arXiv subjects

Thomas Gautier

Publications and source records attributed to Thomas Gautier.

16 recordsLinked to original sources

arXiv2025

Investigating the formation and growth of Titan's atmospheric aerosols using an experimental approach

Titan has a climate system with similarities to Earth, including the presence of a thick atmosphere made up of several atmospheric layers. As on Earth, Titan's climate is influenced by several factors: the gaseous species making up the atmosphere, the energy deposited on the satellite, and solid organic aerosols. Indeed, numerous observations have revealed the presence of solid particles in the form of an opaque orange haze in Titan's atmosphere, influencing radiation balance and atmospheric dynamics, for example. However, the influence of these suspended solid particles seems to evolve according to the atmospheric altitude where they are located, certainly testifying to the presence of organic solids with different physico-chemical properties. At present, it is suspected that several populations/classes of atmospheric aerosols may form following different chemical pathways, and that aerosols undergo growth processes that modify their properties. We propose the calculation of an uptake coefficient between six neutral gaseous products (C2H2, HCN, C2H6, C2H3N, HC3N, C2N2) and the surface of the Titan aerosol analogues produced in this study.

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arXiv2024

Spectro-photometry of Phobos simulants: II. Effects of porosity

Surface porosity has been found to be an important property for small bodies. Some asteroids and comets can exhibit an extremely high surface porosity in the first millimeter layer. This layer may be produced by various processes and maintained by the lack of an atmosphere. However, the influence of porosity on the spectro-photometric properties of small body surfaces is not yet fully understood. In this study, we looked into the effect of porosity on the spectro-photometric properties of Phobos regolith spectroscopic simulants; created by mixing the simulants with ultra-pure water, producing ice-dust particles, and then sublimating the water. The reflectance spectroscopic properties in the visible and near-infrared (0.5-4.2 $\mu$m) show no strong variations between the porous and compact samples. However, one simulant exhibits a bluing of the slope after increasing porosity, providing possible insights into the differences between the blue and red units observed on Phobos. In the mid-infrared range, a contrast increase of the 10-$\mu$m emissivity plateau due to silicates is observed. Photometry reveals a modification in the phase reddening behavior between the compact powder and the sublimation residue for both simulants. However, the observed behavior is different between the simulants, suggesting that the phase reddening may be dependent on the composition of the simulants. The phase curve also appears to be modified by the addition of porosity, with a higher contribution of forward scattering observed for the sublimation residue. The derivation of the Hapke parameters indicates an increase in roughness for the porous sample, but no significant modification of the opposition effect. This study aims to provide new insights into the understanding of porosity by using two Phobos simulants in the context of the upcoming JAXA/Martian Moons eXploration mission.

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arXiv2024

Spectro-photometry of Phobos simulants: I. Detectability of hydrated minerals and organic bands

Previous observations of Phobos and Deimos, the moons of Mars, have improved our understanding of these small bodies. However, their formation and composition remain poorly constrained. Physical and spectral properties suggest that Phobos may be a weakly thermal-altered captured asteroid but the dynamical properties of the martian system suggest a formation by giant collision similar to the Earth moon. In 2027, the JAXA's MMX mission aims to address these outstanding questions. We undertook measurements with a new simulant called OPPS (Observatory of Paris Phobos Simulant) which closely matches Phobos spectra in the visible to the mid-infrared range. The simulant was synthesized using a mixture of olivine, saponite, anthracite, and coal. Since observation geometry is a crucial aspect of planetary surface remote sensing exploration, we evaluated the parameters obtained by modeling the phase curves -- obtained through laboratory measurements -- of two different Phobos simulants (UTPS-TB and OPPS) using Hapke IMSA model. Our results show that the photometric properties of Phobos simulants are not fully consistent with those of Tagish Lake, Allende, or the NWA 4766 shergottite. We also investigated the detection of volatiles/organic compounds and hydrated minerals, as the presence of such components is expected on Phobos in the hypothesis of a captured primitive asteroid. The results indicate that a significant amount of organic compounds is required for the detection of C-H bands at 3.4 $μ$m. In contrast, the 2.7 $μ$m absorption band, due to hydrated minerals, is much deeper and easier to detect than C-H organic features at the same concentration levels. Posing limits on detectability of some possible key components of Phobos surface will be pivotal to prepare and interpret future observations of the MIRS spectrometer onboard MMX mission.

