrated column above the visible cloud tops of Venus, based on spectroscopic observations carried out in early spring, 1982. During the same observing period, an O₂ column abundance of 8.5 cm-am for the atmosphere of Mars was measured, slightly below the O₂ abundances measured a decade earlier.     

Atmospheric erosion and replenishment induced by impacts upon the Earth and Mars during a heavy bombardment

Consequences of a heavy bombardment for the atmospheres of Earth and Mars are investigated with a stochastic model. The main result is the dominance of the accumulation. The atmospheric pressure is strongly increasing both for Earth and Mars in the course of an enhanced bombardment. The effect of atmospheric erosion is found to be minor, regarding escape during meteorite entry, in the expanding vapor plume, and ejection due to free-surface motion. The initial atmospheric surface pressure if comparable to the modern value turns out as a less important additive constant of the final pressure. Impactor retention and atmospheric erosion are parametrized in terms of scaling laws, compatible with recent numerical simulations. The dependence on impactor size, atmospheric and planetary parameters is analyzed among alternative models and numerical results. The stochastic model is fed with the net replenishment originating from impactor material and the loss of preexisting atmospheric gas. Major input parameters are the total cumulative impactor mass and the relative mass of atmophile molecules in comets and asteroids. Input size distributions of the impactor ensemble correspond to presently observed main belt asteroids and KBOs. Velocity distributions are taken from dynamical simulations for the Nice model. Depending on the composition of large cometary impactors, the Earth could acquire a more massive atmosphere, a few bars in terms of surface pressure, mostly as CO and CO₂. For Mars accumulation of 1–4 bars of CO and CO₂ requires an asteroidal ‘late veneer’ of the order of 10²⁴ g containing 2% atmophiles.     

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.     

Effects of impacts on the atmospheric evolution: Comparison between Mars, Earth, and Venus

Classified as a terrestrial planet, Venus, Mars, and Earth are similar in several aspects such as bulk composition and density. Their atmospheres on the other hand have significant differences. Venus has the densest atmosphere, composed of CO₂ mainly, with atmospheric pressure at the planet's surface 92 times that of the Earth, while Mars has the thinnest atmosphere, composed also essentially of CO₂, with only several millibars of atmospheric surface pressure. In the past, both Mars and Venus could have possessed Earth-like climate permitting the presence of surface liquid water reservoirs. Impacts by asteroids and comets could have played a significant role in the evolution of the early atmospheres of the Earth, Mars, and Venus, not only by causing atmospheric erosion but also by delivering material and volatiles to the planets. Here we investigate the atmospheric loss and the delivery of volatiles for the three terrestrial planets using a parameterized model that takes into account the impact simulation results and the flux of impactors given in the literature. We show that the dimensions of the planets, the initial atmospheric surface pressures and the volatiles contents of the impactors are of high importance for the impact delivery and erosion, and that they might be responsible for the differences in the atmospheric evolution of Mars, Earth and Venus.     

