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The Sample Analysis at Mars instrument stepped combustion experiment on a Yellowknife Bay mudstone at Gale crater, Mars revealed the presence of organic carbon of Martian and meteoritic origins. The combustion experiment was designed to access refractory organic carbon in Mars surface sediments by heating samples in the presence of oxygen to combust carbon to CO 2 . Four steps were performed, two at low temperatures (less than ∼550 °C) and two at high temperatures (up to ∼870 °C). More than 950 μg C/g was released at low temperatures (with an isotopic composition of δ 13 C = +1.5 ± 3.8‰) representing a minimum of 431 μg C/g indigenous organic and inorganic Martian carbon components. Above 550 °C, 273 ± 30 μg C/g was evolved as CO 2 and CO (with estimated δ 13 C = −32.9‰ to −10.1‰ for organic carbon). The source of high temperature organic carbon cannot be definitively confirmed by isotopic composition, which is consistent with macromolecular organic carbon of igneous origin, meteoritic infall, or diagenetically altered biomass, or a combination of these. If from allochthonous deposition, organic carbon could have supported both prebiotic organic chemistry and heterotrophic metabolism at Gale crater, Mars, at ∼3.5 Ga.

International audience; The Mars Organic Molecule Analyzer (MOMA) and Sample Analysis at Mars (SAM) instruments onboard the Exomars 2022 and Mars Science Laboratory rovers, respectively, are capable of organic matter detection and differentiating potentially biogenic from abiotic organics in martian samples. To identify organics, both these instruments utilize pyrolysis–gas chromatography coupled to mass spectrometry, and the thermochemolysis agent tetramethylammonium hydroxide (TMAH) is also used to increase organic volatility. However, the reactivity and efficiency of TMAH thermochemolysis are affected by the presence of calcium perchlorate on the martian surface. In this study, we determined the products of TMAH pyrolysis in the presence and absence of calcium perchlorate at different heating rates (flash pyrolysis and SAM-like ramp pyrolysis with a 35°C·min−1 heating rate). The decomposition mechanism of TMAH pyrolysis in the presence of calcium perchlorate was studied by using stepped pyrolysis. Moreover, the effect of calcium perchlorate (at Mars-relevant concentrations) on the recovery rate of fatty acids with TMAH thermochemolysis was studied. Results demonstrate that flash pyrolysis yields more diversity and greater abundances of TMAH thermochemolysis products than does the SAM-like ramp pyrolysis method. There is no obvious effect of calcium perchlorate on TMAH degradation when the [ClO4−] is lower than 10 weight percent (wt %). Most importantly, the presence of calcium perchlorate does not significantly impact the recovery rate of fatty acids with TMAH thermochemolysis under laboratory conditions, which is promising for the detection of fatty acids via TMAH thermochemolysis with the SAM and MOMA instruments on Mars.

Significance Carbon isotopic analysis is among the most pervasive geochemical approaches because the fractionation of carbon isotopes produces a natural tracer of biological and chemical processes. Rover-based carbon isotopic analyses of sedimentary rocks on Mars have the potential to reveal modes of Martian carbon cycling. We report carbon isotopic values of the methane released during pyrolysis of samples obtained at Gale crater. The values show remarkable variation indicating different origins for the carbon evolved from different samples. Samples from multiple locations within Gale crater evolved methane with highly fractionated carbon isotopes. We suggest three routes by which highly fractionated carbon could be deposited on Mars, with each suggesting that Martian carbon cycling is quite distinct from that of the present Earth., Obtaining carbon isotopic information for organic carbon from Martian sediments has long been a goal of planetary science, as it has the potential to elucidate the origin of such carbon and aspects of Martian carbon cycling. Carbon isotopic values (δ13CVPDB) of the methane released during pyrolysis of 24 powder samples at Gale crater, Mars, show a high degree of variation (−137 ± 8‰ to +22 ± 10‰) when measured by the tunable laser spectrometer portion of the Sample Analysis at Mars instrument suite during evolved gas analysis. Included in these data are 10 measured δ13C values less than −70‰ found for six different sampling locations, all potentially associated with a possible paleosurface. There are multiple plausible explanations for the anomalously depleted 13C observed in evolved methane, but no single explanation can be accepted without further research. Three possible explanations are the photolysis of biological methane released from the subsurface, photoreduction of atmospheric CO2, and deposition of cosmic dust during passage through a galactic molecular cloud. All three of these scenarios are unconventional, unlike processes common on Earth.

A key science priority for planetary exploration is to search for signs of life in our Solar System. Life-detection mission concepts aim to assess whether or not biomolecular signatures of life are present, which requires highly sensitive instrumentation. This introduces greater risk of false positives, and perhaps false negatives. Stringent science-derived contamination requirements for achieving science measurements on life-detection missions necessitate mitigation approaches that minimize, protect from, and prevent science-relevant contamination of critical surfaces of the science payload and provide high confidence to life-detection determinations. To this end, we report on technology advances that focus on understanding contamination transfer from pre-launch processing to end of mission using high-fidelity physics in the form of computational fluid dynamics and sorption physics for monolayer adsorption/desorption, and on developing a new full-spacecraft bio-molecular barrier design that restricts contamination of the spacecraft and instruments by the launch vehicle hardware. The bio-molecular barrier isolates the spacecraft from biological, molecular, and particulate contamination from the external environment. Models were used to evaluate contamination transport for a designs reference mission that utilizes the barrier. Results of the modeling verify the efficacy of the barrier and an in-cruise decontamination activity. Overall mission contamination tracking from launch to science operations demonstrated exceptionally low probability on contamination impacting science measurements, meeting the stringent contamination requirements of femtomolar levels of compounds. These advances will enable planetary missions that aim to detect and identify signatures of life in our Solar System.

