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1. Microchip gas chromatographic columns dedicated for space exploration: Stationary phase coating, setup optimization and evaluation of column performances

Author

Arnaud Philippart, Valérie Peulon-Agasse, Malak Rizk-Bigourd, Audrey Boco-Simon, Gabin Bergerot, Guillaume Rioland, Arnaud Buch, Cyril Szopa, and Pascal Cardinael

Subjects
Miniaturization, Microchip column, Space exploration, Stationary phase coating, Gas chromatography, Analytical chemistry, QD71-142
Abstract

This work is the first part of a project aiming to specifically design gas chromatographic microcolumns for space exploration. In particular, this study explored the functionalization and characterization of silicon/glass microchip gas chromatographic columns designed with a serpentine-shaped channel having an internal square cross-section. This microcolumn can be connected using a robust fluidic manifold with removable capillary connections to a conventional gas chromatograph or implemented in a prototype instrument for space exploration. First, benchtop gas chromatographic system was optimized in terms of injector liner volume, internal diameter (I.D.) of the capillary connections and data frequency of detection to ensure an optimal evaluation of column efficiency. Junction capillaries of 100 μm I.D., a liner of 1.2 mm I.D. and a detection acquisition frequency of 100 Hz were found to be the optimal set-up and parameters. Moreover, the stationary phase coating velocity was slowed-down to increase column efficiency by 100 %. Then, the performances of a square cross-section capillary column were compared with those of a conventional circular cross-section column. The coating efficiencies were estimated at 55 % and 42 % for circular and square internal cross-section geometries respectively, demonstrating that the square section geometry did not affect significantly the column performances. Stationary phase films of different thicknesses, from 0.032 to 0.260 µm, were coated on different microchips of the same production batch to assess the influence of film thickness on the chromatographic performances. Microchips performance was evaluated through Golay's plots, and some of the microchips were also studied by optical microscopy. The efficiency and retention capacity of our microchip column is shown to be highly dependent on the film thickness (9,000 plates.m-1 with k = 0.12 for the thinnest film and up to almost 4,000 plates.m-1 with k = 0.93 for the thickest film). Finally, the coating process repeatability was validated by producing three identical microchips with RSD of 4.8 % for the average number of theoretical plates.

Published
2024
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2. Dark microbiome and extremely low organics in Atacama fossil delta unveil Mars life detection limits

Author

Armando Azua-Bustos, Alberto G. Fairén, Carlos González-Silva, Olga Prieto-Ballesteros, Daniel Carrizo, Laura Sánchez-García, Victor Parro, Miguel Ángel Fernández-Martínez, Cristina Escudero, Victoria Muñoz-Iglesias, Maite Fernández-Sampedro, Antonio Molina, Miriam García Villadangos, Mercedes Moreno-Paz, Jacek Wierzchos, Carmen Ascaso, Teresa Fornaro, John Robert Brucato, Giovanni Poggiali, Jose Antonio Manrique, Marco Veneranda, Guillermo López-Reyes, Aurelio Sanz-Arranz, Fernando Rull, Ann M. Ollila, Roger C. Wiens, Adriana Reyes-Newell, Samuel M. Clegg, Maëva Millan, Sarah Stewart Johnson, Ophélie McIntosh, Cyril Szopa, Caroline Freissinet, Yasuhito Sekine, Keisuke Fukushi, Koki Morida, Kosuke Inoue, Hiroshi Sakuma, and Elizabeth Rampe

Subjects
Science
Abstract

Unique microorganisms of a fossil river delta in the Atacama Desert unveil the current limits of life detection on Mars.

Published
2023
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3. Europan Molecular Indicators of Life Investigation (EMILI) for a Future Europa Lander Mission

Author

William B. Brinckerhoff, Peter A. Willis, Antonio J. Ricco, Desmond A. Kaplan, Ryan M. Danell, Andrej Grubisic, Maria F. Mora, Jessica S. Creamer, Aaron Noell, Jennifer Stern, Cyril Szopa, Caroline Freissinet, Florian Kehl, Konstantin Zamuruyev, Conner Castle, Justin Spring, Tomas Drevinskas, Mircea Badescu, Mauro S. Ferreira Santos, Elizabeth A. Jaramillo, Friso van Amerom, Xiang Li, Marco Castillo, Jennifer Eigenbrode, Bethany Theiling, Richard C. Quinn, Fabien Stalport, Arnaud Buch, and Kris Zacny

Subjects
Instrumentation And Photography
Abstract

The Europan Molecular Indicators of Life Investigation (EMILI) is an instrument concept being developed for the Europa Lander mission currently under study. EMILI will meet and exceed the scientific and technical/resource requirements of the organic composition analyzer identified as a core instrument on the Lander. EMILI tightly couples two complementary analytical techniques, based on 1) liquid extraction and processing with capillary electrophoresis and 2) thermal and chemical extraction with gas chromatography, to robustly detect, structurally characterize, and quantify the broadest range of organics and other Europan chemicals over widely-varying concentrations. Dual processing and analysis paths enable EMILI to perform a thorough characterization of potential molecular biosignatures and contextual compounds in collected surface samples. Here we present a summary of the requirements, design, and development status of EMILI with projected scientific opportunities on the Europa Lander as well as on other potential life detection missions seeking potential molecular biosignatures in situ.

Published
2022
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5. Selection and Analytical Performances of the Dragonfly Mass Spectrometer Gas Chromatographic Columns to Support the Search for Organic Molecules of Astrobiological Interest on Titan

Author

Valentin Moulay, Caroline Freissinet, Malak Rizk-Bigourd, Arnaud Buch, Mayline Ancelin, Elise Couturier, Caroline Breton, Melissa G. Trainer, and Cyril Szopa

Subjects
Space and Planetary Science, Agricultural and Biological Sciences (miscellaneous)
Abstract

Titan is a key planetary body for astrobiology, with the presence of a subsurface ocean and a dense atmosphere, in which complex chemistry is known to occur. Approximately 1-Titan-year after the Cassini-Huygens mission arrived in the saturnian system

Published
2022

6. Enceladus as a potential oasis for life: Science goals and investigations for future explorations

Author

Christophe Sotin, Takazo Shibuya, Gaël Choblet, Steven D. Vance, Francis Nimmo, Tomohiro Usui, Eloi Camprubi, Mark P. Panning, Shannon MacKenzie, Tim Van Hoolst, Jürgen Schmidt, Frank Postberg, Alice Lucchetti, Joachim Saur, Laura M. Barge, Geraint H. Jones, O. Cadek, Giuseppe Mitri, Marie Bēhounková, Caroline Freissinet, Ondrej Soucek, Matthew M. Hedman, Gabriel Tobie, Valery Lainey, Cyril Szopa, Marc Neveu, Alice Le Gall, Karen Olsson-Francis, Arnaud Buch, Yasuhito Sekine, Laboratoire de Planétologie et Géodynamique [UMR 6112] (LPG), Université d'Angers (UA)-Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec-Université Paris-Saclay, Charles University [Prague] (CU), Jet Propulsion Laboratory (JPL), NASA-California Institute of Technology (CALTECH), Utrecht University [Utrecht], PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), University of Idaho [Moscow, USA], Mullard Space Science Laboratory (MSSL), University College of London [London] (UCL), Observatoire de Paris, Université Paris sciences et lettres (PSL), INAF - Osservatorio Astronomico di Padova (OAPD), Istituto Nazionale di Astrofisica (INAF), Johns Hopkins University Applied Physics Laboratory [Laurel, MD] (APL), International Research School of Planetary Sciences [Pescara] (IRSPS), Università degli studi 'G. d'Annunzio' Chieti-Pescara [Chieti-Pescara] (Ud'A), Dipartimento di Fisica e Geologia [Perugia], Università degli Studi di Perugia (UNIPG), NASA Goddard Space Flight Center (GSFC), University of California [Santa Cruz] (UCSC), University of California, The Open University [Milton Keynes] (OU), Department of Mathematics and Computer Science (Freie Universität Berlin), Freie Universität Berlin, Universität zu Köln, University of Oulu, Earth-Life Science Institute [Tokyo] (ELSI), Tokyo Institute of Technology [Tokyo] (TITECH), Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Institute of Space and Astronautical Science (ISAS), Japan Aerospace Exploration Agency [Sagamihara] (JAXA), and Royal Observatory of Belgium [Brussels] (ROB)

Subjects
Solar System, 010504 meteorology & atmospheric sciences, Spacecraft, business.industry, Direct sampling, Astronomy and Astrophysics, 01 natural sciences, Natural (archaeology), Astrobiology, Fresh water, [SDU]Sciences of the Universe [physics], 13. Climate action, Space and Planetary Science, Primary (astronomy), 0103 physical sciences, Environmental science, business, Enceladus, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences, Rock blasting
Abstract

International audience; Enceladus is the first planetary object for which direct sampling of a subsurface water reservoir, likely habitable, has been performed. Over a decade of flybys and seven flythroughs of its watery plume, the Cassini spacecraft determined that Enceladus possesses all the ingredients for life. The existence of active eruptions blasting fresh water into space, makes Enceladus the easiest target in the search for life elsewhere in the Solar System. Flying again through the plume with more advanced instruments, landing at the surface near active sources and collecting a sample for return to Earth are the natural next steps for assessing whether life emerges in this active world. Characterizing this habitable world also requires detailed mapping and monitoring of its tidally-induced activity, from the orbit as well as from the surface using complementary platforms. Such ambitious goals may be achieved in the future in the framework of ESA large or medium-class missions in partnership with other international agencies, in the same spirit of the successful Cassini-Huygens mission. For all these reasons, exploring habitable ocean worlds, with Enceladus as a primary target, should be a priority topic of the ESA Voyage 2050 programme.

Published
2021
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8. Analysis of aromatic organic salts with gas chromatography-mass spectrometry and implications for their detection at Mars surface with in situ experiments

Author

Ophélie Mcintosh, Cyril Szopa, Caroline Freissinet, Arnaud Buch, and David Boulesteix

Abstract

Introduction. The harsh oxidative and radiative conditions of the Martian environment influence the fate of organic molecules present on its surface. Formation of radical species was suggested to transform organic macromolecules into carboxylic acid through Fenton chemistry (1, 2) or irradiation semiconductor surfaces (3). Aromatic carboxylic acids such as phthalic acid or benzoic acid are thought to be abundant on the Martian surface as they are in stable intermediate oxidation states and can be formed from the oxidation of Polycyclic Aromatic Hydrocarbons (PAHs) (1, 4) or alkylbenzene compounds (4) coming from endogenous or exogenous sources. Because benzene carboxylates are metastable, they should not be entirely oxidized into volatile molecules such as CO2 or O2, but instead, ionized by solar radiation to form organic salts (2, 4, 5). Benner et al. (2000) suggested that the low volatility of these salts could compromise their in situ detection through thermal extraction analyses as performed by analytic chemistry laboratories onboard Martian surface probes, such as the Sample Analyzer at Mars (SAM) experiment onboard Curiosity rover or the Mars Organic Molecular Analyzer (MOMA) instrument of the Rosalind Franklin Exomars rover (4-6). To determine the possibility to identify these molecules through direct or indirect detection on Mars, we examined laboratory results from SAM and MOMA-like Gas Chromatography-Mass Spectrometry (GC-MS) analyses of two acid/salt couples (phthalic acid/calcium phthalate and benzoic acid/calcium benzoate). We analyzed the difference in behavior and signatures of both molecular forms when using pyrolysis and wet chemistry experiments used in SAM and MOMA, and the relevance of these results in the search of organic molecules on Mars. Method. Synthetic samples were made by mixing the carboxylic acid molecules or their organic salts standards at 1wt.% in fused silica, to simulate a relatively inert mineral matrix. The samples were pyrolyzed in SAM-like conditions with a ramp of 35°C.min-1 and in MOMA-like conditions in flash pyrolysis at 500°C and 800°C. The volatiles released from each sample were analyzed by Evolved Gas Analysis (EGA) and Gas Chromatography-Mass Spectrometry (GC-MS). We also performed derivatization experiments to help detect refractory organic compounds, with N,N-methyl-tert-butyl-dimethylsilyltrifluoroacetamide (MTBSTFA), used for wet chemistry experiments in SAM, and N,N-Dimethylformamide dimethyl acetal (DMF-DMA), to be used in the MOMA experiment of the ExoMars mission. Organic acid/salt behavior under pyrolysis conditions. As predicted by Benner et al. (4), when analyzed through pyrolysis-GC-MS, the organic salts species did not produce the organic parent molecule (phthalic acid or benzoic acid (Fig. 1 (a)). However, we have identified two by-products characteristic of the degradation of the organic salts, diphenylmethane (Fig. 1 (b)) and triphenylmethane (Fig.1 (b)) which were absent of the chromatograms of the acid species. These results show that for both carboxylic acid couples studied, the acid and the salt don’t follow the same degradation pathway resulting in differences in the species detected as well as major differences in the abundance of products observed in the chromatograms. This means that if carboxylic acids are present on Mars in their saline form linked to calcium cations, we would not be able to identify it through the detection of its acid form with the SAM nor MOMA pyrolysis set-ups, but rather through the detection of characteristic by-products that would serve as indirect clues for identification. Figure 1. Chromatograms obtained under the same analytical conditions as the pyrolysis in SAM. (a) benzoic acid mixed at 1 wt. % in fused silica and (b) calcium benzoate mixed at 1 wt. % in fused silica. Organic acid/salt derivatized with MTBSTFA and DMFDMA. Figure 2. Bar chart representing the abundance of derivatized benzoic acid obtained with calcium benzoate and benzoic acid. The derivatization reagent used was DMFDMA (a) and MTBSTFA (b). When derivatized with DMFDMA or MTBSTFA, both the acid and the organic salt produced the derivatized product of the carboxylic acid. Both the phthalic acid and benzoic acids have a higher derivatization yield than their salt counterpart with both derivatization reagents. This is likely due to a better availability of the hydrogen on the carboxylic acid function. Moreover, we obtained a higher yield of both the acid and the salt with MTBSTFA than with DMF-DMA, with the loss of detection of calcium phthalate derivative with the latter. In conclusion, if present in the Martian soil, aromatic organic salts could be directly detected through wet chemistry experiments, showing the complementarity of this technique with pyrolysis. References. (1) Oró et al. (1979) Life Sciences and Space Research, 77-86. (2) Donald et al. (2013) Science. (3) Fox et al. (2019) Journal of Geophysical Research: Planets 124, 3257-3266. (4) Benner et al. (2000) Proceedings of the National Academy of Sciences 97, 2425-2430. (5) Lasne et al. (2016) Astrobiology 16, 977-996. (6) Hakkinen et al. (2014) Environ Sci Technol 48, 13718-13726.

