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Miller et al. [2015, https://doi.org/10.1002/2015JE004825] described the result of experiments testing the potential of Tenax TA, a polymer used on Sample Analysis at Mars (SAM), as a source of chlorinated benzene. Miller et al. [2015] conclude that the amount of chlorobenzene produced is low and that Tenax TA cannot be the source of the chlorobenzene observed on Mars by SAM. Miller et al. [2015] did not provide the identification of two unknown compounds produced during these pyrolysis experiments, though their abundance is orders of magnitude higher than that of chlorobenzene. Here, we tentatively identify these compounds based on the mass spectra provided by Miller et al. [2015], the most abundant of which is a chlorinated monomer of Tenax TA. This chlorinated monomer is likely to accumulate in the hydrocarbon Tenax trap and in the transfer line between the trap and the mass spectrometer. Further breakdown of these compounds could lead the high background of chlorobenzene observed on Mars.

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.

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.

A strong, repeatable seasonal cycle in the background methane mixing ratio has been observed at the Gale Crater landing site of the Mars Science Laboratory rover with the Tunable Laser Spectrometer of the Sample Analysis at Mars instrument. However, as of yet, no physical process has been proposed that can explain both the timing and amplitude of the observations. Here we show that a one-dimensional numerical model considering adsorption onto and diffusion through the regolith can reproduce the variation, including a phase lag, if the regolith is impregnated with methane from a prior plume or supplied from below by microseepage. Combining the model results with geological constraints, we estimate that the amount of microseepage at Gale is at most 3 × 10−5 tonnes km−2 yr−1. Gale’s unique dynamical environment makes such seeps easier to detect in surface sampling measurements. Over most of the Martian surface, atmospheric mixing is stronger or atmospheric transport more effective, and we expect the amplitude of the seasonal cycle to be smaller for the same strength of seep. The seasonal cycle in the methane mixing ratio observed at Gale Crater on Mars can be explained by adsorption onto and diffusion through the regolith, suggests a one-dimensional numerical model with geological constraints.

In August 2015, the Curiosity Mars rover discovered tridymite, a high‐temperature silica polymorph, in Gale crater. The existing model for its occurrence suggests erosion and detrital sedimentation from silicic volcanic rocks in the crater rim or central peak. The chemistry and mineralogy of the tridymite‐bearing rocks, however, are not consistent with silicic volcanic material. Using data from Curiosity, including chemical composition from the Alpha Particle X‐ray Spectrometer, mineralogy from the CheMin instrument, and evolved gas and isotopic analyses from the Sample Analysis at Mars instrument, we show that the tridymite‐bearing rocks exhibit similar chemical patterns with silica‐rich alteration halos which crosscut the stratigraphy. We infer that the tridymite formed in‐place through hydrothermal processes and show additional chemical and mineralogical results from Gale crater consistent with hydrothermal activity occurring after sediment deposition and lithification.

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 Mars Science Laboratory (MSL) Curiosity rover is exploring the Murray formation, a sequence of heterolithic mudstones and sandstones recording fluvial deltaic and lake deposits that comprise over 350 m of sedimentary strata within Gale crater. We examine >4,500 Murray formation bedrock points, employing recent laboratory calibrations for ChemCam laser‐induced breakdown spectroscopy H measurements at millimeter scale. Bedrock in the Murray formation has an interquartile range of 2.3–3.1 wt.% H2O, similar to measurements using the Dynamic Albedo of Neutrons and Sample Analysis at Mars instruments. However, specific stratigraphic intervals include high H targets (6–18 wt.% H2O) correlated with Si, Mg, Ca, Mn, or Fe, indicating units with opal, hydrated Mg sulfates, hydrated Ca sulfates, Mn‐enriched units, and akageneite or other iron oxyhydroxides, respectively. One stratigraphic interval with higher hydrogen is the Sutton Island unit and Blunts Point unit contact, where higher hydrogen is associated with Fe‐rich, Ca‐rich, and Mg‐rich points. A second interval with higher hydrogen occurs in the Vera Rubin ridge portion of the Murray formation, where higher hydrogen is associated with Fe‐rich, Ca‐rich, and Si‐rich points. We also observe trends in the H signal with grain size, separate from chemical variation, whereby coarser‐grained rocks have higher hydrogen. Variability in the hydrogen content of rocks points to a history of water‐rock interaction at Gale crater that included changes in lake water chemistry during Murray formation deposition and multiple subsequent groundwater episodes., Key Points Murray formation bedrock points measured by ChemCam have an interquartile range of 2.3–3.1 wt.% H2OSpecific intervals like the Vera Rubin ridge contain high H and indicate phases including iron oxyhydroxides, akageneite, and jarositeVariations in water content indicate changes in depositional lake water chemistry and multiple subsequent groundwater episodes

