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The Organic Composition of Cometary Nucleus, the COSAC Experiment on Philae

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The organic composition of cometary nucleus, the COSAC experiment on Philae UNIVERSITÉ NICE − SOPHIA ANTIPOLIS Unité de Formation et de Recherche − Sciences L'École Doctorale en Sciences Fondamentales et Appliquées (ED.SFA 364) H E S E pour o"tenir le titre de Docteur en Sciences de l'UN%&ERSITE de Nice – Sop(ia Antipolis Discipline) Chimie présentée et soutenue par Chaitanya GIRI LA *+,-+S% %+$ +'.A$%/#E D'#$ $+0A# *+,É A%'E1 L'%$S '#,E$ *+SA* S#' LA S+$DE -!%LAE Thése dirigèe par Uwe MEIERHENRICH soutenue le 19 Septembre 2014 UNIVERSITÄT NIZZA – SOPHIA ANTIPOLI S Referat für Bildun5 und Forsc(un5 - 7issensc(aft Das Do8torat Pro5ramm in .rundlagen6und An5ewandten Wissensc(aften (ED.SFA 364) D O K O R A R B E I #m den Titel zu erhalten Do8tor der 7issensc(aften #ni<ersit=t Nizza – Sop(ia Antipolis Dis;iplin) Chemie Präsentiert und verteidi5t Chaitanya GIRI D%E +'.A$%S*!E >#SA,,E$SE >#$. DES :+,E E$:E'$S1 DAS *+SA*6E?-E'%,E$ A#F -!%LAE Doktorarbeit unter Uwe MEIERHENRICH überwacht Defense auf 19 September 2014 UNIVERSITY OF NICE − SOPHIA ANTIPOLIS Unit for Training and Research − Sciences (e Doctoral Pro5ram in Basic and Applied Sciences (ED.SFA 364) H E S I S o o"tain t(e title o2 Doctor o2 Sciences #ni<ersit@ of Nice – Sop(ia Antipolis Discipline) Chemistry Presented and Defended b@ Chaitanya GIRI !E +'.A$%* *+,-+S% %+$ +F *+,E A'0 $#*LE#S1 !E *+SA* E?-E'%,E$ +$ -!%LAE Thesis supervised by Uwe MEIERHENRICH Defense on 19 September 2014 Jury Pr. *(ristop(e DEN A#7ER President Pr. FranAois RA#L%$ Reviewer Dr. !arald K'B.ER Reviewer Dr. .uillermo MUC+> CA'+ EDaminer Dr. Fred G+ESMA$$ EDaminer Pr. #9e MEIE'!E$'%*! Director of (esis RESUME Cette thèse constitue un travail novateur dans l’analyse in situ multi disciplinaire de la surface du noyau d’une comète réalisé à l’aide du “Cometary Sampling and Composition Experiment” (COSAC). *OSA* est un chromatographe en phase ga;euse et un spectromètre de masse embarqué à bord du module d’atterrissage Philae de l’Agence Spatiale Européenne dans le cadre de la mission vers la comète 67P/Tchourioumov6Guérassimenko. La thèse aborde de 2aAon 5lobale trois campa5nes eDpérimentales et anal@tiques toutes dirigées vers les objectifs de *OSAC aprEs son futur atterrissa5e sur 67P. La quatrième partie, qui est un travail 5éolo5ique vise à identifier le cratère de Lonar comme analogue martien. La premiEre des eDpériences mentionnée ci6dessus implique l’irradiation d’alanine racémique à l’aide de lumière polarisé circulairement (CPL) générée par synchrotron. Nous avons démontré pour la première fois qu’en changeant l’énergie de la CPL pour une hélicité donné de 6,19 eV à 6,74 eV, le si5ne de la valeur de l’excès énantiomérique des acides amines change (dans ce cas la rac6alanine). Dans une seconde partie, nous avons démontré pour la premiEre fois la présence de carbone 5raphitique dans le tholin, un solide compleDe et organique s@nthétisé I partir de l’irradiation de décharge de plasma d’un mélange de NJ)*!4K9:1. Nous eDpliquons que la présence possible de graphite enrichi de matière organique de t@pe tholin sur la sur2ace de no@aux cométaires pourrait bien contribuer I leur faible albédo géométrique t@pique. La troisiEme partie comporte une é<aluation des performances de *+SAC6MS réalisée a<ec le modèle de vol de secours situé I l'%nstitut ,ax -lanck pour la rec(erche sur le s@stème solaire. *es évaluations ont déterminé les paramètres de fonctionnement optimum pour *+SAC6MS. $ous avons caractérisé avec *OSAC6MS divers échantillons pertinents de mélan5es or5aniques de comètes en ce qui concerne leur composition chimique, leur modèle de fra5mentation de masse, et en comparant les spectres obtenus a<ec des bases de données de spectrométrie