Thesis (Ph. D.)--University of Chicago, 1918. / "Private Edition, Distributed by the University of Chicago Libraries, Chicago, Illinois." Includes bibliographical references. Also available on the Internet.

Dans le cadre de la loi du 30 décembre 1991 relative à la gestion à long terme des déchets nucléaires, plusieurs matrices de confinement spécifique des actinides, dont la monazite et la solution solide monazite/chéralite associée ont été étudiées au cours de ce travail en vue de leur stockage en formation géologique profonde. Ainsi, différentes monazites LnPO4 (Ln = La → Gd) ont été préparées par conversion thermique de rhabdophanes, LnPO4 , 0,667H2O, précipitées à basse température. Sur la base d’expériences menées sous rayonnement synchrotron, la structure cristallographique de la rhabdophane a d’abord été résolue dans un système monoclinique (groupe d’espace C2) tout comme la monazite (groupe d'espace P21/n) puis sa conversion thermique en monazite a été étudiée. Une étude multiparamétrique de la vitesse de dissolution de la monazite LnPO4 (Ln = La → Gd) dans l’acide nitrique a été réalisée en conditions dynamiques. Les valeurs de vitesses de dissolution normalisées sont demeurées très faibles quelles que soient l'acidité du milieu, la température et la nature de l’élément lanthanide, confirmant l’excellente durabilité chimique des matériaux préparés. Des ordres partiels relatifs à l'activité du proton compris entre 0,7 ± 0,2 et 1,5 ± 0,3 ont été relevés. Parallèlement, la diminution de l’énergie d’activation apparente pour T ≥ 313 K a souligné une modification de l’étape cinétiquement limitante du mécanisme de dissolution, liée à l'impact de l’indice de saturation de la solution par rapport à la précipitation de la phase rhabdophane.Les produits de solubilité des rhabdophanes (La → Dy) ainsi que les grandeurs thermodynamiques associées ont été déterminés via des expériences de sur- et de sous-saturation. Le bon accord entre les valeurs obtenues par ces deux approches a confirmé la réversibilité de l’équilibre de solubilité associé à la rhabdophane. Une faible variation du produit de solubilité et des grandeurs thermodynamiques de formation de la rhabdophane a été observée le long de la série des éléments lanthanide (-2151±13 ≤ Df H^o (298K) ≤ -2130±12 kJ.mol-1, -2004±2 ≤ Df G^o (298K) ≤ -1984±2 kJ.mol-1 et -504±11≤ DS^o (298K)≤ -473±12 J.mol-1.K-1), à l’exception de l’europium qui présente des valeurs nettement supérieures d'énergie libre (-1896 ± 2 kJ.mol-1), d'enthalpie (-2057 ± 9 kJ.mol-1) et d'entropie (–538 ± 11 J.mol-1.K-1) de formation. Par ailleurs, une relation directe entre les enthalpies obtenues pour les rhabdophanes et les monazites a été démontrée ; les données associées aux rhabdophanes étant obtenues par simple ajout de la contribution de 0,667 molécule d'eau. Cette observation corrobore aussi bien la structure monoclinique de la rhabdophane que le nombre de molécules d'eau constitutionnelles.Parallèlement, l'évolution structurale et microstructurale de la surface de monazites frittées a été suivie en cours de dissolution par plusieurs techniques complémentaires (MEBE, AFM, XRR, et DRX en mode d’incidence rasante). La très bonne durabilité chimique de ces céramiques préparées a été confirmée : seulement 0,04% et 0,3% en masse de matériau ont été dissous après 300 jours de lixiviation, respectivement dans HNO3 0,1M et 0,25M à 363K. Des analyses de surface, il est apparu que les défauts préexistants (fissures, défauts liés au polissage, pores) constituaient des zones préférentielles de dissolution tandis qu’aucune phase secondaire n'a été clairement mise en évidence malgré un indice de saturation en solution traduisant un état proche de l'équilibre de précipitation de la rhabdophane.Enfin, un