Present-day thermal and water activity environment of the Mars Sample Return collection.

The Mars Sample Return mission intends to retrieve a sealed collection of rocks, regolith, and atmosphere sampled from Jezero Crater, Mars, by the NASA Perseverance rover mission. For all life-related research, it is necessary to evaluate water availability in the samples and on Mars. Within the first Martian year, Perseverance has acquired an estimated total mass of 355 g of rocks and regolith, and 38 µmoles of Martian atmospheric gas. Using in-situ observations acquired by the Perseverance rover, we show that the present-day environmental conditions at Jezero allow for the hydration of sulfates, chlorides, and perchlorates and the occasional formation of frost as well as a diurnal atmospheric-surface water exchange of 0.5-10 g water per m2 (assuming a well-mixed atmosphere). At night, when the temperature drops below 190 K, the surface water activity can exceed 0.5, the lowest limit for cell reproduction. During the day, when the temperature is above the cell replication limit of 245 K, water activity is less than 0.02. The environmental conditions at the surface of Jezero Crater, where these samples were acquired, are incompatible with the cell replication limits currently known on Earth.

Investigating Europa's Habitability with the Europa Clipper.

The habitability of Europa is a property within a system, which is driven by a multitude of physical and chemical processes and is defined by many interdependent parameters, so that its full characterization requires collaborative investigation. To explore Europa as an integrated system to yield a complete picture of its habitability, the Europa Clipper mission has three primary science objectives: (1) characterize the ice shell and ocean including their heterogeneity, properties, and the nature of surface-ice-ocean exchange; (2) characterize Europa's composition including any non-ice materials on the surface and in the atmosphere, and any carbon-containing compounds; and (3) characterize Europa's geology including surface features and localities of high science interest. The mission will also address several cross-cutting science topics including the search for any current or recent activity in the form of thermal anomalies and plumes, performing geodetic and radiation measurements, and assessing high-resolution, co-located observations at select sites to provide reconnaissance for a potential future landed mission. Synthesizing the mission's science measurements, as well as incorporating remote observations by Earth-based observatories, the James Webb Space Telescope, and other space-based resources, to constrain Europa's habitability, is a complex task and is guided by the mission's Habitability Assessment Board (HAB).

Organic Biosignature Degradation in Hydrothermal and Serpentinizing Environments: Implications for Life Detection on Icy Moons and Mars.

Evidence of liquid water is a primary indicator of habitability on the icy moons in our outer solar system as well as on terrestrial planets such as Mars. If liquid water-containing environments host life, some of its organic remains can be fossilized and preserved as organic biosignatures. However, inorganic materials may also be present and water-assisted organic-inorganic reactions can transform the organic architecture of biological remains. Our understanding of the fate of these organic remains can be assisted by experimental simulations that monitor the chemical changes that occur in microbial organic matter due to the presence of water and minerals. We performed hydrothermal experiments at temperatures between 100°C and 300°C involving lipid-rich microbes and natural serpentinite mineral mixtures generated by the subaqueous hydrothermal alteration of ultramafic rock. The products reveal what the signals of life may look like when subjected to water-organic-inorganic reactions. Straight- and branched-chain lipids in unaltered samples are joined by cyclization and aromatization products in hydrothermally altered samples. Hydrothermal reactions produce distinct products that are not present in the starting materials, including small, single-ring, heteroatomic, and aromatic compounds such as indoles and phenols. Hydrothermal reactions in the presence of serpentinite minerals lead to significant reduction of these organic structures and their replacement by diketopiperazines (DKPs) and dihydropyrazines (DHPs), which may be compounds that are distinct to organic-inorganic reactions. Given that the precursors of DKPs and DHPs are normally lost during early diagenesis, the presence of these compounds can be an indicator of coexisting recent life and hydrothermal processing in the presence of minerals. However, laboratory experiments reveal that the formation and preservation of these compounds can only occur within a distinct temperature window. Our findings are relevant to life detection missions that aim to access hydrothermal and serpentinizing environments in the subsurfaces of icy moons and Mars.

Characteristics of fine and ultrafine aerosols in the London underground.