International audience; N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA), mixed with the solvent N,N-dimethylformamide (DMF), is used as a derivatizing reagent by the Sample Analysis at Mars (SAM) experiment onboard NASA's Curiosity rover and will soon be utilized by the Mars Organic Molecule Analyzer experiment onboard the ESA/Roscosmos Rosalind Franklin rover. The pyrolysis products of MTBSTFA, DMF, and the MTBSTFA/DMF mixtures, obtained at different temperatures, were analyzed. Two different pyrolysis modes were studied, flash pyrolysis and ramp pyrolysis (35°C/min), to evaluate the potential influence of the sample heating speed on the production of products in space chromatographs. The effect of the presence of calcium perchlorate on the pyrolysis products of MTBSTFA/DMF was also studied to ascertain the potential effect of perchlorate species known to be present at the martian surface. The results show that MTBSTFA/DMF derivatization should be applied below 300°C when using flash pyrolysis, as numerous products of MTBSTFA/DMF were formed at high pyrolysis temperatures. However, when an SAM-like ramp pyrolysis was applied, the final pyrolysis temperature did not appear to influence the degradation products of MTBSTFA/DMF. All products of MTBSTFA/DMF pyrolysis are listed in this article, providing a major database of products for the analysis of martian analog samples, meteorites, and the in situ analysis of martian rocks and soils. In addition, the presence of calcium perchlorate does not show any obvious effects on the pyrolysis of MTBSTFA/DMF: Only chloromethane and TBDMS-Cl (chloro-tertbutyldimethylsilane) were detected, whereas chlorobenzene and other chlorine-bearing compounds were not detected. However, other chlorine-bearing compounds were detected after pyrolysis of the Murchison meteorite in the presence of calcium perchlorate. This result reinforces previous suggestions that chloride-bearing compounds could be reaction products of martian samples and perchlorate.

Curiosity, the Mars Science Laboratory (MSL) rover, landed on Mars in August 2012 to investigate the ~3.5-billion-year-old (Ga) fluvio-lacustrine sedimentary deposits of Aeolis Mons (informally known as Mount Sharp) and the surrounding plains (Aeolis Palus) in Gale crater. After nearly nine years, Curiosity has traversed over 25 km, and the Chemistry and Mineralogy (CheMin) X-ray diffraction instrument on-board Curiosity has analyzed 30 drilled rock and three scooped soil samples to date. The principal strategic goal of the mission is to assess the habitability of Mars in its ancient past. Phyllosilicates are common in ancient Martian terrains dating to ~3.5–4 Ga and were detected from orbit in some of the lower strata of Mount Sharp. Phyllosilicates on Earth are important for harboring and preserving organics. On Mars, phyllosilicates are significant for exploration as they are hypothesized to be a marker for potential habitable environments. CheMin data demonstrate that ancient fluvio-lacustrine rocks in Gale crater contain up to ~35 wt. % phyllosilicates. Phyllosilicates are key indicators of past fluid–rock interactions, and variation in the structure and composition of phyllosilicates in Gale crater suggest changes in past aqueous environments that may have been habitable to microbial life with a variety of possible energy sources.

Enceladus’s long-lived plume of ice grains and water vapor makes accessing oceanic material readily achievable from orbit (around Saturn or Enceladus) and from the moon’s surface. In preparation for the National Academies of Sciences, Engineering and Medicine 2023–2032 Planetary Science and Astrobiology Decadal Survey, we investigated four architectures capable of collecting and analyzing plume material from orbit and/or on the surface to address the most pressing questions at Enceladus: Is the subsurface ocean inhabited? Why, or why not? Trades specific to these four architectures were studied to allow an evaluation of the science return with respect to investment. The team found that Orbilander, a mission concept that would first orbit and then land on Enceladus, represented the best balance. Orbilander was thus studied at a higher fidelity, including a more detailed science operations plan during both orbital and landed phases, landing site characterization and selection analyses, and landing procedures. The Orbilander mission concept demonstrates that scientifically compelling but resource-conscious Flagship-class missions can be executed in the next decade to search for life at Enceladus.

The plume of Enceladus provides access to fresh material from a habitable, subsurface ocean. We summarize in this white paper the evidence for Enceladus’ ocean and its habitability, identify constraints and outstanding questions on the detectability of life within Enceladus, and recommend a return to Enceladus beginning in the coming decade.

A proof-of-concept, compact, portable Fourier Ptychographic Microscope (FPM) to perform wide field-of-view, high spatial resolution imaging (

International audience; Tetramethylammonium hydroxide (TMAH) is one of the most popular methylation reagents that have been increasingly used for the detection of organic compounds within a wide range of samples, such as soil, coal, lacquer, lignin, polymers and for in situ analysis of solid samples by space experiments. The analytical methods and instruments, experimental conditions, and the qualitative and quantitative analysis of organic compounds using TMAH thermochemolysis for the last 10 years were reviewed; additionally, the mechanism of TMAH thermochemolysis and TMAH degradation are overviewed herein. The objective of this paper is to give a broad view of the TMAH thermochemolysis analysis, to demonstrate how the technique can be used for the detection of organics on Mars and other planets, and to promote cooperation between different disciplines which may use thermochemolysis.

