Analysis and survival of amino acids in Martian regolith analogs

Abstract— We have investigated the native amino acid composition of two analogs of Martian soil, JSC Mars‐1 and Salten Skov. A Mars simulation chamber has been built and used to expose samples of these analogs to temperature and lighting conditions similar to those found at low latitudes on the Martian surface. The effects of the simulated conditions have been examined using high‐performance liquid chromatography (HPLC). Exposure to energetic ultraviolet (UV) light in vacuum appears to cause a modest increase in the concentration of certain amino acids within the materials, which is interpreted as resulting from the degradation of microorganisms. The influence of low temperatures shows that the accretion of condensed water on the soils leads to the destruction of amino acids, supporting the idea that reactive chemical processes involving H₂O are at work within the Martian soil. We discuss the influence of UV radiation, low temperatures, and gaseous CO₂ on the intrinsic amino acid composition of Martian soil analogs and describe, with the help of a simple model, how these studies fit within the framework of life detection on Mars and the practical tasks of choosing and using Martian regolith analogs in planetary research.     

Production and detection of carbon dioxide on Iapetus

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

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.     

Sublimation of the Martian CO2 Seasonal South Polar Cap

The polar condensation/sublimation of CO₂, that involve about one fourth of the atmosphere mass, is the major Martian climatic cycle. Early observations in visible and thermal infrared have shown that the sublimation of the Seasonal South Polar Cap (SSPC) is not symmetric around the geographic South Pole.Here we use observations by OMEGA/Mars Express in the near-infrared to detect unambiguously the presence of CO₂ at the surface, and to estimate albedo. Second, we estimate the sublimation of CO₂ released in the atmosphere and show that there is a two-step process. From Ls=180° to 220°, the sublimation is nearly symmetric with a slight advantage for the cryptic region. After Ls=220° the anti-cryptic region sublimation is stronger. Those two phases are not balanced such that there is 22% ± 9 more mass the anti-cryptic region, arguing for more snow precipitation. We compare those results with the MOLA height measurements. Finally we discuss implications for the Martian atmosphere about general circulation and gas tracers, e.g. Ar.     

Mars regolith versus SNC meteorites: Possible evidence for abundant crustal carbonates

Viking XRF analyses of the Martian regolith are compared with typical igneous rocks of the Earth, the Moon, the eucrite parent asteroid, and especially the shergottites, nakhlites, and Chassigny (SNC) meteorites, which are suspected to be basalts and mafic cumulates from Mars. A striking feature of the Martian regolith, compared to igneous rocks with similar molar (Mg + Fe)/Si ratios, is its extraordinarily low Ca/Si ratio. The regolith's low Ca/Si ratio is probably not a result of simple mixing (isochemical weathering) of SNC-like rocks with other igneous rocks, unless the regolith contains a large component of rock with an improbable combination of extremely low Ca/Si and (Mg + Fe)/Si, and yet low K₂O and Zr. Several other models might conceivably account for the low Ca/Si ratio, but I suggest that most of the “missing” Ca was removed from the regolith as Ca-carbonate. Formation of a mass of carbonate equivalent to a global shell 20 m thick would suffice to remove 1000 mbar of CO₂ from the Martian atmosphere. Thus, the peculiar Ca/Si ratio of the Martian regolith tends to support the hypothesis that the climate of Mars was once far warmer and wetter than it is today.     

Seasonal buffering of atmospheric pressure on Mars

An isothermal reservoir of carbon dioxide in gaseous contact with the Martian atmosphere would reduce the amplitude and advance the phase of global atmospheric pressure fluctuations caused by seasonal growth and decline of polar CO₂ frost caps. Adsorbed carbon dioxide in the upper ～10 m of Martian regolith is sufficient to buffer the present atmosphere on a seasonal basis. Available observations and related polar cap models do not confirm or refute the operation of such a mechanism. Implications for the amplitude and phase of seasonal pressure fluctuations are subject to direct test by the upcoming Viking mission to Mars.     

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

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

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.     

CO2 permafrost and Martian topography

The role of CO₂ permafrost as an erosive agent on Mars is considered. In the CO₂H₂O system, with a CO₂ triple point at 217°K and 5.1-bar pressure, carbon dioxide solid, liquid, or gas, CO₂ clathrate, and ice are possible stable phases in the range of temperatures and pressures likely to be encountered in the Martian regolith. It is argued that conditions may exist in which CO₂ permafrost is extensive on Mars, provided that adequate CO₂ is available: the maximum ratio of H₂O:CO₂ required in the subsurface pore space system is 17:3. Erosional processes likely to result from such permafrost are block slumping, leading to canyon development; pit chains along faults; chaotic terrain where massive permafrost destruction has occured; large-scale flows of slurry; and perhaps even the flash floods which create channels.     

