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The Sample Analysis at Mars (SAM) suite instrument on board NASA's Curiosity rover has characterized the inorganic and organic chemical composition of seven samples from the Glen Torridon (GT) clay‐bearing unit. A variety of organic molecules were detected with SAM using pyrolysis (up to ∼850°C) and wet chemistry experiments coupled with evolved gas analysis (EGA) and gas chromatography‐mass spectrometry. SAM EGA and GCMS analyses revealed a greater diversity and abundance of sulfur‐bearing aliphatic and aromatic organic compounds in the sediments of this Gale crater unit than earlier in the mission. We also report the detection of nitrogen‐containing, oxygen‐containing, and chlorine‐containing molecules, as well as polycyclic aromatic hydrocarbons found in GT, although the sources of some of these organics may be related to the presence of chemical reagents in the SAM instrument background. However, sulfur‐bearing organics released at high temperature (≥600°C) are likely derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources and consistent with the presence of recalcitrant organic materials in the sample. The SAM measurements of the GT clay‐bearing unit expand the inventory of organic matter present in Gale crater and is also consistent with the hypothesis that clay minerals played an important role in the preservation of ancient refractory organic matter on Mars. These findings deepen our understanding of the past habitability and biological potential of Gale crater. Plain Language Summary: Organic molecules are essential to all life as we know it. Clay minerals are known on Earth for their high organic preservation potential and can be key indicators of past habitable environments. On Mars, the Glen Torridon (GT) region in Gale crater was first identified from orbit as a priority target for the Mars Science Laboratory mission due to its abundant clay minerals. To evaluate the organic preservation potential of this region, seven rock samples were collected and characterized using the Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover. The SAM investigation indicated the presence of various organic compounds, including the first observation on Mars of some sulfur‐containing and ring‐structured organics and the highest abundance of sulfur organics observed to date. Our investigation of the sources of these organics revealed that while some of the sulfur‐bearing organics are likely Martian, a portion may also be related to the presence of chemical reagents carried in SAM, making attribution to a definitive source challenging. Nevertheless, these new SAM results confirm that ancient organic matter is preserved in the clay mineral bearing sediments of GT. Its origin—either meteoritic, abiotic or biotic—has yet to be established. Key Points: Curiosity explored the Glen Torridon region of Gale crater, which has a smectite‐rich mineralogy with high organic preservation potentialThe greatest diversity and abundance of sulfur‐bearing organics to date were detected in the solid samples by the SAM instrumentS‐bearing organics extracted ≥600°C and some aromatic compounds likely come from martian refractory organic matter [ABSTRACT FROM AUTHOR]

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 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, amino acids, and carboxylic acids—in presence of calcium perchlorates. Results show that the polycyclic aromatic hydrocarbon 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 Sample Analysis at Mars instrument could come from the three chemical families studied. Plain Language Summary: Organic molecules are the building blocks of life as we know it, and detecting them on the surface of Mars has been one of the major goals of Mars exploration. Viking landers in 1976, followed by the Curiosity rover in 2012, discovered simple chlorine‐bearing organics on Mars. These chlorohydrocarbons are known to be mainly produced by the instrument itself, through chemical reactions at high temperatures between other organic molecules thermally extracted from solid rock and soil samples that react with the oxidizing minerals present on Mars (e.g., perchlorates). Studying the influence of the minerals like perchlorates on the thermal extraction of different parent molecules requires thorough experimental studies like this one. Our work constrains the potential parent molecules of the chlorohydrocarbons detected on Mars in the presence of calcium perchlorate, thereby shedding light on the past and present habitability of Mars. Key Points: A systematic study reveals the influence of calcium perchlorate during the pyrolysis of organic compounds from various chemical familiesSome parent organics can be identified after thermal extraction as well as through the production of characteristic pyrolysis product(s)The precursors of the chlorohydrocarbons detected on Mars with the SAM instrument could originate from the three chemical families studied [ABSTRACT FROM AUTHOR]

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. Plain Language Summary: The Sample Analysis at Mars (SAM) experiment onboard the Curiosity Rover has a polymer‐based chemical trap (Tenax®) that concentrates the evolved species from the Martian samples. We studied the impact that this trap could have on the SAM results when heated, when exposed to the chemical compounds used for sample processing (derivatization) and when exposed to Martian perchlorates. We conclude by demonstrating that some of the organic compounds detected in the background signal of the SAM chromatograms likely came from the degradation of Tenax®. This study will help to discriminate the endogenous organic compounds detected on Mars by SAM from the contamination. Key Points: In this article, we evaluate the impact of the Tenax® traps on the Sample Analysis at Mars experiment results, with concurrent implications for the future Martian Organic Molecule Analyser experiment resultsTenax® is an adsorbent resin used on SAM as a trap; it is an organic polymer that can be degraded into smaller moleculesBy‐products of Tenax® may contribute to the background of the SAM chromatogram. Here we identify them and the conditions of their production [ABSTRACT FROM AUTHOR]

The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover, is specifically designed for in situ molecular and isotopic analyses of martian surface materials and atmosphere. It contributes to the Mars Science Laboratory (MSL) missions primary scientific goal to characterize the potential past, present or future habitability of Mars. In all of the analyses of solid samples delivered to SAM so far, chlorinated organic compounds have been detected above instrument background levels and identified by gas chromatography coupled to mass spectrometry (GC–MS) ( Freissinet et al., 2015 ; Glavin et al., 2013 ). While some of these may originate from reactions between oxychlorines and terrestrial organic carbon present in the instrument background ( Glavin et al., 2013 ), others have been demonstrated to originate from indigenous organic carbon present in samples ( Freissinet et al., 2015 ). We present here laboratory calibrations that focused on the analyses performed with the MXT-CLP GC column (SAM GC-5 channel) used for nearly all of the GC–MS analyses of the martian soil samples carried out with SAM to date. Complementary to the mass spectrometric data, gas chromatography allows us to separate and identify the species analyzable in a nominal SAM-GC run time of about 21 min. To characterize the analytical capabilities of this channel within the SAM Flight Model (FM) operating conditions on Mars, and their implications on the detection of organic matter, it is required to perform laboratory experimental tests and calibrations on spare model components. This work assesses the SAM flight GC-5 column efficiency, confirms the identification of the molecules based on their retention time, and enables a better understanding of the behavior of the SAM injection trap (IT) and its release of organic molecules. This work will enable further optimization of the SAM-GC runs for additional samples to be analyzed during the MSL mission. [ABSTRACT FROM AUTHOR]