Analyses of organic matter with a new mass spectrometer based on CosmOrbitrap in the framework of a new space mission

La spectrométrie de masse joue un rôle clef dans l’exploration spatiale, notamment dans la caractérisation de la matière organique présente sur de nombreux objets du Système Solaire. Dans ce manuscrit, l’accent est particulièrement mis sur Titan, présentant une chimie organique complexe initiée dans son ionosphère et se répercutant jusqu’à sa surface. Les spectromètres de masse embarqués à bord de la mission Cassini-Huygens ont permis de nombreuses détections de composés organiques. Cependant, les limites instrumentales d’un point de vue analytique poussent la communauté scientifique à se pencher sur de nouvelles techniques de spectrométrie de masse dites à haute résolution (HRMS).Mon travail de thèse s’est inscrit dans le développement d’un nouveau type d’analyseur en masse basé sur la technologie Orbitrap, instrumentation HRMS de laboratoire, pour une application spatiale. Ce projet se nomme CosmOrbitrap. L’objectif s’est ainsi concentré sur les possibilités d’analyse de la matière organique avec une configuration instrumentale simple et compacte couplant directement l’analyseur CosmOrbitrap à une ionisation par ablation laser (LAb-CosmOrbitrap), dans un contexte de future mission spatiale. L’identification univoque de composés organiques purs ou formant des mélanges complexes, la démonstration des performances en termes de résolution, de précision en masse et d’étude des rapports isotopiques mais également l’influence de la pression sur la résolution en masse obtenue sur des composés organiques sont détaillées dans ce manuscrit. L’analyse de la matière brute d’analogues d’aérosols de Titan synthétisés en laboratoire (tholins) montre un cas d’étude concret sur les capacités du LAb-CosmOrbitrap à permettre une analyse chimique profonde des échantillons représentatifs d’un environnement d’intérêt exobiologique.Mass spectrometry is a key tool in space exploration, for the analysis of organic matter of many Solar System bodies. In this dissertation, we mainly focus on Titan. This amazing object in the Solar System shows a very rich organic chemistry from the ionosphere to the surface. Mass spectrometers aboard the Cassini-Huygens spacecraft have allowed the detection of many organic compounds. However, instrumental limits in terms of analytical performances lead scientists to develop new high resolution mass spectrometry techniques (HRMS).My PhD is rooted to the development of a new high resolution mass analyzer based on the Orbitrap technology, for a space application. This project is named CosmOrbitrap. The efficiency of a simple and compact instrumental version of CosmOrbitrap coupled with a laser ablation ionization process (LAb-CosmOrbitrap) is demonstrated on organic matter analyses in the framework of a future space mission. Univocal identification of pure organics compounds and complex organic mixtures, analytical performances such as mass resolving power, mass accuracy and isotopic abundances determination as well as the impact of the pressure on the mass resolution of organics are part of this dissertation. The study of laboratory analogs of Titan aerosols (named tholins) shows capabilities of the LAb-CosmOrbitrap to provide a deep chemical analysis of exobiological environment

Optimisation de l'analyse de la matière organique à l'aide d'un nouveau spectromètre de masse basé sur le CosmOrbitrap dans un contexte de future mission spatiale