Underground railway systems are recognised spaces of increased personal pollution exposure. We studied the number-size distribution and physico-chemical characteristics of ultrafine (PM0.1), fine (PM0.1-2.5) and coarse (PM2.5-10) particles collected on a London underground platform. Particle number concentrations gradually increased throughout the day, with a maximum concentration between 18:00 h and 21:00 h (local time). There was a maximum decrease in mass for the PM2.5, PM2.5-10 and black carbon of 3.9, 4.5 and ~ 21-times, respectively, between operable (OpHrs) and non-operable (N-OpHrs) hours. Average PM10 (52 µg m-3) and PM2.5 (34 µg m-3) concentrations over the full data showed levels above the World Health Organization Air Quality Guidelines. Respiratory deposition doses of particle number and mass concentrations were calculated and found to be two- and four-times higher during OpHrs compared with N-OpHrs, reflecting events such as train arrival/departure during OpHrs. Organic compounds were composed of aromatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) which are known to be harmful to health. Specific ratios of PAHs were identified for underground transport that may reflect an interaction between PAHs and fine particles. Scanning transmission electron microscopy (STEM) chemical maps of fine and ultrafine fractions show they are composed of Fe and O in the form of magnetite and nanosized mixtures of metals including Cr, Al, Ni and Mn. These findings, and the low air change rate (0.17 to 0.46 h-1), highlight the need to improve the ventilation conditions.

Solid-Phase Microextraction for Organic Contamination Control Throughout Assembly and Operational Phases of Space Missions.

Space missions concerned with life detection contain highly sensitive instruments for the detection of organics. Terrestrial contamination can interfere with signals of indigenous organics in samples and has the potential to cause false-positive biosignature detections, which may lead to incorrect suggestions of the presence of life elsewhere in the solar system. This study assessed the capability of solid-phase microextraction (SPME) as a method for monitoring organic contamination encountered by spacecraft hardware during assembly and operation. SPME-gas chromatography-mass spectrometry (SPME-GC-MS) analysis was performed on potential contaminant source materials, which are commonly used in spacecraft construction. The sensitivity of SPME-GC-MS to organics was assessed in the context of contaminants identified in molecular wipes taken from hardware surfaces on the ExoMars Rosalind Franklin rover. SPME was found to be effective at detecting a wide range of common organic contaminants that include aromatic hydrocarbons, aliphatic hydrocarbons, nitrogen-containing compounds, alcohols, and carbonyls. A notable example of correlation of contaminant with source material was the detection of benzenamine compounds in an epoxy adhesive analyzed by SPME-GC-MS and in the ExoMars rover surface wipe samples. The current form of SPME-GC-MS does not enable quantitative evaluation of contaminants, nor is it suitable for the detection of every group of organic molecules relevant to astrobiological contamination concerns, namely large and/or polar molecules such as amino acids. However, it nonetheless represents an effective new monitoring method for rapid, easy identification of organic contaminants commonly present on spacecraft hardware and could thus be utilized in future space missions as part of their contamination control and mitigation protocols.

Aqueous alteration processes in Jezero crater, Mars-implications for organic geochemistry.

The Perseverance rover landed in Jezero crater, Mars, in February 2021. We used the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument to perform deep-ultraviolet Raman and fluorescence spectroscopy of three rocks within the crater. We identify evidence for two distinct ancient aqueous environments at different times. Reactions with liquid water formed carbonates in an olivine-rich igneous rock. A sulfate-perchlorate mixture is present in the rocks, which probably formed by later modifications of the rocks by brine. Fluorescence signatures consistent with aromatic organic compounds occur throughout these rocks and are preserved in minerals related to both aqueous environments.

The Winchcombe meteorite, a unique and pristine witness from the outer solar system.

Direct links between carbonaceous chondrites and their parent bodies in the solar system are rare. The Winchcombe meteorite is the most accurately recorded carbonaceous chondrite fall. Its pre-atmospheric orbit and cosmic-ray exposure age confirm that it arrived on Earth shortly after ejection from a primitive asteroid. Recovered only hours after falling, the composition of the Winchcombe meteorite is largely unmodified by the terrestrial environment. It contains abundant hydrated silicates formed during fluid-rock reactions, and carbon- and nitrogen-bearing organic matter including soluble protein amino acids. The near-pristine hydrogen isotopic composition of the Winchcombe meteorite is comparable to the terrestrial hydrosphere, providing further evidence that volatile-rich carbonaceous asteroids played an important role in the origin of Earth's water.

