This thesis focuses on the analysis of heavy noble gases (argon, krypton and xenon) and halogens (chlorine, bromine and iodine) in Martian meteorites. In the absence of a sample-return mission, Martian meteorite analysis is essential for establishing evidence for an active fluid system, evaluating the potential for life and understanding the formation and evolution of Mars. Noble gas analysis has multiple applications for Martian meteorite study, as described in this thesis. The noble gas isotopic signatures of Earth’s atmosphere, Martian atmosphere and Martian interior are sufficiently different that they can be distinguished through noble gas analysis. Analysis of bulk and mineral separates of shergottites showed that Martian atmospheric Xe was distributed evenly amongst samples, whilst terrestrially weathered samples contained elevated concentrations of terrestrial atmospheric Xe. Both atmospheric components were introduced by weathering. Shock redistribution is responsible for the distribution of Martian atmosphere into more retentive sites. Crustal contamination may be responsible for the presence or absence of detectable 129Xe from the Martian atmosphere. Halogen abundances can be determined as an extension of the Ar-Ar dating technique. As the halogen system on Earth acts as a tracer for important fluid related processes, Martian halogen abundances in meteorites may provide a tracer for the Martian fluid system. Analysis of bulk and mineral separates of nakhlites showed that halogens are distributed amongst minor phases and clear variation of Br/Cl and I/Cl ratios was observed amongst samples. Elevated I concentrations in low temperature releases of finds NWA 998 and MIL 03346 are consistent with terrestrial contamination. Analysis of Nakhla, (a meteorite fall), showed a trend of elevated Br/Cl and I/Cl ratios in crush and low temperature releases, consistent with Br/Cl ratios observed in Martian rocks, soils and weathering products. In contrast, high temperature releases had lower I/Cl and Br/Cl ratios, which are broadly comparable to the terrestrial mantle. This trend may represent mixing of hydrothermal fluids (low Br/Cl and I/Cl) and surface brines (high Br/Cl and I/Cl). An impact-induced hydrothermal system may provide a mechanism for mixing of both fluid types. The crystallisation ages of nakhlite meteorites were determined using the Ar-Ar dating technique. The apparent ages measured were similar to previous Ar-Ar analysis, and older than reported for other chronometers. Previously unrecognised components were observed, including evidence for a trapped hydrous fluid. This Cl-rich component showed strong correlation with 40Ar and had 40Ar/36Ar and 40Ar/129XeXS ratios consistent with Martian atmosphere. As this component was released during crush and low temperature analysis, fluid inclusions formed by percolation of brines from the Martian surface are likely hosts. Both finds showed clear evidence of a trapped component with 40Ar/36Ar ratios similar to either terrestrial atmosphere or the Martian interior. A further component observed in olivine phases had low 40Ar/36Ar ratios, and likely formed by the release of 36Ar formed by cosmic-ray spallation reactions on iron.

The Gatun Structure (N 09º 05’ 58.1”, W 79º 47’ 21.8”, situated in the triple-canopy rainforest 10 km to the WSW of the Gamboa and about 2 km south of the Isle of Barbacoas, Republic de Panama), is a partially inundated, quasi-concentric surface feature ~3km in diameter, which appears in aerial photographs and in radar imagery as an arcuate chain of islands with a raised center. Although the structure has been heavily weathered and altered, it has retained morphology consistent with complex craters: an elevated circular central uplift 500-600 m in diameter and approximately 70 m high, and arcuate boundary ridges (a rim structure?) ranging from ~50-110 meters high. Within the central peak, highly altered and fractured siltstone of the Gatuncillo Formation (?) (Eocene) ± older rocks are uplifted and exposed through surrounding calcareous units of the Caimito Formation (Oligocene) and the Las Cascadas Formation (Miocene), the major target rocks in the region. Lithologies in the structure include highly fractured siliciclastic rocks (siltstone, sandstones and greywackes), limestones with anomalous spherical glass inclusions, both black and white hypocrystalline glasses (possible melt rocks), lithic fragmental breccias, and melt-bearing breccias (possible impact melt breccias and suevites) containing flow banding and evidence for selective melting of minerals. Three types of spherules (glass, fluid-drop and lithic), a pyroxenequartz “necklace” disequilibrium structure (coronas), plagioclase feldspars exhibiting mosaicism and partially amorphization and zeolitization, possible liquid immiscibility between melts of calcite and felpspathic glass, as well as decomposition of titano-magnetite, are all petrographic criteria that suggest a hypervelocity impact event. The structure is crosscut by numerous dikes of unshocked basalt and basaltic andesite related to volcanism along the Panamanian segment of the Central American arc to the south. However, the lithologies of the Gatun Structure are chemically inconsistent with the regional volcanic rocks and the unshocked volcanic rocks that crosscut the structure. An impact origin is our preferred interpretation for the Gatun structure due to the lack of an igneous relationship between the Gatun structure and the explosive volcanism of Panamanian arc, the presence of classical impactite lithologies within the site, the occurrence of spherules, maskelynite (as suggested by Raman Spectroscopy) and other disequilibrium shock features in the Gatun suite of rocks.

