Sustained wet-dry cycling on early Mars.

The presence of perennially wet surface environments on early Mars is well documented1,2, but little is known about short-term episodicity in the early hydroclimate3. Post-depositional processes driven by such short-term fluctuations may produce distinct structures, yet these are rarely preserved in the sedimentary record4. Incomplete geological constraints have led global models of the early Mars water cycle and climate to produce diverging results5,6. Here we report observations by the Curiosity rover at Gale Crater indicating that high-frequency wet-dry cycling occurred in early Martian surface environments. We observe exhumed centimetric polygonal ridges with sulfate enrichments, joined at Y-junctions, that record cracks formed in fresh mud owing to repeated wet-dry cycles of regular intensity. Instead of sporadic hydrological activity induced by impacts or volcanoes5, our findings point to a sustained, cyclic, possibly seasonal, climate on early Mars. Furthermore, as wet-dry cycling can promote prebiotic polymerization7,8, the Gale evaporitic basin may have been particularly conducive to these processes. The observed polygonal patterns are physically and temporally associated with the transition from smectite clays to sulfate-bearing strata, a globally distributed mineral transition1. This indicates that the Noachian-Hesperian transition (3.8-3.6 billion years ago) may have sustained an Earth-like climate regime and surface environments favourable to prebiotic evolution.

Behind the movement.

This year, the Albert Lasker Basic Medical Research Award will be shared by Michael Sheetz, James Spudich, and Ronald Vale for discoveries concerning the biophysical actions of cytoskeletal motor-protein machines that move cargo within cells, contract muscles, and enable cell motility.

Seismic detection of a deep mantle discontinuity within Mars by InSight.

Constraining the thermal and compositional state of the mantle is crucial for deciphering the formation and evolution of Mars. Mineral physics predicts that Mars' deep mantle is demarcated by a seismic discontinuity arising from the pressure-induced phase transformation of the mineral olivine to its higher-pressure polymorphs, making the depth of this boundary sensitive to both mantle temperature and composition. Here, we report on the seismic detection of a midmantle discontinuity using the data collected by NASA's InSight Mission to Mars that matches the expected depth and sharpness of the postolivine transition. In five teleseismic events, we observed triplicated P and S waves and constrained the depth of this discontinuity to be 1,006 [Formula: see text] 40 km by modeling the triplicated waveforms. From this depth range, we infer a mantle potential temperature of 1,605 [Formula: see text] 100 K, a result consistent with a crust that is 10 to 15 times more enriched in heat-producing elements than the underlying mantle. Our waveform fits to the data indicate a broad gradient across the boundary, implying that the Martian mantle is more enriched in iron compared to Earth. Through modeling of thermochemical evolution of Mars, we observe that only two out of the five proposed composition models are compatible with the observed boundary depth. Our geodynamic simulations suggest that the Martian mantle was relatively cold 4.5 Gyr ago (1,720 to 1,860 K) and are consistent with a present-day surface heat flow of 21 to 24 mW/m2.

Immunoanalytical Detection of Conserved Peptides: Refining the Universe of Biomarker Targets in Planetary Exploration.

Ancient peptides are remnants of early biochemistry that continue to play pivotal roles in current proteins. They are simple molecules yet complex enough to exhibit independent functions, being products of an evolved biochemistry at the interface of life and nonlife. Their adsorption to minerals may contribute to their stabilization and preservation over time. To investigate the feasibility of conserved peptide sequences and structures as target biomarkers for the search for life on Mars or other planetary bodies, we conducted a bioinformatics selection of well-conserved ancient peptides and produced polyclonal antibodies for their detection using fluorescence microarray immunoassays. Additionally, we explored how adsorbing peptides to Mars-representative minerals to form organomineral complexes could affect their immunological detection. The results demonstrated that the selected peptides exhibited autonomous folding, with some of them regaining their structure, even after denaturation. Furthermore, their cognate antibodies detected their conformational features regardless of amino acid sequences, thereby broadening the spectrum of target peptide sequences. While certain antibodies displayed unspecific binding to bare minerals, we validated that peptide-mineral complexes can be detected using sandwich immunoassays, as confirmed through desorption and competitive assays. Consequently, we conclude that the diversity of peptide sequences and structures suitable for use as target biomarkers in astrobiology can be constrained to a few well conserved sets, and they can be detected even if they are adsorbed in organomineral complexes.

Bacterial model membranes under the harsh subsurface conditions of Mars.