Hydrothermal Processing of Microorganisms: Mass Spectral Signals of Degraded Biosignatures for Life Detection on Icy Moons.

Life detection missions to the outer solar system are concentrating on the icy moons of Jupiter and Saturn and their inferred subsurface oceans. Access to evidence of habitability, and possibly even life, is facilitated by the ejection of subsurface material in plumes and outgassing fissures. Orbiting spacecraft can intersect the plume material or detect past sputtered remnants of outgassed products and analyze the contents using instruments such as mass spectrometers. Hydrothermalism has been proposed for the subsurface environments of icy moons, and the organic remains of any associated life would be expected to suffer some degradation through hydrothermalism, radiolysis, or spacecraft flyby impact fragmentation. Hydrothermalism is treated here for the first time in the context of the Europa Clipper mission. To assess the influence of hydrothermalism on the ability of orbiting mass spectrometers to detect degrading signals of life, we have subjected Earth microorganisms to laboratory hydrothermal processing. The processed microorganism samples were then analyzed using gas chromatography-mass spectrometry (GC-MS), and mass spectra were generated. Certain compound classes, such as carbohydrates and proteins, are significantly altered by hydrothermal processing, resulting in small one-ring and two-ring aromatic compounds such as indoles and phenols. However, lipid fragments, such as fatty acids, retain their fidelity, and their provenance is easily recognized as biological in origin. Our data indicate that mass spectrometry measurements in the plumes of icy moons, using instruments such as the MAss Spectrometer for Planetary Exploration (MASPEX) onboard the upcoming Europa Clipper mission, can reveal the presence of life even after significant degradation by hydrothermal processing has taken place.

COSPAR Sample Safety Assessment Framework (SSAF).

The Committee on Space Research (COSPAR) Sample Safety Assessment Framework (SSAF) has been developed by a COSPAR appointed Working Group. The objective of the sample safety assessment would be to evaluate whether samples returned from Mars could be harmful for Earth's systems (e.g., environment, biosphere, geochemical cycles). During the Working Group's deliberations, it became clear that a comprehensive assessment to predict the effects of introducing life in new environments or ecologies is difficult and practically impossible, even for terrestrial life and certainly more so for unknown extraterrestrial life. To manage expectations, the scope of the SSAF was adjusted to evaluate only whether the presence of martian life can be excluded in samples returned from Mars. If the presence of martian life cannot be excluded, a Hold & Critical Review must be established to evaluate the risk management measures and decide on the next steps. The SSAF starts from a positive hypothesis (there is martian life in the samples), which is complementary to the null-hypothesis (there is no martian life in the samples) typically used for science. Testing the positive hypothesis includes four elements: (1) Bayesian statistics, (2) subsampling strategy, (3) test sequence, and (4) decision criteria. The test sequence capability covers self-replicating and non-self-replicating biology and biologically active molecules. Most of the investigations associated with the SSAF would need to be carried out within biological containment. The SSAF is described in sufficient detail to support planning activities for a Sample Receiving Facility (SRF) and for preparing science announcements, while at the same time acknowledging that further work is required before a detailed Sample Safety Assessment Protocol (SSAP) can be developed. The three major open issues to be addressed to optimize and implement the SSAF are (1) setting a value for the level of assurance to effectively exclude the presence of martian life in the samples, (2) carrying out an analogue test program, and (3) acquiring relevant contamination knowledge from all Mars Sample Return (MSR) flight and ground elements. Although the SSAF was developed specifically for assessing samples from Mars in the context of the currently planned NASA-ESA MSR Campaign, this framework and the basic safety approach are applicable to any other Mars sample return mission concept, with minor adjustments in the execution part related to the specific nature of the samples to be returned. The SSAF is also considered a sound basis for other COSPAR Planetary Protection Category V, restricted Earth return missions beyond Mars. It is anticipated that the SSAF will be subject to future review by the various MSR stakeholders.

Mineral Matrix Effects on Pyrolysis Products of Kerogens Infer Difficulties in Determining Biological Provenance of Macromolecular Organic Matter at Mars.