International audience; Most of the organics detected on Mars so far are aliphatic and aromatic organo‐chlorine compounds. The smallest were first identified by the thermal treatment of the solid samples by Viking in 1976, although at the time, they were attributed to contamination. Since 2012, a larger variety of structures have been identified by the Sample Analysis at Mars (SAM) experiment aboard the Curiosity rover. Evidence suggests that the chlorohydrocarbons formed during pyrolysis of sedimentary materials. Laboratory experiments show that heating of samples containing oxychlorines, such as chlorates (ClO3‐) and perchlorates (ClO4‐), along with organic matter present at Mars’ surface is the logical source of these compounds. Nevertheless, this discovery of indigenous organic matter in the Mars regolith raises important questions: How do the oxychlorines influence the pyrolysis of organics? What are the organics precursors of the organo‐chlorinated molecules detected on Mars? Is there a way to identify the parent molecules in a sample after pyrolysis? This paper presents the results of systematic laboratory experiments of the products formed during the pyrolysis of organic compounds from three chemical families—polycyclic aromatic hydrocarbons (PAHs), amino acids and carboxylic acids—in presence of calcium perchlorates. Results show that the PAH parent molecules and most of the carboxylic acids are still detectable after pyrolysis in presence of calcium perchlorate and that the degradation and/or evolution of all parent molecules mostly depends on their chemical nature. In addition, we demonstrate that the chlorohydrocarbons detected on Mars by the SAM instrument could come from the three chemical families studied.

Perchlorate (ClO₄⁻) was discovered in Martian soil by the Phoenix lander, with important implications for potential Martian biology, photochemistry, aqueous chemistry, and the chlorine cycle on Mars. Perchlorate was subsequently reported in both loose sediment and bedrock samples analyzed by the Sample Analysis at Mars instrument onboard the Curiosity rover in Gale crater based on a release of O₂ at 200–500°C. However, the continually wet paleoenvironment recorded by the sedimentary rocks in Gale crater was not conducive to the deposition of highly soluble salts. Furthermore, the preservation of ancient perchlorate to the modern day is unexpected due to its low thermodynamic stability and radiolytic decomposition associated with its long exposure to radioactivity and cosmic radiation. We therefore investigate alternative sources of O₂ in Sample Analysis at Mars analyses including superoxides, sulfates, nitrate, and nanophase iron and manganese oxides. Geochemical evidence and oxygen release patterns observed by Curiosity are inconsistent with each of these alternatives. We conclude that perchlorate is indeed the most likely source of the detected O2 release at 200–500°C, but contend that it is unlikely to be ancient. Rather than being associated with the lacustrine or early diagenetic environment, the most likely origin of perchlorate in the bedrock is late stage addition by downward percolation of water through rock pore space during transient wetting events in the Amazonian. The conclusion that the observed perchlorate in Gale crater is most likely Amazonian suggests the presence of recent liquid water at the modern surface.