The Mars Science Laboratory mission investigated Vera Rubin ridge, which bears spectral indications of elevated amounts of hematite and has been hypothesized as having a complex diagenetic history. Martian samples, including three drilled samples from the ridge, were analyzed by the Sample Analysis at Mars instrument suite via evolved gas analysis-mass spectrometry (EGA-MS). Here, we report new EGA-MS data from Martian samples and describe laboratory analogue experiments. Analyses of laboratory analogues help determine the presence of reduced sulfur in Martian solid samples, which could have supported potential microbial life. We used evolved carbonyl sulfide (COS) and carbon disulfide (CS) to identify Martian samples likely to contain reduced sulfur by applying a quadratic discriminant analysis. While we report results for 24 Martian samples, we focus on Vera Rubin ridge samples and select others for comparison. Our results suggest the presence of reduced sulfur in the Jura member of Vera Rubin ridge, which can support various diagenetic history models, including, as discussed in this work, diagenetic alteration initiated by a mildly reducing, sulfite-containing groundwater., With funding from the Spanish government through the "María de Maeztu Unit of Excellence" accreditation (MDM-2017-0737)

International audience; Chromatographic analysis of the Cumberland mudstone in Gale crater by the Sample Analysis at Mars (SAM) instrument revealed the detection of two to three isomers of dichlorobenzene. Their individual concentrations were estimated to be in the 0.5–17 ppbw range relatively to the sample mass. We also report the first detection of trichloromethylpropane, and the confirmation of the detection of chlorobenzene previously reported. Supporting laboratory experiments excluded the SAM internal background as the source of those compounds, thus confirming the organic carbon and chlorine of the newly detected chlorohydrocarbons are indigenous to the mudstone sample. Laboratory experiments also demonstrated that the chlorohydrocarbons were mainly produced from chemical reactions occurring in the SAM ovens between organic molecules and oxychlorines contained in the sample. The results we obtained show that meteoritic organics and tested chemical species (a polycyclic aromatic hydrocarbon, an amino acid, and a carboxylic acid) were plausible organic precursors of the chlorinated aromatic molecules detected with SAM, thus suggesting that they could be among the organic molecules present in the mudstone. Results from this study coupled with previously reported detections of chlorinated aromatics (

Dryness is one of the main environmental challenges to microbial survival. Understanding the threshold of microbial tolerance to extreme dryness is relevant to better constrain the environmental limits of life on Earth and critically evaluate long-term habitability models of Mars. Biomolecular proxies for microbial adaptation and growth were measured in Mars-like hyperarid surface soils in the Atacama Desert that experience only a few millimeters of precipitation per decade, and in biologically active soils a few hundred kilometers away that experience two- to fivefold more precipitation. Diversity and abundance of lipids and other biomolecules decreased with increasing dryness. Cyclopropane fatty acids (CFAs), which are indicative of adaptive response to environmental stress and growth in bacteria, were only detected in the wetter surface soils. The ratio of trans to cis isomers of an unsaturated fatty acid, another bacterial stress indicator, decreased with increasingly dry conditions. Aspartic acid racemization ratios increased from 0.01 in the wetter soils to 0.1 in the driest soils, which is indicative of racemization rates comparable to de novo biosynthesis over long timescales (∼10,000 years). The content and integrity of stress proteins profiled by immunoassays were additional indicators that biomass in the driest soils is not recycled at significant levels. Together, our results point to minimal or no in situ microbial growth in the driest surface soils of the Atacama, and any metabolic activity is likely to be basal for cellular repair and maintenance only. Our data add to a growing body of evidence that the driest Atacama surface soils represent a threshold for long-term habitability (i.e., growth and reproduction). These results place constraints on the potential for extant life on the surface of Mars, which is 100-1000 times drier than the driest regions in the Atacama. Key Words: Atacama Desert-Dryness-Growth-Habitability-Biomarker-Mars. Astrobiology 18, 955-966.

Raman spectroscopy and laser induced breakdown spectroscopy (LIBS) are complementary techniques that together can provide a comprehensive characterization of geologic environments. For landed missions with constrained access to target materials on other planetary bodies, discerning signatures of life and habitability can be daunting, particularly where the preservation of organic compounds that contain the building blocks of life is limited. The main challenge facing any spectroscopy measurements of natural samples is the complicated spectra that often contain signatures for multiple components, particularly in rocks that are composed of several minerals with surfaces colonized by microbes. The goal of this study was to use the combination of Raman spectroscopy and LIBS to discern different environmental regimes based on the identification of minerals and biomolecules in rocks and sediments. Iceland is a terrestrial volcano-glacial location that offers a range of planetary analog environments, including volcanically active regions, extensive lava fields, geothermal springs, and large swaths of ice-covered terrain that are relevant to both rocky and icy planetary bodies. We combined portable VIS (532 nm) and NIR (785 nm) Raman spectroscopy, VIS micro-Raman spectroscopic mapping, and UV/VIS/NIR (200 – 1000 nm) and Mid-IR (5.6 – 10 μm, 1785 – 1000 cm−1) laser induced breakdown spectroscopy (LIBS) to characterize the mineral assemblages, hydrated components, and biomolecules in rock and sediment samples collected from three main sites in the volcanically active Kverkfjoll-Vatnajokull region of Iceland: basalt and basalt-hosted carbonate rind from Hveragil geothermal stream, volcanic sediments from the base of Vatnajokull glacier at Kverkfjoll, and lava from the nearby Holuhraun lava field. With our combination of techniques, we were able to identify major mineral polytypes typical for each sample set, as well as a large diversity of biomolecules typical for lichen communities across all samples. The anatase we observed using micro-Raman spectroscopic mapping of the lava compared with the volcanic sediment suggested different formation pathways: lava anatase formed authigenically, sediment anatase could have formed in association with microbial weathering. Mn-oxide, only detected in the carbonate samples, seems to have two possible formation pathways, either by fluvial or microbial weathering or both. Even with our ability to detect a wide diversity of biomolecules and minerals in all of the samples, there was not enough variation between each set to distinguish different environments based on the limited measurements done for this study.

