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 Sample Analysis at Mars (SAM) instrument is a gas chromatograph-mass spectrometer onboard the NASA Curiosity rover, currently operating on the surface of Mars. Organic compounds are of major importance with regard to questions of habitability and the potential presence of life on Mars, and one of the mission's main objectives is to analyze the organic content of soil and rock samples. In SAM's first chromatographic measurements, however, unexpected chlorine-bearing organic molecules were detected. These molecules have different origins but the presence of perchlorates and chlorates detected at the surface of Mars suggests that reactivity between organic molecules and thermal decomposition products from oxychlorines is one of the major sources of the chlorinated organic molecules. Here we perform a comprehensive and systematic study of the separation of volatile chlorohydrocarbons with the chromatographic columns used in the SAM instrument. Despite the constrained operating conditions of the flight instrument, we demonstrate that SAM's capillary chromatographic columns allow for effective separation and identification of a wide range of chlorine-bearing species. We also show that instrumental limitations prevent the detection of certain molecules, obscuring our ability to make definitive conclusions about the origin of these organic materials.

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.

We developed a time-of-flight neutral gas mass spectrometer (NGMS) that was selected as part of the gas analytic package for the Luna-Resurs mission to investigate lunar regolith and the lunar exosphere insitu. The recently presented scientific performance measurements of the NGMS prototype [4] are comparable with preliminary calibration data of the flight model. Hence, NGMS will fully comply with the scientific requirements of the Luna-Resurs mission.

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 21min. 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.

The Mars Science Laboratory (MSL) Curiosity Rover carries a suite of instruments, one of which is the Sample Analysis at Mars (SAM) experiment. SAM is devoted to the in situ molecular analysis of gases evolving from solid samples collected by Curiosity on Mars surface/sub-surface. Among its three analytical devices, SAM has a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) [1]. The GC-QMS is devoted to the separation and identification of organic and inorganic material. Before proceeding to the GC-QMS analysis, the solid sample collected by Curiosity is subjected to a thermal treatment thanks to the pyrolysis oven to release the volatiles into the gas processing system. Depending on the sample, a derivatization method by wet chemistry: MTBSTFA of TMAH can also be applied to analyze the most refractory compounds. The GC is able to separate the organic molecules which are then detected and identified by the QMS (Figure 1).

Pyrolysis of soil or rock samples is the preferred preparation technique used on Mars to search for organic molecules up today. During pyrolysis, oxichlorines present in the soil of Mars release oxidant species that alter the organic molecules potentially contained in the samples collected by the space probes. This process can explain the difficulty experienced by in situ exploration probes to detect organic materials in Mars soil samples until recently. Within a few months, the Curiosity rover should reach and analyze for the first time soils rich in sulfates which could induce a different behavior of the organics during the pyrolysis compared with the types of soils analyzed up today. For this reason, we systematically studied the pyrolysis of organic molecules trapped in magnesium sulfate, in the presence or absence of calcium perchlorate. Our results show that organics trapped in magnesium sulfate can undergo some oxidation and sulfuration during the pyrolysis. But these sulfates are also shown to protect organics trapped inside the crystal lattice and/or present in fluid inclusions from the oxidation induced by the decomposition of calcium perchlorate and probably other oxychlorine phases currently detected on Mars. Trapped organics may also be protected from degradation processes induced by other minerals present in the sample, at least until these organics are released from the pyrolyzed sulfate mineral (similar to 700 degrees C in our experiment). Hence, we suggest magnesium sulfate as one of the minerals to target in priority for the search of organic molecules by the Curiosity and ExoMars 2018 rovers.

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 [1]. The chemical derivatization agent used, N-methyl-N-tert-butyldimethylsilyl-trifluoroacetamide (MTBSTFA – Fig. 1), 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 [2]. 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.

