Models of cation exchange mechanisms and driving forces have proven effective predictors of clay behavior and chemistry, but are largely theoretical, particularly in complex systems involving high ionic strength brines or systems where hydration is controlled by relative humidity. In arid and cold environments, such as Mars, cyclical relative humidity variations may play a role in chemical alteration, particularly if clay minerals such as smectite are in the presence of salts. This study examines the effects of relative humidity on smectite-salt mixtures using environmental scanning electron microscopy (ESEM) to observe the physiochemical effects of salt deliquescence and desiccation on smectite textures and elemental distributions. Results demonstrate that even reaction periods as short as a few minutes allow ample time for relative humidity to affect the smectite-salt mixtures. In addition to smectite swelling and salt deliquescence, we also observed rapid changes in element distributions within the smectite and new crystal growth in the presence of high relative humidity. Even in the absence of bulk liquid water, exchangeable cations migrated out of the smectite and formed new crystals at the smectite-salt interface. The observed microscopic changes in elemental distributions indicate that the migration of cations driven by cation exchange led to secondary mineral precipitation, likely a CaSO4 mineral, within a sub-micrometer-thick layer of water on the smectite grains. The results of this study demonstrate that during periods of elevated relative humidity, active smectite mineral alteration and secondary mineral precipitation may be possible on present-day Mars where salts and smectites are in direct physical contact.

An altar to Mars dedicated by a soldier of legio XI Claudia is shown to have been removed from the fabric of Marton church during restoration work and, along with much of the other stone for the Romanesque tower, nave and chancel probably derived from the Roman small town of Segelocum, Littleborough on Trent. The name of the dedicator, G. IVLIVS ANTONINUS, is discussed in the context of legio XI Claudia deployment on the Lower Danube.

In situ elemental imaging of planetary surface regolith at a spatial resolution of 100s to 1000s of microns can provide evidence of the provenance of rocks or sediments and their habitability, and can identify post-depositional diagenetic alteration affecting preservation. We use high-resolution elemental maps and XRF spectra from MapX, a flight prototype in situ X-ray imaging instrument, to demonstrate this technology in rock types relevant to astrobiology. Examples are given for various petrologies and depositional/diagenetic environments, including ultramafic/mafic rocks, serpentinites, hydrothermal carbonates, evaporites, stromatolitic cherts and diagenetic concretions.

Recent measurements from Mars document X-ray amorphous/nano-crystalline materials in multiple locations across the planet. Despite their prevalence, however, little is known about these materials or what their presence implies for the history of Mars. The X-ray amorphous component of the martian soil in Gale crater has an X-ray diffraction pattern that can be fit partially with allophane (approximately Al2O3⋅(SiO2)1.3–2⋅(H2O)2.5–3), and the low-temperature water-release data are consistent with allophane. The chemical data from Gale crater suggest that other silicate materials similar to allophane, such as Fe-substituted allophane (approximately (Fe2O3)0.01–0.5(Al2O3)0.5–0.99⋅(SiO2)2⋅3H2O), may also be present. In order to investigate the properties of these potential poorly crystalline components of the martian soil, Fe-free allophane (Fe:Al = 0), Fe-poor allophane (Fe:Al = 1:99), and Fe-rich allophane (Fe:Al = 1:1) were synthesized and then characterized using electron microscopy and Mars-relevant techniques, including infrared spectroscopy, X-ray diffraction, and evolved gas analysis. Dissolution experiments were performed under acidic (initial pH values pH0 = 3.01, pH0 = 5.04), near-neutral (pH0 = 6.99), and alkaline (pH0 = 10.4) conditions in order to determine dissolution kinetics and alteration phases for these poorly crystalline materials. Dissolution rates (rdiss), based on the rate of Si release into solution, show that these poorly crystalline materials dissolve approximately an order of magnitude faster than crystalline phases with similar compositions at all pH conditions. For Fe-free allophane, logrdiss = –10.65–0.15 × pH; for Fe-poor allophane, logrdiss = –10.35–0.22 × pH; and for Fe-rich allophane, logrdiss = –11.46–0.042 × pH at 25°C, where rdiss has the units of mol m–2 s–1. The formation of incipient phyllosilicate-like phases was detected in Fe-free and Fe-rich allophane reacted in aqueous solutions with pH0 = 10.4 (steady-state pH ≈ 8). Mars-analog instrument analyses demonstrate that Fe-free allophane, Fe-poor allophane, and Fe-rich allophane are appropriate analogs for silicate phases in the martian amorphous soil component. Therefore, similar materials on Mars must have had limited interaction with liquid water since their formation. Combined with chemical changes expected from weathering, such as phyllosilicate formation, the rapid alteration of these poorly crystalline materials may be a useful tool for evaluating the extent of aqueous alteration in returned samples of martian soils.