Ancient martian organic matter is likely to take the form of kerogen-like recalcitrant macromolecular organic matter (MOM), existing in close association with reactive mineral surfaces, especially iron oxides. Detecting and identifying a biological origin for martian MOM will therefore be of utmost importance for life-detection efforts at Mars. We show that Type I and Type IV kerogens provide effective analogues for putative martian MOM of biological and abiological (meteoric) provenances, respectively. We analyze the pyrolytic breakdown products when these kerogens are mixed with mineral matrices highly relevant for the search for life on Mars. We demonstrate that, using traditional thermal techniques as generally used by the Sample Analysis at Mars and Mars Organic Molecule Analyser instruments, even the breakdown products of highly recalcitrant MOM are transformed during analysis in the presence of reactive mineral surfaces, particularly iron. Analytical transformation reduces the diagnostic ability of this technique, as detected transformation products of both biological and abiological MOM may be identical (low molecular weight gas phases and benzene) and indistinguishable. The severity of transformational effects increased through calcite < kaolinite < hematite < nontronite < magnetite < goethite. Due to their representation of various habitable aqueous environments and the preservation potential of organic matter by iron, it is not advisable to completely avoid iron-rich strata. We conclude that hematite-rich localities, with evidence of extensive aqueous alteration of originally reducing phases, such as the Vera Rubin Ridge, may be relatively promising targets for identifying martian biologically sourced MOM.

Mass Spectrometric Fingerprints of Bacteria and Archaea for Life Detection on Icy Moons.

The icy moons of the outer Solar System display evidence of subsurface liquid water and, therefore, potential habitability for life. Flybys of Saturn's moon Enceladus by the Cassini spacecraft have provided measurements of material from plumes that suggest hydrothermal activity and the presence of organic matter. Jupiter's moon Europa may have similar plumes and is the target for the forthcoming Europa Clipper mission that carries a high mass resolution and high sensitivity mass spectrometer, called the MAss Spectrometer for Planetary EXploration (MASPEX), with the capability for providing detailed characterization of any organic materials encountered. We have performed a series of experiments using pyrolysis-gas chromatography-mass spectrometry to characterize the mass spectrometric fingerprints of microbial life. A range of extremophile Archaea and Bacteria have been analyzed and the laboratory data converted to MASPEX-type signals. Molecular characteristics of protein, carbohydrate, and lipid structures were detected, and the characteristic fragmentation patterns corresponding to these different biological structures were identified. Protein pyrolysis fragments included phenols, nitrogen heterocycles, and cyclic dipeptides. Oxygen heterocycles, such as furans, were detected from carbohydrates. Our data reveal how mass spectrometry on Europa Clipper can aid in the identification of the presence of life, by looking for characteristic bacterial fingerprints that are similar to those from simple Earthly organisms.

Transformation of Cyanobacterial Biomolecules by Iron Oxides During Flash Pyrolysis: Implications for Mars Life-Detection Missions.

Answering the question of whether life ever existed on Mars is a key goal of both NASA's and ESA's imminent Mars rover missions. The obfuscatory effects of oxidizing salts, such as perchlorates and sulfates, on organic matter during thermal decomposition analysis techniques are well established. Less well studied are the transformative effects of iron oxides and (oxy)hydroxides, which are present in great abundances in the martian regolith. We examined the products of flash pyrolysis-gas chromatography-mass spectrometry (a technique analogous to the thermal techniques employed by past, current, and future landed Mars missions) which form when the cyanobacteria Arthrospira platensis are heated in the presence of a variety of Mars-relevant iron-bearing minerals. We found that iron oxides/(oxy)hydroxides have transformative effects on the pyrolytic products of cyanobacterial biomolecules. Both the abundance and variety of molecular species detected were decreased as iron substrates transformed biomolecules, by both oxidative and reductive processes, into lower fidelity alkanes, aromatic and aryl-bonded hydrocarbons. Despite the loss of fidelity, a suite that contains mid-length alkanes and polyaromatic hydrocarbons and/or aryl-bonded molecules in iron-rich samples subjected to pyrolysis may allude to the transformation of cyanobacterially derived mid-long chain length fatty acids (particularly unsaturated fatty acids) originally present in the sample. Hematite was found to be the iron oxide with the lowest transformation potential, and because this iron oxide has a high affinity for codeposition of organic matter and preservation over geological timescales, sampling at Mars should target sediments/strata that have undergone a diagenetic history encouraging the dehydration, dihydroxylation, and oxidation of more reactive iron-bearing phases to hematite by looking for (mineralogical) evidence of the activity of oxidizing, acidic/neutral, and either hot or long-lived fluids.

