This study uses high precision silicon isotopic measurements to understand events that occurred during the earliest stages of formation of the terrestrial planets. The isotopic compositions of diverse materials such as chondrites, lunar rocks and asteroidal basalts can shed light on the homogeneity of the solar nebula, metal-silicate differentiation on planetary bodies, and terrestrial moon formation. Limited variation in the Si isotopic composition of meteorites is evidence for a relatively homogeneous inner solar system with respect to silicon isotopes. The Si isotopic composition of bulk silicate Earth (BSE) is, however, heavier than meteorites. This points to an event unique to Earth that fractionated Si isotopes, such as core formation at terrestrial conditions. The Δ³⁰Si_{BSE-meteorite} value from this study indicates that the Earth’s core contains 8.7 (+8.1/−6.2) wt% Si. No systematic δ³⁰Si differences were found between any of the lunar lithologies analysed, implying a Si isotopic homogeneity of the sampled lunar source regions. The lunar average, δ³⁰Si = −0.29±0.08permil (2σ_SD), is identical to the recent value of Savage et al. (2010) for BSE of δ³⁰Si = −0.29 ± 0.08permil (2σ_SD). The best explanation of the data is that Si isotopes must have homogenised in the aftermath of the Moon-forming impact with no subsequent fractionation in the proto-lunar disk. The Si isotopic composition of olivine within lunar basalts was found to be the same or heavier than δ³⁰Si(pyroxene). This is not consistent with terrestrial data where δ³⁰Si(pyroxene) is always lighter than δ³⁰Si(olivine). Crystallisation history cannot explain the data, and the slow diffusion rates of Si rule out cooling rates as a cause. Therefore, it appears that inter-mineral fractionation of Si isotopes occurs differently on the Moon. The δ³⁰Si of chondrules picked from Allende spanned a range of ~0.6permil, a factor of two greater than the bulk meteorite range. There is no evidence for the variable δ30Si of the chondrules being the result of post-formation alteration and there is no convincing evidence for precursor heterogeneity being the primary cause. It is likely that Si isotopic composition of chondrules is the result of evaporation and reequilibration with the evaporated phase.

Vor 200 Jahren fiel ein Meteorit in der Nähe von Erxleben, der von den drei deutschen Chemikern Stromeyer, Klaproth und Bucholz analysiert wurde. Aus diesem Anlass wird eine Übersicht der chemischen Analyse von Meteoriten beginnend mit den ersten Untersuchungen gegeben. In jenen Jahren wurden die Hauptkomponenten bestimmt. In den meisten Steinmeteoriten fand man sehr ähnliche Gehalte der Hauptbestandteile, charakteristische Körner aus Eisen und Eisensulfid in einer mineralischen Grundmasse aus Bittererde und Kieselerde genannten Oxiden von Magnesium und Silicium. Man fand in den Eisenmeteoriten und den metallischen Körnern der Steinmeteoriten hohe Gehalte an Nickel, wie sie nicht in natürlichen irdischen Materialien vorkommen. Der britische Chemiker Howard und Klaproth waren die ersten, die Chladnis Theorie akzeptierten, dass die Meteoriten aus dem Kosmos stammen / 200 years ago a meteorite was fallen near Erxleben between Magdeburg und Helmstedt, which was analyzed by the three German Chemist Stromeyer, Klaproth and Bucholz. For this reason a survey of chemical analysis of meteorites from the first investigation in 1769 until 1820 is given. In this period the contents of main components were determined and were found to be similar for most of the stony meteorites, which contains characteristic grains of iron and iron sulfide in a mineral matrix of oxides of magnesium and silicon in German named “Bittererde” and “Kieselerde”. The metal in iron meteorites and in the metallic grains of stony meteorites contain a high content of nickel, which was not found in natural iron on the earth. The British Chemist Howard and Klaproth were the first, who accepted the Theory of Chladni, that the meteorites have been fallen from the sky.

