A comprehensive study on the effect of composition on the structural and elastic properties of MPO4 (M = Ce3+, Gd3+, Tb3+, Y3+, Sc3+) compounds has been completed. CePO4 and GdPO4 are isostructural with monazite (P21/n), and TbPO4, YPO4, and ScPO4, are isostructural with xenotime (I41/amd). Raman spectra are consistent with previous studies and high-pressure spectra showed no phase transitions up to 10 GPa under hydrostatic conditions. The spectra were used to develop Kieffer-type lattice vibrational models to calculate heat capacities of CePO4 and YPO4 and the results lie within 1-3% of experimental values. Equations of state were calculated from high-pressure single-crystal X-ray diffraction data. Bulk moduli (K0) determined from a 3rd-order Birch-Murnaghan equation of state are: 109(3) GPa for CePO4, 128.1(8) GPa for GdPO4, 141(1) GPa for TbPO4 and 166(1) GPa for ScPO4. The inverse relationship observed between K0 and the ionic radius of the RE3+ is shown to be linear. This equation can be used to predict K0 for other rare-earth phosphates. Comparison of these studies, performed under hydrostatic conditions, with previous studies show that MPO4 structures are sensitive to shear stresses created from non-hydrostatic environments. The first structural study of a monazite, GdPO4, is also reported. Compression mechanisms are comprised of "squishing" the GdO9 polyhedra and inter-polyhedral movement. This study and the axial compressibility data for Ce-, Tb-, Gd- and ScPO4 suggest that the compression mechanisms favored by MPO4 compounds are those which remain rigid parallel to polyhedral chains. / Master of Science

This study considered the geology, mineralogy, geochemistry, formation and evolution of the heavy rare earth element (HREE) mineralised Lofdal alkaline carbonatite complex (LACC), which is located on the Bergville and Lofdal farms northwest of Khorixas, in the Kunene Region of the Republic of Namibia. . Field methods used included mapping, ground and hyperspectral airborne geophysics, and sampling. Analytical techniques used were optical petrography and CL, XRF, ICP-AES, backscattered and secondary electron imaging, electron microprobe, LA-ICP-MS, leaching, as well as carbon and oxygen stable isotope determination. The LACC comprises a swarm of dykes, mainly calcite carbonatite but also dolomite and ankerite carbonatite dykes (classified into five types) and two newly discovered plugs of calcite carbonatite (‘Main’ and ‘Emanya’), with associated dykes and plugs of phonolites, syenites and rare mafic rocks. These all intrude into the Huab Metamorphic Complex basement rocks within a NE-SW shear zone over 30 km long. The main HREE host mineral is xenotime-(Y). It occurs in highly oxidised iron-rich calcite carbonatite dykes mantling and replacing zircon, associated with hematite, thorite and apatite, or associated with monazite-(Ce), synchysite-(Ce), and parisite-(Ce), replacing the fluorocarbonates; it also forms aggregates in ankerite carbonatite. Although xenotime-(Y) occurs throughout the paragenetic sequence, there is much evidence for hydrothermal fluid activity at Lofdal, altering the dykes, and taking xenotime-(Y) into brecciated carbonate veins in albitised country rock (fenite). Radiogenic (Sr, Nd-Sm, U-Pb) and C and O stable isotope studies confirm that the carbonatite, derived from an enriched mantle, is the source of the REE. Mineralisation was contemporaneous with carbonatite emplacement at 765 ±16 Ma. Magmatic fluids >300°C were diluted with cool meteoric fluids. Abundant fluorite and carbonate indicate roles for F- and CO32- in addition to Cl- in REE transport. These ligands form the most stable complexes with HREE and since xenotime is soluble in concentrated alkali halide solutions, they could have preferentially transported and then deposited xenotime. Many of the features of Lofdal are common to other REE-rich carbonatite complexes but the xenotime-(Y) abundance is so far unique. The high amount of fluid activity in shear zones around the dyke swarm and probably a higher proportion of HREE in the original magmas seem to be the main differentiating features.