de masse standard. Les résultats de l’évaluation obtenus bénéficieront à la bonne interprétation des résultats fournis par COSAC au cours de sa mission. Enfin, dans une étude 5éolo5ique, nous montrons que le cratère de Lonar en Inde est un important analogue aux cratères d’impacts de Mars, apparus lors de sa période hydrologique. Les découvertes de ce travail aideront à établir les objectifs de “Mars Organic Molecule Analyzer”, un chromatographe en phase gazeuse, un spectromètre de masse et un spectromètre de masse à désorption laser, construit à partir de l’héritage de COSAC. Il est prévu que ce6dernier soit embarqué sur le Rover ExoMars de l’Agence Spatiale Européenne. ABSTRACT This cumulative thesis 2orms a multi6disciplinar@ groundwork for the pioneerin5 in situ or5anic anal@ses of a comet nuclei surface to be per2ormed "@ the *ometar@ Sampling and *omposition Experiment (COSA*). *OSAC is a Gas *(romatograph6Mass Spectrometer on board the -hilae Lander probe of European Space Agency’s Rosetta mission to comet 67P/Churyumov6 Gerasimenko. (e thesis holisticall@ addresses three m@riad eDperimental and anal@tical campai5ns all directin5 to the objectives of *+SAC subsequent to its landing on 67P. The fourth ori5inal 5eolo5ical field9ork directs to the identification of Lonar Crater as a Martian analogue. Our first of the above mentioned eDperiments involved irradiation of racemic rac6alanine with s@nc(rotron65enerated circular polarized li5(t (C-L). 7e demonstrated 2or the first time that chan5in5 the ener5@ of a 5iven helicit@ of *-L from 6.19 eV to 6.74 eV s9itches the si5n of the enantiomeric eDcess value of amino acids – in this case rac6alanine. The second eDp eriment for the first time demonstrated the presence of 5rap(itic carbon in tholin, a compleD or5anic solid s@nthesized from plasma discharge irradiation of a miDture $J)*!4KL)M. 7e eDplain that the possible presence of 5raphite enriched tholin6like organic material on the sur2ace of comet nuclei could well be contributing to their t@pical low 5eometric albedos. The third eDperiment was directed at performance evaluation of *OSA*6,S carried out with its Fli5ht Spare Model located at the Max -lanck %nstitute for Solar S@stem 'esearch. These e<aluations determined optimum operating parameters for *OSAC6MS and we characterized with *OSAC6,S various comet-relevant organic mixture samples with regards to their c(emical composition, mass fra5mentation pattern, and comparin5 the obtained spectra with standard mass spectral databases. The obtained evaluation results will ultimatel@ "enefit the successful interpretation of the results obtained from *OSAC during the mission. %n the final 5eolo5ical fieldwork we point that Lonar *rater in %ndia is an important analo5ue to impact craters occurrin5 on a (@drolo5icall@ active ancient Mars. The findin5s of the fieldwork complements the future objectives of Mars Or5anic Molecule Anal@;er, a Gas *hromatograp(6Mass Spectrometer-Laser Desorption Mass Spectrometer built from the heritage of *OSAC1 and which is planned onboard the European Space Agency’s ExoMars Rover. CONTENTS 1. The eter"al chur"in& of or&#"ics in s)#%e: An i"tr'+u%tion to the dissertation !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!............ 1 1.1 The m@sterious composition o2 cometar@ nucleus ...............................................................3 1.2 Comet deli<ered exogenous or5anic material on Eart( ........................................................4 1.3 Amino acids and the eDtraterrestrial ori5in o2 biomolecular homochiralit@ .........................5 1.4 Mars) he nearest planet with a biotic past? ........................................................................8 1.5 A brief introduction to .as Chromatograp(@6,ass Spectrometr@ ......................................9 1.6 Outline of the dissertation ..................................................................................................10 2. Synthesis an+ chirality of amino acids u"+er i"terste$$ar c'"+itions !!!!........... 