Im frühen Sonnensystem fanden während der Kondensation der chemischen Elemente volatilitätskontrollierte Fraktionierungsprozesse statt. Gegenstand dieser Doktorarbeit sind Fraktionierungen refraktär-lithophiler Elemente in einzelnen Chondritkomponenten sowie zwischen Bulk-Chondriten, Achondriten und Planeten. Mittels laser ablation inductively coupled plasma mass spectrometry wurden die Gehalte der Seltenen Erden (REE) sowie von Nb, Ta, Zr und Hf analysiert. Einzelne Chondritkomponenten wurden in-situ an dem CV-Chondrit Leoville untersucht. Von den Bulk-Chondriten, Achondriten und terrestrischen Proben wurden Gesamtgesteinsproben durch Laserschmelzen unter aerodynamischer Levitation angefertigt. Die Untersuchung der verschiedenen Bestandteile des Leoville-Chondrits ergab, dass die refraktären Einschlüsse volatilitätskontrollierte fraktionierte REE group-II-Muster und subchondritische Nb/Ta-Verhältnisse aufweisen. Sie sind demzufolge aus einem residualen Gas entstanden, von dem zuvor eine ultrarefraktäre Komponente isoliert worden war. Chondren haben zumeist relativ unfraktionierte REE-Muster sowie unfraktionierte Zr/Hf- und Nb/Ta-Verhältnisse. Einige Typ-1-Chondren, die Al-reichen Chondren und die Chondritmatrix weisen jedoch fraktionierte REE-Muster auf. Dies ist ein Hinweis auf Beimengungen refraktären Materials mit REE group-II-Muster. Die Analysen an Bulk-Chondriten zeigen, dass kohlige Chondrite im Vergleich zu dem CI-Chondrit Orgueil charakteristische volatilitätskontrollierte REE-Muster (ultrarefraktär oder group-II) besitzen, was auf den Einbau refraktärer Komponenten mit fraktionierten Seltenen Erden zurückgeführt wurde. Die Mehrheit der gewöhnlichen, Rumuruti- und Enstatit-Chondrite hat dagegen relativ unfraktionierte REE-Muster. Es konnte gezeigt werden, dass sowohl gewöhnliche, Enstatit- und Rumuruti-Chondrite als auch Proben von Achondriten, Mars, Mond und Erde geringe negative Tm-Anomalien gegenüber dem CI-Chondrit Orgueil aufweisen. Die Objekte des inneren Sonnensystems wurden daher anhand ihrer relativen Gehalte an schweren Seltenen Erden (HREE) in zwei Gruppen eingeteilt: Ein kohliges und ein nichtkohliges Chondrit-Reservoir, dem auch die Achondrite, Mars, Erde und Mond angehören. Es wurde angenommen, dass die Objekte des nichtkohligen Chondrit-Reservoirs die HREE-Verhältnisse des Sonnensystems widerspiegeln; kohlige Chondrite haben dagegen variable Tm-Anomalien, welche durch den Eintrag fraktionierter refraktärer Komponenten in ihre Entstehungsregion zu erklären sind. CI-Chondrite, welche allgemein als die chemisch primitivste Chondritgruppe angesehen werden, hätten in diesem Fall eine positive Tm-Anomalie von 4,8 ± 0,9 % und stimmten somit chemisch nicht mit dem Sonnensystem überein. Durch eine Beimengung von nur 0,2 Gewichtsprozent einer refraktären Komponente mit REE group-II-Muster zu den CI-Chondriten konnte diese Tm-Anomalie erklärt werden.

Thesis (Ph. D.)--University of Canterbury, 2009. / Typescript (photocopy). Includes bibliographical references (p. 172-183). Also available via the World Wide Web.