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arXiv2023

Humid Evolution of Haze in the Atmosphere of Super-Earths in the Habitable Zone

Photochemical hazes are expected to form and significantly contribute to the chemical and radiative balance of exoplanets with relatively moderate temperatures, possibly in the habitable zone of their host star. In the presence of humidity, haze particles might thus serve as cloud condensation nuclei and trigger the formation of water droplets. In the present work, we are interested in the chemical impact of such a close interaction between photochemical hazes and humidity on the organic content composing the hazes and on the capacity to generate organic molecules with high prebiotic potential. For this purpose, we explore experimentally the sweet spot by combining N-dominated super-Earth exoplanets in agreement with Titan's rich organic photochemistry and humid conditions expected for exoplanets in habitable zones. A logarithmic increase with time is observed for the relative abundance of oxygenated species, with O-containing molecules dominating after 1 month only. The rapidity of the process suggests that the humid evolution of N-rich organic haze provides an efficient source of molecules with high prebiotic potential.

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arXiv2021

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)

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.

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arXiv2020

Interaction dust-plasma in Titan's ionosphere: an experimental simulation of aerosols erosion

Organic aerosols accumulated in Titan's orange haze start forming in its ionosphere. This upper part of the atmosphere is highly reactive and complex ion chemistry takes place at altitudes from 1200 to 900 km. The ionosphere is a nitrogen plasma with a few percent of methane and hydrogen. Carbon from methane enables the formation of macromolecules with long organic chains, finally leading to the organic aerosols. On the other hand, we suspect that hydrogen and the protonated ions have a different erosive effect on the aerosols. Here we experimentally studied the effect of hydrogen and protonated species on organic aerosols. Analogues of Titan's aerosols were formed in a CCP RF plasma discharge in 95% N2 and 5% CH4. Thereafter, the aerosols were exposed to a DC plasma in 99% N2 and 1% H2. Samples were analysed by scanning electron microscopy and in situ infrared transmission spectroscopy. Two pellet techniques - KBr pressed pellets and thin metallic grids - were compared to confirm that modifications seen are not due to the material used to make the pellet. We observed that the spherical aerosols of ~500 nm in diameter were eroded under N2-H2 plasma exposure, with the formation of holes of ~10 nm at their surface. Aerosols were globally removed from the pellet by the plasma. IR spectra showed a faster disappearance of isonitriles and/or carbo-diimides compared to the global band of nitriles. The opposite effect was seen with beta-unsaturated nitriles and/or cyanamides. Double bonds as C=C and C=N were more affected than amines and C-H bonds. N-H and C-H absorption bands kept a similar ratio in intensity and their shape did not vary. Therefore, it seems that carbon and hydrogen play opposite roles in Titan's ionosphere: the carbon from methane lead to organic growth while hydrogen and protonated species erode the aerosols and react preferentially with unsaturated chemical functions.

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arXiv2019

Positive Ion Chemistry in an N$_2$-CH$_4$ Plasma Discharge: Key Precursors to the Growth of Titan Tholins

Titan is unique in the solar system as it hosts a dense atmosphere mainly made of N$_2$ and CH$_4$. Cassini-Huygens revealed the presence of an intense atmospheric photochemistry initiated by the photo-dissociation and ionization of N$_2$ and CH$_4$. In the upper atmosphere, Cassini detected signatures compatible with the presence of heavily charged molecules, precursors for the solid core of the aerosols. However, the processes coupling ion chemistry and aerosol formation and growth are still mostly unknown. In this study, we investigated the cation chemistry responsible for an efficient organic growth that we observe in Titan's upper atmosphere, simulated using the PAMPRE plasma reactor. Cation precursors were measured by in situ ion mass spectrometry in a cold plasma and compared with INMS observations taken during the T40 flyby. A series of positive ion measurements were performed in three CH$_4$ mixing ratios (1%, 5% and 10%) showing a variability in ion population. Low CH$_4$ concentrations result in an abundance of amine cations such as NH$_4^+$ whereas aliphatic compounds dominate at higher methane concentrations. In conditions of favored tholin production, the presence of C2 compounds such as HCNH$^+$ and C$_2$H$_5^+$ is found to be consistent with copolymeric growth structures seen in tholin material. The observed abundance of these two ions particularly in conditions with lower CH$_4$ amounts is consistent with modeling work simulating aerosol growth in Titan's ionosphere, which includes mass exchange primarily between HCNH$^+$ and C$_2$H$_5^+$ and negatively charged particles. These results also confirm the prevalent role of C2 cations as precursors to molecular growth and subsequent mass transfer to the charged aerosol particles as the CH$_4$ abundance decreases towards lower altitudes.