The plume of Enceladus is unique in the solar system in providing direct access to fresh material from an extraterrestrial subsurface ocean. The Cassini Mission, though not specifically designed for it, was able to take advantage of the plume to conduct the best characterization to date of an extraterrestrial ocean. Evidence gathered from multiple instruments points to a global, subsurface liquid water ocean rich in salts and organic compounds, with water-rock interactions occurring presumably in hydrothermal systems at or below the moon’s sea floor. Meeting the criteria of “extended regions of liquid water, conditions favorable for the assembly of complex organic molecules, and energy source(s) to sustain metabolism,” the ocean of Enceladus can therefore be considered habitable. It is also the only confirmed place beyond the Earth where we can easily sample fresh material from a demonstrably habitable environment without the complications of digging or drilling. The next step is to investigate whether Enceladus’ ocean is actually inhabited. Here, we summarize the evidence for Enceladus’ ocean and its habitability, identify constraints and outstanding questions on the detectability of life within its ocean, and recommend a return to Enceladus with a dedicated search-for-life mission (or missions).

The Sample Analysis at Mars (SAM) instrument suite of the Mars Science Laboratory (MSL) Curiosity rover is equipped to analyze both martian atmospheric gases and volatiles released by pyrolysis of solid surface materials, with target measurements including chemical and isotopic composition (Mahaffy et al., 2012). To facilitate assessment of instrument performance and validation of results obtained on Mars, SAM houses a calibration cell containing CO2, Ar, N2, Xe, and several fluorinated hydrocarbon compounds (Franz et al., 2014; Mahaffy et al., 2012). This report describes the first two experiments utilizing this calibration cell on Mars and gives results from analysis of data acquired with the SAM Quadrupole Mass Spectrometer (QMS). These data support the accuracy of isotope ratios obtained with the QMS (Conrad et al., 2016; Mahaffy et al., 2013) and provide ground-truth for reassessment of analytical constants required for atmospheric measurements, which were reported in previous contributions (Franz et al., 2015, 2014). The most significant implication of the QMS data involves reinterpretation of pre-launch contamination previously believed to affect only CO abundance measurements (Franz et al., 2015) to affect N2 abundances, as well. The corresponding adjustment to the N2 calibration constant presented here brings the atmospheric volume mixing ratios for Ar and N2 retrieved by SAM into closer agreement with those reported by the Viking mission (Owen et al., 1977; Oyama and Berdahl, 1977).

The Sample Analysis at Mars (SAM) experiment on the National Aeronautics and Space Administration Curiosity rover seeks evidence of organic compounds on the surface of Mars. Since the beginning of the mission, various organic molecules have been detected and identified. While several have been demonstrated to be indigenous to the Martian soil and rocks analyzed, others appear to have been produced from sources internal to the experiment. The objective of this study is to build an exhaustive molecular database to support the interpretation of SAM results by identifying all the chemical species produced from Tenax® adsorbents, by determining (1) the thermal degradation by‐products of Tenax®, (2) the effect of Tenax® conditioning on the formation of Tenax® by‐products, (3) the impact of MTBSTFA or a mixture of MTBSTFA and DMF on Tenax® decomposition, and (4) the reaction between Tenax® and calcium perchlorate. Our results indicate that the by‐products of the SAM trap are due to the impact of trap heating, the impact of the derivatization reagent (MTBSTFA) and the presence of perchlorate in Martian soil. Some of these by‐products are observed in the SAM gas chromatograph mass spectrometer data from Mars.

International audience; Kenig et al. comment on our 2015 reporting of laboratory analog experiments aimed at testing the stability of the hydrocarbon trap material used in the Sample Analysis on Mars (SAM) instrument on board the Curiosity Rover operating in Gale Crater on Mars. They propose chemical structures for some decomposition products of the Tenax TA polymer when it is exposed at high temperatures to the Cl2 and O2 gases formed by the thermal decomposition of perchlorate. Further, Kenig et al. propose that these decomposition products accumulate and then react further in cooler downstream sections of the SAM analytical pipeline to produce the chlorobenzene that was detected in the Cumberland mudstone of Gale Crater. However, numerous experiments conducted in the laboratory show that Tenax TA decomposition products only appear after repeated exposure to much higher levels of Cl2 and O2 than those seen by the flight instrument. Moreover, the sequence of chlorobenzene detections during gas chromatography‐mass spectrometry experiments conducted on Mars cannot be explained by Tenax TA decomposition, nor can the detection of chlorobenzene in Evolved Gas Analysis experiments that involve pathways devoid of Tenax TA. Kenig et al. are incorrect in their assertion that Tenax TA decomposition products can account for the chlorobenzene detected on Mars by SAM.