Biomembranes are a key component of all living systems. Most research on membranes is restricted to ambient physiological conditions. However, the influence of extreme conditions, such as the deep subsurface on Earth or extraterrestrial environments, is less well understood. The deep subsurface of Mars is thought to harbour high concentrations of chaotropic salts in brines, yet we know little about how these conditions would influence the habitability of such environments. Here, we investigated the combined effects of high concentrations of Mars-relevant salts, including sodium and magnesium perchlorate and sulphate, and high hydrostatic pressure on the stability, structure, and function of a bacterial model membrane. To this end, several biophysical techniques have been employed, including calorimetry, fluorescence and CD spectroscopy, confocal microscopy, and small-angle X-ray scattering. We demonstrate that sulphate and perchlorate salts affect the properties of the membrane differently, depending on the counterion present (Na+vs. Mg2+). We found that the perchlorates, which are believed to be abundant salts in the Martian environment, induce a more hydrated and less ordered membrane, strongly favouring the physiologically relevant fluid-like phase of the membrane even under high-pressure stress. Moreover, we show that the activity of the phospholipase A2 is strongly modulated by both high pressure and salt. Compellingly, in the presence of the chaotropic perchlorate, the enzymatic reaction proceeded at a reasonable rate even in the presence of condensing Mg2+ and at high pressure, suggesting that bacterial membranes could still persist when challenged to function in such a highly stressed Martian environment.

Organophosphorus Compound Formation Through the Oxidation of Reduced Oxidation State Phosphorus Compounds on the Hadean Earth.

Reduced oxidation state phosphorus compounds may have been brought to the early Earth via meteorites or could have formed through geologic processes. These compounds could have played a role in the origin of biological phosphorus (P, hereafter) compounds. Reduced oxidation state P compounds are generally more soluble in water and are more reactive than orthophosphate and its associated minerals. However, to date no facile routes to generate C-O-P type compounds using reduced oxidation state P compounds have been reported under prebiotic conditions. In this study, we investigate the reactions between reduced oxidation state P compounds-and their oxidized products generated via Fenton reactions-with the nucleosides uridine and adenosine. The inorganic P compounds generated via Fenton chemistry readily react with nucleosides to produce organophosphites and organophosphates, including phosphate diesters via one-pot syntheses. The reactions were facilitated by NH4+ ions and urea as a condensation agent. We also present the results of the plausible stability of the organic compounds such as adenosine in an environment containing an abundance of H2O2. Such results have direct implications on finding organic compounds in Martian environments and other rocky planets (including early Earth) that were richer in H2O2 than O2. Finally, we also suggest a route for the sink of these inorganic P compounds, as a part of a plausible natural P cycle and show the possible formation of secondary phosphate minerals such as struvite and brushite on the early Earth.

Effects of chaotropic salts on global proteome stability in halophilic archaea: Implications for life signatures on Mars.

Halophilic archaea thriving in hypersaline environments, such as salt lakes, offer models for putative life in extraterrestrial brines such as those found on Mars. However, little is known about the effect of the chaotropic salts that could be found in such brines, such as MgCl2 , CaCl2 and (per)chlorate salts, on complex biological samples like cell lysates which could be expected to be more representative of biomarkers left behind putative extraterrestrial life forms. We used intrinsic fluorescence to study the salt dependence of proteomes extracted from five halophilic strains: Haloarcula marismortui, Halobacterium salinarum, Haloferax mediterranei, Halorubrum sodomense and Haloferax volcanii. These strains were isolated from Earth environments with different salt compositions. Among the five strains that were analysed, H. mediterranei stood out as a results of its high dependency on NaCl for its proteome stabilization. Interestingly, the results showed contrasting denaturation responses of the proteomes to chaotropic salts. In particular, the proteomes of strains that are most dependent or tolerant on MgCl2 for growth exhibited higher tolerance towards chaotropic salts that are abundant in terrestrial and Martian brines. These experiments bridge together global protein properties and environmental adaptation and help guide the search for protein-like biomarkers in extraterrestrial briny environments.

Resilience of Xanthoria parietina under Mars-like conditions: photosynthesis and oxidative stress response.

