Chemical Biosignatures Research Articles

Radiolytic Effects on Biological and Abiotic Amino Acids in Shallow Subsurface Ices on Europa and Enceladus.

Europa and Enceladus are key targets to search for evidence of life in our solar system. However, the surface and shallow subsurface of both airless icy moons are constantly bombarded by ionizing radiation that could degrade chemical biosignatures. Therefore, sampling of icy surfaces in future life detection missions to Europa and Enceladus requires a clear understanding of the necessary ice depth where unaltered organic biomolecules might be present. We conducted radiolysis experiments by exposing individual amino acids in ices and amino acids from dead microorganisms in ices to gamma radiation to simulate conditions on these icy worlds. In the pure amino acid samples, glycine did not show a detectable decrease in abundance, whereas the abundance of isovaline decreased by 40% after 4 MGy of exposure. Amino acids in dead Escherichia coli (E. coli) organic matter exhibited a gradual decline in abundances with the increase of exposure dosage, although at much slower rates than individual amino acids. The majority of amino acids in dead A. woodii samples demonstrated a step function decline as opposed to a gradual decline. After the initial drop in abundance with 1 MGy of exposure, those amino acids did not display further decreases in abundance after exposure up to 4 MGy. New radiolysis constants for isolated amino acids and amino acids in dead E. coli material for Europa/Enceladus-like conditions have been derived. Slow rates of amino acid destruction in biological samples under Europa and Enceladus-like surface conditions bolster the case for future life detection measurements by Europa and Enceladus lander missions. Based on our measurements, the "safe" sampling depth on Europa is ∼20 cm at high latitudes of the trailing hemisphere in the area of little impact gardening. Subsurface sampling is not required for the detection of amino acids on Enceladus-these molecules will survive radiolysis at any location on the Enceladus surface. If the stability of amino acids observed in A. woodii organic materials is confirmed in other microorganisms, then the survival of amino acids from a potential biosphere in Europa ice would be significantly increased.

Rapid Diagenesis and Microbial Biosignature Degradation in Spring Carbonates from Crystal Geyser, Utah

Carbonate rocks retain a well preserved record of biologically associated structures at the outcrop to millimeter scale, however microscale features such as cellular fossils are rarely represented. The lack of microscale textural information in ancient carbonates is commonly attributed to processes relating to carbonate diagenesis. However, there are relatively few examples of precisely how and when these destructive processes occur, particularly in active precipitating systems. To better understand the taphonomy of carbonate precipitating environments through early diagenesis, we investigated Crystal Geyser, an active cold water carbonate spring ( about 18 deg C) located in Grand County, Utah. Here we show that rapid precipitation is effective at initially capturing cell-like structures and forming associated microscale laminated stromatolites; however, these morphologies degrade immediately after their formation. We attribute destructive diagenetic effects to the recrystallization of metastable aragonite into the more stable polymorph calcite (i.e., inversion) and the associated textural coarsening that homogenizes and erases the original fabric (i.e., aggrading neomorphism). Despite the loss of microscale morphological information, chemical biosignatures in the form of macromolecular organics remain dispersed throughout the disrupted carbonate textures. These observations provide an example of penecontemporaneous diagenesis that obliterates primary microscale textures in carbonate rocks. Similar mechanisms and their rapid timing, as shown here, likely contributes to the observed lack of microscale morphological biosignatures in many ancient carbonates. This work further highlights that within such systems, permineralization by a more stable crystalline phase, such as chert, must occur rapidly after deposition to effectively retain these signatures over geological timescales.

