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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.

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 that 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 that oxychlorine phases (chlorate/perchlorate) (0.05 +/- 0.025-1.05 +/- 0.44 wt % 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 that reduced phases occur despite the presence of oxidized phases (nitrate, oxychlorine, sulfate, and carbonate). SAM results coupled with CheMin mineralogical and Alpha-Particle X-ray Spectrometer 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.

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 K2O concentration of 3.09 +/- 0.20 wt % measured by Alpha-Particle X-ray Spectrometer analysis. A sandstone aliquot heated to approximately 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 approximately 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 He-3 and Ne-21 in the two aliquots are minimum values given the possibility of incomplete extraction. However, the general similarity between the He-3 (57 +/- 49 and 18 +/- 32 Ma, mean 30 Ma) and Ne-21 (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.

Measuring the chemical composition of planetary bodies and their atmospheres is key to understanding the formation of the Solar System and the evolution of the planets and their moons. In situ volatile measurements enable a ground-truth assessment of the distribution and abundance of resources such as water-ice and oxygen, important for a sustained human presence on the Moon and beyond. The Volatile Analysis by Pyrolysis of Regolith (VAPoR) instrument is a compact pyrolysis mass spectrometer designed to detect volatiles released from solid samples that are heated to elevated temperatures and is one technique that should be considered for resource prospecting on the Moon, Mars, and asteroids.

Mars Science Laboratorys Sample Analysis at Mars (SAM) investigation has measured all of the stable isotopes of the heavy noble gases krypton and xenon in the martian atmosphere, in situ, from the Curiosity Rover at Gale Crater, Mars. Previous knowledge of martian atmospheric krypton and xenon isotope ratios has been based upon a combination of the Viking missions krypton and xenon detections and measurements of noble gas isotope ratios in martian meteorites. However, the meteorite measurements reveal an impure mixture of atmospheric, mantle, and spallation contributions. The xenon and krypton isotopic measurements reported here include the complete set of stable isotopes, unmeasured by Viking. The new results generally agree with Mars meteorite measurements but also provide a unique opportunity to identify various non-atmospheric heavy noble gas components in the meteorites. Kr isotopic measurements define a solar-like atmospheric composition, but deviating from the solar wind pattern at 80Kr and 82Kr in a manner consistent with contributions originating from neutron capture in Br. The Xe measurements suggest an intriguing possibility that isotopes lighter than 132Xe have been enriched to varying degrees by spallation and neutron capture products degassed to the atmosphere from the regolith, and a model is constructed to explore this possibility. Such a spallation component, however, is not apparent in atmospheric Xe trapped in the glassy phases of martian meteorites.

The Sample Analysis at Mars (SAM) instrument onboard Curiosity can perform pyrolysis of martian solid samples, and analyze the volatiles by direct mass spectrometry in evolved gas analysis (EGA) mode, or separate the components in the GCMS mode (coupling the gas chromatograph and the mass spectrometer instruments). In addition, SAM has a wet chemistry laboratory designed for the extraction and identification of complex and refractory organic molecules in the solid samples. The chemical derivatization agent used, N-methyl-N-tert-butyldimethylsilyl- trifluoroacetamide (MTBSTFA), was sealed inside seven Inconel metal cups present in SAM. Although none of these foil-capped derivatization cups have been punctured on Mars for a full wet chemistry experiment, an MTBSTFA leak was detected and the resultant MTBSTFA vapor inside the instrument has been used for a multi-sol MTBSTFA derivatization (MD) procedure instead of direct exposure to MTBSTFA liquid by dropping a solid sample directly into a punctured wet chemistry cup. Pyr-EGA, Pyr-GCMS and Der-GCMS experiments each led to the detection and identification of a variety of organic molecules in diverse formations of Gale Crater.

The search for reduced carbon has been a major focus of past and present missions to Mars. Thermal evolved gas analysis was used by the Viking and Phoenix landers and is currently in use by the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to characterize volatiles evolved from solid samples, including those associated with reduced organic species. SAM has the additional capability to perform a combustion experiment, in which a sample of Mars regolith is heated in the presence of oxygen and the composition of the evolved gases is measured using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS) [1]. Organics detection on the Martian surface has been complicated by oxidation and destruction during heating by soil oxidants [2], including oxychlorine compounds, and terrestrial organics in the SAM background contributed by one of the SAM wet chemistry reagents MTBSTFA (N-Methyl-N-tertbutyldimethylsilyl- trifluoroacetamide) [3,4]. Thermal Evolved Gas Analysis (TEGA) results from Phoenix show a mid temperature CO2 release between 400 C - 680 C speculated to be carbonate, CO2 adsorbed to grains, or combustion of organics by soil oxidants [5]. Low temperature CO2 evolutions (approx. 200 C - 400 C) were also present at all three sites in Gale Crater where SAM Evolved Gas Analysis (EGA) was performed, and potential sources include combustion of terrestrial organics from SAM, as well as combustion and/or decarboxylation either indigenous martian or exogenous organic carbon [4,6]. By performing an experiment to intentionally combust all reduced materials in the sample, we hope to compare the bulk abundance of CO2 and other oxidized species evolved by combustion to that evolved during an EGA experiment to estimate how much CO2 could be contributed by reduced carbon sources. In addition, C, O, and H isotopic compositions of CO2 and H2O measured by TLS can contribute information regarding the potential sources of these volatiles.