MAIN CONCLUSION: Xanthoria parietina survivability in Mars-like conditions was supported by water-lysis efficiency recovery and antioxidant content balancing with ROS production after 30 days of exposure. Xanthoria parietina (L.) Th. Fr. is a widespread lichen showing tolerance against air pollutants and UV-radiation. It has been tested under space-like and Mars-like conditions resulting in high recovery performances. Hereby, we aim to assess the mechanisms at the basis of the thalli resilience against multiple space stress factors. Living thalli of X. parietina were exposed to simulated Martian atmospheric conditions (Dark Mars) and UV radiation (Full Mars). Then, we monitored as vitality indicator the photosynthetic efficiency, assessed by in vivo chlorophyll emission fluorescence measurements (FM; FV/F0). The physiological defense was evaluated by analyzing the thalli antioxidant capacity. The drop of FM and FV/F0 immediately after the exposure indicated a reduction of photosynthesis. After 24 h from exposure, photosynthetic efficiency began to recover suggesting the occurrence of protective mechanisms. Antioxidant concentrations were higher during the exposure, only decreasing after 30 days. The recovery of photosynthetic efficiency in both treatments suggested a strong resilience by the photosynthetic apparatus against combined space stress factors, likely due to the boosted antioxidants at the beginning and their depletion at the end of the exposure. The overall results indicated that the production of antioxidants, along with the occurrence of photoprotection mechanisms, guarantee X. parietina survivability in Mars-like environment.

Pyrochlores for Advanced Oxygen Electrocatalysis.

Fuel cells (FCs), water electrolyzers (WEs), unitized regenerative fuel cells (URFCs), and metal-air batteries (MABs) are among the emerging electrochemical technologies for energy storage, fuel (H2), oxidant (O2), and clean energy production. Their commercial applications are hindered by the low oxygen reduction reaction/oxygen evolution reaction (ORR/OER) bifunctional activity (for URFCs and MABs), OER selectivity (brine electrolysis in seawater and Martian environments), and high cost of the benchmark electrocatalysts (OER: RuO2, IrO2 and ORR: Pt/C) which affects the performance and affordability of the devices. Low-cost electrocatalysts with highly symmetric ORR/OER bifunctional activity and high OER selectivity are crucial for large-scale FC, WE, URFC, and MAB application. Recent studies have revealed that tuning the structure of pyrochlore oxides provides a pathway to enhancing OER and ORR activity over a wide range of pH. Pyrochlore oxides commonly contain a cubic A2B2O7-x structure with two types of tetrahedrally coordinated O atoms containing (1) A-O-A and (2) A-O-B types with a cationic radii mismatch of rA/rB > 1.5 and propensity toward oxygen vacancy formation. The variety of pyrochlore oxides and their tunable properties make them attractive for a wide spectrum of applications. Among all the metal oxides, Ru-based pyrochlores (e.g., Pb2Ru2O7-x) exhibit the best bifunctional oxygen electrocatalytic activity, i.e., low bifunctionality index (BI), in alkaline medium. Furthermore, pyrochlores exhibit high OER selectivity in brine electrolytes due to the presence of surface oxygen vacancies, making them suitable for space applications (brine electrolysis on Mars) and coastal hydrogen generation. Their bifunctional activity and selectivity can be further amplified by (1) substituting "A" and "B" sites of pyrochlores (AA'BB'O7-x), (2) tuning metal oxidation states of A and B by varying synthesis conditions, and (3) modulating oxygen vacancy concentration, each of which yield favorable structural and electronic variations. In recent years, research on the synthesis and understanding of pyrochlores has significantly enhanced their viability, offering a new horizon in the quest for economical and active electrocatalysts. However, an account that focuses on critical developments in this field is still lacking.In this Account, we focus on the recent development of a variety of pyrochlore electrocatalysts to understand intrinsic structure-activity-selectivity-stability relationships in these materials. Recent developments and applications of pyrochlore-based electrocatalysts are discussed under the following headings: (1) modulation of crystal and electronic structure of pyrochlores, (2) structure-activity-stability relationships of different pyrochlores for OER and ORR, (3) development of OER-selective pyrochlores for brine electrolysis, and (4) the application of pyrochlores in electrochemical devices. Finally, we highlight some unaddressed issues such as the precise identification of active sites, which can be addressed in the future through advanced in situ and ex situ characterization techniques coupled with the density functional theory-based analyses. This Account provides foundational understanding to guide the comprehensive development of highly active, selective, stable and low-cost structurally engineered pyrochlores for high performance electrochemical devices.

The divergent fates of primitive hydrospheric water on Earth and Mars.