14 2.1 Introduction to interstellar space ........................................................................................15 2.1.1 !nterstel"ar medium .........................................................................................................15 2.1.2 #bjects in !S% .................................................................................................................17 2.2 Ori5in and a"undance o2 or5anics in interstellar space ......................................................20 2.2.1 #rigin o& carbon – carbon stars ......................................................................................20 2.2.2 !nterstel"ar dispersion and abundance of organic molecules .........................................22 2.3 The requisite 2or a substrate: Interstellar dust ....................................................................23 2.3.1 Source o& !SD...................................................................................................................24 2.3.2 Density and diversity of molecu"es ..................................................................................25 2.3.3 Radiation dosage on the icy grain mant"e surface ..........................................................26 2.3.4 Accretion of organics on icy mant"es ..............................................................................31 2.4 The 2ormation o2 amino acids and t(e ori5in of homochiralit@ in interstellar space ..........32 2.4.1 Asymmetry propagates asymmetry ..................................................................................32 2.4.2 The detection of amino acids in interplanetary space .....................................................36 2.5 Production o2 amino acids in laborator@ simulation experiments ......................................37
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  • Artificial Comet Contains Building Blocks of Life 21 March 2012

    Artificial Comet Contains Building Blocks of Life 21 March 2012

    Artificial comet contains building blocks of life 21 March 2012 space mission 'Rosetta'. The program aims to place a lander on the comet Churyumov-Gerasimenko to study the composition of its nucleus. In a bid to anticipate Rosetta's findings, the scientists decided to create an artificial comet, or 'simulation of interstellar/cometary ice', and analyze its composition. The team led by Louis Le Sergeant d'Hendecourt was in charge of creating a micro-comet at the Institut d'Astrophysique Spatiale. Under extreme conditions similar to those found in space (-200 °C and in a vacuum), the researchers condensed a number of compounds found in the interstellar medium, such as water (H2O), ammonia (NH3) and methanol (CH3OH) molecules, onto a solid piece of Chromatogram of the cometary ice obtained using the magnesium fluoride (MgF2), while subjecting them multidimensional gas chromatograph. Each peak to ultraviolet radiation. After ten days, they obtained corresponds to an amino acid. The higher the peak, the a few precious micrograms (10-6 grams) of artificial greater is the amount of amino acid present in the organic material. sample. ChemPlusChem, 77 (2012). Credit: Wiley-VCH GmbH & Co This material was then analyzed at the Institut de Chimie de Nice by a team led by Uwe Meierhenrich and Cornelia Meinert, using high-performance technology: a multidimensional gas chromatograph The first molecules of life form naturally in comets, (GCxGC/TOF-MS). This device, which was reveals a French-German study led by Uwe installed in Nice in 2008, can detect ten times more Meierhenrich and Cornelia Meinert at the Institut molecules in a sample than a traditional one- de Chimie de Nice and by Louis Le Sergeant dimensional chromatograph.