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Thesis. 1977. M.S.--Massachusetts Institute of Technology. Dept. of Earth and Planetary Sciences. / Microfiche copy available in Archives and Science. / Vita. / Bibliography : leaves 77-79. / M.S.

The garnet line is a planar fabric occuring within the intermediate and core zone in many of the Oxford County, Maine pegmatites. This study focuses primarily on the textural and chemical characteristics of the garnet line within the Mt. Mica and western Mt. Apatite quarries. Smaller, but similarly textured garnet line analogs from the Bennett, Emmons, Havey and Tamminen quarries are also investigated. All of these textures represent specific fractionation events within their respective dikes. In some of these locations, multiple stages of crystallization occur and appear to be post-magmatic, related to late stage metasomatism. These late stage fluids are believed to have migrated from localized and highly evolved regions within these pegmatites. The garnet line at Mt. Mica has the greatest diversity of secondary mineral assemblages, e.g. tourmaline and/or muscovite rims around garnets and ferric pollucite. None of these late stage textures have ever been described before.

Due to Earth’s efficient crustal recycling through plate tectonics, the remaining physical record of Earth’s first two billion years consists of mineral fragments and heavily metamorphosed rocks in isolated Archean cratons. Characterization of Earth’s earliest tectonic processes requires investigation of all available records; the mineral garnet has been largely overlooked. The major element chemistry and samarium-neodymium (Sm-Nd) isotope ratios preserved in fragmented detrital garnet and Archean metamorphic garnet record the timing and conditions of early tectonic events. This work presents detailed methodology for a new detrital garnet geochronometer unlocking age information from previously undateable detrital garnet surviving recycling in sediment, sedimentary rocks, and metasedimentary rocks. The new method’s utility is demonstrated by dating garnet from a Scottish sedimentary rock and nineteen individual garnet grains from a tributary to the French Broad River in the southern Appalachians. In the southern Appalachians, garnet and existing monazite ages overlap (though the mean garnet age is slightly younger) to record the most recent metamorphic event and both are younger than inherited zircon ages. Proof-of-concept testing demonstrating protocol development for blank-correction and routine analysis of samples smaller than 1 ng advances small Sm-Nd analysis. Additionally, this work applies existing Sm-Nd garnet geochronology methods to search for garnet older than 2.5 Ga and provide age constraints on the complicated metamorphic histories of two Archean cratons. A search for detrital garnet in a sample from the Jack Hills metasedimentary belt of Western Australia hosting the Earth’s oldest known terrestrial materials (ca. 4.3 Ga) failed to produce garnet. Instead, two samples collected ~4 km south of the Jack Hills belt in the Narryer Terrane were dated to confirm Narryer regional metamorphism at ca. 2.6 Ga. The Acasta gneiss of northern Canada, arguably Earth’s oldest known cohesive rock outcrop (ca. 4.0 Ga), produced one of the Earth’s oldest known garnet ages. Garnet ages of ca. 2.95 Ga constrain the timing of Archean metamorphism and the data also indicate potential for preservation of even older garnet. Finally, a compilation of published garnet ages in the literature is presented to summarize the community’s progress in the search for Earth’s oldest garnet. / 2017-12-06T00:00:00Z

Unrecognized metamorphic complexities can produce erroneous interpretations when using equilibrium thermodynamics and isotope geochronology. Universally employed methods for determining pressure-temperature conditions during regional metamorphism are based on the assumption of chemical equilibrium, and geochronology in metamorphic rocks can suffer from cryptic redistribution of isotopes. In this research, the scales of disequilibrium in regionally metamorphosed rocks and the effects of garnet resorption on Lu-Hf garnet ages were examined through numerical simulations of these processes. Concerning scales of disequilibrium, thirteen porphyroblastic datasets, previously measured using X-ray computed tomography, were examined by numerically simulating diffusion-controlled nucleation and growth of garnet while tracking chemical potential gradients to determine reaction affinity Ar (-[Delta]rG). Maximum nucleation rates are 10⁻¹³̇⁶-10⁻⁹̇⁸ nuclei cm⁻³ s⁻¹, interfacial energies are 0.004-0.14 J m⁻² assuming shape factors of 0.1-1.0, and Al intergranular diffusion (QD = 140 kJ/mol⁻¹) is 10⁻¹⁴̇⁴-10⁻¹¹̇¹ m² s⁻¹ at 600 °C. Limitations in determining crystallization kinetics arise from difficulties in constraining rock-specific properties (e.g., porosity and Al solubility). Ar at the time and location of nucleation is 0.4-5.9 kJ/mol⁻¹ of 12-oxygen garnet ([Delta]T = 4.0-62.0 °C) for the earliest nuclei, and 5.3-29.0 kJ/mol⁻¹ ([Delta]T = 50-125 °C) for nucleation at maximum Ar. The results demonstrate potential for delayed nucleation and metastability that can generate spurious interpretations. The timing of metamorphic events is also critical for understanding geologic history. In the Makhavinekh Lake Pluton aureole, Labrador, garnet resorption caused redistribution of Lu and loss of Hf from consumed rims, creating spuriously young ages. Garnet-ilmenite Lu-Hf geochronology using bulk separates yields apparent ages that young toward the contact from 1876 ± 21 Ma (4025 m) to 1396 ± 8 Ma (450 m). Toward the contact, garnet crystals are progressively more resorbed. Numerical modeling was used to test retention of Lu and loss of Hf during resorption as the dominant control on age. More resorption and Lu retention produce younger apparent ages (false ages). Application of the model to the aureole yields model ages from 1850 Ma to 1374 Ma, younging toward the contact. Thus, Lu-Hf geochronology applied to resorbed garnets requires careful examination of Lu zoning. / text