The Mars Curiosity rover carries a diverse instrument payload to characterize habitable environments in the sedimentary layers of Aeolis Mons. One of these instruments is Sample Analysis at Mars (SAM), which contains a mass spectrometer that is capable of detecting organic compounds via pyrolysis gas chromatography mass spectrometry (py-GC-MS). To identify polar organic molecules, the SAM instrument carries the thermochemolysis reagent tetramethylammonium hydroxide (TMAH) in methanol (hereafter referred to as TMAH). TMAH can liberate fatty acids bound in macromolecules or chemically bound monomers associated with mineral phases and make these organics detectable via gas chromatography mass spectrometry (GC-MS) by methylation. Fatty acids, a type of carboxylic acid that contains a carboxyl functional group, are of particular interest given their presence in both biotic and abiotic materials. This work represents the first analyses of a suite of Mars-analog samples using the TMAH experiment under select SAM-like conditions. Samples analyzed include iron oxyhydroxides and iron oxyhydroxysulfates, a mixture of iron oxides/oxyhydroxides and clays, iron sulfide, siliceous sinter, carbonates, and shale. The TMAH experiments produced detectable signals under SAM-like pyrolysis conditions when organics were present either at high concentrations or in geologically modern systems. Although only a few analog samples exhibited a high abundance and variety of fatty acid methyl esters (FAMEs), FAMEs were detected in the majority of analog samples tested. When utilized, the TMAH thermochemolysis experiment on SAM could be an opportunity to detect organic molecules bound in macromolecules on Mars. The detection of a FAME profile is of great astrobiological interest, as it could provide information regarding the source of martian organic material detected by SAM.

Molecular hydrogen (H2) from volcanic emissions is suggested to warm the Martian surface when carbon dioxide (CO2) levels dropped from the Noachian (4100 to 3700 Myr) to the Hesperian (3700 to 3000 Myr). Its presence is expected to shift the conversion of molecular nitrogen (N2) into different forms of fixed nitrogen (N). Here we present experimental data and theoretical calculations that investigate the efficiency of nitrogen fixation by bolide impacts in CO2‐N2 atmospheres with or without H2. Surprisingly, nitric oxide (NO) was produced more efficiently in 20% H2 in spite of being a reducing agent and not likely to increase the rate of nitrogen oxidation. Nevertheless, its presence led to a faster cooling of the shock wave raising the freeze‐out temperature of NO resulting in an enhanced yield. We estimate that the nitrogen fixation rate by bolide impacts varied from 7 × 10−4 to 2 × 10−3 g N·Myr−1·cm−2 and could imply fluvial concentration to explain the nitrogen (1.4 ± 0.7 g N·Myr−1·cm−2) detected as nitrite (NO2 −) and nitrate (NO3 −) by Curiosity at Yellowknife Bay. One possible explanation is that the nitrogen detected in the lacustrine sediments at Gale was deposited entirely on the crater's surface and was subsequently dissolved and transported by superficial and ground waters to the lake during favorable wet climatic conditions. The nitrogen content sharply decreases in younger sediments of the Murray formation suggesting a decline of H2 in the atmosphere and the rise of oxidizing conditions causing a shortage in the supply to putative microbial life., We acknowledge the NASA Mars Science Laboratory Program, Centre National d'Études Spatiales, the Universidad Nacional Autónoma de México (PAPIIT IN109416, IN111619, and PAPIME PE103216), and the Consejo Nacional de Ciencia y Tecnología de México (CONACyT 220626) for their support.

The Sample Analysis at Mars (SAM) instrument on the Curiosity rover has detected evidence of oxychlorine compounds (i.e., perchlorates and chlorates) in Gale crater, which has implications for past habitability, diagenesis, aqueous processes, interpretation of in situ organic analyses, understanding the martian chlorine cycle, and hazards and resources for future human exploration. Pure oxychlorines and mixtures of oxychlorines with Mars-analog phases have been analyzed for their oxygen (O ) and hydrogen chloride (HCl) releases on SAM laboratory analog instruments in order to constrain which phases are present in Gale crater. These studies demonstrated that oxychlorines evolve O releases with peaks between ~200 and 600 C, although the thermal decomposition temperatures and the amount of evolved O decrease when iron phases are present in the sample. Mg and Fe oxychlorines decompose into oxides and release HCl between ~200 and 542 C. Ca, Na, and K oxychlorines thermally decompose into chlorides and do not evolve HCl by themselves. However, the chlorides (original or from oxychlorine decomposition) can react with water-evolving phases (e.g., phyllosilicates) in the sample and evolve HCl within the temperature range of SAM (, The research reviewed in this paper was funded by the Mars Science Laboratory (MSL) project office. M.-P.Z. acknowledges funding from the Ministerio de Ciencia e Innovación (ref. PID2019-104205GB-C21).

The detection of chlorinated organic compounds in near-surface sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite aboard the Mars Science Laboratory Curiosity rover represents an important step toward characterizing habitable environments on Mars. However, this discovery also raises questions about the identity and source of their precursor compounds and the processes by which they become chlorinated. Here we present the results of analog experiments, conducted under conditions similar to SAM gas chromatography-mass spectrometry analyses, in which we pyrolyzed potential precursor compounds in the presence of various Cl salts and Fe oxides that have been identified in Martian sediments. While chloromethanes could not be unambiguously identified, 1,2-dichloropropane (1,2-DCP), which is one of the chlorinated compounds identified in SAM data, is formed from the chlorination of aliphatic precursors. Additionally, propanol produced more 1,2-DCP than nonfunctionalized aliphatics such as propane or hexanes. Chlorinated benzenes ranging from chlorobenzene to hexachlorobenzene were identified in experiments with benzene carboxylic acids but not with benzene or toluene. Lastly, the distribution of chlorinated benzenes depended on both the substrate species and the nature and concentration of the Cl salt. Ca and Mg perchlorate, both of which release O2 in addition to Cl2 and HCl upon pyrolysis, formed less chlorobenzene relative to the sum of all chlorinated benzenes than in experiments with ferric chloride. FeCl3, a Lewis acid, catalyzes chlorination but does not aid combustion. Accordingly, both the precursor chemistry and sample mineralogy exert important controls on the distribution of chlorinated organics.