abstract: A mineral’s helium content reflects a balance between two competing processes: accumulation by radioactive decay and temperature-dependent diffusive loss. (U-Th)/He dating of zircon and other uranium and thorium-bearing minerals provides insight into the temperature histories of rocks at or near Earth’s surface that informs geoscientists’ understanding of tectonic and climate-driven exhumation, magmatic activity, and other thermal events. The crystal structure and chemistry of minerals affect helium diffusion kinetics, recorded closure temperatures, and interpretations of (U-Th)/He datasets. I used empirical and experimental methods to investigate helium systematics in two minerals chronometers: zircon and xenotime. The same radioactivity that makes zircon a valuable chronometer damages its crystal structure over time and changes zircon helium kinetics. I used a zircon, titanite, and apatite (U-Th)/He dataset combined with previously published data and a new thermal model to place empirical constraints on the closure temperature for helium in a suite of variably damaged zircon crystals from the McClure Mountain syenite of Colorado. Results of this study suggest that the widely-used zircon damage accumulation and annealing model (ZRDAAM) does not accurately predict helium closure temperatures for a majority of the dated zircons. Detailed Raman maps of Proterozoic zircon crystals from the Lyon Mountain Granite of New York document complex radiation damage zoning. Models based on these results suggest that most ancient zircons are likely to exhibit intracrystalline variations in helium diffusivity due to radiation damage zoning, which may, in part, explain discrepancies between my empirical findings and ZRDAAM. Zircon crystallography suggests that helium diffusion should be fastest along the crystallographic c-axis. I used laser depth profiling to show that diffusion is more strongly anisotropic than previously recognized. These findings imply that crystal morphology affects the closure temperature for helium in crystalline zircon. Diffusivity and the magnitude of diffusive anisotropy decrease with low doses of radiation damage. Xenotime would make a promising (U-Th)/He thermochronometer if its helium kinetics were better known. I performed classic step-wise degassing experiments to characterize helium diffusion in xenotime FPX-1. Results suggest that this xenotime sample is sensitive to exceptionally low temperatures (∼50 °C) and produces consistent (U-Th)/He dates. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2019

No description available.

The Northern Highlands Terrane (NHT) in Scotland preserves a long record of metamorphism and convergent deformation related to several orogenic events that occurred from Neoproterozoic to Devonian time. Deconvolving the signatures of multiple tectonic events and determining the rates of metamorphism in settings like the NHT are important parts of better understanding the thermal and mechanical processes controlling convergent tectonics. I have used monazite-xenotime thermometry and geochronology, in conjunction with metamorphic petrology and additional accessory phase geochronology, to place constraints on the timing and rates of thermal metamorphism in a variety of structural settings throughout the NHT. Our data show that the ductile thrust nappes of northernmost Scotland preserve a record of Scandian (435-410 Ma) orogenesis. High grade metamorphism in the hinterland Naver nappe likely resulted from the widespread infiltration of granitic magmas at c. 425 Ma, which coincided with peak metamorphism. The timing of metamorphism in the hinterland Scandian thrust nappes is apparently younger than at least some deformation in the foreland Moine thrust zone, suggesting this orogenic wedge experienced large-scale out-of-sequence deformation and metamorphism. In contrast to the Scandian nappes, the Sgurr Beag nappe records primarily Precambrian metamorphism related to the Knoydartian orogeny (780-725 Ma). Additionally, monazite in the Sgurr Beag nappe preserves a record of widespread metasomatism and metamorphism at c. 600 Ma, possibly related to the break-up of Rodinia at that time. A potentially important heat source in orogenic systems, like those preserved in Scotland, is the thermal energy dissipated during deformation, otherwise known as shear heating. It is important to consider to how shear heating may contribute to metamorphism during orogenesis. This is challenging because there are few, if any, methods of relating observations from typical orogenic systems to magnitudes of shear heating. We have developed a model that is adaptable to a wide range of parameters that can be measured from naturally deformed rocks and places first-order constraints on magnitudes of shear heating. While our models suggest that shear heating is not particularly important in the NHT, in lower initial temperature mylonite zones shear heating could be more significant. / Doctor of Philosophy / The Northern Highlands Terrane (NHT) in Scotland preserves a long record of metamorphism and convergent deformation related to several orogenic events that occurred from Neoproterozoic to Devonian time. Understanding the record of each of these events and the rates at which metamorphic changes occurred is important for improving our understanding of the processes at work in continental collisions. The work presented in this thesis involves determining the temperatures recorded by metamorphic minerals and the ages of those minerals in order to reconstruct the temperature-time evolution of samples in a variety of positions within the NHT. Our data show that the collision and thermal metamorphism at 435-410 Ma is well preserved in northernmost Scotland. We argue that metamorphism in this area resulted from the widespread intrusion of hot magmas, which coincided in time with peak metamorphism. The timing of metamorphism in the core (hinterland) of this mountain belt is apparently younger than shallower deformation at the edges (foreland) of the mountain belt, suggesting active deformation and metamorphism retreated toward the hinterland during crustal shortening. In another part of the NHT, known as the Sgurr Beag nappe, a much older metamorphic event that occurred at 780-725 Ma is better preserved. In this area, the mineral monazite appears to record evidence of widespread fluid alteration at ~600 Ma, which has not previously been widely recognized in Scotland. A potentially important heat source in the Earth’s crust is shear heating associated with the thermal energy produced during deformation. It is important to consider what contribution shear heating may have made to the preserved metamorphic record in orogenic belts. This is challenging because there are few, if any, methods of relating observations from typical metamorphic rocks to estimated magnitudes of shear heating. We have developed a numerical model that is adaptable to a wide range of realistic natural scenarios and places first-order constraints on potential magnitudes of shear heating. While our models suggest that shear heating is not particularly important in the NHT, in some lower temperature fault zones shear heating could be more significant.

