Spectral reflectance properties of carbonates from terrestrial analogue environments: Implications for Mars

Spectroscopic analysis of carbonate-bearing samples from a variety of terrestrial environments provides important insights into spectroscopy-based investigations of Mars designed to detect the presence of carbonate minerals. In order to better address the spectral detectability of carbonates on Mars, we examined the spectral reflectance properties of carbonates and carbonate-bearing lithologies from a variety of terrestrial environments, including impact structures (Haughton, St. Martin, Eagle Butte), landslides (Frank), quarrying operations (Hecla), carbonates affected by weathering (Haughton, East German Creek), and sulfide-sulfate-carbonate assemblages (Central Manitoba). The goal is to identify processes and environments that can affect spectroscopy-based carbonate detection, for more detailed follow-on studies. Common carbonates appear to be stable, from a spectroscopic perspective, to various tectonic processes. Iron oxides/hydroxides do not appear to significantly affect spectral detectability of carbonates, as the spectrum-altering effects of these phases are largely restricted to the region below ∼1 μm, while useful carbonate absorption bands occur longward of ∼1.8 μm. Carbonate detection and characterization in the 0.35-2.5-μm region is largely restricted to a single absorption feature in the 2.3-μm region, which can be problematic for robust carbonate identification. While tectonic processes and iron oxide/hydroxide staining do not appear to significantly impair carbonate detection based on the 2.3-μm region absorption band, a number of other factors can affect carbonate detection. These include the fact that this absorption band is weak compared to many other minerals, a number of other minerals also exhibit absorption bands in this wavelength region (leading to possible misidentifications), and that even small abundances of minerals that absorb strongly in this region will reduce the strength of the carbonate absorption band. Identifying the nature of accessory minerals associated with carbonates can be used to constrain possible formation environments. Ongoing research at carbonate-bearing terrestrial analogue sites will continue to provide new insights into the occurrence and detection of carbonates on Mars.     

Antarctic Dry Valleys and indigenous weathering in Mars meteorites: Implications for water and life on Mars

The Dry Valleys of Antarctica are an excellent analog of the environment at the surface of Mars. Soil formation histories involving slow processes of sublimation and migration of water-soluble ions in polar desert environments are characteristic of both Mars and the Dry Valleys. At the present time, the environment in the Dry Valleys is probably the most similar to that in the mid-latitudes on Mars although similar conditions may be found in areas of the polar regions during their respective Mars summers. It is thought that Mars is currently in an interglacial period, and that subsurface water ice is sublimating poleward. Because the Mars sublimation zones seem to be the most similar to the Antarctic Dry Valleys, the Dry Valleys-type Mars climate is migrating towards the poles. Mars has likely undergone drastic obliquity changes, which means that the Dry Valleys analog to Mars may be valid for large parts of Mars, including the polar regions, at different times in geologic history. Dry Valleys soils contain traces of silicate alteration products and secondary salts much like those found in Mars meteorites. A martian origin for some of the meteorite secondary phases has been verified previously; it can be based on the presence of shock effects and other features which could not have formed after the rocks were ejected from Mars, or demonstrable modification of a feature by the passage of the meteorite through Earth's atmosphere (proving the feature to be pre-terrestrial). The martian weathering products provide critical information for deciphering the near-surface history of Mars. Definite martian secondary phases include Ca-carbonate, Ca-sulfate, and Mg-sulfate. These salts are also found in soils from the Dry Valleys of Antarctica. Results of earlier Wright Valley work are consistent with what is now known about Mars based on meteorite and orbital data. Results from recent and current Mars missions support this inference. Aqueous processes are active even in permanently frozen Antarctic Dry Valleys soils, and similar processes are probably also occurring on Mars today, especially at the mid-latitudes. Both weathering products and life in Dry Valleys soils are distributed heterogeneously. Such variations should be taken into account in future studies of martian soils and also in the search for possible life on Mars.     

