Fe Mössbauer spectroscopy as a tool in astrobiology

The element Fe and Fe-bearing minerals occur ubiquitously throughout the field of astrobiology. Cycling between the various oxidation states of Fe provides a source of energy available for life. Banded iron formations may record the rise of oxygenic photosynthesis. The distribution of Fe between Fe-bearing minerals and its oxidation states can help to characterize and understand ancient environments with respect to the suitability for life by constraining the primary rock type and the redox conditions under which it crystallized, the extent of alteration and weathering, the type of alteration and weathering products, and the processes and environmental conditions for alteration and weathering. Fe Mössbauer spectroscopy is a powerful tool to investigate Fe-bearing compounds. It can identify Fe-bearing minerals, determine Fe oxidation states with high accuracy, quantify the distribution of Fe between mineralogical phases, and provide clues about crystallinity and particle sizes. Two miniaturized Mössbauer spectrometers are on board of the NASA Mars Exploration Rovers Spirit and Opportunity. The Fe-bearing minerals goethite, an iron oxide-hydroxide, and jarosite, an iron hydroxide sulfate, were identified by Mössbauer spectroscopy in Gusev Crater and at Meridiani Planum, respectively, providing in situ proof of an aqueous history of the two landing sites and constraints on their habitability. Hematite identified by Mössbauer spectroscopy at both landing sites adds further evidence for an aqueous history. On Earth, Mössbauer spectroscopy was used to monitor possibly microbially-induced changes of Fe-oxidation states in basaltic glass samples exposed at the Loihi Seamount, a deep sea hydrothermal vent system, which might be analogous to possible extraterrestrial habitats on ancient Mars or the Jovian moon Europa today.     

The miniaturized Möessbauer spectrometer MIMOS II for the Phobos-Grunt mission

Möessbauer spectroscopy is a powerful tool for the mineralogical analysis of Fe-bearing materials. The miniaturized Möessbauer spectrometer MIMOS II has already been working on the surface of Mars for 6 years as part of the NASA Mars Exploration Rovers mission. The improved version of the instrument is a component of the scientific payload of the Phobos-Grunt mission. The scientific objectives of the instrument are the following: to identify the iron-bearing phases, to determine the quantitative distribution of iron among these phases, and to determine the distribution of iron among its oxidation states.     

Titanomaghemite in Icelandic basalt: possible clues for the strongly magnetic phase in Martian soil and dust

It is suggested that the strongly magnetic phase found in the soil and dust on Mars, tentatively identified as maghemite, may have been formed in a similar way as titanomaghemite found in the Icelandic basalt. Earlier work has shown that titanomaghemite in Icelandic basalt can be formed upon thermal oxyexolution of titanomagnetite, a process in which water may not have played any significant role. Here, we present further data on how the formation of titanomaghemite takes place in Icelandic basalt, and illustrate how the Mössbauer spectroscopy can be useful in answering fundamental questions related to the possible formation of maghemite on Mars. This might be of special interest for a robotic Mars mission where a ⁵⁷Fe-Mössbauer spectrometer is included.     

Digging deep for ice in Isidis Planitia—New constraints on subsurface volatile concentrations from thermal modeling