Beidellites may exist on Mars and represent intermediate alteration products; their presence would indicate different alteration environments than previously identified because montmorillonite is a low-grade alteration mineral whereas beidellite is a higher-temperature alteration mineral, and often represents a step toward illite formation. The reflectance spectra of beidellites are under study to support their orbital detection on Mars, where spectral signatures of other Al-rich phyllosilicates have been observed. Reflectance spectra of ten Al-rich smectites are presented here which include pure beidellites and Al smectites having compositions between those of beidellite and montmorillonite, and emphasis is placed here on the OH combination bands near 4545 cm−1 (2.2 μm) as these vibrational features are commonly used in the identification of phyllosilicates on Mars. Shifts were observed in the Al2OH band centers, which occur near 4590 cm−1 (2.18 μm) in reflectance spectra of beidellite and near 4525 cm−1 (2.21 μm) in reflectance spectra of montmorillonite. These are compared with the Al2OH bending vibrations observed near 941–948 cm−1 (10.5–10.6 μm) for beidellite and near 918–926 cm−1 (10.8–10.9 μm) for montmorillonite. Although the octahedral site cation composition provides the greatest influence on the vibrational energies of the M2OH groups, the tetrahedral site cation composition also influences these vibrations. Shifts were observed in the Si-O-Al bending vibrations from 552 and 480 cm−1 (18.1 and 20.8 μm) in beidellite spectra to 544 and 475 cm−1 (18.4 and 21.0 μm) in montmorillonite spectra. Gaussian modeling of the 4545 cm−1 (2.2 μm) bands led to the discrimination of four overlapping bands in each of the ten Al smectite spectra examined in this study. Shifts in the band center and area of the primary spectral band are coordinated with substitution of Al for Si in the tetrahedral sheet. This is consistent with beidellites having a greater tetrahedral layer charge than montmorillonites. The observed spectral differences were sufficiently large that these Al-rich smectites can be differentiated in orbital data of Mars. A pure beidellite-type spectrum is observed in an isolated Al phyllosilicate-bearing outcrop in Libya Montes, a region where Fe-rich smectite is common but Al-rich smectite is rare. Beidellite-type reflectance spectra were also observed in one area of the Nili Fossae region. In contrast, a variety of Al phyllosilicates were found in the ancient rocks at Mawrth Vallis, including some smaller clay-bearing regions exhibiting spectral signatures more consistent with beidellite-like than montmorillonite-like chemistry.