protocole original de synthèse d’échantillons de rhabdophane dopés en thorium (Nd1-2xCaxThxPO4 , 0,667H2O) par voie humide a été développé au cours de ce travail. Les premières expériences de solubilité, menées en conditions de sous-saturation dans HCl 0,25 M, ont conduit à une estimation des produits de solubilité apparents, lesquels présentent une faible variation sur l’intervalle de températures considéré. / In the context of the French research law dedicated to the radioactive waste management, several ceramics were proposed for the specific conditioning of actinides. Among them, monazites and monazite/cheralite solid solutions were particularly considered in this work.Thus, monazites LnPO4 (Ln = La → Gd) were prepared by thermal conversion of low-temperature rhabdophane precursors, LnPO4•0.667H2O. From synchrotron experiments, the crystal structure of rhabdophane was solved. It was found to be monoclinic (space group C2) as monazite (space group P21/n).The multiparametric study of the kinetics of dissolution of monazites LnPO4 (Ln = La → Gd) was performed in nitric acid solutions and using dynamic conditions. The normalized dissolution rates remained very low whatever the acidity, the temperature, and the lanthanide element considered. The partial order of the reaction related to the protons activity varied from 0.7 ± 0.2 to 1.5 ± 0.3. Moreover, the apparent activation energy of the dissolution mechanism was found to vary with temperature, suggesting a change in the rate-limiting step. The decrease of the apparent activation energy for T ≥ 313 K was assigned to the impact of saturation processes with respect to the rhabdophane.Thus, the solubility products as well as thermodynamic data associated to the formation of rhabdophanes were evaluated from over- and under-saturation conditions. The similar values obtained by both approaches confirmed the reversibility of the equilibrium associated to the rhabdophane precipitation. Solubility products as well as thermodynamic data only slightly varied along the lanthanide elements series : -2151±13 ≤ Df H^o (298K) ≤ -2130±12 kJ.mol-1, -2004±2 ≤ Df G^o (298K) ≤ -1984±2 kJ.mol-1 and -504±11 ≤ Df S^o (298K) ≤ -473±12 J.mol-1.K-1, excepted for europium that presented the highest values of free energy (-1896 ± 2 kJ.mol-1), enthalpy (-2057 ± 9 kJ.mol-1) and entropy (–538 ± 11 J.mol-1.K-1) of formation. The comparison of the data obtained for rhabdophanes and monazites showed that the values associated to rhabdophane can be deduced from those of monazite by adding the contribution of 0.667 water molecule. It confirms either the monoclinic structure of the rhabdophane and the number of water molecules present in the structure.For the first time, structural and microstructural evolution of monazite pellets was monitored during dissolution thanks to several complementary surface analysis techniques (ESEM, AFM, GI-XRR and GI-XRD). This study confirmed the very good chemical durability of these ceramics (only 0.04 wt.% and 0.3 wt.% of dissolved ceramic in 0.1 M HNO3 and 0.25 M HNO3, respectively, at 363 K after 300 days of dissolution). These different techniques also highlighted that pre-existing defects (pores, cracks, polishing marks) acted as preferential dissolution zones. However, no secondary phase was clearly evidenced onto the surface of the samples even if the solutions were found to be close to equilibrium with rhabdophane.Finally, an original protocol of precipitation of Th-doped rhabdophanes, Nd1-2xCaxThxPO4•0.667H2O, was developed during this work. The first estimation of the apparent solubility constants, performed in under-saturated conditions in 0.25 M HCl solution, did not evidence any significant variation in the temperature range investigated.