Measuring martian organics and methane The Curiosity rover has been sampling on Mars for the past 5 years (see the Perspective by ten Kate). Eigenbrode et al. used two instruments in the SAM (Sample Analysis at Mars) suite to catch traces of complex organics preserved in 3-billion-year-old sediments. Heating the sediments released an array of organics and volatiles reminiscent of organic-rich sedimentary rock found on Earth. Most methane on Earth is produced by biological sources, but numerous abiotic processes have been proposed to explain martian methane. Webster et al. report atmospheric measurements of methane covering 3 martian years and found that the background level varies with the local seasons. The seasonal variation provides an important clue for determining the origin of martian methane. Science , this issue p. 1096 , p. 1093 ; see also p. 1068

International audience; The Sample Analysis at Mars (SAM) on the Curiosity rover analyzed the major volatile content of four eolian samples at three locations in Gale crater. The Rocknest sample was taken from an inactive sand shadow with a significant component of dust‐sized grains, while Gobabeb and Ogunquit Beach samples were taken from different locations in the Bagnold Dune field and had dust‐free, fine sand sized grains. All eolian samples possessed more oxychlorine, carbon, and nitrate relative to sedimentary materials in Gale crater. Evolved CO2 above 450°C was consistent with ~0.7 and ~0.4 wt. % carbonate in the Bagnold Dunes and Rocknest materials, respectively, with a regional source inside Gale crater. The fine‐grained phase of Rocknest was enriched in adsorbed water and perhaps in Fe sulfate and Fe nitrate/nitrite compared to coarser Bagnold materials, and was estimated to contain up to ~0.1 wt. % of organic carbon.

Variable levels of methane in the martian atmosphere have eluded explanation partly because the measurements are not repeatable in time or location.We report in situ measurements at Gale crater made over a 5-year period by the Tunable Laser Spectrometer on the Curiosity rover.The background levels of methane have a mean value 0.41 ± 0.16 parts per billion by volume (ppbv) (95% confidence interval) and exhibit a strong, repeatable seasonal variation (0.24 to 0.65 ppbv).This variation is greater than that predicted from either ultraviolet degradation of impact-delivered organics on the surface or from the annual surface pressure cycle.The large seasonal variation in the background and occurrences of higher temporary spikes (∼7 ppbv) are consistent with small localized sources of methane released from martian surface or subsurface reservoirs., The authors thank the reviewers for constructive comments that greatly improved the manuscript. The research described here was carried out in part at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration (NASA). Funding: Funding from NASA’s Planetary Science Division is acknowledged by authors C.R.W., P.R.M., S.K.A., G.J.F., C.M., C.P.M., M.H.W., M.G.T., A.S., D.A., C.H.H., R.V.G., A.P., J.L.E., D.P.G., J.C.P., D.K., L.E.C., J.P.-G., S.C.R.R., M.D.S., D.M.H., M.L., J.C., R.W.Z., and A.R.V. R.N.-G. acknowledges funding from the National Autonomous University of Mexico and Consejo Nacional de Ciencia y Tecnología. J.E.M. and C.L.S. acknowledge funding from the Canadian Space Agency MSL participating scientist program. S.P.Sc. acknowledges funding from the UK Space Agency. A.-M.H. acknowledges funding from the Finnish Academy under grant 310509. J.P.-G. acknowledges funding from the Spanish Ministry of Economy and Competitiveness under contract ESP2016-79612-C3-1-R. Author contributions: C.R.W. and P.R.M. performed TLS-SAM instrument design, build, and testing (IDBT); surface operations (SO); test-bed activities (TBA); data analysis (DA); data correlations (DC); and science interpretation (SI). G.J.F. and C.M. performed IDBT, SO, TBA, and DA. S.K.A., J.E.M., C.P.M., C.L.S., A.S., D.A., B.S., P.J.C., C.F., P.-Y.M., R.V.G., C.H.H., A.P., J.L.E., D.P.G., S.P.Sa., and R.W.Z. performed SI. J.C. and A.R.V. performed SO. J.C.P., D.K., and L.E.C. performed IDBT. G.M., J.M.-T., J.G.-E., M.-P.Z., M.G.T., S.P.Sc., R.N.-G., A.V.-R., H.K., D.V.-M., M.D.S., A.-M.H., M.G., D.M.H., and M.L. performed DC. J.P.-G. and S.C.R.R. performed DC and SI. Competing interests: No potential conflicts of interest exist for any of the listed authors. Data and materials availability: The data described in this paper are publicly available from NASA’s Planetary Data System (PDS) under an arrangement with the Mars Science Laboratory (MSL) project at http://pds-geosciences.wustl.edu/missions/msl/sam. htm, under the run numbers given in table S2.

The Sample Analysis at Mars (SAM) instrument suite aboard Curiosity has detected chlorinated organic compounds in Martian sediment samples. The chlorine in these molecules is thought to derive from oxychlorine salts in Martian sediments, but the carbon source remains under investigation. To constrain possible carbon sources, we investigated how the composition and concentration of oxychlorine phases in solid samples affect organic molecules released from the Tenax traps on board SAM. We created Mars analogue soils by spiking olivine sand with calcium perchlorate, magnesium perchlorate, or ferric iron chloride and analyzed the volatiles generated during pyrolysis–gas chromatography–mass spectrometry using commercial instruments operated under SAM-like conditions, with and without a Tenax trap. Benzoic acid, phthalic anhydride, high molecular weight aromatics, and chlorobenzenes are produced from the trap in response to volatiles released during Cl salt pyrolysis. Changes in composition or concentration of oxychlorine phases between samples could thus potentially produce an increase in chlorobenzene, as observed between samples from Rocknest and Cumberland. However, in our experiments benzoic acid, phthalic anhydride, and chlorobenzenes increase in proportion with the amount of HCl sent to the trap, while in Cumberland samples the chlorobenzene increase showed no corresponding increase in HCl. Based on our experiments, the Tenax trap is a possible source of the traces of chlorobenzene observed at Rocknest, John Klein, and Confidence Hills. The order-of-magnitude higher chlorobenzene abundances observed at Cumberland cannot be attributed to the Tenax trap. Furthermore, we found no evidence of significant trap degradation after hundreds of experiments with Cl salt-containing analogue soils.