No description available.

Cette thèse présente les résultats d'étude expérimentales sur (1) le partage du Th entre<br />la monazite et le xenotime, (2) l'effet du recuit sur la structure de la monazite ainsi que (3) la<br />remise à zéro des systèmes géochronologiques U-Pb dans la monazite.<br />(1) Le partage du Th entre la monazite et le xenotime a été déterminé<br />expérimentallement (600-1100°C/2Kbar) en considérant le mécanisme de substitution<br />suivant: Th + Si = REE + P. Le matériel de départ est un gel constitué d'un mélange de<br />CePO4 et YPO4 (1:1) plus 10, 20 ou 50 mole % de ThSiO4. Les produits sont analysés au<br />MET et en DRX. Quelque soit la température et pour une composition initiale de 10 ou 20<br />mole % de ThSiO4, le Th est presque entièrement réparti dans la monazite. Entre 600 et<br />900°C et pour une composition initiale de 50 mole % de ThSiO4, la cristallisation de la thorite<br />montre une saturation en Th de la monazite. A 1000°C, seuls la monazite et un peu de<br />xénotime sont observés; la thorite est absente.<br />(2) Le recuit des dégats d'irradiation dans une monazite naturelle, homogène<br />chimiquement et concordante à 474 ± 1 Ma, a été étudié expérimentallement (500-1200°C/~7<br />jours). Les produits ont été analysés en DXR, MET, Raman et cathodoluminescence. La<br />monazite non-chauffée révèle une structure en “mosaïque” composée de 2 domaines, qui sont<br />2 cristaux de monazites de paramètres de maille différents. Les domaines (A) correspondent<br />aux domaines parfaitement cristallisés, où l'hélium emprisonné provoque une expansion du<br />réseau. Les domaines (B) correspondraient à des domaines exempts d'hélium, où le réseau a<br />été déterioré par les noyaux de recul-alpha. Lors du recuit de la monazite l'hélium diffuse<br />hors du cristal, ce qui induit une relaxation du réseau dans les domaines (A). En même temps,<br />les domaines (B), défectueux, sont recuits. A 900°C, le réseau de la monazite est entièrement<br />recuit.<br />(3) Afin d'étudier l'effet de fluides et de la température sur le “resetting” des systèmes<br />U-Pb dans la monazite, des fragments abrasés (200-400 µm) de l'échantillon utilisé en (2) ont<br />été chauffés (800-1000°C/14-39 jours) en présence de solutions de diverses compositions (eau<br />pure jusqu'à 1200°C/5 jours, fluides à NaCl, SrCl2 CaCl2 et standard de Pb) puis analysés au<br />MEB, EMP, SIMS et ID-TIMS. Quelle que soient les expériences aucun profil de diffusion<br />du Pb n'est observé (EMP). En présence de fluide à CaCl2 ou à standard de Pb et uniquement<br />pour les expériences réalisées à 1000°C on observe des surcroissances. A 1000°C et dans un<br />fluide à CaCl2 on observe une zonation, coeur hérité et bordure enrichie en Ca et exempt de<br />Pb, formée par dissolution/précipitation. Des discordances significatives sont observées<br />uniquement pour les expériences réalisées à 1000°C dans les fluides à SrCl2 (16%) ou CaCl2<br />(68%). Enfin, l'utilisation du fluide à standard de Pb induit un vieillissement des monazites<br />initiales, ce qui indique une contamination de la monazite par ce fluide.