The Sample Analysis at Mars instrument evolved gas analyzer (SAM-EGA) has detected evolved water, H2, SO2, H2S, NO, CO2, CO, O2 and HCl from two eolian sediments and nine sedimentary rocks from Gale Crater, Mars. These evolved gas detections indicate nitrates, organics, oxychlorine phase, and sulfates are widespread with phyllosilicates and carbonates occurring in select Gale Crater materials. Coevolved CO2 (160 ± 248 - 2373 ± 820 μgC(CO2)/g), and CO (11 ± 3 - 320 ± 130 μgC(CO)/g) suggest organic-C is present in Gale Crater materials. Five samples evolved CO2 at temperatures consistent with carbonate (0.32± 0.05 - 0.70± 0.1 wt.% CO3). Evolved NO amounts to 0.002 ± 0.007 - 0.06 ± 0.03 wt.% NO3. Evolution of O2 suggests oxychlorine phases (chlorate/perchlorate) (0.05 ± 0.025 - 1.05 ± 0.44wt. % ClO4) are present while SO2 evolution indicates the presence of crystalline and/or poorly crystalline Fe- and Mg-sulfate and possibly sulfide. Evolved H2O (0.9 ± 0.3 - 2.5 ± 1.6 wt.% H2O) is consistent with the presence of adsorbed water, hydrated salts, interlayer/structural water from phyllosilicates, and possible inclusion water in mineral/amorphous phases. Evolved H2 and H2S suggest reduced phases occur despite the presence of oxidized phases (nitrate, oxychlorine, sulfate, carbonate). SAM results coupled with CheMin mineralogical and APXS elemental analyses indicate that Gale Crater sedimentary rocks have experienced a complex authigenetic/diagenetic history involving fluids with varying pH, redox, and salt composition. The inferred geochemical conditions were favorable for microbial habitability and if life ever existed, there was likely sufficient organic-C to support a small microbial population.

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).

Molecular line parameters of foreign- broadening by air, carbon dioxide, and helium gas have been experimentally determined for infrared ro-vibrational spectral lines of methane isotopologues (^(12)CH_4 and ^(13)CH_4) at 3057 cm^(−1) targeted by the Tunable Laser Spectrometer (TLS) in the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity rover. From multi-spectrum analyses with the speed-dependent Voigt line profile with Rosenkrantz line-mixing, speed-dependence and line-mixing effects were quantified for methane spectra at total pressures up to 200 mbar. The fitted air-broadening coefficients deviated from 8–25% to those reported in the HITRAN-2012 database.

The Cumberland drill sample from the Sheepbed mudstone in Gale Crater, Mars, revealed the first evidence of an indigenous Martian organic molecule, chlorobenzene, with the Sample Analysis at Mars (SAM) instrument on Curiosity. We created in the laboratory a mineralogical analog of the Cumberland sample (CBA) to aid in the understanding of the precursor organic molecule(s) that led to the detection of chlorobenzene. The CBA was analyzed by visible/near-infrared spectrometry, and the results are in accordance with Mastcam multispectral and the Chemical Camera passive analyses of Cumberland on Mars, demonstrating that the CBA is a relevant analog. CBA aliquots were spiked with 0.5 wt. % of benzoic acid and 1–2 wt. % of magnesium perchlorate and were run in SAM Testbed (TB). The TB evolved gas analysis (EGA) showed similarities with the Cumberland EGA on Mars in terms of the major volatiles H2O, CO2, and O2. The TB gas chromatography mass spectrometry displayed the presence of chlorobenzene at 23–28 pmol and dichlorobenzene. CBA aliquots were also analyzed in the laboratory with SAM-like EGA and the results on the laboratory setup confirmed the generation of chlorobenzene by a reaction between the benzoic acid and the magnesium perchlorates. The case for benzoic acid as a potential precursor for the chlorobenzene detected in the Martian regolith is strengthened with this new supporting laboratory data from the CBA. The quantification of chlorobenzene in the TB led to prediction of organic precursor abundance on Mars of hundreds, if not thousands, of parts per millions by weight.