© 2015 by Walter de Gruyter. The Mars Science Laboratory (MSL) rover Curiosity has documented a section of fluvio-lacustrine strata at Yellowknife Bay (YKB), an embayment on the floor of Gale crater, approximately 500 m east of the Bradbury landing site. X-ray diffraction (XRD) data and evolved gas analysis (EGA) data from the CheMin and SAM instruments show that two powdered mudstone samples (named John Klein and Cumberland) drilled from the Sheepbed member of this succession contain up to ∼20 wt% clay minerals. A trioctahedral smectite, likely a ferrian saponite, is the only clay mineral phase detected in these samples. Smectites of the two samples exhibit different 001 spacing under the low partial pressures of H2O inside the CheMin instrument (relative humidity 2+ in olivine to Fe3+ in magnetite, and perhaps in smectites provided a potential energy source for organisms.

The Mars Science Laboratory Curiosity rover has been traversing strata at the base of Aeolis Mons (informally known as Mount Sharp) since September 2014. The Murray formation makes up the lowest exposed strata of the Mount Sharp group and is composed primarily of finely laminated lacustrine mudstone intercalated with rare crossbedded sandstone that is prodeltaic or fluvial in origin. We report on the first three drilled samples from the Murray formation, measured in the Pahrump Hills section. Rietveld refinements and FULLPAT full pattern fitting analyses of X-ray diffraction patterns measured by the MSL CheMin instrument provide mineral abundances, refined unit-cell parameters for major phases giving crystal chemistry, and abundances of X-ray amorphous materials. Our results from the samples measured at the Pahrump Hills and previously published results on the Buckskin sample measured from the Marias Pass section stratigraphically above Pahrump Hills show stratigraphic variations in the mineralogy; phyllosilicates, hematite, jarosite, and pyroxene are most abundant at the base of the Pahrump Hills, and crystalline and amorphous silica and magnetite become prevalent higher in the succession. Some trace element abundances measured by APXS also show stratigraphic trends; Zn and Ni are highly enriched with respect to average Mars crust at the base of the Pahrump Hills (by 7.7 and 3.7 times, respectively), and gradually decrease in abundance in stratigraphically higher regions near Marias Pass, where they are depleted with respect to average Mars crust (by more than an order of magnitude in some targets). The Mn stratigraphic trend is analogous to Zn and Ni, however, Mn abundances are close to those of average Mars crust at the base of Pahrump Hills, rather than being enriched, and Mn becomes increasingly depleted moving upsection. Minerals at the base of the Pahrump Hills, in particular jarosite and hematite, as well as enrichments in Zn, Ni, and Mn, are products of acid-sulfate alteration on Earth. We hypothesize that multiple influxes of mildly to moderately acidic pore fluids resulted in diagenesis of the Murray formation and the observed mineralogical and geochemical variations. The preservation of some minerals that are highly susceptible to dissolution at low pH (e.g., mafic minerals and fluorapatite) suggests that acidic events were not long-lived and that fluids may not have been extremely acidic (pH>2pH>2). Alternatively, the observed mineralogical variations within the succession may be explained by deposition in lake waters with variable Eh and/or pH, where the lowermost sediments were deposited in an oxidizing, perhaps acidic lake setting, and sediments deposited in the upper Pahrump Hills and Marias Pass were deposited lake waters with lower Eh and higher pH.

Approximately 3.5-Ga sedimentary rocks surveyed by the Mars Science Laboratory rover in Gale Crater, Mars, contain secondary mineral phases indicating aqueous alteration and release of cations from mafic minerals during sediment deposition in lakes. However, carbonate phases are not detected, and our model calculations indicate atmospheric CO2 levels at the time of sediment deposition 10s to 100s of times lower than those required by climate models to warm early Mars enough to maintain surficial water. Our results offer a ground-based reference point for the evolution of martian atmospheric CO2 and imply that other mechanisms of warming Hesperian Mars, or processes that allowed for confined hydrological activity under cold conditions, must be sought.

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from ~450 to 800°C during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2 (~3–22 µmol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (~41–109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (~1–5 nmol) and CS2 (~0.2–1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

The Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) rover Curiosity detected evolved gases during thermal analysis of soil samples from the Rocknest aeolian deposit in Gale Crater. Major species detected (in order of decreasing molar abundance) were H₂O, SO₂, CO₂, and O₂, all at the µmol level, with HCl, H₂S, NH₃, NO, and HCN present at the tens to hundreds of nmol level. We compute weight % numbers for the major gases evolved by assuming a likely source and calculate abundances between 0.5 and 3 wt.%. The evolution of these gases implies the presence of both oxidized (perchlorates) and reduced (sulfides or H-bearing) species as well as minerals formed under alkaline (carbonates) and possibly acidic (sulfates) conditions. Possible source phases in the Rocknest material are hydrated amorphous material, minor clay minerals, and hydrated perchlorate salts (all potential H₂O sources), carbonates (CO₂), perchlorates (O₂ and HCl), and potential N-bearing materials (e.g., Martian nitrates, terrestrial or Martian nitrogenated organics, ammonium salts) that evolve NH₃, NO, and/or HCN. We conclude that Rocknest materials are a physical mixture in chemical disequilibrium, consistent with aeolian mixing, and that although weathering is not extensive, it may be ongoing even under current Martian surface conditions.