Polygonal cracks in bedrock on Earth and Mars: Implications for weathering

Polygonal crack systems with domal microrelief imaged by the Mars Exploration Rover (MER) Opportunity show remarkable similarity to terrestrial crack systems developed on outcrop surfaces. Study of Jurassic Navajo Sandstone surfaces show development of crack systems in relatively isotropic host rock as a result of tensile weathering stresses. These terrestrial analogs are utilized to understand potential weathering processes on Mars.     

Electromagnetic characterization of polar ice-wedge polygons: Implications for periglacial studies on Mars and Earth

Polygonal terrain is found in a variety of polar environments on Earth and Mars. As a result, many areas of northern Canada may represent ideal terrestrial analogues for specific regions of Mars - in particular the northern plains. In the Canadian Arctic, polygon troughs are commonly underlain by wedges of massive ice, with rare examples of other wedge types. If the same is true for Mars, this raises interesting implications for the processes that concentrate H₂O at the Martian poles. This study uses an electromagnetic induction sensor to investigate the electromagnetic characteristics of terrestrial polar ice-wedge polygons. Surveys were conducted in two regions of the Canadian Arctic using a DUALEM-1S dual-geometry electromagnetic induction sensor, which measures electrical conductivity in the first 1.5-2 m of the subsurface. At locations where strong geomorphological evidence of ice was found, polygon troughs corresponded to local conductive anomalies. Trenching confirmed the presence of ice wedges at one site and allowed ground-truthing and calibration of the geophysical data. Previously unknown bodies of massive ice were also identified through the use of this geophysical technique. This study shows that an electromagnetic induction sounder is a useful instrument for detecting and mapping out the presence of subsurface ice in the Canadian Arctic. Taking together with its small size, portability and ruggedness, we suggest that this would also be a useful instrument for any future missions to Mars’ polar regions.     

Paucity of candidate coastal constructional landforms along proposed shorelines on Mars: Implications for a northern lowlands-filling ocean

The case for an ocean having once occupied the northern lowlands of Mars has largely been based indirectly on the debouching of the outflow channels into the lowlands, and directly on erosional features along the margins of the lowlands interpreted to be the result of wave action. Two global shorelines were previously mapped from albedo variation, embayment relationships, and scarps interpreted as coastal cliffs. However, not since the early, Viking-based studies, has there been a focused assessment of the presence or absence of coastal constructional landforms such as barrier ridges and spits, located on or near the mapped “shorelines.” Such constructional landforms are typically found in association with coastal erosional features on Earth, and therefore warrant a detailed search for their presence on Mars. All presently available THEMIS VIS and MOC NA images located on or near either of the two “shorelines,” within the Chryse Planitia/Arabia Terra region (10° to 44° N; 300° to 0° E) and the Isidis Planitia region (0° to 30° N; 70° to 105° E), were examined in search of any features that could reasonably be considered candidate coastal ridges. Additionally, raw MOLA profiles were used in conjunction with a technique developed from Differential Global Positioning System profiles across terrestrial paleo-shorelines, to search for coastal ridges throughout these same regions. Out of 447 THEMIS VIS and 735 MOC NA images examined, only four candidates are observed that are plausibly interpreted as coastal ridges; no candidate coastal ridges are observed in the MOLA profiles. This overwhelming paucity of candidate features suggests one of five possible scenarios in terms of the existence of standing bodies of water within the martian lowlands: (1) No ocean existed up to the level of either of the previously mapped “shorelines”; (2) An ocean existed, however wave action, the primary agent responsible for construction of coastal landforms, was minimal to non-existent; (3) An ocean existed, but sediment input was not significant enough to form coastal deposits; (4) An ocean existed, but readily froze, and over time sublimated; and lastly (5) An ocean existed and coastal landforms were constructed, but in the intervening time since their formation they have nearly all been eroded away.     