Mass spectrometry is a key tool in space exploration, for the analysis of organic matter of many Solar System bodies. In this dissertation, we mainly focus on Titan. This amazing object in the Solar System shows a very rich organic chemistry from the ionosphere to the surface. Mass spectrometers aboard the Cassini-Huygens spacecraft have allowed the detection of many organic compounds. However, instrumental limits in terms of analytical performances lead scientists to develop new high resolution mass spectrometry techniques (HRMS).My PhD is rooted to the development of a new high resolution mass analyzer based on the Orbitrap technology, for a space application. This project is named CosmOrbitrap. The efficiency of a simple and compact instrumental version of CosmOrbitrap coupled with a laser ablation ionization process (LAb-CosmOrbitrap) is demonstrated on organic matter analyses in the framework of a future space mission. Univocal identification of pure organics compounds and complex organic mixtures, analytical performances such as mass resolving power, mass accuracy and isotopic abundances determination as well as the impact of the pressure on the mass resolution of organics are part of this dissertation. The study of laboratory analogs of Titan aerosols (named tholins) shows capabilities of the LAb-CosmOrbitrap to provide a deep chemical analysis of exobiological environment.La spectrométrie de masse joue un rôle clef dans l’exploration spatiale, notamment dans la caractérisation de la matière organique présente sur de nombreux objets du Système Solaire. Dans ce manuscrit, l’accent est particulièrement mis sur Titan, présentant une chimie organique complexe initiée dans son ionosphère et se répercutant jusqu’à sa surface. Les spectromètres de masse embarqués à bord de la mission Cassini-Huygens ont permis de nombreuses détections de composés organiques. Cependant, les limites instrumentales d’un point de vue analytique poussent la communauté scientifique à se pencher sur de nouvelles techniques de spectrométrie de masse dites à haute résolution (HRMS).Mon travail de thèse s’est inscrit dans le développement d’un nouveau type d’analyseur en masse basé sur la technologie Orbitrap, instrumentation HRMS de laboratoire, pour une application spatiale. Ce projet se nomme CosmOrbitrap. L’objectif s’est ainsi concentré sur les possibilités d’analyse de la matière organique avec une configuration instrumentale simple et compacte couplant directement l’analyseur CosmOrbitrap à une ionisation par ablation laser (LAb-CosmOrbitrap), dans un contexte de future mission spatiale. L’identification univoque de composés organiques purs ou formant des mélanges complexes, la démonstration des performances en termes de résolution, de précision en masse et d’étude des rapports isotopiques mais également l’influence de la pression sur la résolution en masse obtenue sur des composés organiques sont détaillées dans ce manuscrit. L’analyse de la matière brute d’analogues d’aérosols de Titan synthétisés en laboratoire (tholins) montre un cas d’étude concret sur les capacités du LAb-CosmOrbitrap à permettre une analyse chimique profonde des échantillons représentatifs d’un environnement d’intérêt exobiologique

Laboratory studies of organics with Cosmorbitrap, a new HRMS analyser, in the framework of future missions to Titan and other organic worlds

International audienceThe Cosmorbitrap is a development of a space mass analyzer, based on the OrbitrapTM technology. In the context of Titan future exploration, we have addressed two important questions using it: first, to show that the instrument was able to identify the structure of complex organic molecules, then to characterize the evolution of the instrument performances when increasing the background pressure as it can be critical when exploring Titan's dense atmosphere. These questions are relevant in the framework of a future space exploration of an organic world like Titan environment

Laboratory studies of organics with Cosmorbitrap, a new HRMS analyser, in the framework of future missions to Titan and other organic worlds

International audienceThe Cosmorbitrap is a development of a space mass analyzer, based on the OrbitrapTM technology. In the context of Titan future exploration, we have addressed two important questions using it: first, to show that the instrument was able to identify the structure of complex organic molecules, then to characterize the evolution of the instrument performances when increasing the background pressure as it can be critical when exploring Titan's dense atmosphere. These questions are relevant in the framework of a future space exploration of an organic world like Titan environment

Laboratory studies of organics with Cosmorbitrap, a new HRMS analyser, in the framework of future missions to Titan and other organic worlds

International audienceThe Cosmorbitrap is a development of a space mass analyzer, based on the OrbitrapTM technology. In the context of Titan future exploration, we have addressed two important questions using it: first, to show that the instrument was able to identify the structure of complex organic molecules, then to characterize the evolution of the instrument performances when increasing the background pressure as it can be critical when exploring Titan's dense atmosphere. These questions are relevant in the framework of a future space exploration of an organic world like Titan environment

Uracil evolution under Mars surface-like UV radiation conditions with the MOMIE (Mars Organic Matter Irradiation and Evolution) experiment