Published
2022
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9. Methane vertical profile in Titan’s atmosphere

Author

Thomas Gautier, Joseph Serigano, Koyena Das, Maélie Coutelier, Sarah Hörst, Sandrine Vinatier, Cyril Szopa, and Melissa Trainer

Abstract

More than a decade after the arrival of the Cassini-Huygens mission in Saturn’s system, data returned by the Huygens probe during its descent remain a unique source of in-situ information on the lower atmosphere of Titan. Among the Huygens instrumental suite was the GCMS (Gas Chromatograph Mass Spectrometer) instrument which returned hundreds of mass spectra acquired in the atmosphere below 145 km of altitude. We will present a reanalysis of GCMS data focusing on the methane vertical profile thanks to recent advances in our knowledge of Titan’s atmosphere and in mass spectrometry data treatment [1-3]. We retrieved methane mixing ratio slightly lower than the one reported by the original team[4] and obtained its profile between 145 km and 30 km of altitude with a kilometric vertical resolution, and a sub-kilometric one between 30 km and the surface. Such a vertical resolution unveiled clear oscillations in the methane mixing ratio in Titan’s troposphere and methane vertical concentration diverging from an ideal adiabat. Such features could for example be a sign of small-scale convective zones in the troposphere which could have triggered the gravity waves detected by Huygens in the stratosphere. We hope that the discovery of previously unnoticed features in GCMS data will also enable the reanalysis of data returned by other Huygens instruments such as HASI and DISR on Titan lower atmosphere. [1] Gautier et al. Decomposition of electron ionization mass spectra for space application using a Monte-Carlo approach. Rapid. Com. Mass Spec. 34(8), e8659 (2020) [2] Serigano et al. Compositional measurements of Saturn’s upper atmosphere and rings from Cassini INMS. JGR:Planets, 125 (8), E006427 (2020) [3] Serigano et al. Compositional Measurements of Saturn’s Upper Atmosphere and Rings from Cassini INMS: An extended Analysis of Measurements from Cassini’s Grand Finale Orbits. JGR:Planets, 127, E007238 (2022) [4] Niemann et al. Composition of Titan’s lower atmosphere and simple surface volatiles as measured by the Cassini-Huygens probe gas chromatograph mass spectrometer experiment. JGR 115, E12006, 2010

Published
2022
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10. Study of volatile compounds in the atmosphere of Titan

Author

Koyena Das, Thomas Gautier, Joseph Serigano, Cyril Szopa, Sarah M. Hörst, Maélie Coutelier, Sandrine Vinatier, and Melissa G. Trainer

Abstract

In Titan, the two major gases - dinitrogen (N2) and methane (CH4) are ionized and/or photolyzed at high altitudes by the sunlight and the energetic particles from Saturn's magnetosphere, resulting in rich atmospheric chemistry and a wide variety of carbon and nitrogen-bearing atmospheric compounds. In the present work, we focus on studying the vertical profiles of trace species in the lower atmosphere to obtain a better insight into the atmospheric processes taking place on Titan. To do so, we reanalyzed the data from the Gas Chromatograph Mass Spectrometer (GCMS) onboard the Huygens probe which executed its mission on 14th January 2005. The GCMS instrument sampled for nearly three and a half hours from an altitude of 146 km. It recorded data for two and a half hours in the atmosphere of Titan, then landed on the surface and kept on recording for another hour, after which the signal was lost. We analyzed the measurements made by direct sampling of the atmosphere (Niemann et al. 2010). These mass spectra obtained at different altitudes and pressure levels have been recalibrated to account for deadtime and saturation corrections to the measurements, set boundary conditions for the species, and considered sensitivity measurements from Cassini-Ion and Neutral Mass Spectrometer calibrations. We then analyzed the corrected mass spectra using Monte-Carlo deconvolution simulations. The simulations allow us to vary the peak intensities of fragmentation patterns of known species, which usually bears uncertainties on this kind of data, and then use a least-square fitting to deconvolve the mixed signals (Gautier et al. 2020, Serigano et al. 2020, 2022). We present our ongoing effort to retrieve minor compounds' mixing ratios using this approach. As an example, the vertical profile of one of the trace species ethane (C2H6), is shown in figure 1. Figure 1: Preliminary vertical profile of ethane (C2H6) mixing ratio In the future, we plan to extend this study to develop a sub-surface model of Titan which will help us understand the outgassing of methane that was observed by the probe upon its touchdown on the surface. References: Niemann et al. Composition of Titan’s lower atmosphere and simple surface volatiles as measured by the Cassini-Huygens probe gas chromatograph mass spectrometer experiment. JGR 115, E12006, 2010 Gautier et al. Decomposition of electron ionization mass spectra for space application using a Monte-Carlo approach. Rapid. Com. Mass Spec. 34(8), e8659 (2020) Serigano et al. Compositional measurements of Saturn’s upper atmosphere and rings from Cassini INMS. JGR:Planets, 125 (8), E006427 (2020) Serigano et al. Compositional Measurements of Saturn’s Upper Atmosphere and Rings from Cassini INMS: An extended Analysis of Measurements from Cassini’s Grand Finale Orbits. JGR:Planets, 127, E007238 (2022)

Published
2022
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11. Future in-situ chemical analysis on Europa and Enceladus: impact of salts on the detection of organic compounds in samples from hypersaline Tirez lake (La Mancha, Spain) with GC-MS

Author

Valentin Moulay, Caroline Freissinet, Arnaud Buch, Felipe Gomez Gomez, and Cyril Szopa

Abstract

Introduction: Europa and Enceladus, two ocean worlds in our solar system, are targets of high interest for astrobiology in the decades to come. Past space missions (Cassini-Huygens and Galileo) and recent observations with the Hubble Space telescope have revealed the presence of salts (sulfate and/or chloride) in the plumes of Enceladus and in the components of Europa’s surface (1-4). These salts could interfere in the in-situ chemical analyses of organic molecules present in the collected samples, thus limiting the chance to detect potential biosignatures in these worlds. In order to study this potential analytical interference, terrestrial analog samples to the ocean of Europa and Enceladus were characterized with gas chromatography mass spectrometry (GC-MS) and the associated pretreatment techniques (pyrolysis, derivatization and thermochemolysis) currently used for in-situ analyses of extraterrestrial environments. Analog samples: Tirez lacustrine system is located in La Mancha, Spain. The samples studied in this work were collected from seven salty lakes in 2019. They are in liquid state and characterized by a high concentration of Mg, Na, SO4 and Cl. These samples are of particular interest for oceans worlds because of spectra obtained from Fourier transform infrared technique were similar to the Galileo spectral data for Europa (5). In addition, micro-organisms from the three domains (bacteria, archaea, eukaryotes) were identified in Tirez lake materials (6). Among the numerous samples collected during the field trip, this work focused on ten of them for time of investigations. Results: Thanks to the pretreatment techniques associated to GC-MS, numerous molecules were identified. For instance, with derivatization (dimethylformamide dimethyl acetal) all the components from triglycerides were detected such as fatty acids (Figure) and glycerol. For some sample among the ten selected, phytol coming from the degradation of chlorophyll present in cyanobacteria was also detected. In addition, pyrolysis at different temperatures revealed the presence of furan derivatives, as well as phenol derivatives and naphthalene ones. For the two first, these come from the thermal degradation of carbonates and peptides respectively. In spite of the presence of salts, these few results show that we can identify molecules coming from the living with the usual analytical techniques used for space exploration. Figure: Chromatogram of a derivatized sample (from Lillo Lake) with DMF-DMA after evaporation of the water. I.S.: internal standard. Perspectives: Numerous compounds from micro-organisms were not detected such as amino acids or nitrogenous bases. In the near future, we want to try to desalinate these samples in order to identified more organic biosignatures. In addition, specific extraction will be made, particularly for amino acids, in order to characterize their content and confirm or deny that the salts prevent their detection. References: (1) T. B. McCord, Hydrated salt minerals on Europa's surface from the Galileo near-infrared mapping spectrometer investigation. Journal of Geophysical Research 104, (1999). (2) Waite, Cassini Ion and Neutral Mass Spectrometer Enceladus Plume composition and Structure. Science 311, (2006). (3) S. K. Trumbo, M. E. Brown, K. P. Hand, Sodium chloride on the surface of Europa. Science Advances 5, eaaw7123 (2019). (4) S. K. Trumbo, et al., A New UV Spectral Feature on Europa: Confirmation of NaCl in Leading-hemisphere Chaos Terrain. (2022). (5) O. Prieto-Ballesteros, Tírez Lake as a Terrestrial Analog of Europa. (2003). (6) L. Montoya et al., Microbial community composition of Tirez lagoon (Spain), a highly sulfated athalassohaline environment. Aquatic Biosystems 9, 19 (2013).

Published
2022
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12. Influence of Calcium Perchlorate on the Search for Organics on Mars with Tetramethylammonium Hydroxide Thermochemolysis

Author

Yuanyuan He, Pin Lu, Paul R. Mahaffy, Charles Malespin, Melissa Guzman, Cyril Szopa, Amy J. Williams, Samuel Teinturier, Maeva Millan, Sarah Stewart Johnson, Michel Cabane, Hervé Cottin, Jennifer C. Stern, Jennifer L. Eigenbrode, Rafael Navarro-González, Vincent Butin, Fabien Stalport, Naila Chaouche-Mechidal, Caroline Freissinet, Arnaud Buch, D. Coscia, Daniel P. Glavin, Jamila El Bekri, Jean-Yves Bonnet, Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec-Université Paris-Saclay, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), University of Florida [Gainesville] (UF), NASA Goddard Space Flight Center (GSFC), Georgetown University [Washington] (GU), GSFC Solar System Exploration Division, Telespazio France, Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Instituto de Ciencias Nucleares [Mexico], Universidad Nacional Autónoma de México = National Autonomous University of Mexico (UNAM), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Paris (UP)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), and Universidad Nacional Autónoma de México (UNAM)

Subjects
chemistry.chemical_classification, Tetramethylammonium hydroxide, Perchlorates, Extraterrestrial Environment, Inorganic chemistry, Pyrolysis gc ms, Mars, Calcium perchlorate, Mars Exploration Program, 010402 general chemistry, 01 natural sciences, Agricultural and Biological Sciences (miscellaneous), Gas Chromatography-Mass Spectrometry, 0104 chemical sciences, Quaternary Ammonium Compounds, chemistry.chemical_compound, chemistry, [SDU]Sciences of the Universe [physics], 13. Climate action, Space and Planetary Science, 0103 physical sciences, Sample Analysis at Mars, Calcium, Organic matter, 010303 astronomy & astrophysics
Abstract

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.

Published
2021
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15. COSAC's Only Gas Chromatogram Taken on Comet 67P/Churyumov‐Gerasimenko

Author

Guillaume Leseigneur, Jan Hendrik Bredehöft, Thomas Gautier, Chaitanya Giri, Harald Krüger, Alexandra J. MacDermott, Uwe J. Meierhenrich, Guillermo M. Muñoz Caro, François Raulin, Andrew Steele, Cyril Szopa, Wolfram Thiemann, Stephan Ulamec, Fred Goesmann, Institut de Chimie de Nice (ICN), Université Nice Sophia Antipolis (1965 - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Universität Bremen, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Earth-Life Science Institute [Tokyo] (ELSI), Tokyo Institute of Technology [Tokyo] (TITECH), Max-Planck-Institut für Sonnensystemforschung (MPS), Max-Planck-Gesellschaft, University of Houston [Clear Lake], Centro de Astrobiologia [Madrid] (CAB), Instituto Nacional de Técnica Aeroespacial (INTA)-Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), Carnegie Institution for Science, Deutsches Zentrum für Luft- und Raumfahrt [Bonn] (DLR), G.L and U.M acknowledge the financial support of the ANR (ANR-15-IDEX-01 and ANR-18-CE29-0004). T.G. acknowledges the financial support from the Programme National de Planétologie (PNP) of CNRS/INSU co-funded by CNES and of the ANR (ANR-20-CE49-0004-01). G.M.M.C. acknowledges the Spanish MICINN under project PID2020-118974GB−C21 (AEI/FEDER, UE) and the Unidad de Excelencia ‘María de Maeztu’ MDM-2017-0737 – Centro de Astrobiología (INTA-CSIC)., ANR-18-CE29-0004,AAAs,L'Asymétrie des Acides Aminés(2018), ANR-15-IDEX-0001,UCA JEDI,Idex UCA JEDI(2015), and ANR-20-CE49-0004,TOMTA,Sur la piste de la matière organique dans l'atmosphère de Titan(2020)

Subjects
67P/Churyumov-Gerasimenko, Chromatography, comet, trace analysis, [SDU]Sciences of the Universe [physics], gas chromatography, Rosetta, General Chemistry, Philae, COSAC Instrument, mass spectrometry
Abstract

International audience; The Philae lander of the Rosetta space mission made a non-nominal landing on comet 67P/Churyumov-Gerasimenko on November 12, 2014. Shortly after, using the limited power available from Philae's batteries, the COSAC instrument performed a single 18- minutes gas chromatogram, which has remained unpublished until now due to the lack of identifiable elution. We show that despite the unsuccessful drilling of the comet and deposition of surface material in the SD2 ovens, the measurements from the COSAC instrument were executed nominally. We describe an automated search for extremely small deviations from noise and discuss the possibility of a signal from ethylene glycol at m/z 31. Arguments for and against this detection are listed, but the results remain inconclusive. Still, the successful operations of an analytical chemistry laboratory on a cometary nucleus gives great hope for the future of space exploration.

Published
2022
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16. Back Cover: ESA's Cometary Mission Rosetta—Re‐Characterization of the COSAC Mass Spectrometry Results (Angew. Chem. Int. Ed. 29/2022)

Author

Guillaume Leseigneur, Jan Hendrik Bredehöft, Thomas Gautier, Chaitanya Giri, Harald Krüger, Alexandra J. MacDermott, Uwe J. Meierhenrich, Guillermo M. Muñoz Caro, François Raulin, Andrew Steele, Harald Steininger, Cyril Szopa, Wolfram Thiemann, Stephan Ulamec, and Fred Goesmann

Subjects
General Chemistry, Catalysis
Published
2022
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17. ESA's Cometary Mission Rosetta—Re-Characterization of the COSAC Mass Spectrometry Results

Author

Guillaume Leseigneur, Jan Hendrik Bredehöft, Thomas Gautier, Chaitanya Giri, Harald Krüger, Alexandra J. MacDermott, Uwe J. Meierhenrich, Guillermo M. Muñoz Caro, François Raulin, Andrew Steele, Harald Steininger, Cyril Szopa, Wolfram Thiemann, Stephan Ulamec, Fred Goesmann, Institut de Chimie de Nice (ICN), Université Nice Sophia Antipolis (1965 - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Institute for Applied and Physical Chemistry [Bremen] (IAPC), University of Bremen, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Earth-Life Science Institute [Tokyo] (ELSI), Tokyo Institute of Technology [Tokyo] (TITECH), Max-Planck-Institut für Sonnensystemforschung (MPS), Max-Planck-Gesellschaft, University of Houston [Clear Lake], Centro de Astrobiologia [Madrid] (CAB), Instituto Nacional de Técnica Aeroespacial (INTA)-Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Geophysical Laboratory [Carnegie Institution], Carnegie Institution for Science, Orbitale Hochtechnologie Bremen (OHB Systems AG), Deutsches Zentrum für Luft- und Raumfahrt [Bonn] (DLR), G.L and U.M acknowledge the financial support of the ANR (ANR-15-IDEX-01 and ANR-18-CE29-0004). T.G. acknowledges the financial support from the Programme National de Planétologie (PNP) of CNRS/INSU co-funded by CNES and of the ANR (ANR-20-CE49-0004-01) for the development of the Monte-Carlo inversion method. G.M.M.C. acknowledges the Spanish MICINN under project PID2020-118 974GB-C21 (AEI/FEDER, UE) and the Unidad de Excelencia 'María de Maeztu' MDM-2017-0737—Centro de Astrobiología (INTA-CSIC)., ANR-15-IDEX-0001,UCA JEDI,Idex UCA JEDI(2015), and ANR-18-CE29-0004,AAAs,L'Asymétrie des Acides Aminés(2018)

Subjects
Rosetta Mission, [SDU]Sciences of the Universe [physics], Comet, Rosetta, Comets, Chemical Composition, General Chemistry, Analytical Methods, Philae, Catalysis, Mass Spectrometry
Abstract

International audience; The most pristine material of the Solar System is assumed to be preserved in comets in the form of dust and ice as refractory matter. ESA’s mission Rosetta and its lander Philae had been developed to investigate the nucleus of comet 67P/Churyumov-Gerasimenko in situ. Twenty-five minutes after the initial touchdown of Philae on the surface of comet 67P in November 2014, a mass spectrum was recorded by the time-of-flight mass spectrometer COSAC onboard Philae. The new characterization of this mass spectrum through non-negative least squares fitting and Monte Carlo simulations reveals the chemical composition of comet 67P. A suite of 12 organic molecules, 9 of which also found in the original analysis of this data, exhibit high statistical probability to be present in the grains sampled from the cometary nucleus. These volatile molecules are among the most abundant in the comet’s chemical composition and represent an inventory of the first raw materials present in the early Solar System.