In this thesis, solid state reactions of Ln2O3, Y2O3, B2O3 and (NH4)2HPO4 were investigated to synthesize LnBP2O8 (Ln= Dy, Ho, Er) and YBP2O8 type of borophosphates which were not reported before. The products were analyzed by XRD, IR, DTA, SEM and EDX methods. In the first part of this thesis, synthesis of YBP2O8 through the solid state reaction of Y2O3 + 4(NH4)2HPO4 + B2O3 have been studied in the range 800-1140 &deg / C. Orthophosphates of Dysprosium, Holmium, Erbium and Yttrium have tetragonal xenotime (YPO4) or zircon (ZrSiO4) structure. Examination of X-ray powder diffraction data at 1140 &ordm / C showed that the obtained structure was xenotime type together with weak BPO4 and Y(PO3)3 lines. The formula was calculated as YBxP1+xO4+4x through EDX and XRD data. The pattern was indexed in tetragonal system with the unit cell parameters of a= 6.8863, c= 6.016 &Aring / and s.g. is I41/amd. In the second part of this research, synthesis of LnBP2O8 through the solid state reaction of Ln2O3 + 4(NH4)2HPO4 + B2O3 (Ln= Dy, Ho, Er) have been studied in the range 800-1200 &ordm / C. At 1200 &ordm / C DyBP2O8 was obtained with tetragonal structure with the unit cell parameters of a= 6.905, c= 6.051 &Aring / and s.g. I41/amd. Using the same procedure HoBP2O8 was obtained at 1100-1200 &ordm / C and the XRD pattern was indexed in tetragonal system with the unit cell parameters of a= 6.887, c= 6.024 &Aring / and s.g. I41/amd. In the structural analysis of ErBP2O8 obtained by the same reaction, the system was found as tetragonal and was indexed with a= 6.849, c= 5.998 &Aring / and s.g. I41/amd. Examination of the unit cell parameters with respect to ionic radius showed that the unit cell parameters decrease depending on the lanthanide contraction. The structures of the compounds obtained throughout this thesis were examined by IR spectroscopy and relation between the spectra and IR vibrational modes were established. The presence of bands due to BO4 in the final products revealed that Boron is in the solid solution with the tentative formula YBxP1+xO4+4x for Y and LnBP2O8 for lanthanides.