N-Alkane Biosignatures in a High Arctic Mars Analogue Gossan Deposit

If past life ever existed on Mars, what are the multiple ways it could have been preserved in the Martian geological record? This crucial question is becoming especially relevant the more we uncover about the planet’s ancient wet history. Different acidic and sulfur rich analog environments have been proposed that are comparable to the alteration environments of iron oxides and sulfate minerals on Mars. However, some authors have hypothesized that these past Martian environments might have been cold and semi-dry, similar to polar regions on Earth. As part of the T-MARS team, we studied reactive gossans in the Canadian High Arctic, on Axel Heiberg Island, as an analog environment to similar deposits on Mars. We hypothesized that n-alkane lipids could potentially be an important form of molecular fossils entombed in varying mineral assemblages of sulphates, iron oxides, and phyllosilicates in Arctic gossans, because of their excellent preservation potential relative to most other forms of organic molecules. To determine the preservation potential of lipids in mineralogically varying acidic sulfur rich gossan deposits, this study extracted and quantified n-alkane biomarkers from three different Arctic gossans with gas chromatography–mass spectrometry (GC-MS). Total organic carbon, pH, and mineralogy were also determined. Organic matter was found to be very low in all samples (<1% wt.%). N-alkane analysis also revealed preserved even-over-odd distribution patterns in short chain n-alkanes, most likely from a microbial source, along with evidence for long-chain n-alkanes with odd-over-even distribution from higher plant sources. The presence of these unique chemical biosignatures in low organic, highly acidic, and sulfur rich Mars analog gossans of varying maturity provides evidence that sulfur deposits linked to paleo hydrothermal systems on Mars can be promising targets for preserved organic biosignatures, specifically lipid n-alkanes. The significant diversity in biosignature patterns across samples of varying mineralogy, pH, and oxidation levels within each gossan suggests that n-alkane preservation varies on a small scale in these environments. These factors alone do not definitively account for the variability of n-alkane concentrations and distributions in this study, and additional investigations of these and other influencing factors are needed to determine which specific targets to choose for biosignature search on Mars in future space missions. This exploratory study provides novel insights into the lipid biosignature content in high Arctic Mars analogue gossan deposits.

Astrobiology eXploration at Enceladus (AXE): A New Frontiers Mission Concept Study

The Saturnian moon Enceladus presents a unique opportunity to sample the contents of a subsurface liquid water ocean in situ via the continuous plume formed over its south polar terrain using a multi-flyby mission architecture. Previous analyses of the plume’s composition by Cassini revealed an energy-rich system laden with salts and organic compounds, representing an environment containing most of the ingredients for life as we know it. Following in the footsteps of the Cassini-Huygens mission, we present Astrobiology eXploration at Enceladus (AXE), a New Frontiers class Enceladus mission concept study carried out during the 2021 NASA Planetary Science Summer School program at the Jet Propulsion Laboratory, California Institute of Technology. We demonstrate that a scientifically compelling geophysical and life-detection mission to Enceladus can be carried out within the constraints of a New Frontiers-5 cost cap using a modest instrument suite, requiring only a narrow angle, high-resolution telescopic imager, a mass spectrometer, and a high-gain antenna for radio communications and gravity science measurements. Using a multi-flyby mission architecture, AXE would evaluate the habitability and potential for life at Enceladus through a synergistic combination of in situ chemical analysis measurements aimed at directly detecting the presence of molecular biosignatures, along with geophysical and geomorphological investigations to contextualize chemical biosignatures and further evaluate the habitability of Enceladus over geologic time.

Heat-induced changes in molecular biosignatures and the influence of Mars-relevant minerals

AbstractThe 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.

Investigating the Oxia Planum subsurface with the ExoMars rover and drill

To search for possible signs of life on Mars (past and present), it is necessary to investigate the subsurface. The thin martian atmosphere allows UV and ionizing radiation to damage potential chemical biosignatures at or below the surface. This effect, however, decreases with depth. Thus, organic molecules and potential biomarkers can be better preserved in the subsurface. The ExoMars Rosalind Franklin rover is equipped with a drill able to collect samples from a maximum depth of 2 m for the first time on Mars. In this study we describe how we will use the drill telemetry information in combination with the rover subsurface instruments’ data to better assess the stratification, compositional variations and connection with surface morphology. Understanding the subsurface sample environment is crucial to inform the investigations to be conducted on samples within the rover’s Analytical Laboratory Drawer (ALD). Moreover, the synergic use of drill telemetry and the rover subsurface instruments’ outcomes will inform planning of drilling activities and improve the selection of drilling sites.