Martian gullies in the southern mid-latitudes of Mars: Evidence for climate-controlled formation of young fluvial features based upon local and global topography

A new survey of Mars Orbiter Camera (MOC) narrow-angle images of gullies in the 30°-45° S latitude band includes their distribution, morphology, local topographic setting, orientation, elevation, and slopes. These new data show that gully formation is favored over a specific range of conditions: elevation (−5000 to +3000 m), slope (>10°), and orientation (83.8% on pole-facing slopes). These data, and the frequent occurrence of gullies on isolated topographic highs, lead us to support the conclusion that climatic-related processes of volatile accumulation and melting driven by orbital variations are the most likely candidate for processes responsible for the geologically recent formation of martian gullies.     

Analysis of OMEGA/Mars Express data hyperspectral data using a Multiple-Endmember Linear Spectral Unmixing Model (MELSUM): Methodology and first results

The mineralogical composition of the Martian surface is investigated by a Multiple-Endmember Linear Spectral Unmixing Model (MELSUM) of the Observatoire pour la Minéralogie, l’Eau, les Glaces et l’Activité (OMEGA) imaging spectrometer onboard Mars Express. OMEGA has fully covered the surface of the red planet at medium to low resolution (2–4 km per pixel). Several areas have been imaged at a resolution up to 300 m per pixel. One difficulty in the data processing is to extract the mineralogical composition, since rocks are mixtures of several components. MELSUM is an algorithm that selects the best linear combination of spectra among the families of minerals available in a reference library. The best fit of the observed spectrum on each pixel is calculated by the same unmixing equation used in the classical Spectral Mixture Analysis (SMA). This study shows the importance of the choice of the input library, which contains in our case 24 laboratory spectra (endmembers) of minerals that cover the diversity of the mineral families that may be found on the Martian surface. The analysis is restricted to the 1.0–2.5 μm wavelength range. Grain size variations and atmospheric scattering by aerosols induce changes in overall albedo level and continuum slopes. Synthetic flat and pure slope spectra have therefore been included in the input mineral spectral endmembers library in order to take these effects into account. The selection process for the endmembers is a systematic exploration of whole set of combinations of four components plus the straight line spectra. When negative coefficients occur, the results are discarded. This strategy is successfully tested on the terrestrial Cuprite site (Nevada, USA), for which extensive ground observations exist. It is then applied to different areas on Mars including Syrtis Major, Aram Chaos and Olympia Undae near the North Polar Cap. MELSUM on Syrtis Major reveals a region dominated by mafic minerals, with the oldest crustal regions composed of a mixing between low-calcium pyroxenes (LCPs) (orthopyroxenes (OPx)) and high-calcium pyroxenes (HCPs) (clinopyroxenes (CPx)). The Syrtis volcanic edifice appears depleted in LCP (OPx) and enriched in HCP (CPx), which is consistent with materials produced with a lower partial fusion degree at an age younger to the surrounding crust. Strong olivine signatures are found between the two calderas Nili Patera and Meroe Patera and in Nili Fossae. A strong signature of iron oxides is found within Aram Chaos, with a spatial distribution also consistent with thermal emission spectrometer (TES). Gypsum is unambiguously detected in the northern polar region, in agreement with the study of Langevin et al. [2005. Sulfates in the north polar region of Mars detected by OMEGA/Mars Express. Science 307(5715), 1584–1586]. Our results show that the linear spectral unmixing provides good first order results in a variety of mineralogical contexts, and can therefore confidently be used on a wider scale to analyze the complete archive of OMEGA data.     