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arXiv2019

An EUV Non-Linear Optics Based Approach to Study the Photochemical Processes of Titanś Atmosphere

In situ exploration of the planetary atmospheres requires the development of laboratory experiments to understand the molecular growth pathways initiated by photochemistry in the upper layers of the atmospheres. Major species and dominant reaction pathways are used to feed chemical network models that reproduce the chemical and physical processes of these complex environments. Energetic UV photons initiate very efficient chemistry by forming reactive species in the ionospheres of planets and satellites. Here we present a laboratory experiment based on a new photoreactor with an irradiation beam produced by high order harmonic generation of a near infra-red femtosecond laser. This type of EUV source is nowadays stable enough to enable long-lasting experiments during which a plethora of individual reactions can take place. Its high accessibility is such that chemical initial conditions can be systematically varied to investigate the complexity of the upper atmosphere of planets. In order to demonstrate the validity of our approach, we shone during 7 hours at 14 eV with a flux of 1010 photons sec-1 cm-2, a N2/CH4 (5%) based gas mixture defined by a 60 μm free mean-path. Such conditions are able to mimic the photochemistry of Titan N2 upper atmosphere. The reaction products reveal the formation of hydrocarbons and N-bearing species like dimethyldiazene (C2H6N2), the largest compound detected in this new photoreactor. This work represents an important step in the use of a EUV irradiated closed-cell chamber for the generation of photochemical analogues of Titan aerosols to better constrain the growth pathways of nitrogen incorporation into organic aerosols in the Titan atmosphere.

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arXiv2019

Structural study of analogues of Titan s haze by trapped ion mobility coupled with a Fourier transform ion cyclotron mass spectrometer

The aerosols present in the atmosphere of the Saturn s moon Titan are of particular planetary science interest and several spacecraft missions already allowed to gather spectroscopic data. Titan haze s analogs, so-called tholins, were produced on earth to push forward the comprehension of their formation and properties. In this study, this highly complex mixture was analyzed here for the first time by trapped ion mobility spectrometry coupled to ultra-high resolution mass spectrometry (FTICR MS). Electrospray ionization revealed the characteristic CHNx-class components, with CHN5-6 and DBE 6-7 most abundant. Deploying specialized visualization, enabled by accurate mass measurements and elemental composition assignments, the adapted Kendrick mass defect analysis highlights the C2H3N homolog series, whereas the nitrogen-modified van Krevelen diagram exhibits a clear trend towards H/C 1.5 and N/C 0.5. More interestingly, the representation of m/z versus collision cross section (CCS) allowed hypothesizing a ramified N-PAH structural motif. State-of-the-art IMS is currently not able to resolve the isomeric continuum of ultra-complex mixtures; thus peak parameter other than the CCS-value are explored. As such, analyzing the mobility peak width versus m/z shows a linear increase in isomeric diversity between m/z 170 and 350 and a near plateau in diversity at higher m/z for the N-PAH-like structure. Due to the high complexity of the sample, these structural insights are only to be revealed by TIMS-FTICR MS.

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arXiv2018

Detection opportunity for aromatic signature in Titan s aerosols in the 4.1 to 5.3 micron range

The Cassini/Huygens mission provided new insights on the chemistry of the upper atmosphere of Titan. The presence of large molecules and ions (>100 s of amu) detected by Cassini at high altitude was not expected, and questions the original assumptions regarding the aerosol formation pathways. From recent laboratory studies, it has been shown that the inclusion of trace amounts of aromatic species drastically impacts the chemistry of aerosol formation and induces observable changes in the properties of the aerosols. In the present work we focus on the effect of one of the simplest nitrogenous aromatics, pyridine (C5H5N), on the infrared signature of Titan s aerosol analogs. We introduce initial gas mixtures of: (i) N2-C5H5N (100%/250ppm), (ii) N2-CH4-C5H5N (99%/1%/250ppm), (iii) N2-CH4 (99%/1%) in a cold plasma discharge. The material produced, herein called tholins, is then analyzed by mid-infrared spectroscopy. When adding pyridine in the discharge, the tholins produced present an aromatic signature in the 4.1-5.3 micron (1850-2450 cm-1) spectral region, attributed to overtones of aromatic C-H out-of-plane bending vibrations. We also observe a spectral shift of the nitrile and iso-nitrile absorption band with the inclusion of pyridine in the gas mixture. These results could help to investigate the data obtained at Titan by the Cassini/VIMS instrument in the 1-5 micron infrared window