The combustion experiment on the Sample Analysis at Mars (SAM) suite on Curiosity will heat a sample of Mars regolith in the presence of oxygen and measure composition of the evolved gases using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS). QMS will enable detection of combustion products such as CO, CO2, NO, and other oxidized species, while TLS will enable precise measurements of the abundance and carbon isotopic composition (delta(sup 13)C) of the evolved CO2 and hydrogen isotopic composition (deltaD) of H2O. SAM will perform a two-step combustion to isolate combustible materials below approx.550 C and above approx.550 C. The combustion experiment on SAM, if properly designed and executed, has the potential to answer multiple questions regarding the origins of volatiles seen thus far in SAM evolved gas analysis (EGA) on Mars. Constraints imposed by SAM and MSL time and power resources, as well as SAM consumables (oxygen gas), will limit the number of SAM combustion experiments, so it is imperative to design an experiment targeting the most pressing science questions. Low temperature combustion experiments will primarily target the quantification of carbon (and nitrogen) contributed by SAM wet chemistry reagants MTBSTFA (N-Methyl-N-tert-butyldimethylsilyltrifluoroacetamide) and DMF (Dimethylformamide), which have been identified in the background of blank and sample runs and may adsorb to the sample while the cup is in the Sample Manipulation System (SMS). In addition, differences between the sample and "blank" may yield information regarding abundance and delta(sup 13)C of bulk (both organic and inorganic) martian carbon. High temperature combustion experiments primarily aim to detect refractory organic matter, if present in Cumberland fines, as well as address the question of quantification and deltaD value of water evolution associated with hydroxyl hydrogen in clay minerals.

The combustion experiment on the Sample Analysis at Mars (SAM) suite on Curiosity will heat a sample of Mars regolith in the presence of oxygen and measure composition of the evolved gases using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS). QMS will enable detection of combustion products such as CO, CO2, NO, and other oxidized species, while TLS will enable precision measurements of the abundance and carbon isotopic composition (delta C-13) of the evolved CO2 and hydrogen isotopic composition (delta D) of H2O. SAM will perform a two-step combustion to isolate combustible materials below approx. 550 C and above approx. 550 C.

We determined radiogenic and cosmogenic noble gases in a mudstone on the floor of Gale Crater. A K-Ar age of 4.21 +/- 0.35 billion years represents a mixture of detrital and authigenic components and confirms the expected antiquity of rocks comprising the crater rim. Cosmic-ray-produced 3He, 21Ne, and 36Ar yield concordant surface exposure ages of 78 T 30 million years. Surface exposure occurred mainly in the present geomorphic setting rather than during primary erosion and transport. Our observations are consistent with mudstone deposition shortly after the Gale impact or possibly in a later event of rapid erosion and deposition. The mudstone remained buried until recent exposure by wind-driven scarp retreat. Sedimentary rocks exposed by this mechanism may thus offer the best potential for organic biomarker preservation against destruction by cosmic radiation.

We present the Volatile Analysis by Pyrolysis of Regolith (VAPoR) instrument design and demonstrate the validity of an in situ pyrolysis mass spectrometer for evolved gas analyses of lunar and planetary regolith samples. In situ evolved gas analyses of the lunar regolith have not yet been carried out and no atmospheric or evolved gas measurements have been made at the lunar poles. VAPoR is designed to do both kinds of measurements, is currently under development at NASA's Goddard Space Flight Center, and will be able to heat powdered regolith samples or rock drill fines up to 1400 C in vacuo. To validate the instrument concept, evolved gas species released from different planetary analogs were determined as a function of temperature using a laboratory breadboard. Evolved gas measurements of an Apollo 16 regolith sample and a fragment of the carbonaceous meteorite Murchison were made by VAPoR and our results compared with existing data. The results imply that in situ evolved gas measurements of the lunar regolith at the polar regions by VAPoR will be a very powerful tool for identifying water and other volatile signatures of lunar or exogenous origin as potential resources for future human exploration.