Despite active transport into Earth's mantle, water has been present on our planet's surface for most of geological time. Yet water disappeared from the Martian surface soon after its formation. Although some of the water on Mars was lost to space via photolysis following the collapse of the planet's magnetic field, the widespread serpentinization of Martian crust suggests that metamorphic hydration reactions played a critical part in the sequestration of the crust. Here we quantify the relative volumes of water that could be removed from each planet's surface via the burial and metamorphism of hydrated mafic crusts, and calculate mineral transition-induced bulk-density changes at conditions of elevated pressure and temperature for each. The metamorphic mineral assemblages in relatively FeO-rich Martian lavas can hold about 25 per cent more structurally bound water than those in metamorphosed terrestrial basalts, and can retain it at greater depths within Mars. Our calculations suggest that in excess of 9 per cent by volume of the Martian mantle may contain hydrous mineral species as a consequence of surface reactions, compared to about 4 per cent by volume of Earth's mantle. Furthermore, neither primitive nor evolved hydrated Martian crust show noticeably different bulk densities compared to their anhydrous equivalents, in contrast to hydrous mafic terrestrial crust, which transforms to denser eclogite upon dehydration. This would have allowed efficient overplating and burial of early Martian crust in a stagnant-lid tectonic regime, in which the lithosphere comprised a single tectonic plate, with only the warmer, lower crust involved in mantle convection. This provided an important sink for hydrospheric water and a mechanism for oxidizing the Martian mantle. Conversely, relatively buoyant mafic crust and hotter geothermal gradients on Earth reduced the potential for upper-mantle hydration early in its geological history, leading to water being retained close to its surface, and thus creating conditions conducive for the evolution of complex multicellular life.

Calibration of a Dust Scattering Instrument Using Tomographic Techniques and Its Application to a Dust Sensor Instrument.

The characterization of suspended dust near the Martian surface is extremely relevant to understand the climate of Mars. In this frame, a Dust Sensor instrument, an infrared device designed to obtain the effective parameters of Martian dust using the scattering properties of the dust particles, was developed. The purpose of this article is to present a novel methodology to calculate, from experimental data, an instrumental function of the Dust Sensor that allows solving the direct problem and providing the signal that this instrument would provide given a distribution of particles. The experimental method is based on recording the signal measured when a Lambertian reflector is gradually introduced into the interaction volume at different distances from the detector and source and applying tomography techniques (inverse Radon transform) to obtain the image of a section of the interaction volume. This method provides a complete mapping of the interaction volume experimentally, which determines the Wf function. The method was applied to solve a specific case study. Among the advantages of this method, it should be noted that it avoids assumptions and idealizations of the dimensions of the volume of interaction and reduces the time required to carry out simulations.

How to make the Lunar and Martian soils suitable for food production - Assessing the changes after manure addition and implications for plant growth.

The in-situ resource utilisation (ISRU), in terms of native rocky materials and astronaut wastes, is crucial in contests of soil-based space-farming. Nevertheless, extra-terrestrial soils are very different from Earth soils, lacking any form of organic carbon and associated macro and micronutrients. In this research, we aimed to study and modify two commercially available Lunar and Martian regolith simulants (LHS-1 from Exolith Lab and MMS-1 from Martian Garden) to make them an adequate medium for plant growth. Lettuce was chosen as reference crop to guide the discussion on the results obtained. To reach this main objective, we added to simulants a commercially available monogastric-based organic manure chosen as a substitute of a possible organic amendment produced onboard. The simulant/manure mixture rates were 100:0, 90:10, 70:30, 50:50; w:w. As expected, an approximately linear increase of total and bioavailable contents of macro (N, S, P, Ca, K, Mg) and micro (Fe, Mn, Cu, Zn) nutrients with increasing manure addition to simulants was observed. On the other hand, the very high pH of manure (pH, 9.02) along with its salinity (EC, 6.7 dS m-1) and sodicity (Na, 5.3 g kg-1), did not correct the already high pH of simulants (very high for LHS-1), but rather raised their soluble salt content and sodium amount on the exchange complex. In addition, an increase of toxic soluble aluminium and heavy elements (Pb, Ni, Cr, V) was observed, mainly in the strongly alkaline lunar simulant/manure mixtures. The addition of an organic source also produced a generalised improvement of water retention and hydraulic conductivity of both regolith simulants, in proportion to the percentage of manure addiction. For both situations, the best mixture ratio was 70:30. In terms of water retained, the LHS-1 mixtures benefited more than the MMS-1 ones by manure addition since water was held more in the "dry" (between -100 and -600 cm of matric potential head) than in the "humid" (between -25 and -100 cm of matric potential head) region of water retention. This would make LHS-1 mixtures more useful for cultivation of lettuce, at least in terms of physico-hydraulic properties. Nevertheless, the overall characterisation of the mixtures unveiled that MMS-1-based substrates can ensure better agronomic performances than LHS-1 ones, mainly due to lower pHs and higher nutrient availability; this divergent fertility was particularly evident at 90:10 simulant/manure rate and tend to be mitigated by increasing the levels of manure.