Published
2022
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20. Influence of Calcium Perchlorate on the Search for Martian Organic Compounds with MTBSTFA/DMF Derivatization

Author

Sarah Stewart Johnson, Amy J. Williams, Daniel P. Glavin, Jean-Yves Bonnet, Melissa Guzman, Charles Malespin, Caroline Freissinet, Rafael Navarro-González, Michel Cabane, Arnaud Buch, Yuanyuan He, D. Coscia, Cyril Szopa, Maeva Millan, Jennifer L. Eigenbrode, Samuel Teinturier, Pin Lu, Paul R. Mahaffy, Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec-Université Paris-Saclay, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Department of Biology [Washington], Georgetown University [Washington] (GU), NASA Goddard Space Flight Center (GSFC), Instituto de Ciencias Nucleares [Mexico], Universidad Nacional Autónoma de México (UNAM), Department of Geological Sciences [Gainesville] (UF|Geological), University of Florida [Gainesville] (UF), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), and Telespazio France

Subjects
Extraterrestrial Environment, 010504 meteorology & atmospheric sciences, Inorganic chemistry, Mars, 01 natural sciences, Gas Chromatography-Mass Spectrometry, Perchlorate, chemistry.chemical_compound, 0103 physical sciences, Derivatization, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences, Perchlorates, Chemistry, Chloromethane, Dimethylformamide, Calcium perchlorate, Agricultural and Biological Sciences (miscellaneous), 13. Climate action, Space and Planetary Science, Chlorobenzene, [SDU]Sciences of the Universe [physics], Reagent, Sample Analysis at Mars, Calcium, Pyrolysis
Abstract

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.

Published
2021
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21. Performance of the SAM gas chromatographic columns under simulated flight operating conditions for the analysis of chlorohydrocarbons on Mars

Author

Cyril Szopa, Sarah Stewart Johnson, Maeva Millan, Samuel Teinturier, Paul R. Mahaffy, Michel Cabane, Arnaud Buch, Department of Biology [Washington], Georgetown University [Washington] (GU), NASA Goddard Space Flight Center (GSFC), PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), and CentraleSupélec

Subjects
Chemical substance, Extraterrestrial Environment, Mars, 010402 general chemistry, Mass spectrometry, Life on Mars, 01 natural sciences, Biochemistry, Chlorinated hydrocarbons, Gas Chromatography-Mass Spectrometry, Analytical Chemistry, Soil, Hydrocarbons, Chlorinated, Gas chromatography, Chromatography, Spectrometer, Chemistry, 010401 analytical chemistry, Organic Chemistry, Sample Analysis at Mars, General Medicine, Mars Exploration Program, Curiosity rover, [SDU.ASTR.IM]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Instrumentation and Methods for Astrophysic [astro-ph.IM], 0104 chemical sciences, 13. Climate action, Environmental Monitoring
Abstract

"Multi-column gas chromatography analysis of chlorohydrocarbons 1with the SAM experiment onboard NASA’s Mars Curiosity rover" est le titre provisoire de la publication.; International audience; 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.

Published
2019
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23. Mars Organic Molecule Analyzer (MOMA) Flight Analog Activities in Preparation for ExoMars Surface Operations

Author

William B. Brinckerhoff, Fred Goesmann, François Raulin, Cyril Szopa, NASA Goddard Space Flight Center (GSFC), Max-Planck-Institut für Sonnensystemforschung (MPS), Max-Planck-Gesellschaft, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Paris (UP)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12), PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), and Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Surface (mathematics), Spectrum analyzer, Materials science, [SDU]Sciences of the Universe [physics], Analytical chemistry, Molecule, Mars Exploration Program, ComputingMilieux_MISCELLANEOUS
Abstract

The Mars Organic Molecule Analyzer (MOMA) investigation is part of the scientific payload of the ExoMars rover Rosalind Franklin that will arrive at Oxia Planum on Mars in June, 2023. MOMA is a dual-source (laser desorption, LD, and gas chromatography, GC) mass spectrometer (MS) that will analyze the organic chemical composition of collected samples in support of the ExoMars objective to seek the signs of life in the near subsurface (up to two meters depth) of Mars [1]. The dual-source design allows MOMA to provide broadly sensitive detection of organics over a range of molecular weights and volatilities, as well as probe structural patterns of martian molecules such as enantiomeric ratios or chain length biases in aliphatic moieties. A number of important MOMA activities are being carried out in preparation for ExoMars launch in 2022 and science mission beginning in mid-2023. These activities will optimize the readiness of all relevant MOMA hardware (both flight and reference) and of the full team for surface operation. These include development and certification of the MOMA Testbed Model that will serve as a flight reference instrument, analysis of Mars analog samples with MOMA laboratory capabilities, and preparation for data analysis, decision making, and risk management during the rover mission. The Testbed Model is a ground-based duplicate of the Flight Model (FM), serving a dual role as (i) an engineering reference for verification and validation of flight procedures and for diagnosing flight performance (including any off-nominal situations); and (ii) a science reference with direct traceability to the sensitivity, background, and other characteristics of the FM, with the potential to carry out selected analog studies for scientific interpretation of MOMA flight data. The Testbed must always retain full flight fidelity and be available on tactical (sol-to-sol) timeframes (more-or-less continuously) to serve its engineering reference functions. It can thus be used to test modified operational software scripts to be run subsequently on the FM. There is additionally a strong bias to maintaining the Testbed in a state of low chemical background and overall performance, comparable to the FM, to retain its ability to rule-in/out any detections of low-concentration organic compounds on Mars. As such the bar for introduction of complex Mars analog samples into the Testbed must be set very high, and must be managed responsibly over the mission duration. Only those analyses requiring the full fidelity of the FM, under simulated Mars ambient conditions, for interpretation of critical data products would normally be considered for significant scientific use of the Testbed. A variety of sample studies are conducted in MOMA team laboratories, including use of the Engineering Test Unit (ETU) which lacks the Mars thermal-vacuum (Mars ambient pressure) environmental facility of the Testbed but is otherwise a high-fidelity scientific performance reference of MOMA used for analysis of Mars analog materials. Some of the ongoing and planned ETU-based test campaigns include: (i) development of detailed protocols for collection of LD mass spectra, comparing point-by-point and multi-pulse averaging modes [2] and use of isolation and tandem mass spectrometry, or MS/MS, capabilities to inform chemical assignments; (ii) characterization of the dependence on geochemical (e.g. sample matrix) and environmental factors during analysis of organic compounds using derivatization and GCMS, to include a recently-upgraded GC ETU supporting flight-like column and gas processing line temperatures; and (iii) participation in ExoMars collaborative analysis campaigns, using additional shared analogs including designated “mission samples” (matching projected compositions at Oxia Planum), alongside other payload investigations such as the MicrOmega and Raman spectrometers of the Analytical Laboratory Drawer (ALD). In addition to developing and testing flight-like experimental resources, the MOMA team is actively involved in preparations for ExoMars operations across the spectrum of planning and training for telemetry management, science analysis, and decision-making roles and processes. Team members are participating in rover simulation and software tool training hosted by the Rover Operations Control Center (ROCC) managed by ALTEC SpA, Turin, Italy. As a nominal “end-point” analysis of collected samples during each Experiment Cycle and Vertical Survey campaign, MOMA has significant interest in collaborating fully with all rover scientific payload teams to develop target interpretations and prioritizations based on remote, contact, and collected-sample analyses. As such mission simulations merging and synchronizing strategic and tactical processes of increasing fidelity are critical. Within the context and structure of these rover-level interactions and flows, the MOMA team additionally is establishing a set of scenario- and data-based evaluation metrics and decision-making procedures to aid in efficient and robust science operations in line with overall MOMA analytical objectives. One line of science scenario preparation is understanding what aspects of sample characteristics and preliminary mineralogy, as determined by other rover instruments, will be used to set initial MOMA parameters for LDMS or GCMS runs. Such settings are empirically based on laboratory data as well as rover mission data up to that point. Any follow-up analyses by MOMA on the same sample, such as selection of a particular type of chemical derivatization and GC column, would similarly depend on advance understanding based on analog and flight data. The need for decision making preparation applies to non-optimal, unexpected, and/or anomalous situations as well as nominal operations. Given the few-hour turnaround for tactical decisions, to avoid the potential for loss of a sol MOMA is developing policies and procedures to determine the nature of the situation, and work in conjunction with the rover team to assess options, and to convey, through the MOMA PI and operations team, a recommended path forward, based on prior simulations and flight experience. Examples of such cases may include finding that less (or more) energy is available for a given MOMA run than planned, or more concerning, receiving anomalous data products (e.g., noise) or alarmed housekeeping values. The above activities, carried out across the MOMA team, provide critical inputs to the planned Operational Readiness Reviews in mid-2022 and allow the MOMA investigation and the ExoMars mission to meet its higher-level goals. Goesmann F et al. (2017) Astrobiology 17:655-685. https://doi.org/10.1089/ast.2016.1551 Siljeström S et al. (2021) Astrobiology. https://doi.org/10.1089/ast.2020.2368

Published
2021
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24. Science Goals and Objectives for the Dragonfly Titan Rotorcraft Relocatable Lander

Author

Simon Stähler, E. R. Stofan, Kevin P. Hand, C. D. Neish, William B. Brinckerhoff, Colin Wilson, Ralph D. Lorenz, Scot Rafkin, R. A. Yingst, Tetsuya Tokano, Kris Zacny, Jani Radebaugh, Christopher P. McKay, Patrick N. Peplowski, Alexander Hayes, Erich Karkoschka, Juan M. Lora, Jorge I. Nunez, Jason W. Barnes, Claire E. Newman, Melissa G. Trainer, Alice Le Gall, A. M. Parsons, Caroline Freissinet, Mark P. Panning, Lynnae C. Quick, David J. Lawrence, Carolyn M. Ernst, Cyril Szopa, Thomas P. Wagner, Jeffrey R. Johnson, Hiroaki Shiraishi, R. S. Miller, Kristin S. Sotzen, Sarah M. Hörst, Shannon MacKenzie, Elizabeth P. Turtle, Morgan L. Cable, Scott L. Murchie, Jason M. Soderblom, Angela Stickle, Department of Physics [Moscow,USA], University of Idaho [Moscow, USA], Johns Hopkins University Applied Physics Laboratory [Laurel, MD] (APL), NASA Goddard Space Flight Center (GSFC), Jet Propulsion Laboratory (JPL), NASA-California Institute of Technology (CALTECH), PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Department of Astronomy [Ithaca], Cornell University [New York], Morton K. Blaustein Department of Earth and Planetary Sciences [Baltimore], Johns Hopkins University (JHU), Lunar and Planetary Laboratory [Tucson] (LPL), University of Arizona, Department of Earth and Planetary Sciences [New Haven], Yale University [New Haven], NASA Ames Research Center (ARC), Planetary Science Institute [Tucson] (PSI), Department of Earth Sciences [London, ON], University of Western Ontario (UWO), Aeolis Research, Department of Geological Sciences [BYU], Brigham Young University (BYU), Southwest Research Institute [Boulder] (SwRI), Institute of Space and Astronautical Science (ISAS), Japan Aerospace Exploration Agency [Sagamihara] (JAXA), Department of Earth and Planetary Sciences [Cambridge, USA] (EPS), Harvard University [Cambridge], Smithsonian National Air and Space Museum, Smithsonian Institution, Institut für Geophysik und Meteorologie [Köln], Universität zu Köln, NASA Headquarters, Department of Atmospheric, Oceanic and Planetary Physics [Oxford] (AOPP), University of Oxford [Oxford], Honeybee Robotics Ltd, Institute of Geophysics [ETH Zürich], Department of Earth Sciences [Swiss Federal Institute of Technology - ETH Zürich] (D-ERDW), and Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich)- Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich)

Subjects
Aquifer, 01 natural sciences, Mantle (geology), Astrobiology, Pre-biotic astrochemistry, 03 medical and health sciences, symbols.namesake, Extant taxon, Impact crater, 0103 physical sciences, Earth and Planetary Sciences (miscellaneous), Planetary surfaces, 14. Life underwater, 010303 astronomy & astrophysics, 030304 developmental biology, 0303 health sciences, geography, geography.geographical_feature_category, Habitability, Astronomy and Astrophysics, Prebiotic chemistry, Geophysics, 13. Climate action, Space and Planetary Science, [SDU]Sciences of the Universe [physics], symbols, Water ice, Titan (rocket family), Titan, Planetary atmospheres
Abstract

NASA’s Dragonfly mission will send a rotorcraft lander to the surface of Titan in the mid-2030s. Dragonfly's science themes include investigation of Titan’s prebiotic chemistry, habitability, and potential chemical biosignatures from both water-based “life as we know it” (as might occur in the interior mantle ocean, potential cryovolcanic flows, and/or impact melt deposits) and potential “life, but not as we know it” that might use liquid hydrocarbons as a solvent (within Titan’s lakes, seas, and/or aquifers). Consideration of both of these solvents simultaneously led to our initial landing site in Titan’s equatorial dunes and interdunes to sample organic sediments and water ice, respectively. Ultimately, Dragonfly's traverse target is the 80 km diameter Selk Crater, at 7° N, where we seek previously liquid water that has mixed with surface organics. Our science goals include determining how far prebiotic chemistry has progressed on Titan and what molecules and elements might be available for such chemistry. We will also determine the role of Titan’s tropical deserts in the global methane cycle. We will investigate the processes and processing rates that modify Titan’s surface geology and constrain how and where organics and liquid water can mix on and within Titan. Importantly, we will search for chemical biosignatures indicative of past or extant biological processes. As such, Dragonfly, along with Perseverance, is the first NASA mission to explicitly incorporate the search for signs of life into its mission goals since the Viking landers in 1976.