abstract: Carbonaceous chondrites (CCs) present a unique opportunity for learning about the earliest organic chemistry that took place in our Solar System. The complex and diverse suite of meteoritic organic material is the result of multiple settings and physicochemical processes, including aqueous and thermal alteration. Though meteorites often inform origin-of-life discussions because they could have seeded early Earth with significant amounts of water and pre-biotic, organic material, their record of abiotic, aqueous, and organic geochemistry is of interest as well. CC materials previously resided on asteroidal parent bodies, relic planetesimals of Solar System formation which never accreted enough material to develop long-lived, large-scale geological processes. These bodies were large enough, however, to experience some degree of heating due to the decay of radiogenic isotopes, and the meteorite record suggests the existence of 100-150 parent bodies which experienced varying degrees of thermal and aqueous alteration for the first several 10 Myr of Solar System history. The first chapter of this dissertation reviews literature addressing aqueous alteration as an essential participant in parent body geochemistry, organic synthesis, or both (though papers which address both are rare). The second chapter is a published organic analysis of the soluble organic material of Bells, an unclassified type 2 chondrite. Analytical approaches to assess terrestrial contamination of meteorite samples are also reviewed in the first chapter to allow introduction in chapter 3 of kinetic modeling which rules out certain cases of contamination and constrains the timing of thermal and aqueous alteration. This is the first known application of isoleucine epimerization for either of these purposes. Chapter 4 is a kinetic study of D-allo-isoleucine epimerization to establish its behavior in systems with large, relative abundances of alloisoleucine to isoleucine. Previous epimerization studies for paleontological or geological purposes began with L-isoleucine, the only protein amino acid of the four isoleucine stereoisomers. Kinetic model calculations using isoleucine stereoisomer abundances from 7 CR chondrites constrain the total duration of the amino acids' residence in the aqueous phase. The comparatively short timescales produced by the presented modeling elicit hypotheses for protection or transport of the amino acids within the CR parent body. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2014

This thesis is dedicated to the theoretical study of the methyl cation CH3+ electronic states and, globally, falls within the study of the interstellar clouds molecular synthesis and the chemistry of the hydrocarbons which are present in high-energy plasmas such as in the experimental nuclear fusion reactor ITER. Among the different possible formation reactions, we chose two reactions involved in these fields: the ionization of the methyl radical CH3 ground state and the reactive collisions between simple carbonated or hydrocarbonated (C, CH+ and CH2+) and hydrogen species (H3+, H2 and H, respectively).<p><p>As this cation is characterized by 8 electrons and 4 nuclei, this allowed us to perform high-level ab initio calculations using the CASSCF/MRCI method with the Dunning aug-cc-p(C)VXZ basis sets. These calculations were completed by a study of different methodological effects such as the core-valence electronic correlation, the complete basis set extrapolation and the basis set superposition error.<p><p>We calculated equilibrium geometries (precision within 10^-5 angtröm and 10^-2° and their energies for the methyl radical and cation, studied the potential energy surfaces involved by the Jahn-Teller effect targeting the methyl cation E' states and achieved frequencies calculations. From these values were derived ionization potentials (IP) from the methyl radical ground state towards the methyl cation lowest-lying states (precision within 10^-2 eV). Vibrational corrections and nuclear relaxation effects were taken into account.<p><p>The calculated IPs and frequencies should facilitate the analysis of methyl radical threshold photoelectron spectra leading to the methyl cation lowest-lying states, recorded at the synchrotron facility Soleil by the Dr. Alcaraz group from the Université Paris-Sud.