Study of Titan’s Upper and Lower Atmosphere: An Experimental Approach David Dubois To cite this version: David Dubois. Study of Titan’s Upper and Lower Atmosphere: An Experimental Approach. Plan- etology. Université de Versailles Saint Quentin en Yvelines (UVSQ), France, 2018. English. tel- 01925462v1 HAL Id: tel-01925462 https://hal.archives-ouvertes.fr/tel-01925462v1 Submitted on 16 Nov 2018 (v1), last revised 19 Mar 2019 (v2) HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Study of Titan’s Upper and Lower Atmosphere: An BNNT: 2018SACLV049 Experimental Approach Thèse de doctorat de l’Université Paris-Saclay préparée à l’Université de Versailles Saint-Quentin-en-Yvelines École doctorale n◦ 579 Sciences mécaniques et énergétiques, matériaux et géosciences (SMEMAG) Spécialité de doctorat: Structure et Évolution de la Terre et des autres Planètes Thèse présentée et soutenue à Guyancourt, le 1 octobre 2018, par David Dubois Composition du Jury: Cyril Szopa Professeur, UVSQ — LATMOS Président Véronique Vuitton Chargée de Recherche, UJF-Grenoble — IPAG Rapportrice Nicolas Fray Maître de Conférences, UPEC — LISA Rapporteur Sandrine Vinatier Maître de Conférences, Obs. de Paris-Meudon — LESIA Examinatrice François Leblanc Directeur de Recherche, UVSQ — LATMOS Examinateur Nathalie Carrasco Professeure, UVSQ — LATMOS Directrice de thèse Murthy Gudipati Research Scientist – JPL/Caltech Invité Thèse de doctorat de Thèse iii “The beauty of a living thing is not the atoms that go into it, but the way those atoms are put together.” Carl Sagan v Preface Titan is the only moon in the Solar System to possess its own dense and gravita- tionally bound atmosphere, and is even larger than planet Mercury. Its rocky diam- eter is a mere 117 km shy of Ganymede’s. If we were to scoop up a 1 cm3 sample ∼ from Titan’s upper atmosphere, we would find two dominant molecules: molecular nitrogen N2 and methane CH4. Should we look a bit more carefully, we would find many neutral molecules and positive and negative ion compounds. These chemi- cal species are the outcome of processes resulting from energetic radiation reaching Titan’s upper atmosphere, breaking apart the initial N2 and CH4. A cascade of sub- sequent reactions will trigger the formation of new gas phase products more and more complex. Eventually, these products mainly containing hydrogen, carbon and nitrogen will form large fractal aggregates composing the opaque haze enshrouding the surface of Titan. This haze is what gives Titan such a unique brownish hue. Most of the photochemically-produced volatiles will eventually condense in the lower at- mosphere, where they may aggregate to form micrometer-sized icy particles and clouds. During my PhD, I have focused my studies on (i) the gas phase reactivity of aerosol precursors in experimental conditions analogous to Titan’s upper atmosphere, and (ii) the end of life of some of the products as they condense in the lower and colder atmosphere. I was able to use two experiments to address these respective is- sues: the PAMPRE plasma reactor, located at LATMOS, UVSQ, Guyancourt, France, and the Acquabella chamber at the Jet Propulsion Laboratory, NASA-Caltech, Pasadena, USA. A paper related to the neutral gas phase reactivity using the PAMPRE experi- ment has been accepted for publication in Icarus, and a second paper on the positive ion chemistry is to be submitted. In this current manuscript, I present my work on the neutral and cation reactivity in the PAMPRE plasma discharge, as well as ice photochemistry results using laser irradiation. In Chapter 1, I present the context of my object of interest: Titan. The historical context and scientific discoveries is presented in scope of how our knowledge led to building the Cassini-Huygens Mission. A summary of recent results related to the gas phase upper atmosphere and cold lower atmosphere is also detailed. In light of these findings, I explain how laboratory simulations can provide insight into Titan’s atmospheric chemistry. A brief past and current review of laboratory experiments aimed at reproducing gas and solid phase processes is given in Chapter 2, accompanied with the two ex- periments that I used during this PhD. Chapter 3 consists of an investigation of the neutral precursors to tholins present in the PAMPRE plasma discharge. In this chapter I present results using coupled mass spectrometry and an infrared analysis on the main neutral precursors. These vi measurements were made possible thanks to a cryotrap system developed inside the reactor. For the first time using our PAMPRE experiment, it was possible to probe in- side the plasma