Volcanic controls on the microbial habitability of Mars-analogue hydrothermal environments.

Due to their potential to support chemolithotrophic life, relic hydrothermal systems on Mars are a key target for astrobiological exploration. We analysed water and sediments at six geothermal pools from the rhyolitic Kerlingarfjöll and basaltic Kverkfjöll volcanoes in Iceland, to investigate the localised controls on the habitability of these systems in terms of microbial community function. Our results show that host lithology plays a minor role in pool geochemistry and authigenic mineralogy, with the system geochemistry primarily controlled by deep volcanic processes. We find that by dictating pool water pH and redox conditions, deep volcanic processes are the primary control on microbial community structure and function, with water input from the proximal glacier acting as a secondary control by regulating pool temperatures. Kerlingarfjöll pools have reduced, circum-neutral CO2 -rich waters with authigenic calcite-, pyrite- and kaolinite-bearing sediments. The dominant metabolisms inferred from community profiles obtained by 16S rRNA gene sequencing are methanogenesis, respiration of sulphate and sulphur (S0 ) oxidation. In contrast, Kverkfjöll pools have oxidised, acidic (pH < 3) waters with high concentrations of SO42- and high argillic alteration, resulting in Al-phyllosilicate-rich sediments. The prevailing metabolisms here are iron oxidation, sulphur oxidation and nitrification. Where analogous ice-fed hydrothermal systems existed on early Mars, similar volcanic processes would likely have controlled localised metabolic potential and thus habitability. Moreover, such systems offer several habitability advantages, including a localised source of metabolic redox pairs for chemolithotrophic microorganisms and accessible trace metals. Similar pools could have provided transient environments for life on Mars; when paired with surface or near-surface ice, these habitability niches could have persisted into the Amazonian. Additionally, they offer a confined site for biosignature formation and deposition that lends itself well to in situ robotic exploration.

Biogeochemical probing of microbial communities in a basalt-hosted hot spring at Kverkfjöll volcano, Iceland.

We investigated bacterial and archaeal communities along an ice-fed surficial hot spring at Kverkfjöll volcano-a partially ice-covered basaltic volcano at Vatnajökull glacier, Iceland, using biomolecular (16S rRNA, apsA, mcrA, amoA, nifH genes) and stable isotope techniques. The hot spring environment is characterized by high temperatures and low dissolved oxygen concentrations at the source (68°C and <1 mg/L (±0.1%)) changing to lower temperatures and higher dissolved oxygen downstream (34.7°C and 5.9 mg/L), with sulfate the dominant anion (225 mg/L at the source). Sediments are comprised of detrital basalt, low-temperature alteration phases and pyrite, with <0.4 wt. % total organic carbon (TOC). 16S rRNA gene profiles reveal that organisms affiliated with Hydrogenobaculum (54%-87% bacterial population) and Thermoproteales (35%-63% archaeal population) dominate the micro-oxic hot spring source, while sulfur-oxidizing archaea (Sulfolobales, 57%-82%), and putative sulfur-oxidizing and heterotrophic bacterial groups dominate oxic downstream environments. The δ13 Corg (‰ V-PDB) values for sediment TOC and microbial biomass range from -9.4‰ at the spring's source decreasing to -12.6‰ downstream. A reverse effect isotope fractionation of ~3‰ between sediment sulfide (δ34 S ~0‰) and dissolved water sulfate (δ34 S +3.2‰), and δ18 O values of ~ -5.3‰ suggest pyrite forms abiogenically from volcanic sulfide, followed by abiogenic and microbial oxidation. These environments represent an unexplored surficial geothermal environment analogous to transient volcanogenic habitats during putative "snowball Earth" scenarios and volcano-ice geothermal environments on Mars.

Ionic Strength Is a Barrier to the Habitability of Mars.

UNLABELLED: The thermodynamic availability of water (water activity) strictly limits microbial propagation on Earth, particularly in hypersaline environments. A considerable body of evidence indicates the existence of hypersaline surface waters throughout the history of Mars; therefore it is assumed that, as on Earth, water activity is a major limiting factor for martian habitability. However, the differing geological histories of Earth and Mars have driven variations in their respective aqueous geochemistry, with as-yet-unknown implications for habitability. Using a microbial community enrichment approach, we investigated microbial habitability for a suite of simulated martian brines. While the habitability of some martian brines was consistent with predictions made from water activity, others were uninhabitable even when the water activity was biologically permissive. We demonstrate experimentally that high ionic strength, driven to extremes on Mars by the ubiquitous occurrence of multivalent ions, renders these environments uninhabitable despite the presence of biologically available water. These findings show how the respective geological histories of Earth and Mars, which have produced differences in the planets' dominant water chemistries, have resulted in different physicochemical extremes which define the boundary space for microbial habitability. KEY WORDS: Habitability-Mars-Salts-Water activity-Life in extreme environments. Astrobiology 16, 427-442.

Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules.

The emergence of mechanisms for phosphorylating organic and inorganic molecules is a key step en route to the earliest living systems. At the heart of all contemporary biochemical systems reside reactive phosphorus (P) molecules (such as adenosine triphosphate, ATP) as energy currency molecules to drive endergonic metabolic processes and it has been proposed that a predecessor of such molecules could have been pyrophosphate [P2O74-; PPi(V)]. Arguably the most geologically plausible route to PPi(V) is dehydration of orthophosphate, Pi(V), normally a highly endergonic process in the absence of mechanisms for activating Pi(V). One possible solution to this problem recognizes the presence of reactive-P containing mineral phases, such as schreibersite [(Fe,Ni)3P] within meteorites whose abundance on the early Earth would likely have been significant during a putative Hadean-Archean heavy bombardment. Here, we propose that the reduced oxidation state P-oxyacid, H-phosphite [HPO32-; Pi(III)] could have activated Pi(V) towards condensation via the intermediacy of the condensed oxyacid pyrophosphite [H2P2O52-; PPi(III)]. We provide geologically plausible provenance for PPi(III) along with evidence of its ability to activate Pi(V) towards PPi(V) formation under mild conditions (80 °C) in water.

Volcano-ice interaction as a microbial habitat on Earth and Mars.

Volcano-ice interaction has been a widespread geological process on Earth that continues to occur to the present day. The interaction between volcanic activity and ice can generate substantial quantities of liquid water, together with steep thermal and geochemical gradients typical of hydrothermal systems. Environments available for microbial colonization within glaciovolcanic systems are wide-ranging and include the basaltic lava edifice, subglacial caldera meltwater lakes, glacier caves, and subsurface hydrothermal systems. There is widespread evidence of putative volcano-ice interaction on Mars throughout its history and at a range of latitudes. Therefore, it is possible that life on Mars may have exploited these habitats, much in the same way as has been observed on Earth. The sedimentary and mineralogical deposits resulting from volcano-ice interaction have the potential to preserve evidence of any indigenous microbial populations. These include jökulhlaup (subglacial outflow) sedimentary deposits, hydrothermal mineral deposits, basaltic lava flows, and subglacial lacustrine deposits. Here, we briefly review the evidence for volcano-ice interactions on Mars and discuss the geomicrobiology of volcano-ice habitats on Earth. In addition, we explore the potential for the detection of these environments on Mars and any biosignatures these deposits may contain.

Astrobiological considerations for the selection of the geological filters on the ExoMars PanCam instrument.

The Panoramic Camera (PanCam) instrument will provide visible-near IR multispectral imaging of the ExoMars rover's surroundings to identify regions of interest within the nearby terrain. This multispectral capability is dependant upon the 12 preselected "geological" filters that are integrated into two wide-angle cameras. First devised by the Imager for Mars Pathfinder team to detect iron oxides, this baseline filter set has remained largely unchanged for subsequent missions (Mars Exploration Rovers, Beagle 2, Phoenix) despite the advancing knowledge of the mineralogical diversity on Mars. Therefore, the geological filters for the ExoMars PanCam will be redesigned to accommodate the astrobiology focus of ExoMars, where hydrated mineral terrains (evidence of past liquid water) will be priority targets. Here, we conduct an initial investigation into new filter wavelengths for the ExoMars PanCam and present results from tests performed on Mars analog rocks. Two new filter sets were devised: one with filters spaced every 50 nm ("F1-12") and another that utilizes a novel filter selection method based upon hydrated mineral reflectance spectra ("F2-12"). These new filter sets, along with the Beagle 2 filter set (currently the baseline for the ExoMars PanCam), were tested on their ability to identify hydrated minerals and biosignatures present in Mars analog rocks. The filter sets, with varying degrees of ability, detected the spectral features of minerals jarosite, opaline silica, alunite, nontronite, and siderite present in these rock samples. None of the filter sets, however, were able to detect fossilized biomat structures and small (<2 mm) mineralogical heterogeneities present in silica sinters. Both new filter sets outperformed the Beagle 2 filters, with F2-12 detecting the most spectral features produced by hydrated minerals and providing the best discrimination between samples. Future work involving more extensive testing on Mars analog samples that exhibit a wider range of mineralogies would be the next step in carefully evaluating the new filter sets.