The enhanced spatial and spectral resolution provided by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on the Mars Reconnaissance Orbiter (MRO) has led to the discovery of numerous hydrated silicate minerals on Mars, particularly in the ancient, cratered crust comprising the southern highlands. Phases recently identified using visible/near-infrared spectra include: smectite, chlorite, prehnite, high-charge phyllosilicates (illite or muscovite), the zeolite analcime, opaline silica, and serpentine. Some mineral assemblages represent the products of aqueous alteration at elevated temperatures. Geologic occurrences of these mineral assemblages are described using examples from west of the Isidis basin near the Nili Fossae and with reference to differences in implied temperature, fluid composition, and starting materials during alteration. The alteration minerals are not distributed homogeneously. Rather, certain craters host distinctive alteration assemblages: (1) prehnite-chloritesilica, (2) analcime-silica-Fe,Mg-smectite-chlorite, (3) chlorite-illite (muscovite), and (4) serpentine, which furthermore has been found in bedrock units. These assemblages contrast with the prevalence of solely Fe,Mg-smectites in most phyllosilicate-bearing terrains on Mars, and they represent materials altered at depth then exposed by cratering. Of the minerals found to date, prehnite provides the clearest evidence for subsurface, hydrothermal/metamorphic alteration, as it forms only under highly restricted conditions (T = 200–400°C). Multiple mechanisms exist for forming the other individual minerals; however, the most likely formation mechanisms for the characteristic mineralogic assemblages observed are, for (1) and (2), low-grade metamorphism or hydrothermal (<400°C) circulation of fluids in basalt; for (3), transformation of trioctahedral smectites to chlorite and dioctahedral smectites to illite during diagenesis; and for (4), low-grade metamorphism or hydrothermal (<400°C) circulation of fluids in ultramafic rocks. Evidence for high-grade metamorphism at elevated pressures or temperatures >400°C has not been found.

Altered basaltic tephra from Haleakala, Maui, are characterized using multiple techniques in order to identify the minerals formed under a variety of conditions and to understand the soil formation processes here. We collected samples that are representative of typical bulk weathered material in the crater, as well as solfataric alteration in a hydrothermal environment. For this study X-ray diffraction, electron probe microanalysis, scanning electron microscopy and transmission electron microscopy are coupled with spectroscopic techniques including Mössbauer, visible-infrared reflectance, transmission infrared, and thermal infrared emission spectroscopies to analyze these samples. The unaltered tephra are composed of feldspar, glass, pyroxene and olivine. Observed alteration products include Fe oxides, phyllosilicates and sulfates, as well as SAED amorphous Al-Si-bearing material. These samples are potential analogs for altered volcanic material on Mars as the pedogenic influences and contact with plants and animals are minimal. Results from this study may help to determine spectral signatures of these samples that could be used for identification on Mars of the minerals observed here.

The Al-clay-rich rock units at Mawrth Vallis, Mars, have been identified as mixtures of multiple components based on their spectral reflectance properties and the known spectral character of pure clay minerals. In particular, the spectral characteristics associated with the ~2.2 μm feature in Martian reflectance spectra indicate that mixtures of AlOH- and SiOH-bearing minerals are present. The present study investigated the spectral reflectance properties of the following binary mixtures to aid in the interpretation of remotely acquired reflectance spectra of rocks at Mawrth Vallis: kaolinite-opal-A, kaolinite-montmorillonite, montmorillonite-obsidian, montmorillonite-hydrated silica (opal), and glass-illite-smectite (where glass was hydrothermally altered to mixed-layer illite-smectite). The best spectral matches with Martian data from the present study’s laboratory experiments are mixtures of montmorillonite and obsidian having ~50% montmorillonite or mixtures of kaolinite and montmorillonite with ~30% kaolinite. For both of these mixtures the maximum inflection point on the long wavelength side of the 2.21 μm absorption feature is shifted to longer wavelengths, and in the case of the kaolinite-montmorillonite mixtures the 2.17 μm absorption found in kaolinite is of similar relative magnitude to that feature as observed in CRISM (Compact Reconnaissance Imaging Spectrometer for Mars) data. The reflectance spectra of clay mixed with opal and of hydrothermally altered glass-illite-smectite did not represent the Martian spectra observed in this region as well. A spectral comparison of linear vs. intimate mixtures of kaolinite and montmorillonite indicated that for these sieved samples, the intimate mixtures are very similar to the linear mixtures with the exception of the altered glass-illite-smectite samples. However, the 2.17 μm kaolinite absorption is stronger in the intimate mixtures than in the equivalent linear mixture. Modified Gaussian Modeling of absorption features observed in reflectance spectra of the kaolinite-montmorillonite mixtures indicated a strong correlation between percent kaolinite in the mixture and the ratio of the area of the 2.16 μm band found in kaolinite to the area of the 2.20 μm band found in montmorillonite.