Thesis (B.Sc. Hons.) - Dept. of Geology, University of Adelaide, 1974. / Typescript (photocopy).

L. Gordon's Thesis--University of Michigan. / Two articles, by H.H. Willard and L. Gordon, reprinted from Analytical chemistry, vo. 20, p. 165, Feb. 1948 and v. 25, p. 170, Jan. 1953. Includes bibliographical references.

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.

第23回名古屋大学年代測定総合研究センターシンポジウム平成22(2010)年度報告

The Aegean region contains numerous metamorphic core complexes that reflect post-collision extensional tectonics. The largest of these is the Menderes Massif of western Turkey, which covers an area of ~40,000 km². The Selimiye Shear Zone bounds its southern border and is a key location for studying the metamorphic history of the massif. Models of the tectonic evolution of the region requires an understanding of the peak pressure-temperature (P-T) conditions recorded by rocks in the massif, and the time (t) at which they achieved those conditions. However, limited P-T-t data exists in the Southern Menderes Massif. Here, P-T-t data was obtained from garnet-bearing rocks collected perpendicular to strike along seven transects spaced about 35 km across the Selimiye Shear Zone. Garnets in nine samples from four transects were analyzed using high-resolution back-scattered electron (BSE) imagery, X-ray element (Fe, Mg, Mn, Ca and Y) maps, and quantitative compositional analyses. Both zircon and monazite grains were dated in rock thin section using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Secondary Ion Mass Spectrometry (SIMS) to ascertain the timing of events recorded by the rocks. Some garnet X-ray element maps show zoning consistent with multiple stages of growth, diffusion, and retrogression. Distinct zones in each sample are visible on high contrast BSE images and can be related to Y, Fe, and Mn contents. The conventional garnet + biotite geothermometer and garnet + plagioclase + muscovite + biotite geobarometer were used to estimate peak metamorphic P-T conditions. These range from 556±10°C to 671±27°C, and 15.3±0.2 kbar to 22.4±0.5 kbar. The temperatures are similar to previous estimates, but the pressures appear about ~10 kbar higher the previous estimates. U-Pb zircon ages range from 2022±30 Ma (13.4% disc.) to 254±5 Ma (13.4% disc.). Based on Th/U contents, the oldest ages are likely related to inherited grains from magmatic sources. The youngest zircon age is the first reported Triassic grain from the Southern Menderes Massif and may relate to the closure event of the Paleo-Tethyan Ocean. A younger history is recorded by U-Pb and Th-Pb monazite ages, which range Cretaceous to Miocene. Monazite geochronology is hindered by the contamination of high amounts of common Pb, but U-Pb and Th-Pb age calculations show Miocene to Jurassic ages. The textures of monazite (i.e. drusy, filling cracks of garnet and in reaction with allanite) imply that ages could record crystallization and/or fluid dissolution/reprecipitation mediated events in the Oligocene. Data reported here support the observation that polymetamorphic events are recorded in the Southern Menderes Massif rocks in close proximity to the Selimiye Shear Zone. Two options are possible environments of continental exhumation of rocks along the zone: (1) a polymetamorphic history that records relict high-pressures from previous metamorphic events or (2) a single-stage exhumation of high-pressure rocks. / text

The Aegean region contains numerous metamorphic core complexes that reflect post-collision extensional tectonics. The largest of these is the Menderes Massif of western Turkey, which covers an area of ~40,000 km². The Selimiye Shear Zone bounds its southern border and is a key location for studying the metamorphic history of the massif. Models of the tectonic evolution of the region requires an understanding of the peak pressure-temperature (P-T) conditions recorded by rocks in the massif, and the time (t) at which they achieved those conditions. However, limited P-T-t data exists in the Southern Menderes Massif. Here, P-T-t data was obtained from garnet-bearing rocks collected perpendicular to strike along seven transects spaced about 35 km across the Selimiye Shear Zone. Garnets in nine samples from four transects were analyzed using high-resolution back-scattered electron (BSE) imagery, X-ray element (Fe, Mg, Mn, Ca and Y) maps, and quantitative compositional analyses. Both zircon and monazite grains were dated in rock thin section using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Secondary Ion Mass Spectrometry (SIMS) to ascertain the timing of events recorded by the rocks. Some garnet X-ray element maps show zoning consistent with multiple stages of growth, diffusion, and retrogression. Distinct zones in each sample are visible on high contrast BSE images and can be related to Y, Fe, and Mn contents. The conventional garnet + biotite geothermometer and garnet + plagioclase + muscovite + biotite geobarometer were used to estimate peak metamorphic P-T conditions. These range from 556±10°C to 671±27°C, and 15.3±0.2 kbar to 22.4±0.5 kbar. The temperatures are similar to previous estimates, but the pressures appear about ~10 kbar higher the previous estimates. U-Pb zircon ages range from 2022±30 Ma (13.4% disc.) to 254±5 Ma (13.4% disc.). Based on Th/U contents, the oldest ages are likely related to inherited grains from magmatic sources. The youngest zircon age is the first reported Triassic grain from the Southern Menderes Massif and may relate to the closure event of the Paleo-Tethyan Ocean. A younger history is recorded by U-Pb and Th-Pb monazite ages, which range Cretaceous to Miocene. Monazite geochronology is hindered by the contamination of high amounts of common Pb, but U-Pb and Th-Pb age calculations show Miocene to Jurassic ages. The textures of monazite (i.e. drusy, filling cracks of garnet and in reaction with allanite) imply that ages could record crystallization and/or fluid dissolution/reprecipitation mediated events in the Oligocene. Data reported here support the observation that polymetamorphic events are recorded in the Southern Menderes Massif rocks in close proximity to the Selimiye Shear Zone. Two options are possible environments of continental exhumation of rocks along the zone: (1) a polymetamorphic history that records relict high-pressures from previous metamorphic events or (2) a single-stage exhumation of high-pressure rocks. / text