Since landing at Gale crater, Mars, in August 2012, the Curiosity rover has searched for evidence of past habitability, such as organic compounds, which have proved elusive to previous missions. We report results from pyrolysis experiments by Curiosity’s Sample Analysis at Mars (SAM) instrument, focusing on the isotopic compositions of evolved CO2 and O2, which provide clues to the identities and origins of carbon- and oxygen-bearing phases in surface materials. We find that O2 is enriched in 18O (δ18O about 40‰). Its behaviour reflects the presence of oxychlorine compounds at the Martian surface, common to aeolian and sedimentary deposits. Peak temperatures and isotope ratios (δ18O from −61 ± 4‰ to 64 ± 7‰; δ13C from –25 ± 20‰ to 56 ± 11‰) of evolved CO2 indicate the presence of carbon in multiple phases. We suggest that some organic compounds reflect exogenous input from meteorites and interplanetary dust, while others could derive from in situ formation processes on Mars, such as abiotic photosynthesis or electrochemical reduction of CO2. The observed carbonate abundances could reflect a sink for about 425–640 millibar of atmospheric CO2, while an additional 100–170 millibar could be stored in oxalates formed at the surface. In addition, oxygen isotope ratios of putative carbonates suggest the possibility of widespread cryogenic carbonate formation during a previous era. The pyrolysis experiments of the SAM instrument on board the Curiosity rover reconstruct the origin of organics at Gale crater. Some of them come from meteorites, but others have been formed in situ, with widespread past formation of carbonates via cryogenesis. More than 0.5 bar of CO2 might have precipitated from the atmosphere.

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 (

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; Thermochemolysis of seven nucleobases—adenine, thymine, uracil, cytosine, guanine, xanthine, and hypoxanthine—in tetramethylammonium hydroxide (TMAH) was studied individually by pyrolysis gas chromatography mass spectrometry in the frame of the Mars surface exploration. The analyses were performed under conditions relevant to the Sample Analysis at Mars (SAM) instrument of the Mars Curiosity Rover and the Mars Organic Molecule Analyzer (MOMA) instrument of the ExoMars Rover. The thermochemolysis products of each nucleobase were identified and the reaction mechanisms studied. The thermochemolysis temperature was optimized and the limit of detection and quantification of each nucleobase were also investigated. Results indicate that 600°C is the optimal thermochemolysis temperature for all seven nucleobases. The methylated products trimethyl-adenine, 1, 3-dimethyl-thymine, 1, 3-dimethyl-uracil, trimethyl-cytosine, 1, 3, 7-trimethyl-xanthine (caffeine), and dimethyl-hypoxanthine, respectively, are the most stable forms of adenine, thymine, uracil, cytosine, guanine, and xanthine, and hypoxanthine in TMAH solutions. The limits of detection for adenine, thymine, and uracil were 0.075 nmol; the limits of detection for guanine, cytosine, and hypoxanthine were higher, at 0.40, 0.55, and 0.75 nmol, respectively. These experiments allowed to well constrain the analytical capabilities of the thermochemolysis experiments that will be performed on Mars to detect nucleobases.

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.

We report new measurements of atmospheric methane by the Curiosity rover’s Tunable Laser Spectrometer that is part of the Sample Analysis at Mars suite (TLS-SAM), finding nondetections during two daytime measurements of average value 0.05 ± 0.22 ppbv (95% confidence interval CI). These are in marked contrast with nighttime background levels of 0.52 ± 0.10 (95% CI) from four measurements taken during the same season of northern summer. This large day-night difference suggests that methane accumulates while contained near the surface at night, but drops below TLS-SAM detection limits during the day, consistent with the daytime nondetection by instruments on board the ExoMars Trace Gas Orbiter. With no evidence for methane production by the rover itself, we propose that the source is one of planetary micro-seepage. Dynamical modeling indicates that such methane release is contained within the collapsed planetary boundary layer (PBL) at night due to a combination of nocturnal inversion and convergent downslope flow winds that confine the methane inside the crater close to the point where it is released. The methane abundance is then diluted during the day through increased vertical mixing associated with a higher altitude PBL and divergent upslope flow that advects methane out of the crater region. We also report detection of a large spike of methane in June 2019 with a mean in situ value over a two-hour ingest of 20.5 ± 4 ppbv (95% CI). If near-surface production is occurring widely across Mars, it must be accompanied by a fast methane destruction or sequestration mechanism, or both.

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).