Fossilization potential of iron-bearing minerals in acidic environments of Rio Tinto, Spain: Implications for Mars exploration

Acidic waters of the Rio Tinto, southwestern Spain, evaporate seasonally, precipitating a variety of iron sulfide and oxide minerals. Schwertmannite and nanophase goethite form thin laminae on biological and detrital grain surfaces, replicating, among other things, the morphologies of insect cuticle, plant tissues, fungi, algae, and bacteria. Intergrain cements also incorporate bacterial cells and filaments. Other sulfate minerals precipitated in Rio Tinto environments are transient and contribute little to short-term preservation. Because the Rio Tinto has been cutting its current valley for several million years, terrace deposits provide a window on longer term fossil preservation. Early and later diagenesis are recorded in terrace deposits formed about one thousand and two million years ago, respectively. The sedimentary structures and mineralogies of these deposits suggest that they formed under physical and chemical conditions comparable to those of modern Rio Tinto sediments. The terrace deposits show quantitative loss of sulfate minerals, increasing crystallinity of goethite and, in the older terrace, replacement of goethite by hematite. Fossils formed originally by schwertmannite and nanophase goethite replication persist through diagenesis, preserving a long term record of local biological diversity. Fossil preservation by iron oxides in the acidic environment of Rio Tinto suggests that if life was present when sedimentary rocks formed at Meridiani Planum, Mars, precipitated minerals could record their presence.     

Modeling the formation of bright slope deposits associated with gullies in Hale Crater, Mars: Implications for recent liquid water

Our study investigates possible formation mechanisms of the very recent bright gully deposits (BGDs) observed on Mars in order to assess if liquid water was required. We use two models in our assessment: a one-dimensional (1D) kinematic model to model dry granular flows and a two-dimensional (2D) fluid-dynamic model, FLO-2D (O’Brien et al., 1993, FLO Engineering), to model water-rich and wet sediment-rich flows. Our modeling utilizes a high-resolution topographic model generated from a pair of images acquired by the High Resolution Imaging Science Experiment (HiRISE) aboard the Mars Reconnaissance Orbiter. For the 1D kinematic modeling of dry granular flows, we examine a range of particle sizes, flow thicknesses, initial velocities, flow densities, and upslope initiation points to examine how these parameters affect the flow run-out distances of the center of mass of a flow. Our 1D modeling results show that multiple combinations of realistic parameters could produce dry granular flows that travel to within the observed deposits’ boundaries. We run the 2D fluid-dynamic model, FLO-2D, to model both water-rich and wet sediment-rich flows. We vary the inflow volume, inflow location, discharge rate, water-loss rate (water-rich models only), and simulation time and examine the resulting maximum flow depths and velocities. Our 2D modeling results suggest that both wet sediment-rich and water-rich flows could produce the observed bright deposits. Our modeling shows that the BGDs are not definitive evidence of recent liquid water on the surface of Mars.     

Raman spectroscopic detection of key biomarkers of cyanobacteria and lichen symbiosis in extreme Antarctic habitats: Evaluation for Mars Lander missions

With proposals that micro-miniaturised Raman spectrometers could soon be part of a suite of analytical instrumentation on the surface of Mars, it is critically important to examine the spectral information that could be forthcoming from attempts to determine key molecular biosignatures under the hostile conditions of extra-terrestrial planetary exploration. Current approaches include the analysis of genuine martian geological material in the form of the SNC class meteorites, the formulation of simulated martian regoliths and the examination of putative martian terrestrial analogues; the latter provide the basis of this paper in the form of Antarctic extremophile habitats. In particular, specimens of epilithic, chasmolithic and endolithic lichen and cyanobacterial colonies sampled along a progressively worsening transect towards a “limits of life” situation, beyond which survival of organisms becomes impossible, provide what is arguably the best terrestrial proving-ground for prototype Raman spectrometers for martian exploration. Here, we report the results of experiments on these extant Antarctic extremophile colonies using a range of Raman excitation wavelengths and experimental conditions and also include a compilation of molecular spectral biosignatures, which may be considered as a suitable database for recognition of bioorganic modification of geological strata.     