The Isidis Planitia region on Mars usually is regarded as a comparably attractive site for landing missions based on engineering constraints such as elevation and smooth regional topography. The Mars Express landed element Beagle 2 was deployed to this area, and the southern margin of the basin was selected as one of the backup landing sites for the NASA Mars Exploration Rovers.Especially in the context of the Beagle 2 mission, Isidis Planitia has been discussed as a place which might have experienced a volatile-rich history with associated potential for biological activity [e.g. Bridges et al., 2003. Selection of the landing site in Isidis Planitia of Mars Probe Beagle 2. J. Geophys. Res. 108(E1), 5001, doi: 10.1029/2001JE001820]. However the measurements of by the GRS instrument on Mars Odyssey indicate a maximum inferred water abundance of only 3 wt% in the upper few meters of the surface [Feldman et al., 2004. Global distribution of near-surface hydrogen on Mars. J. Geophys. Res. 109, E09006, doi: 10.1029/2003JE002160]. Based on these measurements this area seems to be one of the driest spots in the equatorial region of Mars.To support future landing site selections we took a more detailed look at the minimum burial depth of stable ice deposits in this area, focusing as an example on the planned Beagle 2 landing site. We are especially interested in the likelihood of ground ice deposits within the range of proposed subsurface sampling tools as drills or ‘mole’-like devices [Richter et al., 2002. Development and testing of subsurface sampling devices for the Beagle 2 Lander. Planet. Space Sci. 50, 903-913] given reasonable physical constraints for the surface and near surface material.For a mission like ExoMars [Kminek, G., Vago, J.L., 2005. The Aurora Exploration Program—The ExoMars Mission. In: Proceedings of the 35th Lunar and Planetary Science Conference, abstract no. 1111, 15-19 March 2004, League City, TX] with a focus on finding traces of fossil life the area might be of potential interest, because these traces would be better conserved in the dry soil. Modeling and measurement indicate that Isidis Planitia is indeed a dry place and any hypothetical ground ice deposits in this region are out of range of currently proposed sampling devices.     

A cold and wet Mars

Water on Mars has been explained by invoking controversial and mutually exclusive solutions based on warming the atmosphere with greenhouse gases (the “warm and wet” Mars) or on local thermal energy sources acting in a global freezing climate (the “cold and dry” Mars). Both have critical limitations and none has been definitively accepted as a compelling explanation for the presence of liquid water on Mars. Here is considered the hypothesis that cold, saline and acidic liquid solutions have been stable on the sub-zero surface of Mars for relatively extended periods of time, completing a hydrogeological cycle in a water-enriched but cold planet. Computer simulations have been developed to analyze the evaporation processes of a hypothetical martian fluid with a composition resulting from the acid weathering of basalt. This model is based on orbiter- and lander-observed surface mineralogy of Mars, and is consistent with the sequence and time of deposition of the different mineralogical units. The hydrological cycle would have been active only in periods of dense atmosphere, as having a minimum atmospheric pressure is essential for water to flow, and relatively high temperatures (over ∼245 K) are required to trigger evaporation and snowfall; minor episodes of limited liquid water on the surface could have occurred at lower temperatures (over ∼225 K). During times with a thin atmosphere and even lesser temperatures (under ∼225 K), only transient liquid water can potentially exist on most of the martian surface. Assuming that surface temperatures have always been maintained below 273 K, Mars can be considered a “cold and wet” planet for a substantial part of its geological history.     

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

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

Meridiani Planum hematite deposit and the search for evidence of life on Mars—iron mineralization of microorganisms in rock varnish

The extensive hematite deposit in Meridiani Planum was selected as the landing site for the Mars Exploration Rover Opportunity because the site may have been favorable to the preservation of evidence of possible prebiotic or biotic processes. One of the proposed mechanisms for formation of this deposit involves surface weathering and coatings, exemplified on Earth by rock varnish. Microbial life, including microcolonial fungi and bacteria, is documented in rock varnish matrices from the southwestern United States and Australia. Limited evidence of this life is preserved as cells and cell molds mineralized by iron oxides and hydroxides, as well as by manganese oxides. Such mineralization of microbial cells has previously been demonstrated experimentally and documented in banded iron formations, hot spring deposits, and ferricrete soils. These types of deposits are examples of the four “water-rock interaction” scenarios proposed for formation of the hematite deposit on Mars. The instrument suite on Opportunity has the capability to distinguish among these proposed formation scenarios and, possibly, to detect traces that are suggestive of preserved martian microbiota. However, the confirmation of microfossils or preserved biosignatures will likely require the return of samples to terrestrial laboratories.     