Quantifying Preservation Potential: Lipid Degradation in a Mars-Analog Circumneutral Iron Deposit.

Comparisons between the preservation potential of Mars-analog environments have historically been qualitative rather than quantitative. Recently, however, laboratory-based artificial maturation combined with kinetic modeling techniques have emerged as a potential means by which the preservation potential of solvent-soluble organic matter can be quantified in various Mars-analog environments. These methods consider how elevated temperatures, pressures, and organic-inorganic interactions influence the degradation of organic biomarkers post-burial. We used these techniques to investigate the preservation potential of deposits from a circumneutral iron-rich groundwater system. These deposits are composed of ferrihydrite (Fe5HO8 · 4H2O), an amorphous iron hydroxide mineral that is a common constituent of rocks found in ancient lacustrine environments on Mars, such as those observed in Gale Crater. Both natural and synthetic ferrihydrite samples were subjected to hydrous pyrolysis to observe the effects of long-term burial on the mineralogy and organic content of the samples. Our experiments revealed that organic-inorganic interactions in the samples are dominated by the transformation of iron minerals. As amorphous ferrihydrite transforms into more crystalline species, the decrease in surface area results in the desorption of organic matter, potentially rendering them more susceptible to degradation. We also find that circumneutral iron-rich deposits provide unfavorable conditions for the preservation of solvent-soluble organic matter. Quantitative comparisons between preservation potentials as calculated when using kinetic parameters show that circumneutral iron-rich deposits are ∼25 times less likely to preserve solvent-soluble organic matter compared with acidic, iron-rich environments. Our results suggest that circumneutral iron-rich deposits should be deprioritized in favor of acidic iron- and sulfur-rich deposits when searching for evidence of life with solvent extraction techniques.

Pyrolysis of Carboxylic Acids in the Presence of Iron Oxides: Implications for Life Detection on Missions to Mars.

The search for, and characterization of, organic matter on Mars is central to efforts in identifying habitable environments and detecting evidence of life in the martian surface and near surface. Iron oxides are ubiquitous in the martian regolith and are known to be associated with the deposition and preservation of organic matter in certain terrestrial environments, thus iron oxide-rich sediments are potential targets for life-detection missions. The most frequently used protocol for martian organic matter characterization (also planned for use on ExoMars) has been thermal extraction for the transfer of organic matter to gas chromatography-mass spectrometry (GC-MS) detectors. For the effective use of thermal extraction for martian samples, it is necessary to explore how potential biomarker organic molecules evolve during this process in the presence of iron oxides. We have thermally decomposed iron oxides simultaneously with (z)-octadec-9-enoic and n-octadecanoic acids and analyzed the products through pyrolysis-GC-MS. We found that the thermally driven dehydration, reduction, and recrystallization of iron oxides transformed fatty acids. Overall detectability of products greatly reduced, molecular diversity decreased, unsaturated products decreased, and aromatization increased. The severity of this effect increased as reduction potential of the iron oxide and inferred free radical formation increased. Of the iron oxides tested hematite showed the least transformative effects, followed by magnetite, goethite, then ferrihydrite. It was possible to identify the saturation state of the parent carboxylic acid at high (0.5 wt %) concentrations by the distribution of n-alkylbenzenes in the pyrolysis products. When selecting life-detection targets on Mars, localities where hematite is the dominant iron oxide could be targeted preferentially, otherwise thermal analysis of carboxylic acids, or similar biomarker molecules, will lead to enhanced polymerization, aromatization, and breakdown, which will in turn reduce the fidelity of the original biomarker, similar to changes normally observed during thermal maturation.

Artificial Maturation of Iron- and Sulfur-Rich Mars Analogues: Implications for the Diagenetic Stability of Biopolymers and Their Detection with Pyrolysis-Gas Chromatography-Mass Spectrometry.