K-Ar and noble gas surface exposure age measurements were carried out on the Windjana sandstone, Kimberley region, Gale Crater, Mars, by using the Sample Analysis at Mars instrument on the Curiosity rover. The sandstone is unusually rich in sanidine, as determined by CheMin X-ray diffraction, contributing to the high K_2O concentration of 3.09 ± 0.20 wt % measured by Alpha-Particle X-ray Spectrometer analysis. A sandstone aliquot heated to ~915°C yielded a K-Ar age of 627 ± 50 Ma. Reheating this aliquot yielded no additional Ar. A second aliquot heated in the same way yielded a much higher K-Ar age of 1710 ± 110 Ma. These data suggest incomplete Ar extraction from a rock with a K-Ar age older than 1710 Ma. Incomplete extraction at ~900°C is not surprising for a rock with a large fraction of K carried by Ar-retentive K-feldspar. Likely, variability in the exact temperature achieved by the sample from run to run, uncertainties in sample mass estimation, and possible mineral fractionation during transport and storage prior to analysis may contribute to these discrepant data. Cosmic ray exposure ages from ^3He and ^(21)Ne in the two aliquots are minimum values given the possibility of incomplete extraction. However, the general similarity between the ^3He (57 ± 49 and 18 ± 32 Ma, mean 30 Ma) and ^(21)Ne (2 ± 32 and 83 ± 24 Ma, mean 54 Ma) exposure ages provides no evidence for underextraction. The implied erosion rate at the Kimberley location is similar to that reported at the nearby Yellowknife Bay outcrop.

The cold (−13.4°C), cryoencapsulated, anoxic, interstitial brine of the >27 m thick ice of Lake Vida (Victoria Valley, Antarctica) contains 49 µg · L−1 of perchlorate and 11 µg · L−1 of chlorate. Lake Vida brine (LVBr) may provide an analog for potential oxychlorine-rich subsurface brine on Mars. LVBr volatiles were analyzed by solid-phase microextraction (SPME) gas chromatography–mass spectrometry (GC-MS) with two different SPME fibers. With the exception of volatile organic sulfur compounds, most other volatiles observed were artifacts produced in the GC injector when the thermal decomposition products of oxychlorines reacted with reduced carbon derived from LVBr and the SPME fiber phases. Analysis of MilliQ water with perchlorate (40 µg · L−1) showed low level of organic artifacts, reflecting carbon limitation. In order to observe sample-derived organic compounds, both in analog samples and on Mars, the molar abundance of reduced carbon in a sample must exceed those of O2 and Cl2 produced during decomposition of oxychlorines. This suggests that the abundance of compounds observed by the Sample Analysis at Mars (SAM) instruments in Sheepbed samples (CB-3, CB5, and CB6) may be controlled by an increase in the reduced-carbon/oxychlorine ratio of these samples. To increase chances of in situ detection of Martian organics during pyrolysis-GC-MS, we propose that the derivatization agents stored on SAM may be used as an external source of reduced carbon, increasing artificially the reduced-carbon to perchlorate ratio during pyrolysis, allowing the expression of more abundant and perhaps more diverse Martian organic matter.

The Dynamic Albedo of Neutron (DAN) instrument on board the Mars Science Laboratory Curiosity rover acquired a series of measurements as part of an observational campaign of the Kimberley area in Gale crater. These observations were planned to assess the variability of bulk hydrogen and neutron-absorbing elements, characterized as chlorine-equivalent concentration, in the geologic members of the Kimberley formation and in surface materials exposed throughout the area. During the traverse of the Kimberley area, Curiosity drove primarily over the “Smooth Hummocky” unit, a unit composed primarily of sand and loose rocks, with occasional stops at bedrock of the Kimberley formation. During the Kimberley campaign, DAN detected ranges of water equivalent hydrogen (WEH) and chlorine-equivalent concentrations of 1.5–2.5 wt % and 0.6–2 wt %, respectively. Results show that as the traverse progressed, DAN observed an overall decrease in both WEH and chlorine-equivalent concentration measured over the sand and loose rocks of the Smooth Hummocky unit. DAN measurements of WEH and chlorine-equivalent concentrations in the well-exposed sedimentary bedrock of the Kimberley formation show fluctuations with stratigraphic position. The Kimberley campaign also provided an opportunity to compare measurements from DAN with those from the Sample Analysis at Mars (SAM) and the Alpha-Particle X-ray Spectrometer (APXS) instruments. DAN measurements obtained near the Windjana drill location show a WEH concentration of ~1.5 wt %, consistent with the concentration of low-temperature absorbed water measured by SAM for the Windjana drill sample. A comparison between DAN chlorine-equivalent concentrations measured throughout the Kimberley area and APXS observations of corresponding local surface targets and drill fines shows general agreement between the two instruments.