Four climate regimes on a land planet with wet surface: Effects of obliquity change and implications for ancient Mars

Series of numerical experiments are performed using a general circulation model to gain insights on the hydrologic cycle on ancient Mars. Since the state of the ancient Mars atmosphere is not well constrained, we did not try to simulate an ancient Mars climate under warm and wet condition. In stead, we used an idealized model and tried to extract general features of the hydrologic cycle by modeling an ideal land planet that has no ocean on its surface. Four different climate regimes, “warm-upright,” “warm-oblique,” “frozen-upright,” and “frozen-oblique” regimes, are recognized depending on the inclination of the spin axis (obliquity) and average surface temperature. The period of active hydrologic cycle suggested from the geomorphology on Mars seems to be consistent with that at the “warm-oblique” regime, which appears at warm (above-freezing) environment with high-obliquity (higher than about 30°) condition.     

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

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

Indications of brine related local seepage phenomena on the northern hemisphere of Mars

Springtime low albedo features, called Dark Dune Spots, on the seasonal frost covered dunes on Mars between 77°N and 84°N latitude have been analyzed. Two groups of these spots have been identified: “small” and “large” ones, where large spots have diameters above 4 m, and complex internal structure. From these “large” spots branching seepage-like features emanate and grow on the steep slopes. They show a characteristic sequence of changes: first only wind-blown features emanate from them, while later a bright circular and elevated ring forms, and dark seepage-features start from the spots. These streaks grow with a speed between 0.3 m/day and 7 m/day respectively, first only from the spots, later from all along the dune crest.During this “seepage period” the temperature is between 150 K and 180 K at a 3-9 km spatial resolution scale, indicating that CO₂ ice-free parts must be present at the observed dark spots. Around the receding northern seasonal CO₂ cap, an annulus of water ice lags behind, which is probably present in the spots too where the CO₂ frost has sublimated. Our model estimates show in the present work and in Kereszturi et al. (Kereszturi, A., Möhlmann, D., Berczi, Sz., Ganti, T., Kuti, A., Sik, A., Horvath, A. [2009b]. Icarus 201, 492-503) that the warming driven by solar insolation may produce not only interfacial water, but also bulk brines around the dune grains. The brine can support the movement of liquids and dune grains, enhances the sublimation of CO₂ frost, and produce the dark features, as well as liquid modifies the optical properties of the surface.Signs of movement of dune material after the total defrosting of the terrain is also visible but it is uncertain because of the limit of resolution. In our previous work (Kereszturi et al., 2009b) we showed that resembling seepage-like streaks at the southern hemisphere might have been formed by ephemeral interfacial water, as well as these northern features. Such wet environments may have astrobiological importance too.     

Development and testing of subsurface sampling devices for the Beagle 2 lander

For planetary landing missions, the capability to acquire samples of soil and rock is of high importance whenever complex analyses (e.g. isotopic studies) on these materials are to be carried out, or when samples are to be returned to Earth. Not only surface samples are of relevance, but in recent concepts at least for Mars landing missions also subsurface samples are required. Subsurface material on Mars is believed to have been protected from the inferred oxidants at the immediate surface while also being protected from the UV influx. Therefore, there is considerable hope that in subsurface soil samples on Mars, at least organic matter delivered by meteorites may be detected, and possibly also relics of earlier simple microbial life on the planet. Likewise, samples from the inside of Martian surface rocks promise to have been protected from weathering and for the same reason they are important for organic chemistry studies. In this paper, an overview is given of the development and science of two different subsurface sampling devices for the Beagle 2 lander of ESA's Mars Express mission, being a “Mole” subsurface soil sampler and a small rock coring and sampling mechanism. Besides their sampling function, both the Mole and the Corer/Grinder will provide data on physical properties of Martian soils and rock, respectively, through the way they interact with the sampled materials. Details of the Mole and Corer/Grinder design are presented, along with results of recent tests with prototypes in the laboratory on physically analogous sample materials.     