Characterization of halophiles in natural MgSO4 salts and laboratory enrichment samples: Astrobiological implications for Mars

The presence of sulfate salts and limited subsurface water (ice) on Mars suggests that any liquid water on Mars today will occur as (magnesium) sulfate-rich brines in regions containing sources of magnesium and sulfur. The Basque Lakes of British Columbia, Canada, represent a hypersaline terrestrial analogue site, which possesses chemical and physical properties similar to those observed on Mars. The Basque Lakes also contain diverse halophilic organisms representing all three Kingdoms of life, growing in surface and near-subsurface environments. Of interest from an astrobiological perspective, crushed magnesium sulfate samples that were analyzed using a modified Lowry protein assay contained biomass in every crystal inspected, with biomass values from 0.078 to 4.21 mg_biomass/g_salt; average=0.74±0.7 mg_biomass/g_salt. Bacteria and Archaea cells were easily observed even in low-biomass samples using light microscopy, and bacteria trapped within magnesium sulfate crystals were observed using confocal microscopy. Regions within the salt also contained bacterial pigments, e.g., carotenoids, which were separate from the cells, indicating that cell lysis might have occurred during entrapment within the salt matrix. These biosignatures, cells, and any ‘soluble’ organic constituents were primarily found trapped within fluid inclusions or fluid-filled void spaces between intergrown crystals. Diffuse reflectance infrared Fourier transform spectroscopy (reflectance IR) analysis of enrichment cultures, containing cyanobacteria, Archaea, or dissimilatory sulfate-reducing bacteria, highlighted molecular biosignature features between 550-1650 and 2400-3000 cm⁻¹. Spectra from natural salts demonstrated that we can detect biomass within salt crystals using the most sensitive biosignatures, which are the 1530-1570 cm⁻¹, C-N, N-H, -COOH absorptions and the 1030-1050 cm⁻¹ C-OH, C-N, PO₄³⁻ bond features. The lowest detection limit for a biosignature absorption feature using reflectance IR was with a natural sample that possessed 0.78 mg_biomass/g_salt. In a model cell, i.e., a 0.5 by 1 μm bacillus, this biomass value corresponds to approximately 7.8×10⁸ cells/g_salt. Based on its ability to detect biomass entrapped within natural sulfate salts, reflectance IR may make an effective remote-sensing tool for finding enrichments of organic carbon within outcrops and surficial sedimentary deposits on Mars.     

Morphology, stratigraphy, and mineralogical composition of a layered formation covering the plateaus around Valles Marineris, Mars: Implications for its geological history

An extensive layered formation covers the high plateaus around Valles Marineris. Mapping based on HiRISE, CTX and HRSC images reveals these layered deposits (LDs) crop out north of Tithonium Chasma, south of Ius Chasma, around West Candor Chasma, and southwest of Juventae Chasma and Ganges Chasma. The estimated area covered by LDs is ∼42,300 km². They consist of a series of alternating light and dark beds, a 100 m in total thickness that is covered by a dark unconsolidated mantle possibly resulting from their erosion. Their stratigraphic relationships with the plateaus and the Valles Marineris chasmata indicate that the LDs were deposited during the Early- to Late Hesperian, and possibly later depending on the region, before the end of the backwasting of the walls near Juventae Chasma, and probably before Louros Valles sapping near Ius Chasma. Their large spatial coverage and their location mainly on highly elevated plateaus lead us to conclude that LDs correspond to airfall dust and/or volcanic ash. The surface of LDs is characterized by various morphological features, including lobate ejecta and pedestal craters, polygonal fractures, valleys and sinuous ridges, and a pitted surface, which are all consistent with liquid water and/or water ice filling the pores of LDs. LDs were episodically eroded by fluvial processes and were possibly modified by sublimation processes. Considering that LDs correspond to dust and/or ash possibly mixed with ice particles in the past, LDs may be compared to Dissected Mantle Terrains currently observed in mid- to high latitudes on Mars, which correspond to a mantle of mixed dust and ice that is partially or totally dissected by sublimation. The analysis of CRISM and OMEGA hyperspectral data indicates that the basal layer of LDs near Ganges Chasma exhibits spectra with absorption bands at ∼1.4 μm, and ∼1.9 μm and a large deep band between ∼2.21 and ∼2.26 μm that are consistent with previous spectral analysis in other regions of LDs. We interpret these spectral characteristics as an enrichment of LDs in opaline silica or by Al-phyllosilicate-rich layers being overlain by hydroxylated ferric sulfate-rich layers. These alteration minerals are consistent with the aqueous alteration of LDs at low temperatures.     