Mars landed and orbiter missions have instrumentation capable of detecting oxychlorine phases (e.g. perchlorate, chlorate) on the surface. Perchlorate (~0.6 wt%) was first detected by the Wet Chemistry Laboratory in the surface material at the Phoenix Mars Landing site. Subsequent analyses by the Thermal Evolved Gas Analyser aboard the same lander detected an oxygen release (~465°C) consistent with the thermal decomposition of perchlorate. Recent thermal analysis by the Mars Science Laboratory's Sample Analysis at Mars instrument has also indicated the presence of oxychlorine phases (up to 1.2 wt%) in Gale Crater materials. Despite being at detectable concentrations, the Chemistry and Mineralogy (CheMin) X-ray diffractometer has not detected oxychlorine phases. This suggests that Gale Crater oxychlorine may exist as poorly crystalline phases or that perchlorate/chlorate mixtures exist, so that individual oxychlorine concentrations are below CheMin detection limits (~1 wt%). Although not initially designed to detect oxychlorine phases, reinterpretation of Viking Gas Chromatography/Mass Spectrometer data also suggest that oxychlorine phases are present in the Viking surface materials. Remote near-infrared spectral analyses by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) instrument indicate that at least some martian recurring slope lineae (RSL) have spectral signatures consistent with the presence of hydrated perchlorates or chlorates during the seasons when RSL are most extensive. Despite the thermal emission spectrometer, Thermal Emission Imaging System, Observatoire pour la Minéralogie, l'Eau, les Glaces et l'Activité and CRISM detection of hundreds of anhydrous chloride (~10–25 vol%) deposits, expected associated oxychlorine phases (>5–10 vol%) have not been detected. Total Cl and oxychlorine data sets from the Phoenix Lander and the Mars Science Laboratory missions could be used to develop oxychlorine versus total Cl correlations, which may constrain oxychlorine concentrations at other locations on Mars by using total Cl determined by other missions (e.g. Viking, Pathfinder, MER and Odyssey). Development of microfluidic or ‘lab-on-a-chip’ instrumentation has the potential to be the next generation analytical capability used to identify and quantify individual oxychlorine species on future landed robotic missions to Mars.

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.

Orbital and in-situ data from the surface of Mars indicate that nanophase weathering products are important constituents of martian rocks and soils. Nanophase minerals have the capacity to chemisorb anions like sulfate and phosphate onto their surfaces, but it is not known whether chemisorption is an important or even detectable process via orbital and in-situ observations. The detection of chemisorbed sulfate and phosphate anions on nanophase minerals would constrain the speciation of these anions and past aqueous environmental conditions. Here, we synthesized two nanophase weathering products that are common in terrestrial volcanic soils and have been identified on the martian surface: allophane and nanophase ferric oxide as represented by ferrihydrite. We specifically adsorbed sulfate and phosphate separately onto the nanophase mineral surfaces (4.5 and 1.6 wt% SO42−, and 6.7 and 8.9 wt% PO43− on allophane and ferrihydrite, respectively) and analyzed the untreated and chemisorbed materials using instruments similar to those on orbital and landed Mars missions (including X-ray diffraction, evolved gas analysis, Mossbauer spectroscopy, and VNIR and thermal-IR spectroscopy). Evolved gas analysis is the optimum method to detect chemisorbed sulfate, with SO2(g) being released at >900 °C for allophane and 400–800 °C for ferrihydrite. Chemisorbed sulfate and phosphate anions affect the thermal-IR spectra of allophane and ferrihydrite in the S-O and P-O stretching region when present in abundances of only a few weight percent; S-O and P-O stretching bands are apparent as short-wavelength shoulders on Si-O stretching bands. Sulfate and phosphate anions chemisorbed to allophane have small but measurable effects on the position of the OH-H2O bands at 1.4 and 1.9 μm in near-IR spectra. Chemisorbed sulfate and phosphate anions did not affect the X-ray diffraction patterns, Mossbauer spectra, and visible/near-IR spectra of ferrihydrite. These data suggest that sulfate chemisorbed onto the surfaces of nanophase minerals can be detected with the Sample Analysis at Mars (SAM) instrument on the Mars science laboratory Curiosity rover, and subtle signatures of chemisorbed sulfate and phosphate may be detectable by IR spectrometers on landed missions. The combined use of SAM, the Chemistry and Mineralogy (CheMin) instrument, and the Alpha Particle X-ray Spectrometer (APXS) on Curiosity allows for the most detailed characterization to date of nanophase minerals in martian rocks and soils and the potential presence of chemisorbed anionic complexes.