Controls on Reactive Oxygen Species Cycles in Yellowstone Hot Springs: Implications for Biosignature Preservation on Mars

Early Earth and Mars had analogous environments. While life developed on our planet, the question of whether it did on Mars remains to be answered. Hot spring deposits are compelling targets for exploration because of their high habitability and potential to retain morphological and chemical biosignatures. As a result in this study, we aim to better understand the potential for biosignature preservation in Fe-bearing hydrothermal systems. Understanding oxidation-reduction reactions involving Fe in hot springs is a key step in elucidating the preservation process. Fe reacts readily with reactive oxygen species (ROS), which are produced in hot spring surface waters through photochemical processes. Furthermore, Fe3+ can bind to cell membranes and preserve complex organic molecules (i.e., biomarkers). ROS formation is typically controlled by photoreactions with dissolved organic matter (DOM). However, Fe redox reactions more likely control ROS formation in these Fe-bearing systems. We deconvolved the relationship of ROS with Fe in hot springs and evaluated the role that DOM and dissolved organic sulfur (DOS) may have in ROS production. To better understand these coupled systems, field and laboratory experiments were conducted in hot springs of Yellowstone National Park. In situ H2O2 concentrations observed in these hot springs were comparable to, or higher than, those of other high-temperature systems. Reaction rates determined by measuring concentrations after specified time intervals varied based on water compositions and the presence of particulate or dissolved matter. Fe speciation (photochemical reactivity), concentration, and solubility further determined ROS cycling rates. Specifically, photochemically active Fe enhanced both ROS formation and decay rates depending on incident UV irradiance, and rates increased along with Fe concentration and solubility (i.e., in acidic conditions). Better understanding how ROS and Fe cycle in predominantly abiotic conditions will eventually aid in distinguishing between biosignatures and abiotic substances in the rock record.

Epistemology and anomaly detection in astrobiology

We examine the epistemological foundations of a leading technique in the search for evidence of life on exosolar planets. Specifically, we consider the “transit method” for spectroscopic analysis of exoplanet atmospheres, and the practice of treating anomalous chemical compositions of the atmospheres of exosolar planets as indicators of the potential presence of life. We propose a methodology for ranking the anomalousness of atmospheres that uses the mathematical apparatus of support vector machines, and which aims to be agnostic with respect to the particular chemical biosignatures of life. We argue that our approach is justified by an appeal to the “hinge” model of epistemic justification first proposed by as reported by Wittgenstein (On certainty, Blackwell, Oxford, 1969). We then compare our approach to previous work due to Walker et al. (Astrobiology 18(6):779–824, 2018) and Cleland (Astrobiology 19(6):722–729, 2019a; Does ‘life’ have a definition?, Cambridge University Press, New York, 2019b).

Chemical, Thermal, and Radiation Resistance of an Iron Porphyrin: A Model Study of Biosignature Stability.

Metal complexes of porphyrins and porphyrin-type compounds are ubiquitous in all three domains of life, with hemes and chlorophylls being the best-known examples. Their diagenetic transformation products are found as geoporphyrins, in which the characteristic porphyrin core structure is retained and which can be up to 1.1 billion years old. Because of this, and their relative ease of detection, metalloporphyrins appear attractive as chemical biosignatures in the search for extraterrestrial life. In this study, we investigated the stability of solid chlorido(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III) [FeCl(oep)], which served as a model for heme-like molecules and iron geoporphyrins. [FeCl(oep)] was exposed to a variety of astrobiologically relevant extreme conditions, namely: aqueous acids and bases, oxidants, heat, and radiation. Key results are: (1) the [Fe(oep)]+ core is stable over the pH range 0.0–13.5 even at 80°C; (2) the oxidizing power follows the order ClO− > H2O2 > ClO3− > HNO3 > ClO4−; (3) in an inert atmosphere, the iron porphyrin is thermally stable to near 250°C; (4) at high temperatures, carbon dioxide gas is not inert but acts as an oxidant, forming carbon monoxide; (5) a decomposition layer is formed on ultraviolet irradiation and protects the [FeCl(oep)] underneath; (6) an NaCl/NaHCO3 salt mixture has a protective effect against X-rays; and (7) no such effect is observed when [FeCl(oep)] is exposed to iron ion particle radiation. The relevance to potential iron porphyrin biosignatures on Mars, Europa, and Enceladus is discussed.