Climatic change on the terrestrial planets

In this paper, we review the observational data on climatic change for the terrestrial planets, discuss the basic factors that influence climate, and examine the manner in which these factors may have been responsible for some of the known changes. Emphasis is placed on trying to understand the similarities and differences in both the basic factors and their climatic impacts on Venus, the Earth, and Mars. Climatic changes have occurred on the Earth over a broad spectrum of time scales that range from the elevated temperatures of Pre-Cambrian times (～10⁹ years ago), through the alternating glacial and interglacial epochs of the last few million years, to the small but significant decadal and centurial variations of the recent past. Evidence for climatic change on Mars is given by certain channel features, which suggest an early to intermediate aged epoch of warmer and wetter climate, and by layered polar deposits, which imply more recent periodic climate variations. No evidence for climatic change on Venus exists as yet, but comparison of its present climate state with that of outer terrestrial planets offers important clues on some of the mechanisms affecting climate. The important determinants of climate for a terrestrial planet include the Sun's output, astronomical perturbations of its orbital and axial characteristics, the gaseous and particulate content of its atmosphere, its land surface, volatile reservoirs, and its interior. All these factors appear to have played major roles in causing climatic changes on the terrestrial planets. Despite a lower solar luminosity in the past, the Earth and Mars have had warmer periods in their early history. In both cases, a more reducing atmosphere may have been the responsible agent through an enhanced greenhouse effect. In this paper, we present detailed calculations of the effect of atmospheric pressure and composition on the temperature state of Mars. We find that the higher temperature period is easier to explain with a reducing atmosphere than with the current fully oxidizing one. Both the very high surface temperature and massive atmosphere of Venus may be the result of the solar flux being a factor of two higher at its orbit than at the Earth's orbit. This difference may have led to a runaway greenhouse effect on Venus, i.e., the emplacement of volatiles entirely in the atmosphere rather than mostly in surface reservoirs. But if Venus formed with relatively little or no water, it may have always had an oxidizing atmosphere. In this case, a lower solar luminosity would have led to a moderate surface temperature in Venus' early history. Quasi-periodic variations in orbital eccentricity and axial obliquity may have contributed to the alternation between Pleistocene glacial and interglacial periods in the case of the Earth and to the formation of the layered polar deposits in the case of Mars. In this paper, we postulate that two mechanisms, acting jointly, account for the creation of the laminated terrain of Mars: dust particles serve as nucleation centers for the condensation of water vapor and carbon dioxide. The combined dust-H₂O-CO₂ particle is much larger and so has a much higher terminal velocity than either a dust-H₂O or a plain dust particle. As a result, dust and water ice are preferentially deposited in the polar regions. In addition, we postulate that the obliquity variations are key drivers of the periodic layering because of their impact on both atmospheric pressure and polar surface temperature, which, in turn, influence the amounts of dust and water ice in the atmosphere. But eccentricity and precessional changes probably also play important roles in creating the polar layers. The drifting of continents on the Earth has caused substantial climatic changes on individual continents and may have helped to set the stage for the Pleistocene ice ages through a positioning of the continents near the poles. While continental drift apparently has not occurred on Mars, tectonic distortions of its lithosphere may, in some circumstances, cause an alteration in the mean value of that planet's obliquity, which would significantly impact its climate. Atmospheric aerosols can influemce climate through their radiative effects. In the case of the Earth, volcanic aerosols appear to have contributed to past climatic changes, while consideration needs to be given to the future impact of man-generated aerosols. In the case of Mars, the atmospheric temperature structure and thereby atmospheric dynamics are greatly altered by suspended dust particles. The sulfuric acid clouds of Venus play a major role in its heat balance. Cometary impacts may have added substantial quantities of water vapor and sulfur gases to Venus' atmosphere and thus have indirectly affected its cloud properties. Calculations presented in this paper indicate substantial changes in surface temperature accompany these compositional changes.     

Role of H2O and CO2 Ices in Martian Climate Changes

In order to study the stability of martian climate, we constructed a two-dimensional (horizontal-vertical) energy balance model. The long-term CO₂ mass exchange process between the atmosphere and CO₂ ice caps is investigated with particular attention to the effect of planetary ice distribution on the climate stability. Our model calculation suggests that high atmospheric pressure presumed for past Mars would be unstabilized if H₂O ice widely prevailed. As a result, a cold climate state might have been achieved by the condensation of atmospheric CO₂ onto ice caps. On the other hand, the low atmospheric pressure, which is buffered by the CO₂ ice cap and likely close to the present pressure, would be unstabilized if the CO₂ ice albedo decreased. This may have led the climate into a warm state with high atmospheric pressure owing to complete evaporation of CO₂ ice cap. Through the albedo feedback mechanisms of H₂O and CO₂ ices in the atmosphere-ice cap system, Mars may have experienced warm and cold climates episodically in its history.     

Infrared heterodyne spectroscopy of CO2 in the atmosphere of Mars

An infrared heterodyne spectrometer with a resolving power of 6 × 10⁶ has been used to obtain detailed profiles of the 10-μm absorption lines of CO₂ in the atmosphere of Mars. An analysis of the results with an empirical model atmosphere calculation indicates a nearly pure CO₂ atmosphere with an average surface pressure of 5.2 ± 0.5 mbar in the observed regions, a subsolar surface temperature near 275°K, an atmospheric temperature of 235 to 240°K above the subsolar point, and a lapse rate of 2°K/km.     