Acidic iron- and sulfur-rich streams are appropriate analogues for the late Noachian and early Hesperian periods of martian history, when Mars exhibited extensive habitable environments. Any past life on Mars may have left behind diagnostic evidence of life that could be detected at the present day. For effective preservation, these remains must have avoided the harsh radiation flux at the martian surface, survived geological storage for billions of years, and remained detectable within their geochemical environment by analytical instrument suites used on Mars today, such as thermal extraction techniques. We investigated the detectability of organic matter within sulfur stream sediments that had been subjected to artificial maturation by hydrous pyrolysis. After maturation, the samples were analyzed by pyrolysis-gas chromatography-mass spectrometry (py-GC-MS) to determine whether organic matter could be detected with this commonly used technique. We find that macromolecular organic matter can survive the artificial maturation process in the presence of iron- and sulfur-rich minerals but cannot be unambiguously distinguished from abiotic organic matter. However, if jarosite and goethite are present in the sulfur stream environment, they interfere with the py-GC-MS detection of organic compounds in these samples. Clay reduces the obfuscating effect of the oxidizing minerals by providing nondeleterious adsorption sites. We also find that after a simple alkali and acid leaching process that removes oxidizing minerals such as iron sulfates, oxides, and oxyhydroxides, the sulfur stream samples exhibit much greater organic responses during py-GC-MS in terms of both abundance and diversity of organic compounds, such as the detection of hopanes in all leached samples. Our results suggest that insoluble organic matter can be preserved over billions of years of geological storage while still retaining diagnostic organic information, but sample selection strategies must either avoid jarosite- and goethite-rich outcrops or conduct preparative chemistry steps to remove these oxidants prior to analysis by thermal extraction techniques.

Organic Records of Early Life on Mars: The Role of Iron, Burial, and Kinetics on Preservation.

Samples that are likely to contain evidence of past life on Mars must have been deposited when and where environments exhibited habitable conditions. Mars analog sites provide the opportunity to study how life could have exploited such habitable conditions. Acidic iron- and sulfur-rich streams are good geochemical analogues for the late Noachian and early Hesperian, periods of martian history where habitable conditions were widespread. Past life on Mars would have left behind fossilized microbial organic remains. These are often-sought diagnostic evidence, but they must be shielded from the harsh radiation flux at the martian surface and its deleterious effect on organic matter. One mechanism that promotes such preservation is burial, which raises questions about how organic biomarkers are influenced by the postburial effects of diagenesis. We investigated the kinetics of organic degradation in the subsurface of Mars. Natural mixtures of acidic iron- and sulfur-rich stream sediments and their associated microbial populations and remains were subjected to hydrous pyrolysis, which simulated the increased temperatures and pressures of burial alongside any promoted organic/mineral interactions. Calculations were made to extrapolate the observed changes over martian history. Our experiments indicate that low carbon contents, high water-to-rock ratios, and the presence of iron-rich minerals combine to provide unfavorable conditions for the preservation of soluble organic matter over the billions of years necessary to produce present-day organic records of late Noachian and early Hesperian life on Mars. Successful sample selection strategies must therefore consider the pre-, syn-, and postburial histories of sedimentary records on Mars and the balance between the production of biomass and the long-term preservation of organic biomarkers over geological time.

Solid Phase Micro Extraction: Potential for Organic Contamination Control for Planetary Protection of Life-Detection Missions to the Icy Moons of the Outer Solar System.

Conclusively detecting, or ruling out the possibility of, life on the icy moons of the outer Solar System will require spacecraft missions to undergo rigorous planetary protection and contamination control procedures to achieve extremely low levels of organic terrestrial contamination. Contamination control is necessary to avoid forward contamination of the body of interest and to avoid the detection of false-positive signals, which could either mask indigenous organic chemistry of interest or cause an astrobiological false alarm. Here we test a new method for rapidly and inexpensively assessing the organic cleanliness of spaceflight hardware surfaces using solid phase micro extraction (SPME) fibers to directly swab surfaces. The results suggest that the method is both time and cost efficient. The SPME-gas chromatography-mass spectrometry (SPME-GC-MS) method is sensitive to common midweight, nonpolar contaminant compounds, for example, aliphatic and aromatic hydrocarbons, which are common contaminants in laboratory settings. While we demonstrate the potential of SPME for surface sampling, the GC-MS instrumentation restricts the SPME-GC-MS technique's sensitivity to larger polar and nonvolatile compounds. Although not used in this study, to increase the potential range of detectable compounds, SPME can also be used in conjunction with high-performance liquid chromatography/liquid chromatography-mass spectrometry systems suitable for polar analytes (Kataoka et al., 2000). Thus, our SPME method presents an opportunity to monitor organic contamination in a relatively rapid and routine way that produces information-rich data sets.