Molecular line parameters of line strengths, self- and foreign-broadening by nitrogen, carbon dioxide and helium gas have been experimentally determined for infrared ro-vibrational spectral lines of water and carbon dioxide at 2.78 µm targeted by the Tunable Laser Spectrometer (TLS) in the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity rover. Good agreement is found by comparison with the line parameters reported in the HITRAN-2012 database.

The Johnson Space Center Rocknest (JSC-RN) simulant was developed in response to a need by NASA's Advanced Exploration Systems (AES) In Situ Resource Utilization (ISRU) project for a simulant to be used in component and system testing for water extraction from Mars regolith. JSC-RN was de-signed to be chemically and mineralogically similar to material from the aeolian sand shadow named Rocknest in Gale Crater, particularly the 1-3 weight percentage water release as measured by the Sample Analysis at Mars (SAM) instrument. Rocknest material is a proxy for average martian soils, which are unconsolidated and could be easily scooped by rovers or landers in order to extract water. One way in which water can be extracted from aeolian material is through heating, where adsorbed and structural water is thermally removed from minerals. The water can then be condensed and used as drinking water or split and used as propellant for spacecraft or as a source of breathable O2. As such, it was essential that JSC-RN contained evolved gas profiles, especially low temperature water (less than 400 degrees Centigrade), that mimicked what is observed in martian soils. Because many of these ISRU tests require hundreds of kilograms of Mars soil simulant, it was essential that JSC-RN be cost-effective and based on com-ponents that could be purchased commercially (i.e., not synthesized in the lab). Here, we describe the JSC-RN martian soil simulant, which is ideal for large-scale production and use in ISRU water extraction studies.

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.