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arXiv2018

Comparison of soluble and insoluble organic matter in analogues of Titan s aerosols

Titan, the biggest moon of Saturn, has a thick atmosphere which presents similarities with the one thought to be on Earth at its beginning. The study of Titan s photochemical haze is thus a precious tool in gaining knowledge of the primitive atmosphere of Earth. The chemistry occurring in Titan s atmosphere and the exact processes at act in the formation of the hazes remain largely unknown. The production of analogs samples on Earth has proved to be a useful tool to improve our knowledge of the aerosols formation on Titan. Such solid organic analogs samples, named tholins, were produced with the PAMPRE experiment (French acronym for Aerosols Microgravity Production by Reactive Plasma). PAMPRE tholins were found to be mostly insoluble, with only one-third of the bulk sample that can be dissolved in methanol. This partial solubility limited the previous studies in mass spectrometry, which were done only on the soluble fraction. The goal of the present study is to compare the two fractions of PAMPRE s tholins (insoluble and soluble) using a ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometer (FTICR) equipped with a laser desorption/ionization source. Using modified Van Krevelen diagrams, we compare the global distribution of the molecules within the samples according to their Hydrogen/Carbon ratio and Nitrogen/Carbon ratio. Major differences are observed in the molecular composition of the soluble and the insoluble fraction. The soluble fraction of tholins was previously identified as a set of polymers of average formula (C2H3N)n. In this work we observe that the insoluble fraction of tholins is comprised of a significantly different set of polymers with an average composition of (C4H3N2)n.

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arXiv2017

Titan organic aerosols: molecular composition and structure of laboratory analogues inferred from systematic pyrolysis gas chromatography mass spectrometry analysis

Numerous studies have been carried out to characterize the chemical composition of laboratory analogues of Titan aerosols (tholins), but their molecular composition as well as their structure are still poorly known. If pyrolysis gas chromatography mass spectrometry (pyr-GCMS) has been used for years to give clues about this composition, the highly disparate results obtained can be attributed to the analytical conditions used and/or to differences in the nature of the analogues studied. In order to have a better description of Titan tholins molecular composition, we led a systematic analysis of these materials using pyr-GCMS with two major objectives: (i) exploring the analytical parameters to estimate the biases this technique can induce and to find an optimum for analyses allowing the detection of a wide range of compounds and thus a characterization of the tholins composition as comprehensive as possible, and (ii) highlighting the role of the CH4 ratio in the gaseous reactive medium on the tholins molecular structure. With this aim, we used a radio-frequency plasma discharge to synthetize tholins with different concentrations of CH4 diluted in N2. The samples were systematically pyrolyzed from 200 to 600°C. The extracted gases were then analyzed by GCMS for their molecular identification.

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arXiv2017

Molecular Isomer Identification of Titan Tholins Organic Aerosols by Photoelectron/Photoion Coincidence Spectroscopy Coupled to VUV Synchrotron Radiation

The chemical composition of Titan organic haze is poorly known. To address this issue, laboratory analogs named tholins are synthesized, and analyzed by methods requiring often an extraction process in a carrier solvent. These methods exclude the analysis of the insoluble tholins fraction and assume a hypothetical chemical equivalence between soluble and insoluble fractions. In this work, we present a powerful complementary analysis method recently developed on the DESIRS VUV synchrotron beamline at SOLEIL. It involves a soft pyrolysis of tholins at ~230 deg C and an electron ion coincidence analysis of the emitted volatiles compounds photoionized by the tunable synchrotron radiation. By comparison with reference photoelectron spectra (PES), the spectral information collected on the detected molecules yields their isomeric structure. The method is more readily applied to light species, while for heavier ones the number of possibilities and the lack of PES reference spectra in the literature limit its analysis. A notable pattern in the analyzed tholins is the presence of species containing adjacent doubly-bonded N atoms, which might be a signature of heterogeneous incorporation of N2 in tholins.