<p><p>Through reaction paths calculations using a quadratic steepest-descent method, we have proposed new reactional pathways enabling the connections between the different dissociation channels correlated to the cation lowest-lying triplet states. The absence of potential barriers in the energy profiles allows us to propose these reactions as sources, in interstellar clouds, of hydrocarbonated molecules whose stability increases with growing size according to the series C -> CH+ -> CH2+ -> CH3+.<p><p>The groups of Pr. Urbain from UCL and Dr. Savin from Columbia University studied the collisions in copropagating beams of C and H3+ leading to the formation of these hydrocarbonated species. The proposed reactional mechanisms are in good agreement with the experimental observations, what permits a better understanding of the chemistry behind these collisional processes of astrochemical interest. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Vor 200 Jahren fiel ein Meteorit in der Nähe von Erxleben, der von den drei deutschen Chemikern Stromeyer, Klaproth und Bucholz analysiert wurde. Aus diesem Anlass wird eine Übersicht der chemischen Analyse von Meteoriten beginnend mit den ersten Untersuchungen gegeben. In jenen Jahren wurden die Hauptkomponenten bestimmt. In den meisten Steinmeteoriten fand man sehr ähnliche Gehalte der Hauptbestandteile, charakteristische Körner aus Eisen und Eisensulfid in einer mineralischen Grundmasse aus Bittererde und Kieselerde genannten Oxiden von Magnesium und Silicium. Man fand in den Eisenmeteoriten und den metallischen Körnern der Steinmeteoriten hohe Gehalte an Nickel, wie sie nicht in natürlichen irdischen Materialien vorkommen. Der britische Chemiker Howard und Klaproth waren die ersten, die Chladnis Theorie akzeptierten, dass die Meteoriten aus dem Kosmos stammen / 200 years ago a meteorite was fallen near Erxleben between Magdeburg und Helmstedt, which was analyzed by the three German Chemist Stromeyer, Klaproth and Bucholz. For this reason a survey of chemical analysis of meteorites from the first investigation in 1769 until 1820 is given. In this period the contents of main components were determined and were found to be similar for most of the stony meteorites, which contains characteristic grains of iron and iron sulfide in a mineral matrix of oxides of magnesium and silicon in German named “Bittererde” and “Kieselerde”. The metal in iron meteorites and in the metallic grains of stony meteorites contain a high content of nickel, which was not found in natural iron on the earth. The British Chemist Howard and Klaproth were the first, who accepted the Theory of Chladni, that the meteorites have been fallen from the sky.

This dissertation has investigated the adsorption, thermal behavior, and radiation (both photon and electron) processing of prebiotically-relevant ices and surfaces. A custom ultra-high vacuum (UHV) chamber has been built that is coupled with a Fourier Transform-Infrared (FT IR) spectrometer and a Temperature Programmed Desorption (TPD) system that utilizes Quadrupole Mass Spectrometry (QMS) to study selected organic:surface systems. Formamide (HCONH₂) has been studied in two related but distinct studies relevant to primitive Earth and interstellar chemistry. First, in collaboration with a theory group, formamide’s interaction with kaolinite (Al6Si6O36H30), a clay mineral relevant to early Earth chemistry, has been studied experimentally and theoretically. Experimental infrared results are compared with calculated infrared frequencies obtained by our collaborators. TPD analysis is compared with the calculated values of adsorption energy, and the optimal kaolinite termination site for adsorption is reported. Second, the first thermal and radiation damage study of pure formamide and HCONH₂:H₂O mixed ices on an interstellar icy grain analog (SiO₂) is reported. A discussion of the pure formamide ice phases identified with FT-IR upon warm-up, as well as the TPD binding energies of HCONH₂ on SiO₂, is presented. The observed Lyman-alpha photochemical products and proposed formation mechanisms from pure formamide ice is reported and discussed. In addition, results of Lyman alpha processing of mixed HCONH₂:H₂O ices are provided. Low-energy electron irradiation of pure HCONH₂ and HCONH₂:H₂O mixed ices has also been reported for the first time. A third investigation has studied acetylene (C₂D₂) and acetonitrile (CH₃CN) interactions and radiation stability in mixed low-temperature ices to simulate possible prebiotic reactions that may occur on Saturn’s moon, Titan. This investigation contributes to understanding the possible consumption, trapping, and degradation of these species on the surface of Titan.