Published
2021
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25. A Feasible Study of In-Situ Measurements of Light Isotopes and Organic Molecules with High Resolution Mass Spectrometer MULTUM on the OKEANOS Mission

Author

Jun Matsumoto, Yoko Kebukawa, Noel Grand, Toshihiro Chujo, Michisato Toyoda, Cyril Szopa, Yosuke Kawai, Shoichiro Yokota, Ryota Ikeda, H. Cottin, Motoo Ito, Osamu Mori, Hajime Yano, Yuki Kubo, Hisayoshi Yurimoto, Arnaud Buch, Ryosuke Nakamura, Motoki Watanabe, Jun Aoki, Tatsuaki Okada, Kochi Institute for Core Sample Research, Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Institute of Space and Astronautical Science (ISAS), Japan Aerospace Exploration Agency [Sagamihara] (JAXA), Department of Aeonautics and Astronautics [Tokyo], The University of Tokyo (UTokyo), Yokohama National University, Osaka University [Osaka], National Institute of Advanced Industrial Science and Technology [Tokyo] (AIST), Hokkaido University [Sapporo, Japan], Aoyama Gakuin University (AGU), Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec-Université Paris-Saclay, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), and Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
In situ, In-Situ Analysis, Materials science, Isotope, Jupitar Trojan, Solar Power Sail, [SDU]Sciences of the Universe [physics], Analytical chemistry, High resolution, HRMS, Mass spectrometry, OKEANOS Mission, Organic molecules
Abstract

International audience; The OKEANOS mission utilizing the Solar Power Sail is one of the candidates of the strategic middle-class space exploration to the outer Solar System lead by the JAXA. The mission is planning to be launched in 2030's, and rendezvous for spectral observations and landing for in-situ measurements of light isotopes and organic molecules to a D or P type Jupitar Trojan asteroid in 2040's. The flagship instrument on board is a high-resolution mass spectrometry (HRMS) system together with suits of remote-sensing instruments. Through in-depth scientific observations, the OKEANOS mission will provide critical input to the key questions of (1) constraining planet formation/migration theories, and (2) inventory and distribution of volatiles in the Solar System. We have conducted experimental tests of a sample canister sealing by a metal seal knife-edge, sample canister-MULTUM test, gas chromatograph-MULTUM coupling test for organics, and H and N isotopic measurements in the atmospheric air. Current performances are (1) high mass resolution was 30,000 at m/z = 20, (2) sample canister system with a knife-edge metal seal kept 90 % of a released gas in 1 hour for Cu or Au gaskets with/without regolith, (3) error meets the required precision and accuracy for nitrogen isotopic measurement but for hydrogen. These experiment tests need to continue for our scientific proposes on the asteroids.

Published
2021
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26. Science goals and new mission concepts for future exploration of Titan's atmosphere geology and habitability: Titan POlar Scout/orbitEr and In situ lake lander and DrONe explorer (POSEIDON)

Author

Sébastien Rodriguez, Sandrine Vinatier, Daniel Cordier, Gabriel Tobie, Richard K. Achterberg, Carrie M. Anderson, Sarah V. Badman, Jason W. Barnes, Erika L. Barth, Bruno Bézard, Nathalie Carrasco, Benjamin Charnay, Roger N. Clark, Patrice Coll, Thomas Cornet, Athena Coustenis, Isabelle Couturier-Tamburelli, Michel Dobrijevic, F. Michael Flasar, Remco de Kok, Caroline Freissinet, Marina Galand, Thomas Gautier, Wolf D. Geppert, Caitlin A. Griffith, Murthy S. Gudipati, Lina Z. Hadid, Alexander G. Hayes, Amanda R. Hendrix, Ralf Jaumann, Donald E. Jennings, Antoine Jolly, Klara Kalousova, Tommi T. Koskinen, Panayotis Lavvas, Sébastien Lebonnois, Jean-Pierre Lebreton, Alice Le Gall, Emmanuel Lellouch, Stéphane Le Mouélic, Rosaly M. C. Lopes, Juan M. Lora, Ralph D. Lorenz, Antoine Lucas, Shannon MacKenzie, Michael J. Malaska, Kathleen Mandt, Marco Mastrogiuseppe, Claire E. Newman, Conor A. Nixon, Jani Radebaugh, Scot C. Rafkin, Pascal Rannou, Ella M. Sciamma-O’Brien, Jason M. Soderblom, Anezina Solomonidou, Christophe Sotin, Katrin Stephan, Darrell Strobel, Cyril Szopa, Nicholas A. Teanby, Elizabeth P. Turtle, Véronique Vuitton, Robert A. West, Institut de Physique du Globe de Paris (IPGP (UMR_7154)), Institut national des sciences de l'Univers (INSU - CNRS)-Université de La Réunion (UR)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Laboratoire d'études spatiales et d'instrumentation en astrophysique (LESIA (UMR_8109)), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Groupe de spectrométrie moléculaire et atmosphérique (GSMA), Université de Reims Champagne-Ardenne (URCA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Planétologie et Géosciences [UMR_C 6112] (LPG), Université d'Angers (UA)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Department of Astronomy [College Park], University of Maryland [College Park], University of Maryland System-University of Maryland System, NASA Goddard Space Flight Center (GSFC), Department of Physics and Astronomy [Leicester], University of Leicester, University of Idaho [Moscow, USA], Southwest Research Institute [Boulder] (SwRI), PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Planetary Science Institute [Tucson] (PSI), Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), European Space Astronomy Centre (ESAC), Agence Spatiale Européenne = European Space Agency (ESA), Physique des interactions ioniques et moléculaires (PIIM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Astrophysique de Bordeaux [Pessac] (LAB), Université de Bordeaux (UB)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Department of Physical Geography [Utrecht], Utrecht University [Utrecht], Department of Physics [Imperial College London], Imperial College London, Department of Physics [Stockholm], Stockholm University, Lunar and Planetary Laboratory [Tucson] (LPL), University of Arizona, Jet Propulsion Laboratory (JPL), NASA-California Institute of Technology (CALTECH), Laboratoire de Physique des Plasmas (LPP), Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École polytechnique (X)-Sorbonne Université (SU)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Cornell University [New York], Institute of Geological Sciences [Berlin], Department of Earth Sciences [Berlin], Free University of Berlin (FU)-Free University of Berlin (FU), Faculty of Mathematics and Physics [Charles University of Praha], Charles University [Prague] (CU), Laboratoire de Météorologie Dynamique (UMR 8539) (LMD), Institut national des sciences de l'Univers (INSU - CNRS)-École polytechnique (X)-École des Ponts ParisTech (ENPC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département des Géosciences - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), Observatoire des Sciences de l'Univers en région Centre (OSUC), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Centre National d’Études Spatiales [Paris] (CNES), Department of Earth and Planetary Sciences [New Haven], Yale University [New Haven], Johns Hopkins University Applied Physics Laboratory [Laurel, MD] (APL), Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA), Aeolis Research, Department of Geological Sciences [BYU], Brigham Young University (BYU), Space Science and Astrobiology Division at Ames, NASA Ames Research Center (ARC), Department of Earth, Atmospheric and Planetary Sciences [MIT, Cambridge] (EAPS), Massachusetts Institute of Technology (MIT), Division of Geological and Planetary Sciences [Pasadena], California Institute of Technology (CALTECH), DLR Institut für Planetenforschung, Deutsches Zentrum für Luft- und Raumfahrt [Berlin] (DLR), Johns Hopkins University (JHU), School of Earth Sciences [Bristol], University of Bristol [Bristol], Institut de Planétologie et d'Astrophysique de Grenoble (IPAG), Centre National d'Études Spatiales [Toulouse] (CNES)-Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut national des sciences de l'Univers (INSU - CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Météo-France -Institut national des sciences de l'Univers (INSU - CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Météo-France, Institut de Physique du Globe de Paris (IPGP), Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Laboratoire de Planétologie et Géodynamique [UMR 6112] (LPG), Université d'Angers (UA)-Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), European Space Agency (ESA), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome], Institut national des sciences de l'Univers (INSU - CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Grenoble Alpes (UGA), Laboratoire d'études spatiales et d'instrumentation en astrophysique = Laboratory of Space Studies and Instrumentation in Astrophysics (LESIA), Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPC), Université Paris sciences et lettres (PSL), Lancaster University, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPC), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPC), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National d’Études Spatiales [Paris] (CNES)

Subjects
geology, space mission concept, 010504 meteorology & atmospheric sciences, [PHYS.ASTR.EP]Physics [physics]/Astrophysics [astro-ph]/Earth and Planetary Astrophysics [astro-ph.EP], Habitability, [SDU.ASTR.EP]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Earth and Planetary Astrophysics [astro-ph.EP], FOS: Physical sciences, orbiter, 7. Clean energy, 01 natural sciences, drones, Orbiter, Poseidon, 0103 physical sciences, 010303 astronomy & astrophysics, Instrumentation and Methods for Astrophysics (astro-ph.IM), 0105 earth and related environmental sciences, Drones, Earth and Planetary Astrophysics (astro-ph.EP), Atmosphere, 500 Naturwissenschaften und Mathematik::520 Astronomie::520 Astronomie und zugeordnete Wissenschaften, Astronomy and Astrophysics, Geology, FOS: Earth and related environmental sciences, habitability, lake lander, 13. Climate action, Space and Planetary Science, atmosphere, Astrophysics - Instrumentation and Methods for Astrophysics, Titan, Lake lander, Astrophysics - Earth and Planetary Astrophysics
Abstract

In response to ESA Voyage 2050 announcement of opportunity, we propose an ambitious L-class mission to explore one of the most exciting bodies in the Solar System, Saturn largest moon Titan. Titan, a "world with two oceans", is an organic-rich body with interior-surface-atmosphere interactions that are comparable in complexity to the Earth. Titan is also one of the few places in the Solar System with habitability potential. Titan remarkable nature was only partly revealed by the Cassini-Huygens mission and still holds mysteries requiring a complete exploration using a variety of vehicles and instruments. The proposed mission concept POSEIDON (Titan POlar Scout/orbitEr and In situ lake lander DrONe explorer) would perform joint orbital and in situ investigations of Titan. It is designed to build on and exceed the scope and scientific/technological accomplishments of Cassini-Huygens, exploring Titan in ways that were not previously possible, in particular through full close-up and in situ coverage over long periods of time. In the proposed mission architecture, POSEIDON consists of two major elements: a spacecraft with a large set of instruments that would orbit Titan, preferably in a low-eccentricity polar orbit, and a suite of in situ investigation components, i.e. a lake lander, a "heavy" drone (possibly amphibious) and/or a fleet of mini-drones, dedicated to the exploration of the polar regions. The ideal arrival time at Titan would be slightly before the next northern Spring equinox (2039), as equinoxes are the most active periods to monitor still largely unknown atmospheric and surface seasonal changes. The exploration of Titan northern latitudes with an orbiter and in situ element(s) would be highly complementary with the upcoming NASA New Frontiers Dragonfly mission that will provide in situ exploration of Titan equatorial regions in the mid-2030s., Comment: arXiv admin note: substantial text overlap with arXiv:1908.01374

Published
2021
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27. Reevaluation of Methane vertical profile at Huygens Landing site from Huygens/GCMS measurements

Author

Thomas Gautier, Joseph Serigano, Cyril Szopa, Sarah Hörst, and Melissa Trainer

Abstract

Introduction More than a decade after its descent through Titan’s atmosphere, the data acquired by the instruments on the Huygens Probe remain the only in situ measurements in Titan’s deep atmosphere. Among these, the Gas Chromatograph Mass Spectrometer (GCMS) experiment aboard Huygens measured hundreds of mass spectra below 150 km to investigate the atmospheric composition [1,2]. However, there has not yet been a comprehensive attempt to decompose the mass spectra acquired by Huygens in order to extract the identity and abundances of many minor components and refine the retrieved mixing ratios of major atmospheric components (N2, CH4, Ar) Actually, at least 60% of the signal in the GCMS spectra has not been identified yet. As an example, while predicted ethane is strikingly absent from GCMS measurements during its descent [3-5]. The absence of ethane in data near the surface can be explained by its condensation, but its non-detection above 100 km re-mains one of the major discrepancies in our understanding of GCMS measurements. In addition to ethane, many organics predicted both by models and measurements at higher altitude remain unquantified in GCMS. In order to fill this gap, we have developed numerical tools to decompose flight mass spectrometry data, and applied it to conduct an in-depth reanalysis of the GCMS data collected during Huygens’ descent, leveraging recent advances in both knowledge of Titan’s atmosphere and mass spectral deconvolution for organic species. Methods We decompose the mass spectra acquired by GCMS below 146 km using the fragmentation pattern of the molecules detected by the instrument. This approach has been previously applied successfully to INMS data of Titan’s higher atmosphere during Cassini flybys [6]. However, up to now, this decomposition method required extensive knowledge of the instrument calibration data, which was the case for INMS. Such calibration data was unfortunately unavailable for the GCMS instrument. We thus developed a Monte-Carlo approach, simulating the diversity of possible fragmentation for a given molecule in the spectrometer ionization chamber, to handle degeneracy in the mass spectra decomposition. Results We analyzed all GCMS acquired mass spectra, from 135km altitude down to the surface. Between m/z 5 and 50. We thus retrieved the relative abundances of most volatiles species in Titan’s lower atmosphere. We were able to clearly identify and relatively quantify not only CH4, N2 and Ar as in the original GCMS paper [2], but we also identify 8 new species in this mass spectrum, including ethane. By decomposing the mass spectra at every altitude during Huygens descent, we obtained the vertical profile of major volatile species in Titan’s lower atmosphere Figure 1: Preliminary retrieved methane vertical profile above Huygens landing site. Our work is in red, to be compared with the original retrieval (dark blue). Discrepancies appear at altitudes above 80 km which might be able to reconcile GCMS measurements with Cassini CIRS and VIMS observations. Retrieved mixing ratio at high altitude (120 – 135 km) were compared with mixing ratios determined from CIRS or ground based observations and showed an excellent agreement between the methods. This allowed us to carry on at lower altitude and to retrieve volatiles mixing ratios throughout Huygens descent. We will present the retrieved mixing ratios for several minor volatiles species in Titan’s atmosphere, together with their associated probability density function and vertical profiles. Acknowledgements T.G. was supported by the Programme National de Planétologie (PNP) of CNRS/INSU, cofunded by CNES. This work was originally supported by the National Aeronautics and Space Administration under16-CDAP16_2-0087, initially issued through the Cassini Data Analysis Program, and NASA's Planetary Science Division Internal Scientist Funding Program through the Fundamental Laboratory Research (FLaRe) work package to M.G.T. References [1] Owen, T., Planetary science: Huygens rediscovers Titan, Nature 438(7069), pp. 756-757, 2005 [2] Niemann, H. B., S. K. Atreya, S. J. Bauer, G. R. Carignan, J. E. Demick, R. L. Frost, D. Gautier, J. A. Haberman, D. N. Harpold, D. M. Hunten, G. Israel, J. I. Lunine, W. T. Kasprzak, T. C. Owen, M. Paulkovich, F. Raulin, E. Raaen and S. H. Way: The abundances of constituents of Titan's atmosphere from the GCMS instrument on the Huygens probe, Nature 438(7069), pp. 779-784, 2005 [3] Bézard, B.; Yelle, R.; Nixon, C. A.: The Composition Of Titan's Atmosphere, In Titan: Surface, Atmosphere and Magnetosphere, Eds: I. Muller-Wodarg, C. Griffith, E. Lellouch and T. Cravens, Chap. 6, Cambridge University Press, 2014. [4] Vinatier S., B. Bézard, T. Fouchet, N. A. Teanby, R. de Kok, P.G.J. Irwin, B. J. Conrath, C. A. Nixon, P. N. Romani, F. M. Flasar, A. Coustenis: Vertical abundance profiles of hydrocarbons in Titan's atmosphere at 15° S and 80° N retrieved from Cassini/CIRS spectra, Icarus 188 (1), pp. 120-138, 2007 [5] Lavvas, P., C. A. Griffith and R. V. Yelle: Condensation in Titan’s atmosphere at the Huygens landing site, Icarus 215(2), pp. 732-750, 2011 [6] Gautier, T., Serigano, J., Bourgalais, J., Hörst, S.M., Trainer, M.G., 2020. Decomposition of electron ionization mass spectra for space application using a Monte‐Carlo approach. Rapid Commun. Mass Spectrom. 34. https://doi.org/10.1002/rcm.8684 [7] Serigano, J., Hörst, S.M., He, C., Gautier, T., R. V. Yelle, T.T. Koskinen, M. Trainer, 2020 Compositional Measurements of Saturn’s Upper Atmosphere and Rings from Cassini INM. Journal of Geophysical Research: Planets. [8] Cui, J., R.V. Yelle, V. Vuitton, J.H. Waite, W.T. Kasprzak, D.A. Gell, H.B. Niemann, I.C.F. Muller-Wodarg, N. Borggren, G.G. Fletcher, E. L. Patrick, E. Raaen, B.A. Magee: Analysis of Titan’s neutral upper atmosphere from Cassini Ion Neutral Mass Spectrometer Measurements, Icarus 200, pp. 581-615, 2009