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19728号 / 工博第4183号 / 新制||工||1645(附属図書館) / 32764 / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 田中 勝久, 教授 平尾 一之, 教授 三浦 清貴 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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Equilibrium relations between garnet and orthopyroxene have been investigated by reversal experiments in the range of 20-45Kb and 975-1400°C in the FeO-MgO-Al₂O₃-SiO₂(FMAS) system. The Fe-Mg exchange reaction seems to have little or no compositional dependence at these conditions. The experimental results can be fitted adequately by the linear relation: ln K(D) = 2243/T°K - 0.9522 at 25Kb where K(D) = (X(Fe)/X(Mg))ᴳᵗ/(X(Fe)/X(Mg))ᴼᵖˣ. Combination of the available data for the mixing properties of garnet and V° for the Fe-Mg exchange reaction with the above experimental results yields the following geothermometric expression for the common natural assemblages that can be represented essentially within the system CaO-MnO-FeO-MgO-Al₂O₃-SiO₂. T°K = (1968 + 11P(Kb) + 1510(X(Ca)+X(Mn))ᴳᵗ)/(ln K(D) + 0.9522). The stability field of pyrope+quartz, defined by the reaction pryope+quartz=opx+sill, has been calculated as a function of P,T,X(Fe)ᴳᵗ in the FMAS system using the reversal experimental data of Perkins (1983) in the MAS system, and the present data on K(D)(Fe-Mg) between garnet and orthopyroxene. This reaction is very sensitive to pressure and compositional effects. Combination of P,T conditions for the garnet stability and that defined by (K(D)(Fe-Mg))ᴳᵗ⁻ᴼᵖˣ yields a simultaneous solution for both P and T of equilibration of garnet and orthopyroxene in the presence of Al₂SiO₅ and SiO₂. The effect of FeO on Al₂O₃ solubility in orthopyroxene in equilibrium with garnet has been determined experimentally at several pressures at 975 and 1200°C. These data have been modeled to develop a thermodynamic method for the calculation of Al₂O₃ in orthopyroxene as a function of P,T and composition. The Al₂O₃ isopleths have moderate P-T slopes, and provide virtually the only means of determining the pressure of mantle derived rocks.

This dissertation focuses on two areas of garnet porphyroblast crystallization that have until now remained largely uninvestigated: epitaxial nucleation of garnet porphyroblasts and yttrium and rare earth (Y+REE) uptake in metamorphic garnet. The mechanism of epitaxial nucleation is explored as a step towards determining which aspects of interfaces are significant to interfacial energies and nucleation rates. Garnet from the aureole of the Vedrette di Ries tonalite, Eastern Alps, shows a clear case of epitaxial nucleation in which garnet nucleated on biotite with (110)grt || (001)bt with [100]grt || [100]bt. The occurrence is remarkable for the clear genetic relationships revealed by the microstructures and for its preservation of the mica substrate, which allows unambiguous determination of the coincident lattice planes and directions involved in the epitaxy. Not all epitaxial nucleation is conspicuous; to increase the ability to document epitaxial relationships between garnet and micas, I develop and apply a method for determining whether evidence for epitaxial nucleation of garnet is present in porphyroblasts containing an included fabric. Although the magnitude of uncertainties in orientation measurements for garnets from Passo del Sole (Switzerland), the Nevado Filabride Complex (Spain), and Harpswell Neck (USA) preclude definitive identification of epitaxial relationships, the method has potential to become a viable technique for creating an inventory of instances and orientations of epitaxial nucleation with appropriate sample selection. Using lattice-dynamics simulations, I explore the most commonly documented epitaxial relationship, (110)grt || (001)ms. The range of interfacial energies resulting from variations in the intracrystalline layer within garnet at the interface, the initial atomic arrangement at the interface, and the rotational orientation of the garnet structure relative to the muscovite structure shows that the intracrystalline layer within garnet has the greatest effect on interfacial energy. A complete understanding of the role of intergranular diffusion for yttrium and rare-earth-element uptake in porphyroblastic garnet is critical because the complexities of Y+REE zoning in garnets and the mechanisms of Y+REE uptake have implications for petrologic interpretations and garnet-based geochronology. Y+REE distributions in garnets from the Picuris Mountains (USA), Passo del Sole (USA), and the Franciscan Complex (USA) imply diverse origins linked to differing degrees of mobility of these elements through the intergranular medium during garnet growth.