Eolian controlled modification of the martian south polar layered deposits

Data from the Mars Orbiter Laser Altimeter (MOLA) and Mars Orbiter Camera (MOC) aboard the Mars Global Surveyor (MGS) mission and the Thermal Emission Imaging System (THEMIS) aboard the Mars Odyssey mission have revealed unique surface features in a particular region of the South Polar Layered Deposits (SPLD). The dominant morphology is large-scale quasi-parallel grooves that extend for hundreds of kilometers with only tens of meters of vertical relief, that we have termed here the “Wire Brush” terrain. The grooves are also transected by disjointed, yet roughly continuous, low-relief sinuous ridges that cross roughly perpendicular to the trend-direction of the large-scale grooves and show only tens of meters of relief. We interpret these ridges to be eroded remnants of folded layers. At the northern end of the large-scale grooves there are non-symmetric mounds. They are frequently preceded by a significant depression and/or trailing grooves that are parallel to the Wire Brush trend. We find that a two-stage process involving winds that intermittently remove a low-density crust exposing the underlying ice to ablation is the interpretation that best explains the multitude of features observed here. These features appear to be currently inactive indicating higher winds in previous epochs.     

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.     

Mineralogical constraints on the high-silica martian surface component observed by TES

The Thermal Emission Spectrometer (TES) has observed a high-silica material in the dark regions of Mars that is spectrally similar to obsidian glass and may have a volcanic origin. An alternate interpretation is that the spectrally amorphous material consists of clay minerals or some other secondary material, formed by chemical alteration of surface rocks. The regions where this material is observed (e.g., Acidalia Planitia) have relatively high spectral contrast, suggesting that the high-silica material exists as coarse particulates, indurated soils or cements, within rocks, or as indurated coatings on rock surfaces. The geologic interpretation of this spectral result has major implications for understanding magmatic evolution and weathering processes on Mars. One of the complications in interpreting spectral observations of glasses and clay minerals is that both are structurally and compositionally complex. In this study, we perform a detailed spectroscopic analysis of indurated smectite clay minerals and relate their thermal emission spectral features to structural and crystal chemical properties. We examine the spectral similarities and differences between smectite clay minerals and obsidian glass from a structural-chemical perspective, and make further mineralogical interpretations from previous TES results. The results suggest that neither smectite clays nor any clay mineral with similar structural and chemical properties can adequately explain TES observations of high-silica materials in some martian dark regions. If the spectrally amorphous materials observed by TES do represent an alteration product, then these materials are likely to be poorly crystalline aluminosilicates. While all clay minerals have Si/O ratios ?0.4, the position of the emissivity minimum at Mars suggests a Si/O ratio of 0.4-0.5. The spectral observation could be explained by the existence of a silica-rich alteration product, such as Al- or Fe-bearing opal, an intimate physical mixture of relatively pure silica and other aluminosilicates (such as clay minerals or clay precursors), or certain zeolites. The chemical alteration of basaltic rocks on Mars to phyllosilicate-poor, silica-rich alteration products provides a geologically reasonable and consistent explanation for the global TES surface mineralogical results.     

Synthesis of a spinifex‐textured basalt as an analog to Gusev crater basalts,Mars

Abstract– Analyses by the Mars Exploration Rover (MER), Spirit, of Martian basalts from Gusev crater show that they are chemically very different from terrestrial basalts, being characterized in particular by high Mg‐ and Fe‐contents. To provide suitable analog basalts for the International Space Analogue Rockstore (ISAR), a collection of analog rocks and minerals for preparing in situ space missions, especially, the upcoming Mars mission MSL‐2011 and the future international Mars‐2018 mission, it is necessary to synthesize Martian basalts. The aim of this study was therefore to synthesize Martian basalt analogs to the Gusev crater basalts, based on the geochemical data from the MER rover Spirit. We present the results of two experiments, one producing a quench‐cooled basalt (<1 h) and one producing a more slowly cooled basalt (1 day). Pyroxene and olivine textures produced in the more slowly cooled basalt were surprisingly similar to spinifex textures in komatiites, a volcanic rock type very common on the early Earth. These kinds of ultramafic rocks and their associated alteration products may have important astrobiological implications when associated with aqueous environments. Such rocks could provide habitats for chemolithotrophic microorganisms, while the glass and phyllosilicate derivatives can fix organic compounds.     