Published
2020
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28. Influence of Calcium Perchlorate on Organics Under SAM‐Like Pyrolysis Conditions: Constraints on the Nature of Martian Organics

Author

Roger E. Summons, Cyril Szopa, Paul R. Mahaffy, Maeva Millan, Sarah Stewart Johnson, Rafael Navarro-González, Arnaud Buch, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Department of Biology [Washington], Georgetown University [Washington] (GU), NASA Goddard Space Flight Center (GSFC), Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec-Université Paris-Saclay, Department of Earth, Atmospheric and Planetary Sciences [MIT, Cambridge] (EAPS), Massachusetts Institute of Technology (MIT), and Universidad Nacional Autónoma de México (UNAM)

Subjects
Martian, chemistry.chemical_classification, 010504 meteorology & atmospheric sciences, Chemistry, Calcium perchlorate, Mars Exploration Program, 01 natural sciences, Regolith, chemistry.chemical_compound, Geophysics, [SDU]Sciences of the Universe [physics], 13. Climate action, Space and Planetary Science, Geochemistry and Petrology, Environmental chemistry, Sample Analysis at Mars, Earth and Planetary Sciences (miscellaneous), Molecule, Organic matter, Pyrolysis, 0105 earth and related environmental sciences
Abstract

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.

Published
2020
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29. The search for organic compounds with TMAH thermochemolysis: From Earth analyses to space exploration experiments

Author

Arnaud Buch, D. Coscia, Daniel P. Glavin, Michel Cabane, Caroline Freissinet, Melissa Guzman, Charles Malespin, Jennifer L. Eigenbrode, Maeva Millan, Cyril Szopa, Yuanyuan He, Samuel Teinturier, Amy J. Williams, Paul R. Mahaffy, Pin Lu, Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec-Université Paris-Saclay, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), University of Florida [Gainesville] (UF), Georgetown University [Washington] (GU), NASA Goddard Space Flight Center (GSFC), and GSFC Solar System Exploration Division

Subjects
Tetramethylammonium hydroxide, Internal standard, Tetramethylammonium hydroxide (TMAH), SAM and MOMA, 010401 analytical chemistry, Pyrolysis gc ms, Space experiment, 01 natural sciences, Derivatization, 0104 chemical sciences, Analytical Chemistry, Thermally assisted hydrolysis and methylation (THM), chemistry.chemical_compound, TMAH degradation, chemistry, Pyrolysis-GC/MS, [SDU]Sciences of the Universe [physics], In situ analysis, Environmental chemistry, Thermochemolysis, Quantitative analysis, Spectroscopy, Earth (classical element)
Abstract

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

Published
2020
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30. The Mars Organic Molecule Analyzer (MOMA) Instrument: Characterization of Organic Material in Martian Sediments

Author

Andrej Grubisic, Caroline Freissinet, Jorge L. Vago, Fred Goesmann, Arnaud Buch, Xiang Li, Stephanie Getty, Ryan M. Danell, Fabien Stalport, John Robert Brucato, Mitchell D. Schulte, Ricardo Arevalo, Veronica Pinnick, William B. Brinckerhoff, Cyril Szopa, Noël Grand, Uwe J. Meierhenrich, Daniel P. Glavin, Harald Steininger, François Raulin, Walter Goetz, Robert Lindner, Friso H. W. van Amerom, Sandra Siljeström, Helge Mißbach, Max-Planck-Institut für Sonnensystemforschung (MPS), Max-Planck-Gesellschaft, NASA Goddard Space Flight Center (GSFC), Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Danell Consulting Inc., RISE Bioscience and Materials/Chemistry and Materials, RISE Research Institutes of Sweden, Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), CentraleSupélec, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Nice (ICN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA)-Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA), European Space Research and Technology Centre (ESTEC), European Space Agency (ESA), NASA Headquarters, INAF - Osservatorio Astrofisico di Arcetri (OAA), Istituto Nazionale di Astrofisica (INAF), Mini-Mass Consulting, Inc., Université Nice Sophia Antipolis (1965 - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), IMPEC - LATMOS, Université Nice Sophia Antipolis (... - 2019) (UNS), Université Côte d'Azur (UCA)-Université Côte d'Azur (UCA)-Centre National de la Recherche Scientifique (CNRS), Max-Planck-Institut für Sonnensystemforschung = Max Planck Institute for Solar System Research (MPS), and Agence Spatiale Européenne = European Space Agency (ESA)

Subjects
Martian, Spectrum analyzer, Mass spectrometry, 010504 meteorology & atmospheric sciences, Special Collection of Papers: ExoMars Rover MissionGuest Editor: Jorge L. Vago, Chemistry, Planetary instrumentation, Mars, Mars Exploration Program, 01 natural sciences, Agricultural and Biological Sciences (miscellaneous), [SDU.ASTR.IM]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Instrumentation and Methods for Astrophysic [astro-ph.IM], Astrobiology, Characterization (materials science), 13. Climate action, Space and Planetary Science, Life detection, Martian surface, 0103 physical sciences, Subsurface sediments, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences, Remote sensing
Abstract

The Mars Organic Molecule Analyzer (MOMA) instrument onboard the ESA/Roscosmos ExoMars rover (to launch in July, 2020) will analyze volatile and refractory organic compounds in martian surface and subsurface sediments. In this study, we describe the design, current status of development, and analytical capabilities of the instrument. Data acquired on preliminary MOMA flight-like hardware and experimental setups are also presented, illustrating their contribution to the overall science return of the mission. Key Words: Mars—Mass spectrometry—Life detection—Planetary instrumentation. Astrobiology 17, 655–685., Table of Contents 1. Introduction: The Mars Organic Molecule Analyzer (MOMA) Investigation 2. Science Goals 3. Objectives and Requirements 4. Instrument Top-Level Description 5. Instrument Development 5.1. Team organization 5.2. Instrument integration flow 5.3. Instrument verification 5.4. Achieved milestones and deliveries 6. Instrument Subsystems 6.1. Oven and tapping station subsystems 6.1.1. Derivatization 6.1.1.1. MTBSTFA 6.1.1.2. DMF-DMA 6.1.2. Thermochemolysis 6.1.3. Wet chemistry: storage and release of chemical agents 6.2. Gas chromatograph subsystem 6.2.1. Design requirements 6.2.2. Design overview 6.2.2.1. General architecture 6.2.2.2. Injection system 6.2.2.3. Separation of volatiles 6.2.2.4. Detection of volatiles 6.2.2.5. Gas handling system 6.2.2.6. GCMS coupling campaigns 6.3. Laser subsystem 6.3.1. Design requirements 6.3.2. Laser architecture 6.3.3. Verification data 6.4. Mass spectrometer subsystem 6.4.1. Design requirements 6.4.2. Analyzer architecture 6.4.2.1. Linear Ion Trap assembly 6.4.2.2. Detection channels 6.4.2.3. Electron Ionization Source 6.4.2.4. Fast-actuating aperture valve 6.4.2.5. Micropirani pressure sensor 6.4.2.6. Wide-Range Pump 6.4.3. Temperature control 6.4.4. Driving electronics 7. Operation of MOMA on the Surface of Mars 7.1. Expected measurement scenarios 7.2. Sequenced operational modes 7.3. Synergy with other instruments 7.3.1. Data interpretation 7.4. LDMS operations on Mars and test experiments on LDMS prototype system 7.5. Test experiments on GCMS prototype system: a case study 7.5.1. Sample and setup 7.5.2. Methods 7.5.2.1. Stepwise pyrolysis 7.5.2.2. Derivatization/thermochemolysis 7.5.2.3. GCMS parameters 7.5.3. Results and discussion 7.5.3.1. Pyrolysis 7.5.3.2. Derivatization and thermochemolysis 8. Discussion 9. Summary Acknowledgments Author Disclosure Statement References Abbreviations Used

Published
2017
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31. Analysis of carbon and nitrogen signatures with laser-induced breakdown spectroscopy; the quest for organics under Mars-like conditions

Author

Tristan Dequaire, Cyril Szopa, Jérôme Lasne, William Rapin, Sylvestre Maurice, Maguy Jaber, Arnaud Buch, Patrice Coll, Olivier Gasnault, Pierre Beck, Agnes Cousin, Pierre-Yves Meslin, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Institut de recherche en astrophysique et planétologie (IRAP), Institut national des sciences de l'Univers (INSU - CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Observatoire Midi-Pyrénées (OMP), Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS), Institut de Planétologie et d'Astrophysique de Grenoble (IPAG), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Laboratoire d'Archéologie Moléculaire et Structurale (LAMS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), CentraleSupélec, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Centre National de la Recherche Scientifique (CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Centre National d'Études Spatiales [Toulouse] (CNES)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC), IMPEC - LATMOS, Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Midi-Pyrénées (OMP), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Midi-Pyrénées (OMP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Centre National de la Recherche Scientifique (CNRS), and Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Martian, chemistry.chemical_classification, 010504 meteorology & atmospheric sciences, [SDU.ASTR.SR]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Solar and Stellar Astrophysics [astro-ph.SR], Chemistry, 010401 analytical chemistry, [SDU.ASTR.EP]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Earth and Planetary Astrophysics [astro-ph.EP], chemistry.chemical_element, Mars Exploration Program, 01 natural sciences, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Analytical Chemistry, Abiogenic petroleum origin, Astrobiology, Meteorite, 13. Climate action, Environmental chemistry, Organic matter, Laser-induced breakdown spectroscopy, Spectroscopy, Instrumentation, Carbon, 0105 earth and related environmental sciences
Abstract

International audience; Organic matter has been continuously delivered by meteorites and comets to Mars since its formation, and possibly formed in situ by abiogenic and/or biogenic processes. This organic matter may be preserved from the harsh oxidizing environment of Mars in specific locations. Together with water, organic molecules are necessary to the emergence of life as we know it. Since the first martian landers, scientists have been searching for organics and until today, only one positive detection has been made by a Gas Chromatography Mass Spectrometer (GCMS) instrument onboard the Curiosity rover. In this article we investigate a complementary approach to guide the search for organic matter using ChemCam, the first Laser-Induced Breakdown Spectroscopy (LIBS) instrument on Mars. This experimental study focuses on the analysis of carbon and nitrogen LIBS signatures in organoclay samples and allows the determination of the critical level (Lc) and limit of detection (LoD) of these elements with LIBS under Mars-like conditions, giving new insights into the search of organic matter on Mars.

Published
2017
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32. Benzoic Acid as the Preferred Precursor for the Chlorobenzene Detected on Mars: Insights from the Unique Cumberland Analog Investigation

Author

Paul R. Mahaffy, Richard V. Morris, Heather Graham, Charles Malespin, Jérémie Lasue, Erwin Dehouck, Cyril Szopa, Caroline Freissinet, C. A. Knudson, Amy McAdam, J. M. T. Lewis, Samuel Teinturier, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), NASA Goddard Space Flight Center (GSFC), Department of Physics and Astronomy [Washington], Howard University, Center for Research and Exploration in Space Science and Technology [GSFC] (CRESST), Institut de recherche en astrophysique et planétologie (IRAP), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Midi-Pyrénées (OMP), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Centre National de la Recherche Scientifique (CNRS), GSFC Solar System Exploration Division, Laboratoire de Géologie de Lyon - Terre, Planètes, Environnement (LGL-TPE), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut national des sciences de l'Univers (INSU - CNRS)-Université Jean Monnet - Saint-Étienne (UJM)-Centre National de la Recherche Scientifique (CNRS), NASA Johnson Space Center (JSC), NASA, Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Observatoire Midi-Pyrénées (OMP), Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Géologie de Lyon - Terre, Planètes, Environnement [Lyon] (LGL-TPE), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010504 meteorology & atmospheric sciences, Evolved gas analysis, Mars, Mass spectrometry, 01 natural sciences, Pre-biotic astrochemistry, chemistry.chemical_compound, 0103 physical sciences, Earth and Planetary Sciences (miscellaneous), Planetary science, 010303 astronomy & astrophysics, Magnesium perchlorate, 0105 earth and related environmental sciences, Benzoic acid, Astronomy and Astrophysics, Mars Exploration Program, Astrobiology, Geophysics, chemistry, 13. Climate action, Space and Planetary Science, Chlorobenzene, [SDU]Sciences of the Universe [physics], Sample Analysis at Mars, Gas chromatography–mass spectrometry, Nuclear chemistry
Abstract

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.