In preparation for the Russian Luna-Resurs mission we combined our compact time-of-flight mass spectrometer (TOF-MS) with a chemical pre-separation of the species by gas chromatography (GC). Coupled measurements with both instruments were successfully performed with the prototype of the mass spectrometer and a flight-like gas chromatograph. The system was tested with two test gas mixtures, a mixture of hydrocarbons and a mixture of noble gases. Due to its capability to record mass spectra over the full mass range at once with high sensitivity and a dynamic range of up to 106 within 1s, the TOF-MS system is a valuable extension of the GC analytical system. Based on the measurements with calibration gases performed with the combined GC–MS prototype and under assumption of mean characteristics for the Moon's regolith, the detection limit for volatile species in a soil sample is estimated to 2·10−10 by mass for hydrocarbons and 2·10−9 by mass for noble gases.

The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally evolved from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. The first sample analyzed by SAM at the Rocknest (RN) aeolian deposit revealed chlorohydrocarbons derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background. No conclusive evidence for martian chlorohydrocarbons in the RN sand was found. After RN, Curiosity traveled to Yellowknife Bay and drilled two holes separated by 2.75 m designated John Klein (JK) and Cumberland (CB). Analyses of JK and CB by both SAM and the CheMin x-ray diffraction instrument revealed a mudstone (called Sheepbed) consisting of approx.20 wt% smectite clays, which on Earth are known to aid the concentration and preservation of organic matter. Last year at LPSC we reported elevated abundances of chlorobenzene (CBZ) and a more diverse suite of chlorinated hydrocarbons including dichloroalkanes in CB compared to RN, suggesting that martian or meteoritic organic compounds may be preserved in the mudstone. Here we present SAM data from additional analyses of the CB sample and of Confidence Hills (CH), another drill sample collected at the base of Mt. Sharp. This new SAM data along with supporting laboratory analog experiments indicate that most of the chlorobenzene detected in CB is derived from martian organic matter preserved in the mudstone.

Among the experiments which explore the martian soil aboard the Curiosity Rover, SAM experiment is mainly dedicated to the search for indigenous organic compounds. To reach its goals SAM can operate in different analysis modes: Pyrolysis-GC-MS and Pyrolysis-MS (EGA). In addition SAM includes wet chemistry experiments [1] to supports extraction of polar organic compounds from solid samples that improves their detection either by increasing the release of chemical species from solid sample matrices, or by changing their chemical structure to make compounds more amenable to gas chromatography mass spectrometry (GCMS). The two wet chemistry experimental capabilities of SAM provide alternatives to the nominal inert-thermal desorption/pyrolysis analytical protocol and are more aptly suited for polar components: MTBSTFA derivatization [2-3] and TMAH thermochemolysis [4-5]. Here we focus on the MTBSTFA derivatization experiment. In order to build a support used to help the interpretation of SAM results, we have investigated the artifacts and backgrounds sources generated by the all analysis process: Solid sample were heated up to approximately 840°C at a rate of 35°C/min under He flow. For GC analyses, the majority of the gas released was trapped on a hydrocarbon trap (Tenax®) over a specific temperature range. Adsorbed volatiles on the GC injection trap (IT) were then released into the GC column (CLP-MXT 30m x 0.25mm x 0.25µm) by rapidly heating the IT to 300°C. Then, in order better understand the part of compounds detected coming from internal reaction we have performed several lab experiments to mimic the SAM device: Among the sources of artifact, we test: (1) the thermal stability and the organic material released during the degradation of Tenax® and carbosieve, (2) the impact of MTBSTFA and a mixture of DMF and MTBSTFA on the adsorbent, (3) the reaction between the different adsorbents (Tenax® and Carbosieve) and calcium perchlorate and then (4) the sources and molecules that may constitute organic material precursors sources. References: [1] Mahaffy, P. et al. (2012) Space Sci Rev, 170, 401-478. [2] Glavin, D. et al. (2013), JGR. [3] Leshin L. et al. (2013), Science, [4] Williams, A.J., Eigenbrode, J.L.,m Floyd, M.M., Wilhelm, M.B., and Mahaffy, P.R., (2015), GSA. [5] Eigenbrode, J.L. et al. (2010), LPSC, abst.1460.