Remote and in-Situ Characterization of Mars Analogs: Coupling Scales to Improve the Search for Microbial Signatures on Mars

Past environments on Mars contained abundant water, suggesting certain regions may have been conducive to life as we know it and implying the potential for microbial inhabitants. Gale and Jezero craters, home of the Perseverance and Curiosity rovers, hosted ancient lakes that experienced periods of active hydrologic cycling and prolonged drying intervals. Exploration of these basins (and future operations on Mars) will benefit from detailed characterizations of analogous environments on Earth, where life detection strategies at various spatial scales (i.e., rover to orbiter) can be tested and validated. Investigations of terrestrial analogs are critical for understanding (1) how microorganisms generate chemical biosignatures in environments characterized by multiple extreme conditions; (2) the impact of environmental conditions and mineralogy on biosignature preservation; and (3) what technologies and techniques are needed to detect biosignatures remotely or in situ. Here, we survey five terrestrial sites analogous to climate conditions proposed for Late Noachian to Early Hesperian Mars, when craters are thought to have hosted active lakes. We review the geologic setting, environmental conditions, microbial habitability, extant microbial communities, and preserved biomarkers at each analog and discuss their relevance to the search for signs of life in Martian craters with in situ and remote instrumentation. The analogs range from active to desiccated lake systems, temperate to hyper-arid climates, and have acidic to neutral-pH and hypo- to hyper-saline waters. Each analog hosts microorganisms adapted to multiple extremes (polyextremophiles), including aspects of water availability (i.e., surface waters versus shallow subsurface water versus groundwater) and physiochemistry (e.g., water activity, salinity, temperature, alkalinity, pH, and redox potential) that can form macrobiological features such as microbial mats. Comparing the expected achievable spatial resolution of several key Mars instruments to the spatial extent of macrobiological features at each analog reveals that most features are unlikely to be resolved from orbit and require rover-scale instruments for detection. We recommend that future studies at these analogs use multi-scale remote sensing surveys to determine thresholds for detecting macrobiological features and map how patterns in mineralogy or physical characteristics of environments correlate to modern-day microbial communities or preserved biomarkers. It will also be critical to determine how the characteristics of macrobiological features, such as areal extent, percent cover, thickness, pigments, etc., impact detectability thresholds. These findings can provide vital information on potential topographic or spectroscopic signatures of life, and at what scales they are detectable. This research is critical to guide sample collection locations within craters like Jezero, and for selecting landing sites for future missions in evaporative Martian basins and other rocky bodies.

Planetary Mass Spectrometry for Agnostic Life Detection in the Solar System

For the past fifty years of space exploration, mass spectrometry has provided unique chemical and physical insights on the characteristics of other planetary bodies in the Solar System. A variety of mass spectrometer types, including magnetic sector, quadrupole, time-of-flight, and ion trap, have and will continue to deepen our understanding of the formation and evolution of exploration targets like the surfaces and atmospheres of planets and their moons. An important impetus for the continuing exploration of Mars, Europa, Enceladus, Titan, and Venus involves assessing the habitability of solar system bodies and, ultimately, the search for life—a monumental effort that can be advanced by mass spectrometry. Modern flight-capable mass spectrometers, in combination with various sample processing, separation, and ionization techniques enable sensitive detection of chemical biosignatures. While our canonical knowledge of biosignatures is rooted in Terran-based examples, agnostic approaches in astrobiology can cast a wider net, to search for signs of life that may not be based on Terran-like biochemistry. Here, we delve into the search for extraterrestrial chemical and morphological biosignatures and examine several possible approaches to agnostic life detection using mass spectrometry. We discuss how future missions can help ensure that our search strategies are inclusive of unfamiliar life forms.

Laser Desorption Mass Spectrometry at Saturn’s moon Titan

NASA's Dragonfly mission will send a rotorcraft lander to the surface of Titan to investigate the prebiotic chemistry, habitability, and potential presence of chemical biosignatures on Saturn’s largest moon. One of the key analytical instruments onboard is the Dragonfly Mass Spectrometer (DraMS) that will perform detailed chemical analyses of the Titan surface and atmosphere. The DraMS instrument is capable of multiple analytical modalities, including Laser Desorption Mass Spectrometry (LDMS), in which DraMS primarily seeks to characterize the low volatility/refractory organic content in acquired Titan surface samples. Several key design adaptations will be needed for DraMS to meet its LDMS measurement objectives at Titan as compared to previous development efforts for similar analysis at Mars. These adaptations include an altered sample collection and delivery approach, modifications to the LDMS ion source, and performance optimization for operations with Titan atmospheric gas.