Geologic context of in situ rocky exposures in Mare Serpentis, Mars: Implications for crust and regolith evolution in the cratered highlands

Global acquisition of infrared spectra and high-resolution visible and infrared imagery has enabled the placement of compositional information within stratigraphic and geologic context. Mare Serpentis, a low albedo region located northwest of Hellas Basin, is rich in spectral and thermophysical diversity and host to numerous isolated exposures of in situ rocky material. Most martian surfaces are dominated by fine-grained particulate materials that bear an uncertain compositional and spatial relationship to their source. Thus location and characterization of in situ rock exposures is important for understanding the origin of highland materials and the processes which have modified those materials. Using spectral, thermophysical and morphologic information, we assess the local and regional stratigraphy of the Mare Serpentis surface in an effort to reconstruct the geologic history of the region. The martian highlands in Mare Serpentis are dominated by two interspersed surface units, which have distinct compositional and thermophysical properties: (1) rock-dominated surfaces relatively enriched in olivine and pyroxene, and depleted in high-silica phases, and (2) sediment or indurated material depleted in olivine and pyroxene, with relatively higher abundance of high-silica phases. This is a major, previously unrecognized trend which appears to be pervasive in the Mare Serpentis region and possibly in other highland areas. The detailed observations have led us to form two hypotheses for the relationship between these two units: either (1) they are related through a widespread mechanical and/or chemical alteration process, where less-mafic plains materials are derived from the mafic bedrock, but have been compositionally altered in the process of regolith formation, or (2) they are stratigraphically distinct units representing separate episodes of upper crust formation. Existing observations suggest that the second scenario is more likely. In this scenario, plains materials represent older, degraded, and possibly altered, “basement” rock, whereas the rocky exposures represent later additions to the crust and are probably volcanic in origin. These hypotheses should be further testable with decimeter-resolution imagery and meter-resolution short wavelength infrared spectra.     

A sensitive search for SO2 in the martian atmosphere: Implications for seepage and origin of methane

Mars was observed near the peak of the strongest SO₂ band at 1364-1373 cm⁻¹ with resolving power of 77,000 using the Texas Echelon Cross Echelle Spectrograph on the NASA Infrared Telescope Facility. The observation covered the Tharsis volcano region which may be preferable to search for SO₂. The spectrum shows absorption lines of three CO₂ isotopomers and three H₂O isotopomers. The water vapor abundance derived from the HDO lines assuming D/H = 5.5 times the terrestrial value is 12±1.0 pr. μm, in agreement with the simultaneous MGS/TES observations of 14 pr. μm at the latitudes (50° S to 10° N) of our observation. Summing of spectral intervals at the expected positions of sixteen SO₂ lines puts a 2σ upper limit on SO₂ of 1 ppb. SO₂ may be emitted into the martian atmosphere by seepage and is removed by three-body reactions with OH and O. The SO₂ lifetime, 2 years, is longer than the global mixing time 0.5 year, so SO₂ should be rather uniformly distributed across Mars. Seepage of SO₂ is less than 15,000 tons per year on Mars which is smaller than the volcanic production of SO₂ on the Earth by a factor of 700. Because CH₄/SO₂ is typically 10⁻⁴-10⁻³ in volcanic gases on the Earth, our results show seepage is unlikely to be the source of the recently discovered methane on Mars and therefore strengthen its biogenic origin.     