No description available.

[pt] Corpos relativamente pequenos do sistema solar não possuem atmosfera (ou muito rarefeita, chamada exosfera) e nem campo magnético: encontram-se praticamente desprotegidos da influência do ambiente espacial no qual estão inseridos. Tais corpos (como a maioria dos asteroides, luas e cometas distantes do Sol), estão sujeitos aos efeitos do chamado intemperismo espacial. Com o objetivo de simular e estudar este fenômeno em laboratório, três amostras de meteoritos do tipo condrito ordinário foram irradiadas por feixes de H(positivo) com energia de 1,0 MeV. Uma das amostras foi, também, irradiada por feixe de N(positivo) de 2,0 MeV. Os efeitos da irradiação foram monitorados por espectroscopias Raman e UV-VIS-NIR. Os resultados Raman mostram variações sistemáticas do número de onda, da intensidade e da largura das bandas vibracionais estudadas, evidências de modificações estruturais. As seções de choque de destruição das ligações Si-O presentes nas estruturas cristalinas foram determinadas. A espectroscopia UV-VIS-NIR por refletância de esfera integrada foi usada para monitorar as modificações nas características espectrais. Os espectros obtidos mostram escurecimento e avermelhamento progressivos das amostras irradiadas; a amplitude destas modificações depende do conteúdo inicial de ferro na estrutura. É proposto que o avermelhamento observado com o aumento da fluência (ou dose) da irradiação deve-se ao aumento do coeficiente de absorção na faixa azul que, por sua vez, decorre da diminuição do gap óptico do material. Estes resultados são relevantes para a modelagem da evolução físico-química de asteroides expostos ao vento solar. / [en] Relatively small bodies in the solar system have no atmosphere (or very thin, called the exosphere) and no magnetic field: they are virtually unprotected from the influence of the space environment in which they are inserted. Such bodies (like most asteroids, moons, and comets far from the sun), are subject to the effects of so-called space weathering. To simulate and study this phenomenon in the laboratory, three samples of ordinary chondrite meteorites were irradiated by H(positive) beams with 1.0 MeV energy. One of the samples was also irradiated by a 2.0 MeV N(positive) beam. The effects of irradiation were monitored by Raman and UV-VIS-NIR spectroscopies. The Raman results show systematic variations in the wavenumber, intensity, and width of the studied vibrational bands, evidence of structural modifications. The shock sections of the destruction of Si-O bonds present in the crystalline structures were determined. Integrated sphere reflectance UV-VIS-NIR spectroscopy was used to monitor changes in spectral characteristics. The obtained spectra show progressive darkening and reddening of the irradiated samples; The extent of these modifications depends on the initial iron content in the structure. It is proposed that the redness observed with the increase of irradiation creep (or dose) is due to the increase in the absorption coefficient in the blue band, which, in turn, results from the decrease of the optical gap of the material. These results are relevant for modeling the physicochemical evolution of asteroids exposed to the solar Wind.