The Aegean region contains numerous metamorphic core complexes that reflect post-collision extensional tectonics. The largest of these is the Menderes Massif of western Turkey, which covers an area of ~40,000 km². The Selimiye Shear Zone bounds its southern border and is a key location for studying the metamorphic history of the massif. Models of the tectonic evolution of the region requires an understanding of the peak pressure-temperature (P-T) conditions recorded by rocks in the massif, and the time (t) at which they achieved those conditions. However, limited P-T-t data exists in the Southern Menderes Massif. Here, P-T-t data was obtained from garnet-bearing rocks collected perpendicular to strike along seven transects spaced about 35 km across the Selimiye Shear Zone. Garnets in nine samples from four transects were analyzed using high-resolution back-scattered electron (BSE) imagery, X-ray element (Fe, Mg, Mn, Ca and Y) maps, and quantitative compositional analyses. Both zircon and monazite grains were dated in rock thin section using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Secondary Ion Mass Spectrometry (SIMS) to ascertain the timing of events recorded by the rocks. Some garnet X-ray element maps show zoning consistent with multiple stages of growth, diffusion, and retrogression. Distinct zones in each sample are visible on high contrast BSE images and can be related to Y, Fe, and Mn contents. The conventional garnet + biotite geothermometer and garnet + plagioclase + muscovite + biotite geobarometer were used to estimate peak metamorphic P-T conditions. These range from 556±10°C to 671±27°C, and 15.3±0.2 kbar to 22.4±0.5 kbar. The temperatures are similar to previous estimates, but the pressures appear about ~10 kbar higher the previous estimates. U-Pb zircon ages range from 2022±30 Ma (13.4% disc.) to 254±5 Ma (13.4% disc.). Based on Th/U contents, the oldest ages are likely related to inherited grains from magmatic sources. The youngest zircon age is the first reported Triassic grain from the Southern Menderes Massif and may relate to the closure event of the Paleo-Tethyan Ocean. A younger history is recorded by U-Pb and Th-Pb monazite ages, which range Cretaceous to Miocene. Monazite geochronology is hindered by the contamination of high amounts of common Pb, but U-Pb and Th-Pb age calculations show Miocene to Jurassic ages. The textures of monazite (i.e. drusy, filling cracks of garnet and in reaction with allanite) imply that ages could record crystallization and/or fluid dissolution/reprecipitation mediated events in the Oligocene. Data reported here support the observation that polymetamorphic events are recorded in the Southern Menderes Massif rocks in close proximity to the Selimiye Shear Zone. Two options are possible environments of continental exhumation of rocks along the zone: (1) a polymetamorphic history that records relict high-pressures from previous metamorphic events or (2) a single-stage exhumation of high-pressure rocks. / text

名古屋大学年代測定総合研究センターシンポジウム報告