Atmospheric chemistry on Venus, Earth, and Mars: Main features and comparison

This paper deals with two common problems and then considers major aspects of chemistry in the atmospheres of Mars and Venus. (1) The atmospheres of the terrestrial planets have similar origins but different evolutionary pathways because of the different masses and distances to the Sun. Venus lost its water by hydrodynamic escape, Earth lost CO₂ that formed carbonates and is strongly affected by life, Mars lost water in the reaction with iron and then most of the atmosphere by the intense meteorite impacts. (2) In spite of the higher solar radiation on Venus, its thermospheric temperatures are similar to those on Mars because of the greater gravity acceleration and the higher production of O by photolysis of CO₂. O stimulates cooling by the emission at 15 μm in the collisions with CO₂. (3) There is a great progress in the observations of photochemical tracers and minor constituents on Mars in the current decade. This progress is supported by progress in photochemical modeling, especially by photochemical GCMs. Main results in these areas are briefly discussed. The problem of methane presents the controversial aspects of its variations and origin. The reported variations of methane cannot be explained by the existing data on gas-phase and heterogeneous chemistry. The lack of current volcanism, SO₂, and warm spots on Mars favor the biological origin of methane. (4) Venus’ chemistry is rich and covers a wide range of temperatures and pressures and many species. Photochemical models for the middle atmosphere (58-112 km), for the nighttime atmosphere and night airglow at 80-130 km, and the kinetic model for the lower atmosphere are briefly discussed.     

On the abundances of carbon dioxide isotopologues in the atmospheres of mars and earth

The isotopic composition of carbon dioxide in the Martian atmosphere from the measurements of Mars Science Laboratory have been used to estimate the relative abundances of CO₂ isotopologues in the Martian atmosphere. Concurrently, this study has revealed long-standing errors in the amounts of some of low-abundance CO₂ isotopologues in the Earth’s atmosphere in the databases of spectroscopic parameters of gases (HITRAN, etc.).     

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.     

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.     

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.     

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.     

Suprathermal electron fluxes on the nightside of Mars: ASPERA-3 observations

Recently aurora-type UV emissions were discovered on the nightside of Mars [Bertaux, J.-L., Leblanc, F., Witasse, O., et al., 2005. Discovery of an aurora on Mars. Nature 439, doi:10.1038/nature03603]. It was suggested that these emissions are produced by suprathermal electrons with energies of tens of eV, rather than by the electrons with spectra peaked above 100 eV [Leblanc, F., Witasse, O., Winningham J., et al., 2006. Origin of the martian aurora observed by spectroscopy for investigation of characteristics of the atmosphere of Mars (SPICAM) onboard Mars Express. J. Geophys. Res. 111, A09313, doi:10.1029/2006JA011763]. In this paper we present observations of fluxes of suprathermal electrons (E_e≈30-100 eV) on the Martian nightside by the ASPERA-3 experiment onboard the Mars Express spacecraft. Narrow spikes of suprathermal electrons are often observed in energy-time spectrograms of electron fluxes at altitudes between 250 and 600 km. These spikes are spatially organized and form narrow strips in regions with strong upward or downward crustal magnetic field. The values of electron fluxes in such events generally could explain the observed auroral UV emissions although a question of their origin (transport from the dayside or local precipitation) remains open.     

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 salts of Mars

Salt compounds are apparently an important component of the finite-grained regolith on Mars. Salt enrichment may be explained either as a secondary concentration of chemical weathering products or as direct incorporation of planetary released volatiles. Geochemical measurements and chemical relationships constrain the salt species and resultant physicochemical consequences. A likely assemblage is dominated by (Mg,Na)SO₄, NaCl, and (Mg,Ca)CO₃. Formation of brine in equilibrium with such a salt mixture is unlikely under the temperature and water-vapor restrictions prevalent over most, if not all, of the Martian surface. Acidic conditions, accompanying salt formation, favor the preferential destruction of susceptible igneous minerals.     

The effect of ground ice on the Martian seasonal CO2 cycle

The mostly carbon dioxide (CO₂) atmosphere of Mars condenses and sublimes in the polar regions, giving rise to the familiar waxing and waning of its polar caps. The signature of this seasonal CO₂ cycle has been detected in surface pressure measurements from the Viking and Pathfinder landers. The amount of CO₂ that condenses during fall and winter is controlled by the net polar energy loss, which is dominated by emitted infrared radiation from the cap itself. However, models of the CO₂ cycle match the surface pressure data only if the emitted radiation is artificially suppressed suggesting that they are missing a heat source. Here we show that the missing heat source is the conducted energy coming from soil that contains water ice very close to the surface. The presence of ice significantly increases the thermal conductivity of the ground such that more of the solar energy absorbed at the surface during summer is conducted downward into the ground where it is stored and released back to the surface during fall and winter thereby retarding the CO₂ condensation rate. The reduction in the condensation rate is very sensitive to the depth of the soil/ice interface, which our models suggest is about 8 cm in the Northern Hemisphere and 11 cm in the Southern Hemisphere. This is consistent with the detection of significant amounts of polar ground ice by the Mars Odyssey Gamma Ray Spectrometer and provides an independent means for assessing how close to the surface the ice must be. Our results also provide an accurate determination of the global annual mean size of the atmosphere and cap CO₂ reservoirs, which are, respectively, 6.1 and 0.9 hPa. They also indicate that general circulation models will need to account for the effect of ground ice in their simulations of the seasonal CO₂ cycle.     

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

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