<p>The class of meteorites called carbonaceous chondrites are examples of material from the solar system which have been relatively unchanged from the time of their initial formation. We investigate the carbonaceous chondrite subclasses CI, CM, CR, CV, and CO, which contain high levels of water and organic material, including amino acids. These subclasses span petrologic types 1 through 3, indicating the degree of internal chemistry undergone by the meteoritic parent body. The goal of this thesis is two-fold: to obtain a comprehensive view of amino acid abundances and relative frequencies in carbonaceous chondrites, and to recreate these patterns via thermodynamic computational models.</p> <p>We collate available amino acid abundance data for a variety of meteorites to identify patterns in total abundance and relative frequencies. We consider only a set of 20 proteinogenic alpha-amino acids created via a specific chemical pathway called Strecker synthesis. We plot abundances of individual amino acids for each subclass, as well as total abundances across all subclasses. We see a predominance in abundance and variety of amino acids in the CM and CR subclasses, which contain concentrations of amino acids greater by several orders of magnitude than other carbonaceous subclasses. These subclasses correspond to an aqueous alteration temperature range of 200 deg. C to 400 deg. C. Within the CM2 and CR2 meteorites, we identify trends in the relative frequencies of amino acids in preparation for computational modeling.</p> <p>Now having a baseline observed amino acid abundance plot, we recreate both the total amino acid abundance pattern as well as the relative frequency of amino acids within the CM2 chondrite subclass using computational models. We use thermodynamic theory of Gibbs free energies to calculate the output of amino acids in a meteoritic parent body assuming chemical equilibrium and some set of initial concentrations of organic material. Our model recreates abundance patterns in the temperature range 200 deg. C to 400 deg. C, ~10⁵ parts-per billion (ppb), and the temperature range 400 deg. C to 500 deg. C, ~10² ppb. Our model does not fit well between temperatures of 150 deg. C to 200 deg. C. Our current model assumes a uniform composition of initial chemical reactants; likely an inhomogeneous composition would be a more accurate physical representation of a parent body. In addition, we match relative frequencies to observed frequencies for each amino acid in the CM2 subclass to well within an order of magnitude.</p> / Master of Science (MSc)

Cette thèse est consacrée à l'histoire des solides du système solaire primitif. Nous étudions la dynamique des composants chondritiques et trouvons que leur préservation pendant plusieurs Ma dans le disque protoplanétaire nécessite une zone morte. Cette dynamique est essentiellement gouvernée par un paramètre de découplage gaz-solide S que nous conjecturons avoir été <1 et >1 lors de l'accrétion des chondrites carbonées et non carbonées, respectivement. Nous étudions aussi des modèles réduits pour l'interaction entre la turbulence magnétohydrodynamique et la sédimentation de la poussière ainsi que l'instabilité d'écoulement linéaire. Nous mesurons la concentration d'éléments en trace dans les phases des chondres dans Vigarano, Renazzo, Acfer 187, Bishunpur et Sahara 97096. L'olivine dans les chondres de type I semble résulter d'une cristallisation à l'équilibre tandis que le pyroxène enregistre des taux de refroidissement rapides et est compatible avec une interaction gaz-liquide.