Science Goals and Objectives for the Dragonfly Titan Rotorcraft Relocatable Lander

Abstract NASA’s Dragonfly mission will send a rotorcraft lander to the surface of Titan in the mid-2030s. Dragonfly's science themes include investigation of Titan’s prebiotic chemistry, habitability, and potential chemical biosignatures from both water-based “life as we know it” (as might occur in the interior mantle ocean, potential cryovolcanic flows, and/or impact melt deposits) and potential “life, but not as we know it” that might use liquid hydrocarbons as a solvent (within Titan’s lakes, seas, and/or aquifers). Consideration of both of these solvents simultaneously led to our initial landing site in Titan’s equatorial dunes and interdunes to sample organic sediments and water ice, respectively. Ultimately, Dragonfly's traverse target is the 80 km diameter Selk Crater, at 7° N, where we seek previously liquid water that has mixed with surface organics. Our science goals include determining how far prebiotic chemistry has progressed on Titan and what molecules and elements might be available for such chemistry. We will also determine the role of Titan’s tropical deserts in the global methane cycle. We will investigate the processes and processing rates that modify Titan’s surface geology and constrain how and where organics and liquid water can mix on and within Titan. Importantly, we will search for chemical biosignatures indicative of past or extant biological processes. As such, Dragonfly, along with Perseverance, is the first NASA mission to explicitly incorporate the search for signs of life into its mission goals since the Viking landers in 1976.

Root membrane lipids as potential biomarkers to discriminate silage-corn genotypes cultivated on podzolic soils in boreal climate.

Root membrane lipids are important biomolecules determining plant's ability to adapt to different growing environmental or climatic conditions. Herein, we demonstrate the potential use of root membrane lipids as biomarkers to discriminate silage-corn genotypes based on herbicide and insect/pest resistance genetic traits when cultivated on podzolic soils under short growing and moderately warm summer season in boreal climate. Lipids in root membranes of field grown silage-corn genotypes were previously quantified at crop maturity by ultra-high-performance liquid chromatography-hydrophilic interaction chromatography-heated electrospray ionization mass spectrometry. The lipid identified and quantified in silage-corn roots were phospholipids, glycolipids and sphingolipids. Following hierarchical cluster analysis, three groups of membrane lipids were observed to be very effective in segregating the five silage-corn genotypes. The first group consisted of hexosylceramide (HexCer), phosphatidylcholine (PC) and phosphatidylinositol (PI). The second group consisted of lysophosphatidic acid (LPA16:0) and lysophosphatidylcholine (LPC16:0), while the third group consisted of 37 molecular species from observed lipids (phospholipids, glycolipids, sphingolipids). Partial least squares-discriminant analysis (PLS-DA) based on 37 membrane lipid species, as well as principal component analysis using the variables important in projection derived from the PLS-DA segregated the five silage-corn genotypes into three groups according to their pesticide/herbicide resistant traits. This study is second to none using root lipidomics in discriminating different silage-corn genotypes based on their herbicide and insect/pest resistance genetic traits for cultivation in boreal climates. The segregated genotypes possess three different genetic traits for herbicide and insect/pest resistance including VT Double Pro (VT2P), VT Triple Pro Roundup Ready (VT3P/RR) and Roundup Ready-2 corn (RR2). These findings demonstrate that root membrane lipids could serve as appropriate chemical biosignatures to identify silage-corn genotypes based on herbicide and insect/pest resistance genetic traits suitable for cultivation in boreal climates.

Geological appraisals of core samples using the ExoMars 2020 rover instrumentation