Liquid water on Mars: An energy balance climate model for CO2/H2O atmospheres

Geologic evidence of the prior existence of liquid water on Mars suggests surface temperatures T_s were once considerably warmer than at present; and that such a condition may have arisen from a larger atmospheric greenhouse. Here we develop a simple climate model for a CO₂/H₂O Mars atmosphere including water vapor-longwave opacity feedback in the atmosphere and temperature-albedo feedback at surface icecaps, under the assumption that once the Martian surface pressure was p_s ≥ 1 atm CO₂. Longwave flux to space is computed as a function of T_s and p_s using band-absorption models for the effect of the 15-μm fundamental, and the 10- and 15-μm hot bands, of the CO₂ molecule; as well as the pure rotation bands and e continuum of H₂O. The derived global radiative balance predicts a global mean surface temperature of 283°K at 1 atm CO₂. When the emission model is coupled to a latitudinally resolved energy balance climate model, including the effect of poleward heat transfer by atmospheric baroclinic eddies, the solutions vary, depending on p_s. We considered two cases: (1) the present Mars (p_s ? 0.007 atm) with pressure-buffering by solid CO₂ icecaps, and limited poleward heat flux by the atmosphere; and (2) a hypothetical “hot Mars” (p_s ? 1.0 atm), whose much higher CO₂ amount augmented by H₂O evaporative feedback yields a theoretical T_s distribution with latitude admitting liquid water over 95% of the surface, water icecaps at the poles, and a diminished equator-to-pole temperature gradient relative to the present.     

Loss of water from Mars:: Implications for the oxidation of the soil

The evolution of the martian atmosphere with regard to its H₂O inventory is influenced by thermal loss processes of H, H₂, nonthermal atmospheric loss processes of H⁺, H₂⁺, O, O⁺, CO₂, and O₂⁺ into space, as well as by chemical weathering of the surface soil. The evolution of thermal and nonthermal escape processes depend on the history of the intensity of the solar XUV radiation and the solar wind density. Thus, we use actual data from the observation of solar proxies with different ages from the Sun in Time program for reconstructing the Sun's radiation and particle environment from the present to 3.5 Gyr ago. The correlation between mass loss and X-ray surface flux of solar proxies follows a power law relationship, which indicates a solar wind density up to 1000 times higher at the beginning of the Sun's main sequence lifetime. For the study of various atmospheric escape processes we used a gas dynamic test particle model for the estimation of the pick up ion loss rates and considered pick up ion sputtering, as well as dissociative recombination. The loss of H₂O from Mars over the last 3.5 Gyr was estimated to be equivalent to a global martian H₂O ocean with a depth of about 12 m, which is smaller than the values reported by previous studies. If ion momentum transport, a process studied in detail by Mars Express is significant on Mars, the water loss may be enhanced by a factor of about 2. In our investigation we found that the sum of thermal and nonthermal atmospheric loss rates of H and all nonthermal escape processes of O to space are not compatible with a ratio of 2:1, and is currently close to about 20:1. Escape to space cannot therefore be the only sink for oxygen on Mars. Our results suggest that the missing oxygen (needed for the validation of the 2:1 ratio between H and O) can be explained by the incorporation into the martian surface by chemical weathering processes since the onset of intense oxidation about 2 Gyr ago. Based on the evolution of the atmosphere-surface-interaction on Mars, an overall global surface sink of about 2×10⁴² oxygen particles in the regolith can be expected. Because of the intense oxidation of inorganic matter, this process may have led to the formation of considerable amounts of sulfates and ferric oxides on Mars. To model this effect we consider several factors: (1) the amount of incorporated oxygen, (2) the inorganic composition of the martian soil and (3) meteoritic gardening. We show that the oxygen incorporation has also implications for the oxidant extinction depth, which is an important parameter to determine required sampling depths on Mars aimed at finding putative organic material. We found that the oxidant extinction depth is expected to lie in a range between 2 and 5 m for global mean values.     

Mars: A water-rich planet?