Of water and methane on Mars The Curiosity rover has been collecting data for the past 2 years, since its delivery to Mars (see the Perspective by Zahnle). Many studies now suggest that many millions of years ago, Mars was warmer and wetter than it is today. But those conditions required an atmosphere that seems to have vanished. Using the Curiosity rover, Mahaffy et al. measured the ratio of deuterium to hydrogen in clays that were formed 3.0 to 3.7 billion years ago. Hydrogen escapes more readily than deuterium, so this ratio offers a snapshot measure of the ancient atmosphere that can help constrain when and how it disappeared. Most methane on Earth has a biological origin, so planetary scientists have keenly pursued its detection in the martian atmosphere as well. Now, Webster et al. have precisely confirmed the presence of methane in the martian atmosphere with the instruments aboard the Curiosity rover at Gale crater. Science , this issue p. 412 , p. 415 ; see also p. 370

[1] A single scoop of the Rocknest aeolian deposit was sieved (

Our understanding of long-term organic matter preservation comes mostly from studies in aquatic systems. In contrast, taphonomic processes in extremely dry environments are relatively understudied and are poorly understood. We investigated the accumulation and preservation of lipid biomarkers in hyperarid soils in the Yungay region of the Atacama Desert. Lipids from seven soil horizons in a 2.5 m vertical profile were extracted and analyzed using GC-MS and LC-MS. Diagnostic functionalized lipids and geolipids were detected and increased in abundance and diversity with depth. Deeper clay units contain fossil organic matter (radiocarbon dead) that has been protected from rainwater since the onset of hyperaridity. We show that these clay units contain lipids in an excellent state of structural preservation with functional groups and unsaturated bonds in carbon chains. This indicates that minimal degradation of lipids has occurred in these soils since the time of their deposition between >40,000 and 2 million years ago. The exceptional structural preservation of biomarkers is likely due to the long-term hyperaridity that has minimized microbial and enzymatic activity, a taphonomic process we term xeropreservation (i.e. preservation by drying). The degree of biomarker preservation allowed us to reconstruct major changes in ecology in the Yungay region that reflect a shift in hydrological regime from wet to dry since the early Quaternary. Our results suggest that hyperarid environments, which comprise 7.5% of the continental landmass, could represent a rich and relatively unexplored source of paleobiological information on Earth.

Mars Science Laboratory’s Curiosity rover carries a set of five external verification standards in hermetically sealed containers that can be sampled as would be a Martian rock, by drilling and then portioning into the solid sample inlet of the Sample Analysis at Mars (SAM) suite. Each organic check material (OCM) canister contains a porous ceramic solid, which has been doped with a fluorinated hydrocarbon marker that can be detected by SAM. The purpose of the OCM is to serve as a verification tool for the organic cleanliness of those parts of the sample chain that cannot be cleaned other than by dilution, i.e., repeated sampling of Martian rock. SAM possesses internal calibrants for verification of both its performance and its internal cleanliness, and the OCM is not used for that purpose. Each OCM unit is designed for one use only, and the choice to do so will be made by the project science group (PSG).

The largest excursion in kerogen δ13C and bulk/mineral δ56Fe values yet measured in the ancient rock record occurs in rocks of ∼ 2.7 to 2.5 Ga age. New Fe isotope data integrated with previously collected C isotope data on the same samples document the metabolic diversity of microbial communities in the Neoarchean Hamersley Province of the Pilbara Craton in Western Australia. Samples of shales, carbonates, and mixed carbonate/shale lithologies were collected from three drill cores; two cores from the depocenter of the province and one from the margin. Shallow-water clastic/carbonate rocks deposited in the center of the province (Tumbiana Formation) record kerogen δ13C values that indicate C cycling by various anaerobic or aerobic methane pathways, but the restricted range in δ56Fe values indicates little or no Fe redox cycling. Deep-water sediments deposited contemporaneously in both parts of the Hamersley Province (Jeerinah Formation) record slightly positive δ56Fe values in the relatively shallower and suboxic margin, but strongly negative δ56Fe values in the deeper euxinic depocenter of the province, a pattern consistent with Fe cycling via a basin Fe shuttle, driven by bacterial dissimilatory iron reduction (DIR). Kerogen δ13C values from these units indicate coupling of microbial Fe cycling to aerobic methanotrophy or anaerobic oxidation of methane. Younger black shales, intercalated with iron formation (Marra Mamba Iron Formation) in the depocenter, record a shift to near-zero δ56Fe values reflecting an Fe budget dominated by hydrothermal and clastic sources. However, time-equivalent, Fe-rich carbonate/shale lithologies deposited on the margin of the province (Carawine Dolomite) have δ56Fe values that steadily decrease from near zero to strongly negative values. These relatively Fe-rich carbonates may reflect a carbonate trap of a DIR-driven Fe shuttle, similar to the sulfidic trap in the euxinic portion of the Jeerinah Formation. In contrast, younger shallow-water carbonates deposited by turbidity currents in relatively deep water in the center of the province (Wittenoom Formation), have δ56Fe values that correlate with Fe concentrations, a pattern that indicates Fe cycling by Rayleigh fractionation through precipitation of iron oxides from aqueous ferrous iron.