The ExoMars 2020 mission will characterise a Martian locality with potential former habitability – Oxia Planum – and attempt to identify preserved morphological and chemical biosignatures. The payload will include a drill retrieving cores from the subsurface (up to 2 m depth), which will be imaged at high resolution by two instruments: the Panoramic Camera High Resolution Camera (PanCam HRC) and CLose UP Imager (CLUPI). These instruments will provide guiding interpretation and govern the approach used by the analytical instruments, which will conduct their analyses after crushing of the core sample. Blind tests using Mars-analogue lithological samples provide valuable mission training in terms of maximising scientific return. Previous blind tests evaluating the abilities of the ExoMars 2020 payload to conduct geological approaches used solid rock hand samples as test specimens. Here, we prepared test samples of ExoMars mission-equivalent shapes and dimensions (3 × 1 cm cores) to evaluate the extent of geological interpretation possible using only the images of the core that will obtained during the mission. In the worst-case scenario, core samples will be different from outcrop rock and these images and associated organogeochemical analyses on crushed powders by the other rover instruments will be the sole basis for their interpretation. Imaging these samples using mission-equivalent original resolutions to avoid image processing artefacts, we found that the difficulty inherent in making definitive geological conclusions using traditional ‘field petrography’ approaches is increased when only limited amounts of core sample are available for observation. Challenges involved in the interpretation of core samples include representativeness problems inherent to small samples, distinction between layer-specific characteristics at the sub-centimetre to centimetre scale, and mechanical effects, such as drill marks and dust covering. These issues vary depending upon the rock type and change as a function of the mechanical properties (and thus composition) of the sample. Despite these challenges, we find that CLUPI and PanCam HRC images alone allow many accurate and detailed geological observations; however, confidence and detail of interpretation are notably increased when additional geochemical data are provided, in this case, Raman spectra reflecting the contribution of the Raman Laser Spectrometer (RLS) instrument. Our results argue for the importance of detailed core imaging during the experimental phase of the rover mission despite the challenges involved in interpretation, since HRC and CLUPI images offer a degree of synergy. Inter-instrumental collaboration will be essential during the ExoMars 2020 rover mission (and indeed in any rover mission), since no single payload instrument is able to perform a comprehensive assessment of a putative biosignature within its geological context, and since the instrument suite provides highly complementary data at multiple scales that are key to maximising scientific return.

Artifact formation during Raman measurements and its relevance to the search for chemical biosignatures on Mars

Raman spectroscopy will be a powerful tool in the in situ search for Martian biosignatures within the ESA/Roscosmos ExoMars and NASA Mars 2020 missions. However, a Raman laser can alter the chemical nature of a sample. This prompted us to investigate the stability of potential biosignatures during Raman measurements. For our study, we selected the photosynthetic pigment β-carotene, the biological membrane component 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE), the iron porphyrin hemin, and the electron transfer protein cytochrome c. The excitation wavelength was 532 nm, which is the wavelength at which the lasers of the RLS (ExoMars) and SuperCam (Mars 2020) instruments will operate. We found that β-carotene and DOPE were stable up to 7.0 mW, which was the maximum laser power in our experiments, corresponding to an irradiance of 378 kW/cm2. Hemin and cytochrome c, by contrast, decomposed when the energy input exceeded a certain threshold. For example, hemin started to decompose in the 0.05–0.8 mW range (2.5–40 kW/cm2) under Mars-like conditions (200 K, vacuum, 50 s total irradiation time). Carbonaceous materials were the final decomposition products of both compounds. Our experiments also showed that low temperatures near the average Martian surface temperature of ~210 K can delay the decomposition of biomolecules. In addition to loose powders, we studied thin layers pressed on NaCl pellets, where NaCl served as a model mineral matrix. In the case of hemin and cytochrome c on NaCl, the measurements could be performed with higher laser powers because of more efficient heat dissipation by the salt. For comparison, spectra were also recorded under standard laboratory conditions, i.e., at room temperature and atmospheric pressure. A major conclusion of this work is that Raman lasers used on Mars may alter biomolecules by heating the sample and, in specific cases, transform them into carbonaceous matter. The resulting spectra may be misinterpreted as evidence of extinct rather than extant life or even as evidence of non-biological material.

Investigating the effects of gamma radiation on selected chemicals for use in biosignature detection instruments on the surface of Jupiter's moon Europa

Jupiter's moon Europa is a prime target for the search for potential signs of life in the solar system. The Europa Lander Science Definition Team Report outlined investigations and measurement requirements on a future Europa Lander and has led us to consider application of powerful techniques such as pyrolysis and derivatization gas chromatography mass spectrometry (GC-MS) and laser desorption mass spectrometry (LD-MS) to elucidate the organic composition of near-surface ice and minerals. Definitive identification of chemical biosignatures using such techniques is strongly enabled by the use of various chemicals, such as perfluorotributylamine (PFTBA) for the MS calibration, α-cyano-hydroxycinnamic acid (CHCA) for matrix-assisted laser desorption and ionization (MALDI) and N,N-dimethylformamide dimethyl acetal (DMF-DMA), N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) and tetramethylammonium hydroxide (TMAH) for wet chemistry GC-MS protocols. The jovian radiation environment is known to represent a uniquely challenging risk to mission performance and lifetime, principally due to high radiation levels. To assess the potential ionizing radiation damage to these important chemicals, we tested their effectiveness following gamma radiation exposure doses up to the anticipated Europa Lander rating requirement of 300 krad(Si). The chemicals were sealed in glass ampules under vacuum (<10 mTorr), to reduce trapped oxygen gas, as the oxidation by O2 may be enhanced in the presence of radiation. We report that all five chemicals exposed to total ionizing doses of 0, 150 and 300 krad(Si) maintained their full effectiveness, and no significant degradation was observed.