Made available in DSpace on 2017-07-21T19:26:07Z (GMT). No. of bitstreams: 1 Simoneapa.pdf: 1470043 bytes, checksum: b380a790ad5236069470caa27e038eed (MD5) Previous issue date: 2007-03-02 / In this work, it was accomplished an experimental study about the substitution of the yttrium atom (Y) in the YBa2Cu3O7-x superconductor system for a rare earth oxide (RE2O3), gotten from the xenotime ore. Chemically, this substitution is possible due to the equality of the oxidation state between the Y3+ ions and the earth rare ions, which form the oxide. This way, this substitution should not modify the properties of the superconductor system significantly. The xenotime in its natural form is composed of a rare earth phosphate, zirconita and other heavy elements. The zirconita and the heavy elements can be separated by magnet or gravimetric process. The rare earth phosphate is chemically treated by the acid or the alkaline leaching process, resulting in a rare earth oxide (RE2O3). The xenotime ore used in this work was extracted from the Pitinga mine (AM, Brazil). Four polycrystalline samples were processed through the solid-state reaction, from the precursors: rare earth oxide (RE2O3), barium carbonate (BaCO3) and copper oxide (CuO), forming the REBa2Cu3O7-x superconducting oxide. The chracterization of the samples crystalline structures was studied by x-ray diffraction. The analysis of the samples superficial morphology was studied by optical microscopy and scanning electron microscopy (SEM). The properties of electronic transportation were analyzed by measurements of electric resistivity. Among the analyzed samples, one did not present null state of electric resistance. The measurements of electric resistivity for the other samples revealed superconductor behavior and showed that the critical temperature of the REBa2Cu3O7-x system is around 90 K, as in the YBa2Cu3O7-x system. Such values were confirmed by the measurement of magnetic susceptibility. The analyses of the Xray diffractograms of the samples revealed that the cell parameters of both systems are equal. These results indicate that the substitution of the Y for the rare earth oxide is possible, which may have important implications both from the point of view of basic research and the applied research. / Neste trabalho foi realizado um estudo experimental da substituição do átomo de ítrio (Y) no sistema supercondutor YBa2Cu3O7-x, por um óxido de terras-raras (RE2O3), obtido a partir do minério xenotima. Quimicamente essa substituição é possível devido à igualdade do estado de oxidação entre os íons Y3+ e os íons de terras-raras que formam o óxido. Dessa forma, essa substituição não deve alterar de forma significativa as propriedades supercondutoras do sistema. A xenotima em sua forma natural é constituída por um fosfato de terras-raras, zirconita e outros elementos pesados. A zirconita e os elementos pesados podem ser separados por processos magnéticos ou gravimétricos. O fosfato de terras-raras é tratado quimicamente pelo processo de lixiviação ácida ou alcalina, resultando em um óxido de terras-raras (RE2O3). O minério xenotima utilizado neste trabalho foi extraído da mina do Pitinga (AM, Brasil). Foram processadas quatro amostras policristalinas através da reação de estado sólido, a partir dos precursores: óxido de terras raras (RE2O3), carbonato de bário (BaCO3) e óxido de cobre (CuO), formando o óxido supercondutor REBa2Cu3O7-x. A caracterização das estruturas cristalinas das amostras foi estudada por difração de raios X. A análise da morfologia superficial das amostras foram estudadas por microscopia óptica e microscopia eletrônica de varredura (MEV). As propriedades de transporte eletrônico foram analisadas através de medidas de resistividade elétrica. Das amostras processadas, uma não apresentou estado de resistência elétrica nula. As medidas de resistividade elétrica para as demais amostras revelaram comportamento supercondutor e mostraram que a temperatura crítica do sistema REBa2Cu3O7-x, está em torno de 90 K, como no sistema YBa2Cu3O7-x. Esses valores foram confirmados pelas medidas de susceptibilidade magnética. As análises dos difratogramas de raios X das amostras revelaram que os parâmetros de cela dos dois sistemas são iguais. Esses resultados indicam que substituição do Y pelo óxido de terras-raras é possível, podendo ter importantes implicações tanto do ponto de vista de pesquisa básica como da pesquisa aplicada.

[Truncated abstract] The realization in 1999 that the authigenic phosphate, xenotime, could be used in geochronological studies to place age constraints on burial events that affected sedimentary basins has opened numerous opportunities for establishing timeframes for sedimentary basin analysis. Since then, the mineral has been used to place new and novel age constraints on diagenesis, metamorphism, and hydrothermal alteration and mineralization events. Whilst these studies were successful, they identified many complexities in xenotime growth and were restricted to specific areas or single basins: they do not convey, demonstrate or explore the immense variety of geological applications in which xenotime may provide unique geochronological constraints. This thesis explores the nature of authigenic xenotime, utilizing studies in three different Proterozoic sedimentary basins: two in Australia, southwestern Australia and the Northern Territory, and the third in the United States of America. The thesis includes a number of discrete studies demonstrating different aspects of xenotime growth, elucidated from detailed petrography, geochronology and geochemistry of authigenic xenotime. An integrated textural, geochemical and geochronological study of authigenic xenotime from the Mt Barren Group, SW Australia, establishes an absolute timescale on some of the many processes involved during the diagenesis of siliciclastic units. ... positions and trends and broadly confirm the chemical discrimination criteria established for an Archaean basin. However, the Proterozoic data are shifted to lower Gd-Dy values and extend beyond the original field outlines, causing more overlap between fields intended to discriminate xenotimes of different origin. The plots were revised to encompass the new data. This study has significantly extended our knowledge of the nature of authigenic xenotime. It was found that xenotime may form in (meta)sediments in response to a large number of post-depositional processes, including early- and latediagenesis, (multiple) basinal hydrothermal events and low-grade metamorphism. A combination of detailed petrography and in situ geochronology provides the best avenue to decipher complex growth histories in xenotime. With further development, it is likely that xenotime geochemistry will also prove diagnostic of origin and can be incorporated into the interpretation of age data. The number of potential applications for xenotime geochronology has been expanded by this study.