Published
2020
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33. Dimerization of Uracil in a simulated Mars-like UV radiation environment

Author

Sara Mahfouf, Thomas Georgelin, Patrice Coll, François Raulin, Cyril Colas, Hervé Cottin, Fabien Stalport, Jérôme Lasne, Laura Rouquette, Cyril Szopa, Laura Selliez, Naila Chaouche-Mechidal, HAL UVSQ, Équipe, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Réactivité de Surface (LRS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Centre National d’Études Spatiales [Paris] (CNES), PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)

Subjects
010504 meteorology & atmospheric sciences, Extraterrestrial Environment, Ultraviolet Rays, [SDU.ASTR.EP]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Earth and Planetary Astrophysics [astro-ph.EP], Mars, [SDU.ASTR.EP] Sciences of the Universe [physics]/Astrophysics [astro-ph]/Earth and Planetary Astrophysics [astro-ph.EP], 01 natural sciences, UV radiation, Nucleobase, Astrobiology, chemistry.chemical_compound, Martian surface, 0103 physical sciences, Exobiology, Molecule, Surface layer, Uracil, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences, Chemistry, Mars Exploration Program, Agricultural and Biological Sciences (miscellaneous), Monomer, 13. Climate action, Space and Planetary Science, Organic matter, Interplanetary spaceflight, Dimerization
Abstract

International audience; The search for organic molecules at the surface of Mars is a key objective in astrobiology, given that many organic compounds are possible biosignatures and their presence is of interest with regard to the habitability of Mars. Current environmental conditions at the martian surface are harsh and affect the stability of organic molecules. For this reason, and because current and future Mars rovers collect samples from the upper surface layer, it is important to assess the fate of organic molecules under the conditions at the martian surface. Here, we present an experimental study of the evolution of uracil when exposed to UV radiation, pressure, and temperature conditions representative of the surface of Mars. Uracil was selected because it is a nucleobase that composes RNA, and it has been detected in interplanetary bodies that could be the exogenous source of this molecule by meteoritic delivery to the surface of Mars. Our results show that the experimental quantum efficiency of photodecomposition of uracil is 0.16 ± 0.14 molecule/photon. Although these results suggest that uracil is quickly photodegraded when directly exposed to UV light on Mars, such exposure produces dimers that are more stable over time than the monomer. The identified dimers could be targets of interest for current and future Mars space missions.

Published
2020
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34. First Detections of Dichlorobenzene Isomers and Trichloromethylpropane from Organic Matter Indigenous to Mars Mudstone in Gale Crater, Mars: Results from the Sample Analysis at Mars Instrument Onboard the Curiosity Rover

Author

Michel Cabane, Heather B. Franz, Jennifer L. Eigenbrode, Paul R. Mahaffy, Cyril Szopa, Samuel Teinturier, R. Williams, Rafael Navarro-González, Maeva Millan, Melissa Guzman, Dawn Y. Sumner, Charles Malespin, Brad Sutter, Roger E. Summons, Arnaud Buch, Caroline Freissinet, Daniel P. Glavin, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), GSFC Solar System Exploration Division, NASA Goddard Space Flight Center (GSFC), Department of Biology [Washington], Georgetown University [Washington] (GU), Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec-Université Paris-Saclay, Department of Earth, Atmospheric and Planetary Sciences [MIT, Cambridge] (EAPS), Massachusetts Institute of Technology (MIT), Department of Earth and Planetary Sciences [Davis], University of California [Davis] (UC Davis), University of California-University of California, Jacobs Technology ESCG, Department of Astronomy [College Park], University of Maryland [College Park], University of Maryland System-University of Maryland System, Center for Research and Exploration in Space Science and Technology [College Park] (CRESST), Instituto de Ciencias Nucleares [Mexico], Universidad Nacional Autónoma de México (UNAM), and Universities Space Research Association (USRA)

Subjects
Geologic Sediments, 010504 meteorology & atmospheric sciences, Polycyclic aromatic hydrocarbon, Mars, Chlorobenzenes, 01 natural sciences, Chemical reaction, Gas Chromatography-Mass Spectrometry, Dichlorobenzene, chemistry.chemical_compound, Propane, 0103 physical sciences, Exobiology, Organic matter, Spacecraft, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences, chemistry.chemical_classification, Total organic carbon, Stereoisomerism, Mars Exploration Program, 15. Life on land, Agricultural and Biological Sciences (miscellaneous), chemistry, 13. Climate action, Space and Planetary Science, Chlorobenzene, [SDU]Sciences of the Universe [physics], Environmental chemistry, Sample Analysis at Mars
Abstract

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 (

Published
2020
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35. Role of the Tenax® adsorbent in the interpretation of the EGA and GC‐MS analyses performed with the Sample Analysis at Mars in Gale crater

Author

Caroline Freissinet, Roger E. Summons, D. Coscia, Rafael Navarro-González, Daniel P. Glavin, Sarah Stewart Johnson, Imene Belmahdi, Cyril Szopa, Charles Malespin, Michel Cabane, Jennifer C. Stern, Paul R. Mahaffy, Jean-Yves Bonnet, Samuel Teinturier, Jennifer L. Eigenbrode, Maeva Millan, Yuanyuan He, Arnaud Buch, Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), CentraleSupélec, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), NASA Goddard Space Flight Center (GSFC), Department of Earth, Atmospheric and Planetary Sciences [MIT, Cambridge] (EAPS), Massachusetts Institute of Technology (MIT), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Instituto de Ciencias Nucleares [Mexico], Universidad Nacional Autónoma de México (UNAM), and Georgetown University [Washington] (GU)

Subjects
010504 meteorology & atmospheric sciences, Tenax, Martian soil, Mars Exploration Program, 01 natural sciences, chemistry.chemical_compound, Perchlorate, Geophysics, chemistry, 13. Climate action, Space and Planetary Science, Geochemistry and Petrology, [SDU]Sciences of the Universe [physics], Reagent, Environmental chemistry, Sample Analysis at Mars, Earth and Planetary Sciences (miscellaneous), Gas chromatography–mass spectrometry, Derivatization, 0105 earth and related environmental sciences
Abstract

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.

Published
2019
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36. Thermal stability of adsorbents used for gas chromatography in space exploration

Author

Arnaud Buch, Leila Bouchra, D. Coscia, Cyril Szopa, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec-Université Paris-Saclay, and Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)

Subjects
Chromatography, Gas, Time Factors, Polymers, Oxide, Thermal desorption, chemistry.chemical_element, 010402 general chemistry, Molecular sieve, 01 natural sciences, Biochemistry, Analytical Chemistry, chemistry.chemical_compound, Adsorption, Thermal stability, chemistry.chemical_classification, Gas chromatography, Space exploration, Chromatography, 010401 analytical chemistry, Organic Chemistry, Temperature, General Medicine, Polymer, Carbon black, Space Flight, 0104 chemical sciences, chemistry, Chemical engineering, Adsorbents, [SDU]Sciences of the Universe [physics], 13. Climate action, Thermogravimetry, Gases, Volatilization, Carbon, Pyrolysis
Abstract

International audience; For analytical purpose, thermal desorption is now used in gas chromatographs developed to analyse the chemical composition of planetary environments. Due to technical constraints, the thermal desorption cannot be as finely controlled as in the laboratory resulting in possible thermal alteration of the adsorbents used. For these reasons, the influence of heat on physical and chemical properties of various adsorbents, either used or that could be used in gas chromatographs for space exploration, is studied. If the adsorbents made of carbon molecular sieves and graphitised carbon black that were tested show a very high thermal stability up to 800°C, the porous polymers tested are highly degraded from a minimum temperature that depends on the nature of the polymer. Poly-2,6-diphenylphenylene oxide is shown to be the more thermally robust as it is degraded at higher temperatures, confirming it is currently the best choice for analysing organic molecules with a space instrument. Finally, the products of degradation of the porous polymers tested were analysed after heating the porous polymers at 400°C and 800°C. They were identified and listed as potential contaminants of analyses performed with this type of adsorbent. If the exposure to the higher temperature produces numerous organic compounds, mainly aromatic ones, a few ones are also detected at the lower temperature tested, meaning they should be considered as potential contaminants. Again poly-2,6-diphenylphenylene oxide should be preferred because it releases less organic compounds, the structure of which is completely specific to the adsorbent composition.

Published
2019
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37. The Photochemistry on Space Station (PSS) Experiment: Organic Matter under Mars-like Surface UV Radiation Conditions in Low Earth Orbit

Author

Olivier Poch, Shanèle Payart, Didier Chaput, Tristan Dequaire, Laura Rouquette, Naila Chaouche-Mechidal, Maguy Jaber, Fabien Stalport, Cyril Szopa, Patrice Coll, François Raulin, Hervé Cottin, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Institut de Planétologie et d'Astrophysique de Grenoble (IPAG), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Centre National d'Études Spatiales [Toulouse] (CNES), Laboratoire d'Archéologie Moléculaire et Structurale (LAMS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Centre National d'Études Spatiales [Toulouse] (CNES)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS), IMPEC - LATMOS, Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)

Subjects
Surface (mathematics), Extraterrestrial Environment, Spectrophotometry, Infrared, 010504 meteorology & atmospheric sciences, Earth, Planet, Photochemistry, Ultraviolet Rays, Mars, Radiation, Space (mathematics), 01 natural sciences, Space exploration, Astrobiology, Low earth orbit, 0103 physical sciences, Organic matter, Organic Chemicals, Spacecraft, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences, chemistry.chemical_classification, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], Mars Exploration Program, ComputerSystemsOrganization_PROCESSORARCHITECTURES, Agricultural and Biological Sciences (miscellaneous), EXPOSE, Kinetics, ComputingMethodologies_PATTERNRECOGNITION, chemistry, 13. Climate action, Space and Planetary Science, Environmental science, Half-Life
Abstract

International audience; The search for organic molecules at the surface of Mars is a top priority of the Mars Science Laboratory (NASA) and ExoMars 2020 (ESA) space missions. Their main goal is to search for past and/or present molecular compounds related to a potential prebiotic chemistry and/or a biological activity on the Red Planet. A key step to interpret their data is to characterize the preservation or the evolution of organic matter in the martian environmental conditions. Several laboratory experiments have been developed especially concerning the influence of ultraviolet (UV) radiation. However, the experimental UV sources do not perfectly reproduce the solar UV radiation reaching the surface of Mars. For this reason, the International Space Station (ISS) can be advantageously used to expose the same samples studied in the laboratory to UV radiation representative of martian conditions. Those laboratory simulations can be completed by experiments in low Earth orbit (LEO) outside the ISS. Our study was part of the Photochemistry on the Space Station experiment on board the EXPOSE-R2 facility that was kept outside the ISS from October 2014 to February 2016. Chrysene, adenine, and glycine, pure or deposited on an iron-rich amorphous mineral phase, were exposed to solar UV. The total duration of exposure to UV radiation is estimated to be in the 1250–1420 h range. Each sample was characterized prior to and after the flight by Fourier transform infrared (FTIR) spectroscopy. These measurements showed that all exposed samples were partially degraded. Their quantum efficiencies of photodecomposition were calculated in the 200–250 nm wavelength range. They range from 10−4 to 10−6 molecules·photon−1 for pure organic samples and from 10−2 to 10−5 molecules·photon−1 for organic samples shielded by the mineral phase. These results highlight that none of the tested organics are stable under LEO solar UV radiation conditions. The presence of an iron-rich mineral phase increases their degradation.

Published
2019
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38. Experimenting with Mixtures of Water Ice and Dust as Analogues for Icy Planetary Material

Author

B. Jost, Zurine Yoldi, Bastian Gundlach, André Galli, Peter Wurz, Nathalie Carrasco, Romain Cerubini, A. Gracia-Berná, Antoine Pommerol, Jürgen Blum, Yann Brouet, Nicolas Thomas, Cyril Szopa, and Olivier Poch

Subjects
Solar System, Climatic Processes, Physical model, 010504 meteorology & atmospheric sciences, Astronomy and Astrophysics, 01 natural sciences, Space exploration, Astrobiology, Planetary science, Impact crater, Space and Planetary Science, 0103 physical sciences, Environmental science, Planetary Evolution, Water ice, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences
Abstract

Due to its abundance and unique properties, water is a major actor in the formation and evolution of many planetary surfaces as well as a sensitive and reliable tracer of past geologic and climatic processes. Water ice is found in variable abundance at the surfaces of many Solar System objects, from the floor of permanently shadowed craters at the poles of Mercury to large fractions of the surfaces of several trans-Neptunian objects. With few exceptions, water is not found in pure form but associated to contaminants of various nature and concentration. These associations and the nature of the mixing and segregation processes that affect and control them are key for our understanding of some of the most important aspects of planetary evolution processes. The observation and characterization of water ice at the surface of Solar System objects is therefore among the primary scientific objectives of many space missions. The quantitative interpretation of remote sensing data in terms of surface composition and physical properties requires the use of complex physical models that rely on experimental data in two different ways. First, the models require as inputs the fundamental properties of the pure materials, such as the optical or dielectric constant. Second, the models can only be fully tested if their results are confronted to actual measurements performed on samples whose complexity comes close to the one encountered on natural planetary surfaces but which are nevertheless well-enough characterized to serve as reference. Such measurements are challenging as macroscopic ice-rich samples prepared as analogues of icy planetary surfaces tend to be unstable, the ice component being prone to metamorphism and phase change. The questions of the reproducibility of the samples and the relevance of the measurements are therefore critical. The Ice Laboratory at the University of Bern has been set up in 2010 to overcome some of these difficulties. We have developed protocols to prepare, store, handle and characterize various associations of ice with mineral and organics contaminants as analogues of different types of icy Solar System surfaces. The aims of this article are to present the context and background for our investigations, describe these protocols and associated hardware in a comprehensive way, provide quantitative characterization of the samples obtained using these protocols and summarize the main results obtained so far by experimenting with these samples. The current state and possible future evolutions of this project are then discussed in the context of the next generation of space missions to visit icy objects in the Solar System and longer term perspectives on future observations of protoplanetary discs and exoplanetary systems.