Interest of exploration on Mars Mars is interesting given that its early history is similar to one on the Earth. In fact, volcanoes were still active, the environment was wetter and warmer and the magneto-sphere still existed. Source of organic Mars: Various sources of endoge-nous organic matter (OM) could have existed including (a) abiotic production via hydrothermal vents, volcanism and atmospheric synthesis and (b) biotic synthesis. Currently, the sources of extraterrestrial organic compounds that should be delivered to Mars are known: carbon-rich meteorites , micrometeorites, comets and interstellar dust particles. Stabilization of the OM takes place through three mechanisms described in the article of Lutzow (1): (1) First, the selective preservation of OM is described as a phenomenon of accumulation of some compounds because of their resistance against the environment. (2) The second path which allows the persistence of OM is the space isolation of OM from environmental stress. (3) The last way to stabilize the OM is intermolecular interactions between minerals or metal ions with OM. One of the primary objectives of the Mars Science Laboratory (MSL) mission is to search for environments on the Martian surface that have preserved OM. Structure and aim of SAM Sample Analysis at Mars (SAM) is one of the instruments of the MSL mission. Three analytical devices are onboard SAM: the Tunable Laser Spectrometer (TLS), the Gas Chromatograph (GC) and the Mass Spectrometer (MS) (2). Solid sample preparation: To adapt the nature of a sample to the analytical devices used, a sample preparation and gas processing system implemented with (a) a pyrolysis system, (b) wet chemistry: MTBSTFA and TMAH (c) the hydrocarbon trap (silica beads, Tenax® TA and Car-bosieve G) which is employed to concentrate volatiles released from the sample prior to the GC-MS analyses. Detection of chlorinated hydrocarbons All chlorinated hydrocarbons detected during the Viking I and II missions and MSL (Rocknest (RN), John Klein (JK), Cumberland (CB) and Confidence Hill (CH)) are listed in Table 1. Viking landers (1976): The origin of chloromethane and dichloromethane was explained at the time by terrestrial contamination from the instruments (3). In a recent paper from Navarro-Gonzalez (4), these results have been rein-terpreted and chlorinated compounds could have been the product of the reaction of perchlorates identified by Phoe-nix (5) with martian organic carbon present in the sample or terrestrial organic carbon in the instrument or sample handling chain. MSL (2011): A diverse range of chlorinated hydrocarbons have been detected with SAM after GCMS analysis of samples collected from several sites explored by Curiosity rover (Table 1). Some of these chlorohydrocarbons are produced during pyrolysis by the reaction of martian oxychlorine compounds in the samples with terrestrial carbon from a derivatization agent (MTBSTFA) present in SAM (6, 7). Chlorobenzene (CBZ) cannot be formed by the reaction of MTBSTFA and perchlorates (6) and two other reaction pathways for CBZ were therefore proposed : (1) reactions between the volatile thermal degradation products of perchlorates (e.g. O2, Cl2 and HCl) and Tenax® and (2) the interaction of perchlorates (T > 200 °C) with OM from Mars's soil such as benzenecarbox-ylates (8, 9). Among all the sample analyzed by SAM, JK and CB sites are interesting; smectites (phyllosilicates-18 to 22 wt %) and quartz (0.1 to 1 wt %) were detected at the two sites (10) and could have an important role in the preservation of OM (1). Objectives This study investigates several hypotheses for chlorin-ated hydrocarbon formation by looking for: (a) all products coming from the interaction of Tenax® and perchlorates, (b) products between various soil sample and perchlorates and (c) sources of chlorinated hydrocarbon precursors. Experiments and methods: To answer some of our remaining questions, laboratory experiments were done in several solid matrices which Viking MSL RN JK CB CH

All the aliphatic and aromatic molecules detected will be presented and the phenomenon involved on the pyrolysis of samples will be shown. From these results we will be able to better understand the origin of the organic molecules detected with SAM.

The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long‐term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150–300 parts per billion by weight (ppbw)) and C2 to C4 dichloroalkanes (up to 70 ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles.

Volatiles were recently discovered to be present at the Lunar pole. These volatiles probably comes from meteorites and micrometeorites which continue to deliver their material at the surface of the satellite. Thus, their characterisation would enable to better constrain the nature of the species brought by the meteorites to the solar system bodies, evaluate their evolution under Moon surface conditions. Thus is what we expect to be able to do within a few years with the Gas Analytical Package experiment onboard the Louna Globe mission.