Doctor of Philosophy

dissertationI will describe a low-pressure flow-through 129Xe polarizer and report its performance by examining both the output 129Xe and in situ Rb polarization. The 129Xe polarization was made using standard NMR techniques, and the Rb polarization measurement was made using optically detected electron paramagnetic resonance. I compared the results of these measurements to a one-dimensional numerical model of the system. While we qualitatively understand the behavior of the system, the comparison between measurement and model reveals several inadequacies in our understanding of many important physical mechanisms. I will discuss the relevant physics necessary to qualitatively understand the system's behavior and suggest what mechanisms may cause the discrepancies in the modeled and measured behavior. I will demonstrate the utility of this Xe polarizer by measuring xenon's chemical shift dependence on the concentration of Bovine Pancreatic Trypsin Inhibitor (BPTI) and some of its mutants. Mutants Y23A and F45G have measured dependence of 0.56±0.05 ppm/mM and 0.47±0.07 ppm/mM, respectively, which is consistent with relatively strong, manufactured binding sites in the structure. Wild type BPTI has a measured dependence of only 0.15±0.02 ppm/mM, suggesting that there exists no specific binding site to which Xe can bind. Finally, the mutant Y35G has a dependence of 0.10±0.07 ppm/mM. This, with previous data, suggests that a large fraction of solution-phase Y35G does not exist in a conformation that allows Xe access to its binding cavity

Strain shadow “megapores” in mid-crustal ultramylonites

Mylonitic shear zones are important fluid conduits in the Earth's crust. They host transient and permeable porosity that facilitates fluid transfer and controls fluid-rock interaction. Here we present microstructural observations from a mid-crustal ultramylonite with very large pores that occupy the strain shadows of albite porphyroclasts. Our non-invasive three-dimensional X-ray microtomographic data show that the largest of these strain shadow megapores have substantial volumes of as much as ∼1.7 × 105 µm3. Given that the sample shows no signs of retrogressive overprint or weathering, these pores must be synkinematic. Importantly, the close proximity of the pores to creep cavities in dynamically recrystallized quartz ribbon grains suggests a potential hydraulic link between fluid in the strain shadow megapores and fluid in the creeping rock matrix. The evolving megapores constitute very large syndeformational local fluid reservoirs in mylonites that likely fed into the granular fluid pump established by the dynamically evolving creep cavities. Our findings add to an emerging picture of the dynamic transport properties of ultramylonitic shear zones, where the formation and destruction of porosity are intrinsically linked to microscale deformation processes. They also suggest that despite many studies on porphyroclast systems, open questions remain, especially concerning the interaction of clasts with their matrix

The evolution of slate microfabrics during progressive accretion of foreland basin sediments

Here, we study slate microfabrics from the exhumed accretionary wedge of the central European Alps and focus on the development of foliation. High-resolution micrographs from novel BIB-SEM imaging and Synchrotron X-ray Fluorescence Microscopy are analysed with 2D auto-correlation functions to quantify the geometry and spacing of slate microfabrics along a metamorphic gradient covering the outer and inner wedge (200–330 °C). The sedimentary layering primarily controls the morphology of the slate microfabrics. However, from outer to inner wedge, a fabric evolution is observed where diagenetic foliations gradually transform to secondary continuous and spaced foliations. With increasing metamorphic grade, the amount of recrystallized phyllosilicate grains and their interconnectivity increase, as does clast/microlithon elongation (aspect ratios up to 11), while foliation spacing decreases to 230 °C and accommodates background strain in the inner wedge. The evolving microstructural anisotropy is interpreted to lead to strain weakening by structural softening and may provide preferential fluid pathways parallel to the foliation, enabling the dehydration of large rock volumes in accretionary sediment wedges undergoing prograde metamorphism