Providing evidence for possible oil-type occurrences on Mars means providing an indication for the past life on Mars. We do this via analysis of the combed (aligned) gravity strike angles, one of the gravity (gravitational) aspects (descriptors) derived from one of the recent gravitational field models of Mars, currently having the highest accessible precision and resolution. After intensive testing for features on the Earth and the Moon, the gravity aspects are applied for Mars. We detect candidates for the groundwater/hydrocarbon/mud/petroleum-bearing sites in the largest areas with as many as possible combed gravity strike angles, uniformly ordered into ‘plates’. They appear mainly but not only in the hypothetical northern Martian palaeo-ocean (the northern lowlands). It turns out that the combed strike angles are sensitive not only to uniformly ordered sediments of the basins, but also to supposed lahars.

Discoveries of transient liquid water in the Martian polar caps and the presence of liquid lakes and subsurface oceans in icy satellites have increased the interest of scientists in the capabilities of terrestrial extremophiles to grow and remain metabolically active in these extreme environments. The principal goal of this research is to understand the metabolic capacity of the anaerobic psychrophile, Desulfotalea psychrophila, cultured at subfreezing temperatures in media containing various concentrations of sulphate minerals. In this regard, our experiments focused on the detection of D. psychrophila survival and active metabolism, employing a biochamber that can recreate Martian temperatures. Using standard bacteriological methods for determining growth, combined with molecular and enzymatic determination of sulphate reduction, we have found that D. psychrophila is capable to carry out biological processes at temperatures down to −5°C, at concentrations that range from 0.35 to 18 wt% of MgSO4, 0.1 wt% of CaSO4 and 10 to 14 wt% of FeSO4 in which the highest sulphate concentration gradually returned the biosynthetic rate to basal limits, and the lowest temperature decreased bacterial cell division. These chemical salts, whose ions are classified as chaotropes, are known to act by maintaining water molecules in liquid state at subfreezing temperatures and by altering the stability of cellular components. This ‘chaotropic effect’ could potentially benefit the microbial metabolic activity up to a concentration in which cellular viability is jeopardized. Consequently, our hypothesis is directed towards the detection of metabolic activity as an indirect measurement of the potential influence of these ions in the flexibility/functionality of biological structures that at cold temperatures are highly rigid, compact and partially/non-functional due to water freezing. Studies of this type of microorganism are critical considering the possibility of survival and colonization of psychrophilic sulphate reducers in other planets and icy satellites.

The search for signs of life is a major objective in the exploration of Mars. Of particular interest are chemical biosignatures such as biomolecules. However, molecular biosignatures are susceptible to extreme environmental conditions such as heat, ionising radiation and strong oxidants. Therefore, a knowledge of the stability of possible biosignature molecules under present and past conditions on Mars is important, as well as the nature of possible alteration products. In the light of the long volcanically active history of Mars, we have studied the thermal behaviour of selected biological compounds, namely, haemin (an iron porphyrin closely related to the haem prosthetic group), cytochrome c (a small protein) and lecithin (a mixture of phospholipids). Samples were exposed to temperatures up to 900°C under an inert atmosphere of nitrogen, either in neat form or in mineral matrices. The matrix materials used were sodium chloride, gypsum (CaSO4 ⋅ 2H2O), Ca-montmorillonite (STx-1b), the Martian regolith simulant JSC Mars-1A and some mixtures thereof. Key results are: (1) The onset of significant decomposition for haemin, cytochrome c and lecithin occurs around 240°C. At slightly higher temperatures the disappearance of all characteristic infrared spectral bands indicates complete decomposition and loss of the primary biosignatures. (2) Haemin stoichiometrically releases CO2 and HCl during the initial thermal decomposition phase, at the end of which the iron porphyrin core is still intact. High-temperature products of haemin include graphite, α-iron and cementite (Fe3C). (3) Neat lecithin forms long-chain polyphosphates at 500°C, whereas lecithin‒NaCl mixtures form diphosphate (pyrophosphate). As these anions are absent and rare, respectively, in minerals, they may potentially serve as secondary biosignatures. (4) Heating a mixture of NaCl and JSC Mars-1A at 800°C in the presence of lecithin produces the aluminosilicate mineral sodalite (Na8[AlSiO4]6Cl2), which however appears to be of limited use as a secondary biosignature.