Effects of Oxygen-Containing Salts on the Detection of Organic Biomarkers on Mars and in Terrestrial Analog Soils.

The detection of chlorinated hydrocarbons by Curiosity on Mars has been attributed to the presence of unidentified indigenous organic matter. Similarly, oxychlorines on Earth have been proposed to be responsible for the apparent lack of organics in the Atacama Desert. The presence of perchlorate (ClO4-) poses a unique challenge to the measurement of organic matter due to the oxidizing power of oxychlorines during commonly used pyrolysis-gas chromatography-mass spectrometry (py-GC-MS) methods. Here, we show that perchlorates and other oxyanion salts inhibit the detection of organic compounds but that removing these problematic species prior to pyrolysis by using an optimal sample extraction duration and suitable ratios of water to sample mass enables analysis. We have characterized leached and unleached samples containing perchlorates from the Atacama Desert and have found that after leaching, the py-GC-MS chromatograms of the dried mineral residues show identifiable biomarkers associated with indigenous cyanobacteria. Samples which were pyrolyzed without leaching showed no detectable organic matter other than background siloxane and very weak or no trace of detectable polychlorinated benzenes. Dried sample residues remaining after leaching, the mineral matrix and water-insoluble organic matter, showed a strong organic response in all cases when analyzed by py-GC-MS. These residues are most likely the product of the pyrolysis of water-insoluble organics originally present in the samples. In addition, our results imply that previous soil analyses which contained high levels of oxyanions and concluded that organics were either not present or were present at extremely low levels should be reexamined.

How to Detect Life on Icy Moons.

The icy moons of the outer Solar System present the possibility of subsurface water, habitable conditions, and potential abodes for life. Access to evidence that reveals the presence of life on the icy moons can be facilitated by plumes that eject material from the subsurface out into space. One instrument capable of performing life-search investigations at the icy moons is the MAss SPectrometer for Planetary EXploration/Europa (MASPEX), which constitutes a high-resolution, high-sensitivity multibounce time-of-flight mass spectrometer capable of measuring trace amounts (ppb) of organic compounds. MASPEX has been selected for the NASA Europa Clipper mission and will sample any plumes and the surface-sputtered atmosphere to assess any evidence for habitability and life. MASPEX is capable of similar investigations targeted at other icy moons. Data may be forthcoming from direct sampling but also impact dissociation because of the high speed of some analytes. Impact dissociation is analogous to the dissociation provided by modern analytical pyrolysis methods. Radiolytic dissociation on the europan surface before or during the sputtering process can also induce fragmentation similar to pyrolysis. In this study, we have compiled pyrolysis mass spectrometry data from a variety of biological and nonbiological materials to demonstrate the ability of MASPEX to recognize habitability and detect life in any plumes and atmospheres of icy moons. Key Words: Europa-Icy moons-Life detection-Mass spectrometry-Organic matter. Astrobiology 18, 843-855.

The Fate of Lipid Biosignatures in a Mars-Analogue Sulfur Stream.

Past life on Mars will have generated organic remains that may be preserved in present day Mars rocks. The most recent period in the history of Mars that retained widespread surface waters was the late Noachian and early Hesperian and thus possessed the potential to sustain the most evolved and widely distributed martian life. Guidance for investigating late Noachian and early Hesperian rocks is provided by studies of analogous acidic and sulfur-rich environments on Earth. Here we report organic responses for an acid stream containing acidophilic organisms whose post-mortem remains are entombed in iron sulphates and iron oxides. We find that, if life was present in the Hesperian, martian organic records will comprise microbial lipids. Lipids are a potential sizeable reservoir of fossil carbon on Mars, and can be used to distinguish between different domains of life. Concentrations of lipids, and particularly alkanoic or "fatty" acids, are highest in goethite layers that reflect high water-to-rock ratios and thus a greater potential for habitability. Goethite can dehydrate to hematite, which is widespread on Mars. Mars missions should seek to detect fatty acids or their diagenetic products in the oxides and hydroxides of iron associated with sulphur-rich environments.