International audienceThe detection and identification of organic molecules at Mars are of primary importance for astrobiology, as some of these molecules are life precursors and components. While in situ exploration missions are searching for them at the surface of the planet, it is essential to understand how organic molecules evolve and are preserved at the surface of Mars. Indeed the harsh conditions of the environment of Mars, such as ultraviolet (UV) radiation or oxidative processes, due for example to perchlorate ions, could explain the low abundance and diversity of organic molecules detected so far [1][2]. The MOMIE (Mars Organic Matter Irradiation and Evolution) experiment has been set up to study the evolution of organic matter under simulated martian radiation within the laboratory [3]. Organic samples are exposed under a wide range UV lamp (200-400 nm) as thin homogenous solid films (a fraction of μm thick), by a mean temperature of -55°C and a mean pressure of 6 mbar, close to Mars surface conditions. Most of the organic molecules studied so far were quickly destroyed under Mars surface-like UV radiation conditions [4]. Uracil is a one-ringed heterocyclic compound, a nucleobase found in RNA, and has been detected in meteorites thus is likely to be found at Mars [5]. Pure uracil samples were irradiated for several weeks in the MOMIE experiment, as well as uracil mixed with perchlorate salts. To characterize the evolution of uracil samples, analyses by infrared spectroscopy (FTIR) were performed all along the experiment. These analyses allowed determining whether uracil is preserved or photodegraded, and if so, its photolysis rate. The FTIR successive analysis showed new absorption band appearance and increase along the UV irradiation. High-Resolution Mass Spectrometry (HRMS) analysis of irradiated uracil samples has shown that uracil seems to form polymers under martian-like UV radiation. These polymers are far more resistant to UV radiation. The effect of perchlorates salts on uracil evolution and preservation has been investigated as well. The MOMIE experiment allows to understand which organic molecules in situ missions should target, as some of them are quickly destroyed in Mars surface-like conditions while others are likely to form new compounds. Uracil polymers, formed by uracil molecules under Mars surface-like radiation conditions, would be very relevant compounds to search for at the surface of Mars

Uracil evolution under Mars surface-like UV radiation conditions with the MOMIE (Mars Organic Matter Irradiation and Evolution) experiment

International audienceThe detection and identification of organic molecules at Mars are of primary importance for astrobiology, as some of these molecules are life precursors and components. While in situ exploration missions are searching for them at the surface of the planet, it is essential to understand how organic molecules evolve and are preserved at the surface of Mars. Indeed the harsh conditions of the environment of Mars, such as ultraviolet (UV) radiation or oxidative processes, due for example to perchlorate ions, could explain the low abundance and diversity of organic molecules detected so far [1][2]. The MOMIE (Mars Organic Matter Irradiation and Evolution) experiment has been set up to study the evolution of organic matter under simulated martian radiation within the laboratory [3]. Organic samples are exposed under a wide range UV lamp (200-400 nm) as thin homogenous solid films (a fraction of μm thick), by a mean temperature of -55°C and a mean pressure of 6 mbar, close to Mars surface conditions. Most of the organic molecules studied so far were quickly destroyed under Mars surface-like UV radiation conditions [4]. Uracil is a one-ringed heterocyclic compound, a nucleobase found in RNA, and has been detected in meteorites thus is likely to be found at Mars [5]. Pure uracil samples were irradiated for several weeks in the MOMIE experiment, as well as uracil mixed with perchlorate salts. To characterize the evolution of uracil samples, analyses by infrared spectroscopy (FTIR) were performed all along the experiment. These analyses allowed determining whether uracil is preserved or photodegraded, and if so, its photolysis rate. The FTIR successive analysis showed new absorption band appearance and increase along the UV irradiation. High-Resolution Mass Spectrometry (HRMS) analysis of irradiated uracil samples has shown that uracil seems to form polymers under martian-like UV radiation. These polymers are far more resistant to UV radiation. The effect of perchlorates salts on uracil evolution and preservation has been investigated as well. The MOMIE experiment allows to understand which organic molecules in situ missions should target, as some of them are quickly destroyed in Mars surface-like conditions while others are likely to form new compounds. Uracil polymers, formed by uracil molecules under Mars surface-like radiation conditions, would be very relevant compounds to search for at the surface of Mars

The potential of the LAb-CosmOrbitrap for future space studies in astrobiology

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The potential of the LAb-CosmOrbitrap for future space studies in astrobiology

International audienc

The potential of the LAb-CosmOrbitrap for future space studies in astrobiology

International audienc