Published
2019
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39. Investigating the effects of gamma radiation on selected chemicals for use in biosignature detection instruments on the surface of Jupiter's moon Europa

Author

Cyril Szopa, Stephanie Getty, Daniel P. Glavin, Jason P. Dworkin, Arnaud Buch, Melissa Guzman, Andrej Grubisic, Xiang Li, Martin A. Carts, William B. Brinckerhoff, Jennifer C. Stern, Maeva Millan, Caroline Freissinet, Jennifer E. Eigenbrode, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), GSFC Solar System Exploration Division, NASA Goddard Space Flight Center (GSFC), Department of Biology [Washington], Georgetown University [Washington] (GU), Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), CentraleSupélec, Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), and GSFC Radiation Effects Facility

Subjects
010504 meteorology & atmospheric sciences, Perfluorotributylamine, 01 natural sciences, LD-MS, Ionizing radiation, Astrobiology, Jupiter, chemistry.chemical_compound, Desorption, 0103 physical sciences, Biosignature, 010303 astronomy & astrophysics, Chemical resistance, 0105 earth and related environmental sciences, Tetramethylammonium hydroxide, Radiation, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], Astronomy and Astrophysics, chemistry, 13. Climate action, Space and Planetary Science, Environmental science, Biosignatures, Gas chromatography–mass spectrometry, GC-MS, Europa, Wet chemistry
Abstract

International audience; Jupiter's moon Europa is a prime target for the search for potential signs of life in the solar system. The Europa Lander Science Definition Team Report outlined investigations and measurement requirements on a future Europa Lander and has led us to consider application of powerful techniques such as pyrolysis and derivatization gas chromatography mass spectrometry (GC-MS) and laser desorption mass spectrometry (LD-MS) to elucidate the organic composition of near-surface ice and minerals. Definitive identification of chemical biosignatures using such techniques is strongly enabled by the use of various chemicals, such as perfluorotributylamine (PFTBA) for the MS calibration, α-cyano-hydroxycinnamic acid (CHCA) for matrix-assisted laser desorption and ionization (MALDI) and N,N-dimethylformamide dimethyl acetal (DMF-DMA), N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) and tetramethylammonium hydroxide (TMAH) for wet chemistry GC-MS protocols. The jovian radiation environment is known to represent a uniquely challenging risk to mission performance and lifetime, principally due to high radiation levels. To assess the potential ionizing radiation damage to these important chemicals, we tested their effectiveness following gamma radiation exposure doses up to the anticipated Europa Lander rating requirement of 300 krad(Si). The chemicals were sealed in glass ampules under vacuum (

Published
2019
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40. Application of TMAH thermochemolysis to the detection of nucleobases: Application to the MOMA and SAM space experiment

Author

Pin Lu, Paul R. Mahaffy, M. Morisson, Cyril Szopa, Melissa Guzman, Jason P. Dworkin, Maeva Millan, J. L. Eigenbrode, Jean-Yves Bonnet, Caroline Freissinet, Sarah Stewart Johnson, Amy J. Williams, Yuanyuan He, D. Coscia, Arnaud Buch, Daniel P. Glavin, Charles Malespin, Rafael Navarro-González, Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), CentraleSupélec, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), University of Florida [Gainesville] (UF), Georgetown University [Washington] (GU), NASA Goddard Space Flight Center (GSFC), Laboratorio de Química de Plasmas y Estudios Planetarios [Mexico], Instituto de Ciencias Nucleares [Mexico], Universidad Nacional Autónoma de México (UNAM)-Universidad Nacional Autónoma de México (UNAM), Telespazio France, and Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)

Subjects
Hot Temperature, Guanine, Mars, MOMA, 02 engineering and technology, Pyrimidinones, 01 natural sciences, Gas Chromatography-Mass Spectrometry, Analytical Chemistry, Nucleobase, chemistry.chemical_compound, Limit of Detection, Hypoxanthine, [SDU.OCEAN]Sciences of the Universe [physics]/Ocean, Atmosphere, Tetramethylammonium hydroxide, Nucleobases, Chromatography, Tetramethylammonium hydroxide (TMAH)SAM, 010401 analytical chemistry, Uracil, Space Flight, 021001 nanoscience & nanotechnology, Derivatization, 0104 chemical sciences, Thymine, chemistry, 13. Climate action, Purines, Sample Analysis at Mars, Thermochemolysis, GC-MS, 0210 nano-technology, Cytosine, Pyrolysis
Abstract

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.

Published
2019
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41. Characterization of aromaticity in analogues of titan's atmospheric aerosols with two-step laser desorption ionization mass spectrometry

Author

Yves Bénilan, Martin Schwell, Nathalie Carrasco, Cyril Szopa, Ahmed Mahjoub, Guy Cernogora, Marie-Claire Gazeau, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), IMPEC - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Creteil Paris 12, European Research Council (ERC), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), PLANETO - LATMOS, and European Project: 636829,H2020,ERC-2014-STG,PRIMCHEM(2015)

Subjects
L2DI-MS, 010504 meteorology & atmospheric sciences, Infrared, [SDU.ASTR.EP]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Earth and Planetary Astrophysics [astro-ph.EP], Analytical chemistry, FOS: Physical sciences, Mass spectrometry, 01 natural sciences, symbols.namesake, Ionization, 0103 physical sciences, Capacitively coupled plasma, Atmosphere of Titan, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences, Earth and Planetary Astrophysics (astro-ph.EP), Aerosols, [SDU.OCEAN]Sciences of the Universe [physics]/Ocean, Atmosphere, Chemistry, Astronomy and Astrophysics, Aromaticity, Tholin, Aromatics, 13. Climate action, Space and Planetary Science, symbols, Titan's atmosphere, Titan (rocket family), Astrophysics - Earth and Planetary Astrophysics
Abstract

International audience; The role of polycyclic aromatic hydrocarbons (PAH) and Nitrogen containing PAH (PANH) as intermediates of aerosol production in the atmosphere of Titan has been a subject of controversy for a long time. An analysis of the atmospheric emission band observed by the Visible and Infrared Mapping Spectrometer (VIMS) at 3.28 µm suggests the presence of neutral polycyclic aromatic species in the upper atmosphere of Titan. These molecules are seen as the counter part of negative and positive aromatics ions suspected by the Plasma Spectrometer onboard the Cassini spacecraft, but the low resolution of the instrument hinders any molecular speciation.In this work we investigate the specific aromatic content of Titan's atmospheric aerosols through laboratory simulations. We report here the selective detection of aromatic compounds in tholins, Titan's aerosol analogues, produced with a capacitively coupled plasma in a N2:CH4 95:5 gas mixture. For this purpose, Two-Step Laser Desorption Ionization Time-of-Flight Mass Spectrometry (L2DI-TOF-MS) technique is used to analyze the so produced analogues. This analytical technique is based on the ionization of molecules by Resonance Enhanced Multi-Photon Ionization (REMPI) using a λ=248 nm wavelength laser which is selective for aromatic species. This allows for the selective identification of compounds having at least one aromatic ring. Our experiments show that tholins contain a trace amount of small PAHs with one to three aromatic rings. Nitrogen containing PAHs (PANHs) are also detected as constituents of tholins. Molecules relevant to astrobiology are detected as is the case of the substituted DNA base adenine.

Published
2016
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42. Sublimation of water ice mixed with silicates and tholins: Evolution of surface texture and reflectance spectra, with implications for comets

Author

Nicolas Thomas, Olivier Poch, Nathalie Carrasco, Antoine Pommerol, Bernhard Jost, Cyril Szopa, Center for Space and Habitability (CSH), University of Bern, Physikalisches Institut [Bern], Universität Bern [Bern] (UNIBE), PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), and Universität Bern [Bern]

Subjects
Solar System, Materials science, Olivine, 010504 meteorology & atmospheric sciences, Ice crystals, Interstellar ice, [SDU.ASTR.EP]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Earth and Planetary Astrophysics [astro-ph.EP], Astronomy and Astrophysics, Tholin, engineering.material, 01 natural sciences, Mantle (geology), Astrobiology, 13. Climate action, Space and Planetary Science, 0103 physical sciences, Amorphous ice, engineering, Sublimation (phase transition), 010303 astronomy & astrophysics, 0105 earth and related environmental sciences
Abstract

International audience; The surfaces of many objects in the Solar System comprise substantial quantities of water ice sometimes mixed with minerals and/or organic molecules. The sublimation of the ice changes the structural and optical properties of these objects. We present laboratory data on the evolution of the structure and the visible and near-infrared spectral reflectance of icy surface analogues of cometary ices, made of water ice, complex organic matter (tholins) and silicates, as they undergo sublimation under low temperature (

Published
2016
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43. Testing the capabilities of the Mars Organic Molecule Analyser (MOMA) chromatographic columns for the separation of organic compounds on Mars

Author

Melissa Guzman, Fabien Stalport, Arnaud Buch, Desmond Allen Kaplan, François Raulin, Cyril Szopa, Caroline Freissinet, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec-Université Paris-Saclay, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), KapScience LLC, Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité)

Subjects
chemistry.chemical_classification, Martian, Chromatography, 010504 meteorology & atmospheric sciences, Resolution (mass spectrometry), Analyser, Astronomy and Astrophysics, Mars Exploration Program, 01 natural sciences, Hydrocarbon, chemistry, [SDU]Sciences of the Universe [physics], 13. Climate action, Space and Planetary Science, Martian surface, 0103 physical sciences, Environmental science, Organic matter, Gas chromatography, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences
Abstract

International audience; Mars is our planetary neighbor and is now known to host trace levels of organic matter at its surface. However, little is known of the organic molecular composition or the survival potential for organic biosignatures, such as the enantiomeric excess of amino acids or the carbon chain patterns of lipid hydrocarbons, as a function of depth below the martian surface. The Mars Organic Molecule Analyser (MOMA) is an instrument onboard the Rosalind Franklin rover that is scheduled to be launched to Mars in the summer of 2020 as part of the ExoMars mission. This experiment includes a gas chromatograph instrument dedicated to the in situ analysis of organic molecules and their enantiomers present in martian samples collected by the rover at the surface down to 2 m depth. In order to evaluate the performance of the integrated chromatographic system which was selected for the flight model, experiments were carried out with a laboratory setup that reproduced the flight configuration and mimicked the in situ operating conditions. We show that the column instrument package can separate and detect a wide range of organic and inorganic volatile compounds, from noble gases to hydrocarbon chains with up to 29 carbon atoms (C29). We study the enantiomeric resolution of selected chiral chemical standards and compare our laboratory results to: i. tests performed with the same instrumental setup but using a natural sample spiked with amino acids in order to evaluate the influence of a mineral phase on the analysis, and ii. tests run on a MOMA engineering test unit (ETU) which is representative of the flight model. In each case, tests on the more complex sample and the more flight-like instrument allows a comparison with laboratory results, in order to confirm that laboratory data are reliable for supporting peak identification within flight data. The obtained results demonstrate the ability of the gas chromatographic subsystem to identify a wide range of organic and inorganic volatile compounds, including biomolecular signatures, within the constrained space operating conditions of MOMA. The results form a retention time and mass spectral database for MOMA which will be critical for analysis of the eventual flight data.

Published
2020
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44. Reply to Comment by F. Kenig, L. Chou, and D. J. Wardrop on 'Evaluation of the Tenax Trap in the Sample Analysis at Mars Instrument Suite on the Curiosity Rover as a Potential Hydrocarbon Source for Chlorinated Organics Detected in Gale Crater' by Miller et al., 2015

Author

Arnaud Buch, Jennifer L. Eigenbrode, Cyril Szopa, Caroline Freissinet, Imene Belmahadi, Roger E. Summons, Daniel P. Glavin, Kristen E. Miller, Benjamin Kotrc, Department of Earth, Atmospheric and Planetary Sciences [MIT, Cambridge] (EAPS), Massachusetts Institute of Technology (MIT), Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), CentraleSupélec, NASA Goddard Space Flight Center (GSFC), PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), and Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)

Subjects
010504 meteorology & atmospheric sciences, Evolved gas analysis, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], Thermal decomposition, Analytical chemistry, Tenax, Mars Exploration Program, Mass spectrometry, 01 natural sciences, Decomposition, chemistry.chemical_compound, Geophysics, chemistry, 13. Climate action, Space and Planetary Science, Geochemistry and Petrology, Chlorobenzene, Sample Analysis at Mars, Earth and Planetary Sciences (miscellaneous), Environmental science, 0105 earth and related environmental sciences
Abstract

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.

Published
2019
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45. Recovery of Fatty Acids from Mineralogic Mars Analogs by TMAH Thermochemolysis for the Sample Analysis at Mars Wet Chemistry Experiment on the Curiosity Rover

Author

R. Williams, Rafael Navarro-González, Cyril Szopa, Paul R. Mahaffy, Amy J. Williams, Daniel P. Glavin, Jennifer L. Eigenbrode, Charles Malespin, Maeva Millan, Kathleen C. Benison, Roger E. Summons, Sarah Stewart Johnson, Arnaud Buch, Mary Beth Wilhelm, C. A. Knudson, Amy McAdam, J. M. T. Lewis, Kathleen L. Craft, Melissa Floyd, Shane S. O'Reilly, Caroline Freissinet, Slavka Andrejkovičová, Department of Physics, Astronomy, and Geosciences [Towson], Towson University [Towson, MD, United States], University of Maryland System-University of Maryland System, Center for Research and Exploration in Space Science and Technology [Baltimore] (CRESST), University of Maryland [Baltimore County] (UMBC), GSFC Solar System Exploration Division, NASA Goddard Space Flight Center (GSFC), NASA Ames Research Center (ARC), Department of Earth, Atmospheric and Planetary Sciences [MIT, Cambridge] (EAPS), Massachusetts Institute of Technology (MIT), UCD School od Earth Sciences, University College Dublin [Dublin] (UCD), Department of Biology [Washington], Georgetown University [Washington] (GU), Johns Hopkins University Applied Physics Laboratory [Laurel, MD] (APL), Center for Research and Exploration in Space Science and Technology [College Park] (CRESST), University of Maryland [College Park], Universities Space Research Association (USRA), Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), CentraleSupélec, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Department of Geology and Geography [Morgantown], West Virginia University [Morgantown], Instituto de Ciencias Nucleares [Mexico], and Universidad Nacional Autónoma de México (UNAM)

Subjects
Time Factors, Extraterrestrial Environment, 010504 meteorology & atmospheric sciences, Iron, Carboxylic acid, Sample Analysis at Mars (SAM) instrument, Inorganic chemistry, Carboxylic Acids, Mars, Iron sulfide, Mass spectrometry, 01 natural sciences, Gas Chromatography-Mass Spectrometry, TMAH, chemistry.chemical_compound, Exobiology, 0103 physical sciences, MSL, Spacecraft, 010303 astronomy & astrophysics, Research Articles, 0105 earth and related environmental sciences, chemistry.chemical_classification, Minerals, Tetramethylammonium hydroxide, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], Methanol, Fatty Acids, Temperature, Esters, Mars Exploration Program, Silicon Dioxide, Agricultural and Biological Sciences (miscellaneous), FAME, Quaternary Ammonium Compounds, Pyrolysis–gas chromatography–mass spectrometry, chemistry, 13. Climate action, Space and Planetary Science, Molecular biosignatures, Sample Analysis at Mars, Clay, Gas chromatography–mass spectrometry
Abstract

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.

