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Thesis (M.Sc.) - Carleton University, 2005. / Includes bibliographical references (p. 106-119). Also available in electronic format on the Internet.

La présence de magmas en profondeur permet de contraindre des processus géologiques passés et actuels. Ces magmas (i.e. liquides silicatés) participent aux cycles géochimiques des éléments volatils comme vecteur de matière.Nous étudions deux éléments volatils complémentaires : l'iode (I), un halogène, et le xénon (Xe), un gaz rare. Leur système radioactif éteint 129I/129Xe (T1/2 = 15.7Ma) est utilisé pour dater les processus hadéens et la formation de l'atmosphère, issu de l'évolution d'un océan magmatique. Or on connait peu le comportement de l'iode et du xénon dans les magmas en profondeur à haute pression et température.Notre protocole expérimental vise l'étude de l'incorporation de l'iode et du xénon et de leur solubilité dans les magmas. Pour étudier l'incorporation, la structure des silicates liquides a été caractérisée par diffraction de rayons X avec des expériences in situ réalisées dans des cellules à enclumes de diamant et dans des presses Paris-Édimbourg. Les teneurs de solubilité de l'iode et du xénon ainsi que l'eau ont été mesurés par les méthodes PIXE et ERDA.À hautes pressions, l'iode possède une forte solubilité (quelques %pds) dans les magmas. Les résultats préliminaires sur son incorporation dans du basalte montrent que l'iode ne formerait pas des liaisons covalentes. À haute pression et température (T>300°C - P>1GPa), le xénon forme une liaison covalente Xe-O avec les oxygènes des anneaux de 6 tétraèdres SiO44-. Le xénon a une solubilité élevée dans les magmas (4pds% - 1600°C - 3.5GPa).Les modèles de datation et des cycles géochimiques de l'iode et du xénon doivent être revus en tenant compte de leur comportement différentiel dans les magmas. / The presence of magmas at depth helps to constrain past and actual geological processes. Magmas (i.e. silicate melts) participate in geochemical cycles of volatile elements, as vectors of chemical transfers. We study two complementary volatile elements: iodine (I), a halogen, and xenon (Xe), a noble gas. Their extinct 129I/129Xe isotopic system (half-life of 15.7Ma) is used to date Hadean processes and Earth’s atmosphere formation since the atmosphere originated from the Magma Ocean’s evolution. However, little is known about the behavior of both iodine and xenon in silicate melts at depth, under HT and HP conditions. Our experimental protocol aims at elucidating the incorporation process of xenon and iodine in silicate melts, and their solubility. To understand the incorporation of iodine and xenon in magmas, the structure of silicate melts was investigated by in situ diamond anvil cells and Paris-Edinburgh press experiments coupled with X-ray diffraction characterization. Iodine and xenon’s solubility, along with water content are obtained by PIXE and ERDA methods using a nuclear microprobe. At high pressure, iodine has a high solubility (about few wt.%) in magmas. Preliminary results on iodine incorporation in basaltic melt show an absence of covalent bond. At high pressure and temperature conditions (T>300°C – P>1GPa), xenon forms a Xe-O covalent bond with the oxygens of the 6-membered-rings of the melt network. Its solubility in silicate melts is also high (about 4wt.% in haplogranite melts at 1600°C and 3.5GPa). Considering the xenon and iodine differential behavior in melts at depth, a revision of dating models in xenon and iodine cycles must be considered.