Microbiological activities can be detected in various extreme environments on Earth, which suggest that extraterrestrial environments, such as on Mars, could host life. There have been proposed a number of biomarkers to detect extant life mostly based on specific molecules. Because terrestrial organisms have catalytic proteins (enzymes), enzymatic activity may also be a good indicator to evaluate biological activities in extreme environments. Phosphatases are essential for all terrestrial organisms because phosphate esters are ubiquitously used in genetic molecules (DNA/RNA) and membranes. In this study, we evaluated microbial activity in soils of the Atacama Desert, Chile, by analysing several biomarkers, including phosphatase activity. Phosphatases extracted with Tris buffer were assayed fluorometrically using 4-methylumbelliferyl phosphate as a substrate. The horizontal distribution of phosphatase activity and other parameters in soils from the Atacama Desert showed that phosphatase activity was positively correlated with amino acid concentration and colony-forming units and negatively correlated with precipitation amount. We found consistent that biochemical indicators including phosphatase significantly decreased in the extreme hyper-arid zone where rainfall of <25 mm year−1. The results were compared with phosphatase activities detected in extreme environments, such as submarine hydrothermal systems and Antarctic soils, as well as soils from ordinary environments. Overall, our results suggested that phosphatase activity could be a good indicator for evaluating biological activities in extreme environments.

The question about the stability of certain biomolecules is directly connected to the life-detection missions aiming to search for past or present life beyond Earth. The extreme conditions experienced on extraterrestrial planet surface (e.g. Mars), characterized by ionizing and non-ionizing radiation, CO2-atmosphere and reactive species, may destroy the hypothetical traces of life. In this context, the study of the biomolecules behaviour after ionizing radiation exposure could provide support for the onboard instrumentation and data interpretation of the life exploration missions on other planets. Here, as a part of STARLIFE campaign, we investigated the effects of gamma rays on two classes of fungal biomolecules–nucleic acids and melanin pigments – considered as promising biosignatures to search for during the ‘in situ life-detection’ missions beyond Earth.

Carbon reduction is an important process for Earth-like origins of life events and of great interest to the astrobiology community. In this paper, we have collected experimental results, field work and modelling data on CO and CO2 reduction in order to summarize the research that has been carried out particularly in relation to the early Earth and Mars. By having a database of this work, researchers will be able to clearly survey the parameters tested and find knowledge gaps wherein more experimentation would be most beneficial. We focused on reviewing the modelling parameters, field work and laboratory conditions relevant to Mars and the early Earth. We highlight important areas addressed as well as suggest future work needed, including identifying relevant parameters to test in both laboratory and modelling work. We also discuss the utility of organizing research results in such a database in astrobiology.

In this work, we study the passage through the Martian atmosphere of micrometeorites with a white soft mineral (WSM) composition, which have been proposed as transporters of organic molecules in the solar system. The atmospheric entry model includes the dynamics of the atmospheric entry and the physico-chemical aspects of the thermal decomposition process. The results show that, due to the reduced entry speed, Mars may have been a promising collector of matter in this form. In particular, the chemical decomposition process is much more effective than in the case of the Earth's atmosphere in maintaining a moderate temperature of the micrometeorite during most of the entry process.