The Sample Analysis at Mars (SAM) instrument onboard the Mars Science Laboratory Curiosity rover measures the chemical composition of major atmospheric species (CO2, N2, 40Ar, O2, and CO) through a dedicated atmospheric inlet. We report here measurements of volume mixing ratios in Gale Crater using the SAM quadrupole mass spectrometer, obtained over a period of nearly 5 years (3 Mars years) from landing. The observation period spans the northern summer of MY 31 and solar longitude (LS) of 175° through spring of MY 34, LS = 12°. This work expands upon prior reports of the mixing ratios measured by SAM QMS in the first 105 sols of the mission. The SAM QMS atmospheric measurements were taken periodically, with a cumulative coverage of four or five experiments per season on Mars. Major observations include the seasonal cycle of CO2, N2, and Ar, which lags approximately 20¿40° of LS behind the pressure cycle driven by CO2 condensation and sublimation from the winter poles. This seasonal cycle indicates that transport occurs on faster timescales than mixing. The mixing ratio of O2 shows significant seasonal and interannual variability, suggesting an unknown atmospheric or surface process at work. The O2 measurements are compared to several parameters, including dust optical depth and trace CH4 measurements by Curiosity. We derive annual mean volume mixing ratios for the atmosphere in Gale Crater: CO2 = 0.951 (±0.003), N2 = 0.0259 (±0.0006), 40Ar = 0.0194 (±0.0004), O2 = 1.61 (±0.09) x 10-3, and CO = 5.8 (±0.8) x 10-4. ©2019. The Authors., All MSL data used in this manuscript (REMS and SAM) are freely available on NASA's Planetary Data System (PDS) Geosciences Node, from within 6 months after receipt on Earth (http://pds‐geosciences.wustl.edu/missions/msl/). The mixing ratios developed and presented in this paper are available at a publicly available archive (dataverse.org: doi.org/10.7910/DVN/CVUOWW) as cited within the manuscript. The successful operation of the Curiosity rover and the SAM instrument on Mars is due to the hard work and dedication of hundreds of scientists, engineers, and managers over more than a decade. Essential contributions to the successful operation of SAM on Mars and the acquisition of SAM data were provided by the SAM development, operations, and test bed teams. The authors gratefully thank the SAM and MSL teams that have contributed in numerous ways to obtain the data that enabled this scientific work. We also thank NASA for the support of the development of SAM, SAM data analysis, and the continued support of the Mars Science Laboratory mission. The contribution of F. Lefèvre was supported by the Programme National de Planétologie (PNP). R. Navarro‐Gonzalez acknowledges support from the Universidad Nacional Autónoma de México (PAPIIT IN111619). LPI is operated by USRA under a cooperative agreement with the Science Mission Directorate of the National Aeronautics and Space Administration. We thank members of the SAM and larger MSL team for insightful discussions and support. In particular, we thank R. Becker and R. O. Pepin for careful review of data analysis and interpretation. We thank M. D. Smith for discussion of CRISM CO measurements. We thank A. Brunner, M. Johnson, and M. Lefavor for their development of customized data analysis tools used here and in other SAM publications.

This chapter discusses the detection of evolved gases from Gale crater sedimentary rock and eolian sediment by the Mars Science Laboratory rover's Sample Analysis at Mars (SAM) instrument. An overview is presented of the SAM instrument along with summary of key results from previous evolved gas analyses conducted at the Viking and Phoenix landing sites. The SAM measurements of evolved water, sulfur dioxide, carbon dioxide, carbon monoxide, oxygen, and nitrous oxide from Gale crater samples are presented. The phases responsible for the evolved gas detections and the implications for their presence are then evaluated. The water deuterium to hydrogen (D/H) ratio is discussed in context of understanding the degree of water loss from Mars. In the introduction of this book, we briefly explored the history of the exploration of Mars, where we discussed a major shift in the scientific thinking and public perception of the nature of the surface of Mars as new missions explored the Red Planet. The first observations of the surface sparked speculations of Mars being inhabited by intelligent beings, inspiring fantasy, science fiction, and, of course, further exploration. The turn came when Mariner 4 returned images of a lunar-like landscape, a monotonous basaltic world with many impact craters but no water, and therefore no prospects for life to find a habitable niche. The authors of the chapters of this book show how different our understanding of Mars is today from the historical Mariner 4 perspective!

This chapter summarizes the history of hydrogen isotope studies of Martian meteorites since the first detection of nonterrestrial hydrogen from the meteorites. Contamination of terrestrial water has been a major issue throughout most of this history. This review, in particular, focuses on recent ion microprobe studies that have contributed to the identification of Martian hydrogen reservoirs and have constrained their evolution throughout the planet’s history. NASA’s Curiosity rover has also provided valuable insights on the water history based on in situ hydrogen isotopic measurements of rocks in Gale crater since 2012 (see Chapter 12, Volatile Detections in Gale Crater Sediment and Sedimentary Rock: Results from the Mars Science Laboratory’s Sample Analysis at Mars Instrument).

On 6 August 2012, the Sample Analysis at Mars (SAM) instrument suite ( 1 ) arrived on Mars onboard the Curiosity rover. SAM's main aim was to search for organic molecules on the martian surface. On page 1096 of this issue, Eigenbrode et al. ( 2 ) report SAM data that provide conclusive evidence for the presence of organic compounds—thiophenic, aromatic, and aliphatic compounds—in drill samples from Mars' Gale crater. In a related paper on page 1093, Webster et al. ( 3 ) report a strong seasonal variation in atmospheric methane, the simplest organic molecule, in the martian atmosphere. Both these finding are breakthroughs in astrobiology.