Orbital identification of clays and carbonates in Gusev crater

Gusev crater was selected as the landing site of one of the two NASA Mars Exploration Rovers because water once could have ponded within the crater and partly filled it with sediments as suggested by the presence of a feeder channel and the fluvial-lacustrine morphology of the in-filling. However, the paucity of mineralogical evidence for fluvial-lacustrine activity revealed by the Spirit rover has remained a puzzle for years. Using orbital, near-infrared imaging spectroscopy, we report the detection of phyllosilicates and carbonates within and around the landing site of Spirit on the floor of Gusev crater. Placed in their geomorphological context, these minerals shed new light on the aqueous history of this crater, and offer a framework for the Spirit in situ measurements.     

Attitude and angular rates of planetary probes during atmospheric descent: Implications for imaging

Attitude dynamics data from planetary missions are reviewed to obtain a zeroth-order expectation on the tilts and angular rates to be expected on atmospheric probes during descent: these rates are a strong driver on descent imager design. While recent Mars missions have been equipped with capable inertial measurements, attitude measurements for missions to other planetary bodies are rather limited but some angular motion estimates can be derived from accelerometer, Doppler or other data. It is found that robust camera designs should tolerate motions of the order of 20-40°/s, encountered by Mars Pathfinder, Pioneer Venus, Venera and the high speed part of the Huygens descent on Titan. Under good conditions, parachute-stabilized probes can experience rates of 1-5°/s, seen by the Mars Exploration Rovers and Viking, Galileo at Jupiter, and the slow speed parts of the Huygens descent. In the lowest 20 km of the descent on Titan, the Huygens probe was within 2° of vertical over 95% of the time. Some factors influencing these motions are discussed.     

New insights into the mineralogy and weathering of the Meridiani Planum meteorite,Mars

Meridiani Planum is the first officially recognized meteorite find on the surface of Mars. It was discovered at and named after the landing site of the Mars Exploration Rover Opportunity. Based on its composition, it was classified as a IAB complex iron meteorite. Mössbauer spectra obtained by Opportunity are dominated by kamacite (α‐Fe‐Ni) and exhibit a small contribution of ferric oxide. Several small features in the spectra have been neglected to date. To shed more light on these features, five iron meteorite specimens were investigated as analogs to Meridiani Planum with a laboratory Mössbauer setup. Measurements were performed on (1) their metallic bulk, (2) troilite (FeS) inclusions, (3) cohenite ((Fe,Ni,Co)₃C) and schreibersite ((Fe,Ni)₃P), and (4) corroded rims. In addition to these room‐temperature measurements, a specimen from the Mundrabilla IAB‐ungrouped meteorite was measured at Mars‐equivalent temperatures. Based on these measurements, the features in Meridiani Planum spectra can be explained with the presence of small amounts of schreibersite and/or cohenite and iron oxides. The iron oxides can be attributed to a previously reported coating on Meridiani Planum. Their presence indicates weathering through the interaction of the meteorite with small amounts of water.     

New analysis of the Mössbauer spectra of olivine basalt rocks from Gusev crater on Mars

The Mars Exploration Rover, Spirit, landed on 4 January 2004, in a lava field in Gusev crater on Mars. Samples interpreted as olivine basalt have been investigated with Mössbauer spectroscopy and chemically with Alpha-particle-X-ray spectrometry (APXS).In this contribution we present the results of a new analysis of the Mössbauer spectra of selected rock targets in Gusev crater. The results show that the rock surfaces investigated are inhomogeneous, and show strong enhancement of olivine in the surface layer. By subtraction of the surface signal to obtain the spectrum of the true interior of the rock samples, the measurements show the usual correlation between olivine and iron oxides of olivine basalt.It is argued that the compositional changes observed are related to high temperature oxidation of the rocks, probably during solidification, a process known to lead to anomalously magnetic rocks. The rock Mazatzal is discussed in some detail, and it is suggested that the surface is covered with deposits rich in ferric iron rather than these ferric phases being due to oxidation of the rock. The fact that all the surfaces in this investigation show this same pattern, suggests that the dominating erosion of the surface layer of basaltic rocks at Gusev crater has been mechanical rather than chemical.     

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

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