Experimental study of the sublimation of ice through an unconsolidated clay layer: Implications for the stability of ice on Mars and the possible diurnal variations in atmospheric water

We have studied the sublimation of ice and water vapor transport through various thicknesses of clay (<63 μm grain size). We experimentally demonstrate that both adsorption and diffusion strongly affect the transport of water, and that the processes of diffusion and adsorption can be separately quantified once the system comes to a steady state. At shallow depths of clay, water vapor transport is determined by diffusion through both the atmosphere and the clay layer, whereas at greater depth the rate of sublimation of the ice is governed only by diffusion through the clay. Using two different models, we determine the diffusion coefficient for water vapor through unconsolidated clay layer to be 1.08±0.04×¹⁰⁻⁴ and . We also determined the adsorption isotherms for the clay layer, which follow the Langmuir theory at low water vapor pressure (<100 Pa, where a monolayer of water molecules forms on the surface of the clay) and the BET theory at higher pressure (where multiple water layers form). From our analysis of both types of isotherms we determined the adsorption constants to be and c=30±10, respectively, and specific surface areas of 1.10±0.2×¹⁰⁵ and , respectively. Finally, we report a theoretical kinetic model for the simultaneous diffusion and adsorption from which we determine adsorption kinetic constants according to the Langmuir theory of and . If the martian regolith possesses diffusive properties similar to those of the unconsolidated montmorillonite soil we investigated here, it would not represent a significant barrier to the sublimation of subsurface ice. However, at the low subsurface temperatures of high latitude (180 K on average), ice could survive from the last glaciation period (about 300 to 400,000 years ago). Higher subsurface temperatures in the equatorial regions would prevent long-timescale survival of ice in the shallow subsurface. In agreement with previous work, we show that adsorption of water by a clay regolith could provide a significant reservoir of subsurface water and it might account for the purported diurnal cycle in the water content of the atmosphere.     

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.     

Sublimation extraction coupled with gas chromatography-mass spectrometry: A new technique for future in situ analyses of purines and pyrimidines on Mars

We have developed a sublimation technique coupled with chemical derivatization and gas chromatography mass spectrometry (GC-MS) to detect nucleobases and other volatile organic compounds derived from bacteria in Mars analog materials. To demonstrate this technique, a sample of serpentine inoculated with Escherichia coli (E. coli) cells was heated to 500 °C for several seconds under Martian ambient pressure. The sublimate was collected on a cold finger, then derivatized and analyzed by GC-MS. We found that adenine, cytosine, thymine and uracil were the most abundant molecules detected in the sublimed E. coli extract by GC-MS. In addition, nucleobases were also detected in sublimed extracts of a deep-sea sediment sample, seawater, and soil collected from the Atacama Desert in Chile after heating the samples under the same conditions. Our results indicate that nucleobases can be easily isolated directly from natural samples using sublimation and then detected by GC-MS after chemical derivatization. The sublimation-based extraction technique is one approach that should be considered for use by future in situ instruments designed to detect organic compounds relevant to life in the Martian regolith.     

Raman spectra of nitrogen-containing organic compounds obtained in high altitude sites using a portable spectrometer: Possible application for remote robotic Titan studies

Well-resolved Raman spectra of examples of nitrogen-containing compounds were detected using a portable Raman instrument (Ahura First Defender XL) outdoors at a low temperature of −15 °C at an altitude of 2860 m (Pitztall, Austria). The portable Raman spectrometer tested here is equipped with a 785 nm diode laser and fixed frontal probe. Solid forms of formamide, urea, 3-methylpyridine, aniline, indene, 1-(2-aminoethyl)piperazine, benzofuran and indoline were detected unambiguously under field high-mountain conditions. The main Raman features (strong, medium and partially weak bands) were observed at their correct wavenumber positions (spectral resolution 7-10 cm⁻¹) in the range 200-2000 cm⁻¹. The results obtained demonstrate the possibility of applying a miniaturised Raman spectrometer as key instrument for investigating the presence of nitrogen-containing organic compounds and biomolecules under low temperature field conditions. Within the payload designed by ESA and NASA for future missions focusing not only on Mars, Raman spectroscopy will be an important non-destructive analytical tool for the in-situ identification of both organic and inorganic compounds relevant to life detection on planetary surfaces or near sub-surfaces.