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arXiv2017

Decay of COSAC and Ptolemy Mass Spectra at Comet 67P/Churyumov-Gerasimenko

The Rosetta lander Philae successfully landed on the nucleus of comet 67P/Churyumov-Gerasimenko on 12 November 2014. Philae is equipped with two gas analyzers: The Cometary Sampling and Composition experiment (COSAC) and the gas chromatograph and mass spectrometer Ptolemy. On 12 to 14 November 2014 both instruments measured the organic composition of the comet nucleus material through seven measurements in sniffing mode during Philae's hopping and at its final landing site Abydos. We compare the temporal evolution of intensities of several ion species identified by both mass spectrometers. For COSAC this is the first analysis of the temporal behaviour of the measured ion species. All ion species showed the highest intensities in the first spectra measured by both instruments about 20 to 30 minutes after Philae's first touchdown at Agilkia, and a decay during the six consecutive measurements at Abydos. Both instruments measured a nearly identical decay of the water peak (m/z 18), and also CO (m/z 28) behaved similarly. In the COSAC measurements the peak at m/z 44 decays much slower than all the other ion species, including the water peak. In particular, the m/z 44 peak decays much slower in the COSAC measurements than in the Ptolemy data. This supports our earlier interpretation that COSAC for the first time analyzed a regolith sample from a cometary nucleus in situ, while Ptolemy measured cometary gas from the ambient coma. The m/z 44 peak measured by COSAC was likely dominated by organic species, whereas the peak measured by Ptolemy was interpreted to be mostly due to $CO_2$. Ion species heavier than m/z 30 tend to decay somewhat slower in the COSAC measurements than in the Ptolemy data, which may be related to differences in the exhaust designs between both instruments.

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arXiv2016

Development of HPLC-Orbitrap method for identification of N-bearing molecules in complex organic material relevant to planetary environments

Although the Cassini Spacecraft and the Huygens lander provided numerous information about Titan atmospheric chemistry and the formation of its aerosols, the exact composition of these aerosols still remains unknown. A fruitful proxy to investigate these aerosols is the use of laboratory experiments that allow producing and studying analogs of Titan aerosol, the so35 called tholins. Even when produced in the laboratory, unveiling the exact composition of the aerosol remains problematic due to the high complexity of the material. Numerous advances have been recently made using high-resolution mass spectrometry (HRMS) (Pernot et al. 2010, Somogyi et al. 2012, Gautier et al. 2014) that allowed the separation of isobaric compounds and a robust identification of chemical species composing tholins regarding their molecular formulae. Nevertheless isomeric species cannot be resolved by a simple mass measurement. We propose here an analysis of tholins by high performance liquid chromatography (HPLC) coupled to HRMS to unveil this isomeric ambiguity for some of the major tholins compounds. By comparing chromatograms obtained when analyzing tholins and chemical standards, we strictly identified seven molecules in our tholins samples: melamine, cyanoguanidine, 6-methyl-1,3,5-triazine-2,4-diamine, 2,4,6-triaminopyrimidine, 3-amino- 1,2,4-triazole, 3,5-Dimethyl-1,2,4-triazole and 2,4-diamino-1,3,5-triazine. Several molecules, including hexamethylenetriamine (HMT) were not present at detectable levels in our sample. The use for the first time of a coupled HPLC-HRMS technique applied to tholins study demonstrated the interest of such a technique compared to single high-resolution mass spectrometry for the study of tholins composition.

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arXiv2011

WISE/NEOWISE observations of Active Bodies in the Main Belt

We report results based on mid-infrared photometry of 5 active main belt objects (AMBOs) detected by the Wide-field Infrared Survey Explorer (WISE) spacecraft. Four of these bodies, P/2010 R2 (La Sagra), 133P/Elst-Pizarro, (596) Scheila, and 176P/LINEAR, showed no signs of activity at the time of the observations, allowing the WISE detections to place firm constraints on their diameters and albedos. Geometric albedos were in the range of a few percent, and on the order of other measured comet nuclei. P/2010 A2 was observed on April 2-3, 2010, three months after its peak activity. Photometry of the coma at 12 and 22 μm combined with ground-based visible-wavelength measurements provides constraints on the dust particle mass distribution (PMD), dlogn/dlogm, yielding power-law slope values of α = -0.5 +/- 0.1. This PMD is considerably more shallow than that found for other comets, in particular inbound particle fluence during the Stardust encounter of comet 81P/Wild 2. It is similar to the PMD seen for 9P/Tempel 1 in the immediate aftermath of the Deep Impact experiment. Upper limits for CO2 & CO production are also provided for each AMBO and compared with revised production numbers for WISE observations of 103P/Hartley 2.

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