Perchlorate-specific proteomic stress responses of Debaryomyces hansenii could enable microbial survival in Martian brines.

If life exists on Mars, it would face several challenges including the presence of perchlorates, which destabilize biomacromolecules by inducing chaotropic stress. However, little is known about perchlorate toxicity for microorganisms on the cellular level. Here, we present the first proteomic investigation on the perchlorate-specific stress responses of the halotolerant yeast Debaryomyces hansenii and compare these to generally known salt stress adaptations. We found that the responses to NaCl and NaClO4 -induced stresses share many common metabolic features, for example, signalling pathways, elevated energy metabolism, or osmolyte biosynthesis. Nevertheless, several new perchlorate-specific stress responses could be identified, such as protein glycosylation and cell wall remodulations, presumably in order to stabilize protein structures and the cell envelope. These stress responses would also be relevant for putative life on Mars, which-given the environmental conditions-likely developed chaotropic defence strategies such as stabilized confirmations of biomacromolecules or the formation of cell clusters.

Selection of Anabaena sp. PCC 7938 as a Cyanobacterium Model for Biological ISRU on Mars.

Crewed missions to Mars are expected to take place in the coming decades. After short-term stays, a permanent presence will be desirable to enable a wealth of scientific discoveries. This will require providing crews with life-support consumables in amounts that are too large to be imported from Earth. Part of these consumables could be produced on site with bioprocesses, but the feedstock should not have to be imported. A solution under consideration lies in using diazotrophic, rock-weathering cyanobacteria as primary producers: fed with materials naturally available on site, they would provide the nutrients required by other organisms. This concept has recently gained momentum but progress is slowed by a lack of consistency across contributing teams, and notably of a shared model organism. With the hope to address this issue, we present the work performed to select our current model. We started with preselected strains from the Nostocaceae family. After sequencing the genome of Anabaena sp. PCC 7938-the only one not yet available-we compared the strains' genomic data to determine their relatedness and provide insights into their physiology. We then assessed and compared relevant features: chiefly, their abilities to utilize nutrients from Martian regolith, their resistance to perchlorates (toxic compounds present in the regolith), and their suitability as feedstock for secondary producers (here a heterotrophic bacterium and a higher plant). This led to the selection of Anabaena sp. PCC 7938, which we propose as a model cyanobacterium for the development of bioprocesses based on Mars's natural resources. IMPORTANCE The sustainability of crewed missions to Mars could be increased by biotechnologies which are connected to resources available on site via primary producers: diazotrophic, rock-leaching cyanobacteria. Indeed, this could greatly reduce the mass of payloads to be imported from Earth. The concept is gaining momentum but progress is hindered by a lack of consistency across research teams. We consequently describe the selection process that led to the choice of our model strain, demonstrate its relevance to the field, and propose it as a shared model organism. We expect this contribution to support the development of cyanobacterium-based biotechnologies on Mars.

Focused ultrasound extraction versus microwave-assisted extraction for extraterrestrial objects analysis.

Search for organic bioindicators in the solar system is a fundamental challenge for the space research community. If tremendous improvements have been achieved in detection, little or no research has been dedicated to extraction of the targets from the studied mineral matrices. Apart from thermodesorption, no extraction step was ever performed in situ within the context of biomarker detection experiments. This work presents an extraction protocol compatible with in situ space constraints. Two extraction methods, i.e., microwave-assisted extraction (MAE) and focused ultrasonic extraction (FUSE), were optimized with the aim of extracting molecules having an astrobiological interest (amino acids, nucleobases, polyaromatic carboxylic acids) and that are included in mineral matrices representative of the Martian soil. Higher efficiency was obtained with the FUSE method (20 kHz, amplitude 80%, pulse and relaxation 1 s each, for 10 min) with yields ranging from 30 to 95%. It was then applied on an Atacama Desert soil sample and Aguas Zarcas meteorite fragment. Both water-soluble and organic-soluble compounds present at trace levels were extracted using this short extraction time, and small amounts of sample and solvent compliant with in situ requirements (50 mg, 500 µL). This unique FUSE/derivatization-GC-MS approach gave similar yields to usual 24 h hot water extraction and increased the recovery of the target molecules compared to the derivatization-GC-MS method already used for in situ space experiments by a factor from 2 to 8. The data highlighted the suitability of a focused ultrasonic method for the extraction of trace organic compounds from extraterrestrial samples.