The recent discovery of the 31-km-wide Hiawatha impact crater has raised unanswered questions about its age, impactor and highly unusual organic carbon component. Previous research suggests a fractionated iron meteorite impactor, a probable maximum 3–2.4 Ma impact age and a possible Younger Dryas impact age. The first objective in this study has been to investigate a possible link between the Cape York meteorites and the Hiawatha impact crater by comparing the chromium isotopic signature in chromite from a Cape York meteorite with the chromium isotopic signature in potential chromite from the Hiawatha impactor. The second objective has been to investigate a possible Hiawatha signature in the Younger Dryas deposits from Baffin Bay. The third objective has been to study the organic carbon component in impactites derived from the Hiawatha impact crater. Heavy mineral grains were separated from glaciofluvial sediment which contains Hiawatha impactite grains. Not a single chromite grain was found and the possible link to the Cape York meteorites could not be tested. The petrographic examination of Younger Dryas marine deposits resulted in absence of impact-related Hiawatha grains. A petrological investigation revealed that organic carbon was likely found in five of six variably shocked impactites derived from the Hiawatha impact crater. The character of the organic carbon varies between the samples and also within individual samples. Vitrinite reflectance measurements of the organic carbon in two impactites yielded low reflectance values compared to charcoalification experiments of wood. Organic particles with different reflectance in the same sample suggest that the particles had different impact histories prior to settling and becoming a rock. Diagnostic conifer cellular texture was found in at least one of the samples. The character of the organic particles in the impactites supports the suggestion in a previous study that the sources of the Hiawatha organic carbon component are unmetamorphosed surficial deposits containing dead conifer tree trunks and fine-grained layered clay and organic matter.  In this study it is concluded that the apparent absence of chromite in the examined glaciofluvial sediment sample corroborates the significance of previous research which suggests that the Hiawatha impactor was an iron meteorite. The apparent absence of impact related grains in the Younger Dryas deposits suggests that although a Younger Dryas age for the Hiawatha impact crater is less likely now, the possibility remains open. The organic carbon with diagnostic conifer cellular texture in the Hiawatha impactites corroborates the conclusion in a previous study that the Hiawatha impact-related organic carbon component stems from local, thermally degraded conifer trees with a probable age of ca. 3–2.4 Ma. It is also concluded that the relatively low reflectance values of the organic carbon in the Hiawatha impactites seem to be related to the short duration of the high-temperature excursion during the hypervelocity impact event.

No description available.

Le Lebanese Atomic Energy Commission (LAEC) poursuit un programme de développement des techniques analytiques pour compléter l’analyse par faisceau d’ions (IBA). Il a décidé de s’équiper d’un spectromètre de masse couplée à l’imagerie 2D puis récemment 3D avec l’acquisition d’un spectromètre de masse IONTOF V™ équipé de deux colonnes ioniques délivrant des faisceaux d’agrégats de bismuth et d’argon. Dans ce cadre, mon sujet de thèse a porté sur l'optimisation de l’instrument nouvellement acquis pour l’analyse d’échantillons contenant des composés organiques. Les premiers sujets de recherche sont la mise au point du protocole d’analyse quantitative de médicaments en utilisant la technique « cluster-SIMS-imaging » et l’analyse de la météorite Paris pour localiser la matière organique et déterminer sa composition. Dans les deux cas une approche multi-technique a été utilisée : IBA au LAEC, µ-Raman et µ-IR autour des équipements de Soleil et µPIXE réalisée auprès de l’accélérateur AGLAE (Centre de recherche et de restauration des musées de France, C2RMF).L’analyse de médicaments a été initiée au Liban en collaboration avec un fabricant local de produits pharmaceutiques (Mediphar Laboratories) dans le but d’établir de nouveaux procédés de contrôle qualité de produits finis. Mon étude a montré la complexité du dosage de médicament due à la présence de plusieurs molécules actives (Principe Actif, PA) et de substances organiques et minérales inactives (excipients) mélangées dans des conditions secrètes. Les effets de matrice sont dominants et modifient l’émission ionique conduisant à des erreurs systématiques importantes. Cette complexité a été analysée avec l’étude du Fludinium™ possédant deux PAs. Les résultats de cette étude ont permis d’obtenir la première courbe d’étalonnage du rapport des deux PAs et de quantifier ceux-ci dans les conditions du médicament commercial. Le protocole pour effectuer cette courbe d’étalonnage et les contrôles « qualité » ont été déterminés. Ceux-ci incorporeront une analyse en profil pour contrôler l’homogénéité des échantillons et l’obtention d’étalons produits par le fabricant en suivant ses processus de fabrication. En effet, les expériences ont montré que la réalisation du médicament en laboratoire à