Nuclear magnetic resonance (NMR) spectroscopy has been extensively used to investigate numerous systems of interest, ranging from collections of molecules to living organisms. However, NMR suffers from one key drawback: an inherent lack of detection sensitivity, as compared to other common forms of spectroscopy. This is due to the minute nuclear magnetic moments and low nuclear spin polarization levels at thermal equilibrium (~10-5 to 10-6), and thus necessitates the use of relatively large sample volumes. One way to overcome this low detection sensitivity is to introduce a species with highly non-equilibrium nuclear spin polarization, such as `hyperpolarized' xenon-129. Hyperpolarized xenon can either be used as its own chemical sensor (due to its exquisitely sensitive chemical shift range), or the non-equilibrium polarization may be transferred from xenon to another molecule of interest (such as a protein or inclusion complex). Hyperpolarized xenon is produced through a process known as spin-exchange optical pumping (SEOP), where the angular momentum from resonant, circularly-polarized light is transferred to the electronic spins of an alkali-metal, and is subsequently transferred to the xenon nuclei through gas-phase collisions. While SEOP has been extensively characterized throughout the years, new experimental techniques and emerging technologies have considerably advanced the field in recent years, and may enable a new understanding of the underlying physics of the system. The first five chapters in this dissertation review background information and the principal motivations for this work. Chapter one reviews the basics of NMR, from the various components of the nuclear spin Hamiltonian and different spin-relaxation pathways to the reasons behind the low polarization of nuclear spins at thermal equilibrium and a few alternative methods to `boost' the NMR signal. Chapter two discusses the fundamental aspects of SEOP, including the electronic spin polarization of the alkali-metal, polarization transfer to the xenon nuclei, and different avenues for the spin polarization to be depleted. The third chapter covers the practical considerations of SEOP from the viewpoint of an experimentalist; namely, the experimental differences when using a variety of alkali metals and noble gases, as well as different SEOP apparatuses and experimental parameters. Chapter four details a variety of different light sources that may be used for SEOP; specifically, the use of laser diode arrays (LDAs) are reviewed, including LDAs that have been frequency-narrowed for more efficient light absorption by the alkali metal. The fifth background chapter covers a variety of magnetic resonance applications of hyperpolarized xenon, including molecular biosensors, specific and non-specific binding with proteins, materials studies, and in vivo applications. The sixth chapter is used as an overview of the dissertation research, which is presented in chapters seven through eleven. Chapter seven details the arrangement of the particular SEOP apparatus used in this research, as well as the experimental protocol for producing hyperpolarized xenon. The eighth chapter accounts the implementation and characterization of the first frequency-narrowed LDA used in this research, as well as an equal comparison to a traditional broadband LDA. Chapter nine introduces the use of in situ low-field NMR polarimetry, which was used to distinguish an anomalous dependence of the optimal OP cell temperature on the in-cell xenon density; the low-field set-up is also used to examine the build-up of nuclear spin polarization in the OP cell as it occurs. The tenth chapter covers the use of high power, frequency-narrowed light sources that are spectrally tunable independent of laser power; this allows for the study of changes to the optimal spectral offset as a function of in-cell xenon density, OP cell temperature, and laser power. Xenon polarization build-up curves are also studied to determine if the spectral offset of the laser affects the nuclear spin polarization dynamics within the OP cell. Finally, chapter eleven accounts the use of high power, broadband LDAs to perform SEOP in which cesium is used as the alkali metal; these results demonstrate (for the first time) that the xenon polarization generated by cesium optical pumping can surpass that of rubidium OP under conditions of high laser flux and elevated in-cell xenon densities.

El análisis químico de los meteoritos que más se parecen a la materia que dio lugar a la formación de la Tierra revela que la concentración del gas xenón en la atmósfera de nuestro planeta es menor de la que se debería esperar. Investigaciones recientes parecen indicar que el origen de esta deficiencia podría estar relacionado con la solubilidad de los gases nobles en las vacantes de oxígeno de la estructura perovskita del silicato de magnesio, MgSiO3, principal componente del manto terrestre. / The chemical analysis of the meteorites considered to resemble closely the primordial matter which led to the formation of the Earth indicates that the concentration of xenon gas in our atmosphere is lower than expected. It seems that this deficiency is related to the noble gases’ solubility in the oxygen vacancies present in the perovskite structure of magnesium silicate, MgSiO3, the main constituent of the Earth’s mantle.

This thesis project has focussed on the experimental study of simple molecular systems at extreme conditions. High-pressure and high-temperature techniques have been used in combination with Raman spectroscopy and X-ray diffraction diagnostics to characterise three simple molecular systems which are unified by the inclusion of nitrogen as a constituent element. The N2 molecule contains the only triple-bond amongst the elemental diatomics and is considered a model system for exploring the changes in structure and bonding induced by tuning pressure and temperature conditions. As such the nitrogen phase-diagram is a focus-point in current extreme conditions research and nitrogen has been found to exhibit a high-degree of polymorphism not observed in other simple molecular systems such as hydrogen or oxygen. Understanding molecular mixtures of nitrogen with other simple molecules at extreme conditions is significant to many scientific fields varying from chemistry to astronomy. The first system presented is the binary mixture of nitrogen and xenon which was studied as a function of pressure. The study constitutes the first comprehensive study of the xenon-nitrogen system at high-pressures. A new van der Waals compound was observed which underwent a phase transition at 14 GPa and was stable up to at least 180 GPa and 3000 K, conditions where pure nitrogen becomes amorphous. Optical measurements suggested possible metallization of the new compound around 120 GPa. The second system presented is the binary mixture of nitrogen and hydrogen which was studied both as a function of pressure and composition. Two known nitrogen-hydrogen structures were confirmed and a pressure-temperature path-dependent formation of hydrazine or ammonia was discovered. Additionally, one mixture was compressed to 242 GPa, the highest pressure investigated in the nitrogen-hydrogen system. The third system presented is the elemental nitrogen phase known as i-nitrogen, an elusive high-temperature polymorph which has hitherto eluded structure determination and proved challenging to access. i-nitrogen was successfully characterised as having an extraordinarily large unit cell containing 48 N2 molecules, making it the most complex molecular nitrogen structure to be determined unambiguously.

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Made available in DSpace on 2014-10-09T12:52:20Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:49Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:45:51Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:42Z (GMT). No. of bitstreams: 1 07495.pdf: 2608837 bytes, checksum: 5ed4e518bad34d7898d3a3a357b431fc (MD5) / Dissertacao (Mestrado Profissionalizante em Lasers em Odontologia) / IPEN/D-MPLO / Instituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP; Faculdade de Odontologia, Universidade de Sao Paulo