and measure the positive ion compounds. Their coupling to neutral species is indeed important (Chapter 1). These results are detailed in Chapter 4. Moreover, I compared these first results with spectra taken by the INMS instrument onboard Cassini. In complement to these gas phase study, I had the opportunity of carrying out ice spectroscopy experiments in conditions analogous to Titan’s lower atmosphere. Near the tropopause, most of the volatiles undergo a gas-solid phase change and icy particles rich in hydrocarbons and nitrogenous species may form. In partic- ular, HCN clouds have been detected and monitored, and spectral signatures of other more complex icy particles likely to be nitrogen-rich are still not fully under- stood. Our current understanding of how these particles evolve in the lower atmo- sphere and how they interact with near-UV-vis wavelengths is relatively limited. This project, led at the Jet Propulsion Laboratory, focused on HCN and HCN-C4H2 ice mixtures which I irradiated at near-UV wavelengths. The spectral evolutions of these ices are presented in Chapter 5 and put in context of what these results suggest in characterizing the potential solid-state photochemistry in Titan’s lower atmosphere. Over the centuries, our understanding of Titan’s atmosphere has drastically ex- panded, with the help of observations, laboratory measurements and theoretical modeling. The exploration of Titan will certainly flourish over the decades to come, hopefully aided by future robotic missions probing further into its atmosphere, sur- face and liquid hydrocarbon lakes. “[...] I am a part of the whole that is governed by nature; next, that I stand in some intimate connection with other kindred parts.” Marcus Aurelius (Stoic philospher and emperor), Meditations Book X (II A.D.) “[...] And that the other Planets are round like it, and like it receive all the Light they have from the Sun, theres no room (since the Discoveries made by Telescopes) to doubt, Another thing they are like it in is, that they are moved round their own Axis; for since tis certain that Jupiter and Saturn are, who can doubt it of the others? Again, as the Earth has its Moon moving round it, so Jupiter and Saturn have theirs.” Christiaan Huygens, Cosmotheoros (1698) “The nitrogen in our DNA, the calcium in our teeth, the iron in our blood, the carbon in our apple pies were made in the interiors of collapsing stars. We are made of star stuff.” Carl Sagan, Cosmos (1980) vii Acknowledgements Mentorship While I attended a lecture on Titan’s atmospheric chemistry during my first year of Master’s in 2013, I was thoroughly inspired by this organics-rich world. The lec- ture was given by Pr. Nathalie Carrasco, who would a few years later become my PhD advisor. Nathalie, I wish to thank you endlessly for the opportunities and trust you have given me. Your constant positivity and team-spirit influenced me daily and inspired me throughout the last three years. These were the best 3 years of my life, and you always made sure I was working in the best conditions possible. You always gave me a lot of freedom in my work, while also following it closely. I could not have asked for anything better. I also thank Murthy Gudipati (bahut dhanyavaad!) for having guided me and inspired me. I thoroughly enjoyed work- ing at the ISL, and being an ISLer during the summers. Research is a team effort and would never have been possible alone. Above anything else, I feel humbled and extremely grateful for this long journey, which came to fruition with the help of family, close friends, colleagues and mentors. Because much like in martial arts, this is not an ending but an open door to new beginnings. I encourage every student to pursue their dreams, brush off the negativity, turn obstacles into opportunities and work hard towards daring mighty things. Again, thank you Nathalie and Murthy to Titan and back for being awesome mentors, and giving me the opportunity to work in two amazing labs. I very much look forward to collaborating with you again, pur- suing our current work and meeting you at conferences. You have taught me how to be critical of my results, while still giving me enough freedom in my work to make my own path. Murthy, I also thank you (and your family) for the wonderful hiking, camping and biking trips and moments spent altogether in the beautiful California wilderness. These occasional escapades were very resourceful. I also wish to thank my jury members, for having accepted to be on my commit- tee, thoroughly read my thesis and provided very useful comments on the manuscript: Pr. Cyril Szopa, Dr. Véronique Vuitton, Dr.