partir de ses éléments (PAs et excipients) ne donnait pas la même réponse ionique que le médicament commercial. L’analyse de la météorite Paris a été initiée par une collaboration avec une équipe de l’Institut d’Astrophysique Spatial d’Orsay impliquée dans l’exobiologie et la recherche des premières molécules pré-biotiques dans des échantillons extraterrestres. Le but des recherches est de caractériser la matière organique représentant quelques pourcents en poids dans une matrice minérale complexe, sans utiliser des méthodes chimiques pouvant induire une modification de ces molécules. Cette étude a démontré l’intérêt de l’approche multi-technique centrée autour de la spectrométrie de masse couplée à l’imagerie ionique pour déterminer les éléments principaux de la matrice minérale et organique. L’analyse par µPIXE avec une cartographie micrométrique a permis d’attribuer les distributions d’ions moléculaires et agrégats des spectres de masse aux différents composés minéraux. Ces attributions se poursuivent avec la constitution d’une base de données de spectres de référence. La composante organique a été extraite et les premières hypothèses de composition ont été envisagées autour des HAPs (Hydrocarbure Aromatique Polycyclique), MOI (Matière Organique Insoluble) et analogues de carbone amorphe produits par irradiation UV de glaces dont les compositions en gaz représentent différentes hypothèses pour les nuages interstellaires. Les protocoles d’analyses multi-techniques établis (incorporant un suivi de l’échantillon par spectrométrie de masse et imagerie ionique) permettent le démarrage d’analyse d’autres échantillons extra-terrestres collectés sur terre ou dans l’espace. / The Lebanese Atomic Energy Commission (LAEC) is incorporated in a development program of the analytical techniques in order to complete the Ion Beam Analysis (IBA). It was decided to get a mass spectrometer coupled to 2D and recently to 3D imaging, by acquiring an ION TOFVTM system equipped with two ionic columns delivering bismuth and argon cluster beams.In this context, my thesis is focused on the optimization of the instrument, recently purchased, for the analysis of samples containing organic compounds. The first subjects of research are the development of a protocol for quantitative analysis of drugs using the « cluster-SIMS-imaging » technique and the Paris meteorite analysis to determine its composition and to localize the organic matter. In the last case a multi-techniques approach was used : IBA in LAEC, µ-Raman et µ-IR around the Soleil synchrotron equipments and µPIXE carried with the AGLAE accelerator (Centre de recherche et de restauration des musées de France, C2RMF).The drug analysis was initiated in Lebanon in collaboration with a local pharmaceutical manufacturer (Mediphar Laboratories) in order to establish new processes for quality control of the final products. My study showed the complexity of the drug quantification which is due to the presence of several active ingredients (AI) and inactive organic and minerals components (excipients) mixed in secret conditions. Matrix effects are dominant and modify the ionic emission leading to significant systematic errors. This complexity has been analyzed with the study of FludiniumTM with two active ingredients. The results of this study allowed to obtain the first calibration curves of the ratio between the two AIs and to quantify them in the commercial drug. The protocol to perform the calibration curve and the « quality» controls were determined. These incorporate a profile analysis to control the homogeneity of the samples and the obtaining standards produced by the pharmaceutical manufacturer following the same process used for the commercial drug. Indeed, the experiments have shown that the preparation of the drug in the laboratory from its elements (AIs and excipients) doesn’t give the same ionic emission as for the commercial drug.The Paris meteorite analysis was initiated by a collaboration with the Institut d’Astrophysique Spatiale d’Orsay team involved in the exobiology and the research of the first prebiotic molecules in the extraterrestrial samples. The work objective is to characterize the organic matter representing few percents in mass in a complex mineral matrix, without any chemical extraction that can induce a modification of these molecules. This study has demonstrated the interest of the multi-techniques approach centered on the mass spectrometry coupled to the ionic imaging for the determination of the main mineral and organic elements of the matrix. µPIXE analysis coupled to the micrometric mapping permits to attribute the distribution of molecular ions and clusters of the mass spectra with different mineral compounds. These attributions continue with the creation of the data base of standard spectra. The organic component was determined and the first hypotheses were considered concerning PAHs (Polycyclic Aromatic Hydrocarbon), IOM (Insoluble Organic Matter) and analogues of amorphous carbon produced par UV irradiation of ices with a gas composition representing different hypotheses for the interstellar clouds. The establish protocols for multi-techniques (incorporating a follow of the sample by mass spectrometry and ion imaging) permits to start the analysis of other extra terrestrial samples collected on earth or in space.