Mars had outgassed at least 0.5 to 1 km of water, 10 to 20 bar of CO₂, and 0.1 to 0.3 bar of N₂. The volatiles that have been retained are mostly in the cratered uplands. Terrain softening, fretted channels, debris flows, and closed depressions indicate that at least the upper 2 km of the cratered uplands at high latitudes (>30°) contain ice in amounts that exceed the porosity, estimated to be 10–20%. Theoretical studies, and lack of these features in the cratered uplands at low latitudes, suggest that the upper 1 km of the uplands at low latitudes is ice poor. However, valley networks indicate that water was present near the surface early in the planet's history, although in amounts smaller than at high latitudes. The entire upper 1 km, planetwide is estimated to have contained 75–125 m of water at the end of heavy bombardment. The largest sink for water is the megaregolith below 1 km. Episodic eruption of water from the deep megaregolith cut many of the large outflow channels. From the volume of water needed to cut the circum-Chryse channels, and assuming uniform planetwide distribution of water, the deep megaregolith is estimated to have contained at least 350 m of water at the end of heavy bombardment, thereby giving a total minimum inventory of 424–475 m planetwide. Most of the water lost from the low-latitude uplands by diffusion and in cutting the valley networks is now believed to be in the polar layered terrains. Most of the water involved in cutting the outflow channels is in the low-lying northern plains where a variety of features that have been attributed to ground ice is present. A large fraction of the planet's surface has been overplated with water-poor volcanics, of which we have samples in the SNC meteorites. The younger volcanics have reacted extensively with the old volatile-rich basement. Some of the CO₂ and N₂ outgassed was lost during heavy bombardment by impact erosion of the atmosphere and other processes. The remaining was fixed carbonates and folded deep into the megaregolith during heavy bombardment.     

Oxygen and carbon isotope ratios in the martian atmosphere

Oxygen and carbon isotope ratios in the martian CO₂ are key values to study evolution of volatiles on Mars. The major problems in spectroscopic determinations of these ratios on Mars are uncertainties associated with: (1) equivalent widths of the observed absorption lines, (2) line strengths in spectroscopic databases, and (3) thermal structure of the martian atmosphere during the observation. We have made special efforts to reduce all these uncertainties. We observed Mars using the Fourier Transform Spectrometer at the Canada–France–Hawaii Telescope. While the oxygen and carbon isotope ratios on Mars were byproducts in the previous observations, our observation was specifically aimed at these isotope ratios. We covered a range of 6022 to 6308 cm⁻¹ with the highest resolving power of ν/δν=3.5×10⁵ and a signal-to-noise ratio of 180 in the middle of the spectrum. The chosen spectral range involves 475 lines of the main isotope, 184 lines of ¹³CO₂, 181 lines of CO¹⁸O, and 119 lines of CO¹⁷O. (Lines with strengths exceeding 10⁻²⁷ cm at 218 K are considered here.) Due to the high spectral resolution, most of the lines are not blended. Uncertainties of retrieved isotope abundances are in inverse proportion to resolving power, signal-to-noise ratio, and square root of the number of lines. Laboratory studies of the CO₂ isotope spectra in the range of our observation achieved an accuracy of 1% in the line strengths. Detailed observations of temperature profiles using MGS/TES and data on temperature variations with local time from two GCMs are used to simulate each absorption line at various heights in each part of the instrument field of view and then sum up the results. Thermal radiation of Mars' surface and atmosphere is negligible in the chosen spectral range, and this reduces errors associated with uncertainties in the thermal structure on Mars. Using a combination of all these factors, the highest accuracy has been achieved in measuring the CO₂ isotope ratios: ¹³C/¹²C = 0.978 ± 0.020 and ¹⁸O/¹⁶O = 1.018 ± 0.018 times the terrestrial standards. Heavy isotopes in the atmosphere are enriched by nonthermal escape and sputtering, and depleted by fractionation with solid-phase reservoirs. The retrieved ratios show that isotope fractionation between CO₂ and oxygen and carbon reservoirs in the solid phase is almost balanced by nonthermal escape and sputtering of O and C from Mars.     

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.