207Pb*/206Pb* chronometry was used to obtain the ages of Ca,Al-rich inclusions (CAIs) and chondrules found in ancient meteorites. Assuming a 238U/235U=137.88, Pb/Pb ages of chondrules in NWA801 (a CR2 meteorite) are 4564.6±1.0 Ma, chondrules in Mokoia (a CV3 chondrite) are 4564.2±1.1Ma, and CAIs in Mokoia are 4567.9±5.4 Ma. The Pb/Pb age of NWA801 chondrules is concordant with 26Al/26Mg ages of CR chondrules. However if a 238U/235U < 137.88 is used, the age for NWA801 chondrules becomes younger by ~1Ma and discordant with 26Al/26Mg ages of CR chondrules. This suggests either a discrepancy with the U compositions or the initial Mg isotopic compositions of NWA801 chondrules. The shapes of NWA801 chondrules, and blebs of FeNi metal in the meteorite matrix, were further studied by 3D X-ray micro-computed tomography (CT). Most chondrules (92%) were ‘armoured’ with one discontinuous layer of FeNi metal. Two layers of FeNi metal (one on the exterior and one concentric through the interior separated by silicate) were rare <8%. Chondrules and matrix blebs occur as oblates, prolate, spheres and triaxial spheroids. It is proposed that the shapes were made free-floating in the nebula likely by flash-melting precursors into molten droplets that were vibrating as harmonic oscillators that ‘froze-in’ their shapes during cooling. Parent-body metamorphism and shock are not likely processes affecting the matrix-bleb and chondrule shapes. Chondrules with ≥2 FeNi metal layers were likely formed by mergers and not by successive deposition and annealing of metal in multiple flash-melting events. Attempts to obtain 207Pb*/206Pb* ages from chondrules and CAIs by thermal extraction (TE)- TIMS were unsuccessful. However LA-ICP-MS was shown to be useful for rapidly determining Pb isotopic trends in meteorites and unknown objects. In particular, it was shown that 137La (T1/2=60ky) should be detectable in recently fallen meteorites using LaF−4 to suppress the 137Ba isobar during tandem accelerator mass spectrometry combined with a novel instrumental technique for isobar separation.

207Pb*/206Pb* chronometry was used to obtain the ages of Ca,Al-rich inclusions (CAIs) and chondrules found in ancient meteorites. Assuming a 238U/235U=137.88, Pb/Pb ages of chondrules in NWA801 (a CR2 meteorite) are 4564.6±1.0 Ma, chondrules in Mokoia (a CV3 chondrite) are 4564.2±1.1Ma, and CAIs in Mokoia are 4567.9±5.4 Ma. The Pb/Pb age of NWA801 chondrules is concordant with 26Al/26Mg ages of CR chondrules. However if a 238U/235U < 137.88 is used, the age for NWA801 chondrules becomes younger by ~1Ma and discordant with 26Al/26Mg ages of CR chondrules. This suggests either a discrepancy with the U compositions or the initial Mg isotopic compositions of NWA801 chondrules. The shapes of NWA801 chondrules, and blebs of FeNi metal in the meteorite matrix, were further studied by 3D X-ray micro-computed tomography (CT). Most chondrules (92%) were ‘armoured’ with one discontinuous layer of FeNi metal. Two layers of FeNi metal (one on the exterior and one concentric through the interior separated by silicate) were rare <8%. Chondrules and matrix blebs occur as oblates, prolate, spheres and triaxial spheroids. It is proposed that the shapes were made free-floating in the nebula likely by flash-melting precursors into molten droplets that were vibrating as harmonic oscillators that ‘froze-in’ their shapes during cooling. Parent-body metamorphism and shock are not likely processes affecting the matrix-bleb and chondrule shapes. Chondrules with ≥2 FeNi metal layers were likely formed by mergers and not by successive deposition and annealing of metal in multiple flash-melting events. Attempts to obtain 207Pb*/206Pb* ages from chondrules and CAIs by thermal extraction (TE)- TIMS were unsuccessful. However LA-ICP-MS was shown to be useful for rapidly determining Pb isotopic trends in meteorites and unknown objects. In particular, it was shown that 137La (T1/2=60ky) should be detectable in recently fallen meteorites using LaF−4 to suppress the 137Ba isobar during tandem accelerator mass spectrometry combined with a novel instrumental technique for isobar separation.