Inhabited or Uninhabited? Pitfalls in the Interpretation of Possible Chemical Signatures of Extraterrestrial Life.

The “Rare Earth” hypothesis—put forward by Ward and Brownlee in their 2000 book of the same title—states that prokaryote-type organisms may be common in the universe but animals and higher plants are exceedingly rare. If this idea is correct, the search for extraterrestrial life is essentially the search for microorganisms. Various indicators may be used to detect extant or extinct microbial life beyond Earth. Among them are chemical biosignatures, such as biomolecules and stable isotope ratios. The present minireview focuses on the major problems associated with the identification of chemical biosignatures. Two main types of misinterpretation are distinguished, namely false positive and false negative results. The former can be caused by terrestrial biogenic contaminants or by abiotic products. Terrestrial contamination is a common problem in space missions that search for biosignatures on other planets and moons. Abiotic organics can lead to false positive results if erroneously interpreted as biomolecules, but also to false negatives, for example when an abiotic source obscures a less productive biological one. In principle, all types of putative chemical biosignatures are prone to misinterpretation. Some, however, are more reliable (“stronger”) than others. These include: (i) homochiral polymers of defined length and sequence, comparable to proteins and polynucleotides; (ii) enantiopure compounds; (iii) the existence of only a subset of molecules when abiotic syntheses would produce a continuous range of molecules; the proteinogenic amino acids constitute such a subset. These considerations are particularly important for life detection missions to solar system bodies such as Mars, Europa, and Enceladus.

Habitability on Early Mars and the Search for Biosignatures with the ExoMars Rover.

The second ExoMars mission will be launched in 2020 to target an ancient location interpreted to have strong potential for past habitability and for preserving physical and chemical biosignatures (as well as abiotic/prebiotic organics). The mission will deliver a lander with instruments for atmospheric and geophysical investigations and a rover tasked with searching for signs of extinct life. The ExoMars rover will be equipped with a drill to collect material from outcrops and at depth down to 2 m. This subsurface sampling capability will provide the best chance yet to gain access to chemical biosignatures. Using the powerful Pasteur payload instruments, the ExoMars science team will conduct a holistic search for traces of life and seek corroborating geological context information. Key Words: Biosignatures—ExoMars—Landing sites—Mars rover—Search for life. Astrobiology 17, 471–510.

Limited influence of Si on the preservation of Fe mineral-encrusted microbial cells during experimental diagenesis.

The reconstruction of the history of microbial life since its emergence on early Earth is impaired by the difficulty to prove the biogenicity of putative microfossils in the rock record. While most of the oldest rocks on Earth have been exposed to different grades of diagenetic alterations, little is known about how the remains of micro-organisms evolve when exposed to pressure (P) and temperature (T) conditions typical of diagenesis. Using spectroscopy and microscopy, we compared morphological, mineralogical, and chemical biosignatures exhibited by Fe mineral-encrusted cells of the bacterium Acidovorax sp. BoFeN1 after long-term incubation under ambient conditions and after experimental diagenesis. We also evaluated the effects of Si on the preservation of microbial cells during the whole process. At ambient conditions, Si affected the morphology but not the identity (goethite) of Fe minerals that formed around cells. Fe-encrusted cells were morphologically well preserved after 1week at 250°C-140MPa and after 16weeks at 170°C-120MPa in the presence or in the absence of Si. Some goethite transformed to hematite and magnetite at 250°C-140MPa, but in the presence of Si more goethite was preserved. Proteins-the most abundant cellular components-were preserved over several months at ambient conditions but disappeared after incubations at high temperature and pressure conditions, both in the presence and in the absence of Si. Other organic compounds, such as lipids and extracellular polysaccharides seemed well preserved after exposure to diagenetic conditions. This study provides insights about the composition and potential preservation of microfossils that could have formed in Fe- and Si-rich Precambrian oceans.