Published
2019
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46. Abiotic Input of Fixed Nitrogen by Bolide Impacts to Gale Crater During the Hesperian: Insights From the Mars Science Laboratory

Author

Patrice Coll, Jennifer C. Stern, Daniel P. Glavin, Christopher P. McKay, Heather B. Franz, Paul R. Mahaffy, Jennifer L. Eigenbrode, P. Douglas Archer, Rafael Navarro-González, Arnaud Buch, Benny Prats, Michel Cabane, María Paz Zorzano-Mier, Charles Malespin, Caroline Freissinet, Ashwin Vasavada, Douglas W. Ming, J. V. Hogancamp, Richard V. Morris, José Antonio Rodríguez-Manfredi, Karina F. Navarro, Amy McAdam, Brad Sutter, F. Javier Martin-Torres, Sushil K. Atreya, François Raulin, Melissa G. Trainer, Pamela G. Conrad, Cyril Szopa, Universidad Nacional Autónoma de México, Consejo Nacional de Ciencia y Tecnología (México), Instituto de Ciencias Nucleares [Mexico], Universidad Nacional Autónoma de México = National Autonomous University of Mexico (UNAM), Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), NASA Ames Research Center (ARC), NASA Goddard Space Flight Center (GSFC), Jacobs Technology ESCG, NASA Johnson Space Center (JSC), NASA, Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), CentraleSupélec, PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Department of Computer Science, Electrical and Space Engineering [Luleå], Luleå University of Technology (LUT), Centro de Astrobiologia [Madrid] (CAB), Instituto Nacional de Técnica Aeroespacial (INTA)-Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Department of Atmospheric, Oceanic, and Space Sciences [Ann Arbor] (AOSS), University of Michigan [Ann Arbor], University of Michigan System-University of Michigan System, Jet Propulsion Laboratory (JPL), NASA-California Institute of Technology (CALTECH), Universidad Nacional Autónoma de México (UNAM), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), IMPEC - LATMOS, Instituto Nacional de Técnica Aeroespacial (INTA)-Consejo Superior de Investigaciones Científicas [Spain] (CSIC), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), and California Institute of Technology (CALTECH)-NASA

Subjects
[PHYS.PHYS.PHYS-AO-PH]Physics [physics]/Physics [physics]/Atmospheric and Oceanic Physics [physics.ao-ph], 010504 meteorology & atmospheric sciences, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], Noachian, chemistry.chemical_element, 01 natural sciences, Nitrogen, Atmosphere, chemistry.chemical_compound, Geophysics, chemistry, Nitrate, 13. Climate action, Space and Planetary Science, Geochemistry and Petrology, Bolide, Environmental chemistry, Carbon dioxide, Earth and Planetary Sciences (miscellaneous), Nitrogen fixation, Hesperian, 0105 earth and related environmental sciences
Abstract

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

Published
2019
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47. Identification of organic molecules with a laboratory prototype based on the Laser Ablation-CosmOrbitrap

Author

P. Zapf, Gilles Chalumeau, Motoo Ito, Alexander Makarov, F. Colin, Laura Selliez, Nicolas Fray, S. Ruocco, B. Gaubicher, R. Thissen, François-Régis Orthous-Daunay, Laurent Thirkell, Noël Grand, Hervé Cottin, Cécile Engrand, Laurène Flandinet, Jean-Pierre Lebreton, Cyril Szopa, Véronique Vuitton, Nathalie Carrasco, C. Briois, Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, PSL Research University (PSL)-PSL Research University (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, PSL Research University (PSL)-PSL Research University (PSL)-Centre National d’Études Spatiales [Paris] (CNES), IMPEC - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Laboratoire de Chimie Physique D'Orsay (LCPO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Kochi Institute for Core Sample Research, Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Institut de Planétologie et d'Astrophysique de Grenoble (IPAG), Centre National d'Études Spatiales [Toulouse] (CNES)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Centre de Sciences Nucléaires et de Sciences de la Matière (CSNSM), Université Paris-Sud - Paris 11 (UP11)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS), Thermo Fisher Scientific (Bremen) GmbH, Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), CNES (Centre National d’Etudes Spatiales) and the Région Centre-Val de Loire for the funding of her PhD., European Project: 636829,H2020,ERC-2014-STG,PRIMCHEM(2015), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Centre National d’Études Spatiales [Paris] (CNES), PLANETO - LATMOS, Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)

Subjects
Materials science, 010504 meteorology & atmospheric sciences, Analyser, FOS: Physical sciences, High mass resolution, Mass spectrometry, Orbitrap, 01 natural sciences, 7. Clean energy, Space mass spectrometry, Space exploration, law.invention, law, 0103 physical sciences, Aerospace engineering, Aerospace, Enceladus, 010303 astronomy & astrophysics, Instrumentation and Methods for Astrophysics (astro-ph.IM), 0105 earth and related environmental sciences, Earth and Planetary Astrophysics (astro-ph.EP), Chemical identification, Laser ablation, business.industry, Astronomy and Astrophysics, Mars Exploration Program, Astrobiology, [SDU.ASTR.IM]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Instrumentation and Methods for Astrophysic [astro-ph.IM], CosmOrbitrap, 13. Climate action, Space and Planetary Science, business, Astrophysics - Instrumentation and Methods for Astrophysics, [CHIM.OTHE]Chemical Sciences/Other, Astrophysics - Earth and Planetary Astrophysics
Abstract

International audience; In the Solar System, extra-terrestrial organic molecules have been found on cometary primitive objects, on Titan and Enceladus icy moons and on Mars. Identification could be achieved for simple organic species by remote sensing based on spectroscopic methods. However in situ mass spectrometry is a key technology to determine the nature of more complex organic matter. A large panel of mass spectrometers has already been developed for space exploration combining different types of analysers and ion sources. Up to now the highest mass resolution reached with a space instrument is 9,000 at m/z 28 and corresponds to the DFMS-ROSINA instrument (Balsiger et al., 2007) dedicated to the study of the comet 67P/Churyumov-Gerasimenko's atmosphere and ionosphere, in a low pressure environment. A new concept of mass analyser offering ultra-high mass resolving power of more than 50,000 at m/z 56 (under high vacuum condition about 10−9 mbar) is currently being developed for space applications: the CosmOrbitrap (Briois et al., 2016), based on the Orbitrap™ technology.This work challenges the use of LAb-CosmOrbitrap, a space instrument prototype combining Laser Ablation ionisation and the CosmOrbitrap mass analyser, to identify solid organic molecules of relevance to the future space exploration. For this purpose a blind test was jointly organised by the JAXA-HRMS team (Japan Aerospace Exploration Agency-High Resolution Mass Spectrometry) and the CosmOrbitrap consortium. The JAXA team provided two organic samples, whereas the CosmOrbitrap consortium analysed them without prior information. Thanks to the high analytical performances of the prototype and our HRMS data post-processing, we successfully identified the two molecules as HOBt, hydroxybenzotriazole (C6H5N3O) and BBOT, 2,5-Bis(5-tert-butyl-benzoxazol-2-yl)thiophene (C26H26N2O2S), with a mass resolving power of, respectively, 123 540 and 69 219. The success of this blind test on complex organic molecules shows the strong potential of LAb-CosmOrbitrap for future space applications.

Published
2019
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48. Organic matter preserved in 3-billion-year-old mudstones at Gale crater, Mars

Author

Patrice Coll, Arnaud Buch, Paul R. Mahaffy, Pamela G. Conrad, John P. Grotzinger, Heather B. Franz, Sanjeev Gupta, Caroline Freissinet, Daniel P. Glavin, Brad Sutter, Maeva Millan, Dawn Y. Sumner, Andrew Steele, P. D. Archer, Joel A. Hurowitz, Amy McAdam, Jennifer L. Eigenbrode, Rafael Navarro-González, Cyril Szopa, Charles Malespin, D. W. Ming, Roger E. Summons, NASA Goddard Space Flight Center (GSFC), Department of Earth, Atmospheric and Planetary Sciences [MIT, Cambridge] (EAPS), Massachusetts Institute of Technology (MIT), Geophysical Laboratory [Carnegie Institution], Carnegie Institution for Science [Washington], PLANETO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Georgetown University [Washington] (GU), Instituto de Ciencias Nucleares [Mexico], Universidad Nacional Autónoma de México (UNAM), Jacobs Technology ESCG, Astromaterials Research and Exploration Science (ARES), NASA Johnson Space Center (JSC), NASA-NASA, Stony Brook University [SUNY] (SBU), State University of New York (SUNY), Division of Geological and Planetary Sciences [Pasadena], California Institute of Technology (CALTECH), Department of Earth Science and Engineering [Imperial College London], Imperial College London, Department of Earth and Planetary Sciences [Davis], University of California [Davis] (UC Davis), University of California-University of California, Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), CentraleSupélec, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), NASA Goddard Space Flight Center ( GSFC ), Department of Earth, Atmospheric and Planetary Sciences [MIT, Cambridge] ( EAPS ), Massachusetts Institute of Technology ( MIT ), IMPEC - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales ( LATMOS ), Université de Versailles Saint-Quentin-en-Yvelines ( UVSQ ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Institut national des sciences de l'Univers ( INSU - CNRS ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Versailles Saint-Quentin-en-Yvelines ( UVSQ ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Institut national des sciences de l'Univers ( INSU - CNRS ) -Centre National de la Recherche Scientifique ( CNRS ), Georgetown University [Washington] ( GU ), Universidad Nacional Autónoma de México ( UNAM ), Astromaterials Research and Exploration Science ( ARES ), NASA Johnson Space Center ( JSC ), Stony Brook University [The State University of New York] ( SBU ), California Institute of Technology ( CALTECH ), Department of Earth Science and Engineering [London], University of California [Davis] ( UC Davis ), Laboratoire de Génie des Procédés et Matériaux - EA 4038 ( LGPM ), Laboratoire inter-universitaire des systèmes atmosphèriques ( LISA ), Centre National de la Recherche Scientifique ( CNRS ) -Université Paris-Est Créteil Val-de-Marne - Paris 12 ( UPEC UP12 ) -Université Paris Diderot - Paris 7 ( UPD7 ) -Institut national des sciences de l'Univers ( INSU - CNRS ), Carnegie Institution for Science, Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Universidad Nacional Autónoma de México = National Autonomous University of Mexico (UNAM), Department of Earth and Planetary Sciences [Univ California Davis] (EPS - UC Davis), University of California (UC)-University of California (UC), Laboratoire de Génie des Procédés et Matériaux (LGPM), CentraleSupélec-Université Paris-Saclay, Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), and Science and Technology Facilities Council (STFC)

Subjects
010504 meteorology & atmospheric sciences, Evolved gas analysis, General Science & Technology, chemistry.chemical_element, 01 natural sciences, Astrobiology, PHASES, [SDU.STU.PL]Sciences of the Universe [physics]/Earth Sciences/Planetology, 0103 physical sciences, Organic matter, 010303 astronomy & astrophysics, [ SDU.ASTR ] Sciences of the Universe [physics]/Astrophysics [astro-ph], 0105 earth and related environmental sciences, Total organic carbon, Martian, chemistry.chemical_classification, Science & Technology, Multidisciplinary, [ SDU.STU.PL ] Sciences of the Universe [physics]/Earth Sciences/Planetology, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], PYROLYSIS, Mars Exploration Program, 15. Life on land, Multidisciplinary Sciences, chemistry, 13. Climate action, Sample Analysis at Mars, Science & Technology - Other Topics, Environmental science, Carbon, Pyrolysis
Abstract

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

Published
2018
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49. Operations of the Sample Analysis at Mars instrument suite onboard the Curiosity rover

Author

Caroline Freissinet, Arnaud Buch, Samuel Teinturier, Micah Johnson, Jean-Yves Bonnet, Eric Lorigny, Cyril Szopa, Michel Cabane, Paul R. Mahaffy, Mehdi Benna, Charles Malespin, Stephen Indyk, David Coscia, B. D. Prats, Laboratoire Atmosphères, Milieux, Observations Spatiales ( LATMOS ), Université de Versailles Saint-Quentin-en-Yvelines ( UVSQ ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Institut national des sciences de l'Univers ( INSU - CNRS ) -Centre National de la Recherche Scientifique ( CNRS ), Telespazio France, IMPEC - LATMOS, Université de Versailles Saint-Quentin-en-Yvelines ( UVSQ ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Institut national des sciences de l'Univers ( INSU - CNRS ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Versailles Saint-Quentin-en-Yvelines ( UVSQ ) -Université Pierre et Marie Curie - Paris 6 ( UPMC ) -Institut national des sciences de l'Univers ( INSU - CNRS ) -Centre National de la Recherche Scientifique ( CNRS ), CentraleSupélec, Honeybee Robotics Ltd, NASA Goddard Space Flight Center ( GSFC ), eINFORMe inc., Centre National d'Etudes Spatiales ( CNES ), Goddard Earth Sciences and Technology and Research ( GESTAR ), Universities Space Research Association ( USRA ) -NASA, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), PLANETO - LATMOS, Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Laboratoire de Génie des Procédés et Matériaux - EA 4038 (LGPM), NASA Goddard Space Flight Center (GSFC), Centre National d'Études Spatiales [Toulouse] (CNES), Goddard Earth Sciences and Technology and Research (GESTAR), and Universities Space Research Association (USRA)-NASA

Subjects
[PHYS.PHYS.PHYS-AO-PH]Physics [physics]/Physics [physics]/Atmospheric and Oceanic Physics [physics.ao-ph], Martian, Scientific instrument, Engineering, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], 010504 meteorology & atmospheric sciences, Spectrometer, business.industry, Payload, Suite, Mars Exploration Program, 01 natural sciences, Workflow, [ PHYS.PHYS.PHYS-AO-PH ] Physics [physics]/Physics [physics]/Atmospheric and Oceanic Physics [physics.ao-ph], 0103 physical sciences, Sample Analysis at Mars, Aerospace engineering, business, 010303 astronomy & astrophysics, [ SDU.ASTR ] Sciences of the Universe [physics]/Astrophysics [astro-ph], 0105 earth and related environmental sciences
Abstract

The Sample Analysis at Mars instrument suite, onboard the Curiosity rover, has been analyzing the martian environment since August 05th 2012, as one of the main tools of the Mars Science Laboratory mission. This suite is composed of three independent but interoperable instruments, namely a Quadrupole Mass Spectrometer, a Tunable Laser Spectrometer and a Gas Chromatograph, plus a sophisticated Sample Manipulation System. SAM is used to analyze soils, rocks and atmosphere. For instance, it detected in situ martian complex organics for the first time, provide us with a several years survey of the atmospheric composition and helped understand how the martian environment evolved through the planet history. At 40 kg, it represents half of the scientific payload weight of Curiosity and is one of the two analytical instruments of the mission. This instrument suite is the result of an international collaboration between the NASA Goddard Space Flight Center, the NASA Jet Propulsion Laboratory and a consortium of French laboratories supported by the Center National d’Etudes Spatiales (the French space agency). This contribution will present the organization of the SAM operational workflow from the ground infrastructure, to flight operations and laboratory supporting work. It will also describe how the CNES hosts and supports the SAM team during this exciting mission.

Published
2018
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50. Magnesium sulfate as a key mineral for the detection of organic molecules on Mars using pyrolysis

Author

Paul R. Mahaffy, Arnaud Buch, Rafael Navarro-González, Pascaline Francois, Michel Cabane, Patrice Coll, Cyril Szopa, Amy McAdam, Daniel P. Glavin, and Caroline Freissinet

Subjects
010504 meteorology & atmospheric sciences, Chemistry, Magnesium, Mineralogy, chemistry.chemical_element, Mars Exploration Program, Martian soil, 01 natural sciences, Decomposition, Perchlorate, chemistry.chemical_compound, Geophysics, 13. Climate action, Space and Planetary Science, Geochemistry and Petrology, Environmental chemistry, 0103 physical sciences, Sample Analysis at Mars, Earth and Planetary Sciences (miscellaneous), Sulfate, 010303 astronomy & astrophysics, Pyrolysis, 0105 earth and related environmental sciences
Abstract

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 (~700 °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.

Published
2016
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