Metasomatism and magmatic assimilation at a gabbro-limestone contact, Christmas Mountains, Big Bend region, Texas

A composite stock of alkaline gabbro and syenite is intrusive into limestone of the Del Carmen, Sue Peake and Santa Elena Formations at the northwest end of the Christmas Mountains. There is abundant evidence of solution of wallrock by magma but nowhere are gabbro and limestone in direct contact. The sequence of lithologies developed across the intrusive contact and across xenoliths is gabbro, pyroxenite, calc-silicate skarn, marble. Pyroxenite is made up of euhedral crystals of titanaugite and sphene in a leucocratic matrix of nepheline, Wollastonite and alkali feldspar. The uneven modal distribution of phases in pyroxenite and the occurrence' of nepheline syenite dikes, intrusive into pyroxenite and skarn, suggest that pyroxenite represents an accumulation of clinopyroxene "cemented" together by late-solidifying residual magma of nepheline syenite composition. Assimilation of limestone by gabbroic magma involves reactions between calcite and magma and/or crystals in equilibrium with magma and crystallization of phases in which the magma is saturated, to supply energy for the solution reaction. Gabbroic magma was saturated with plagioclase and clinopyroxene at the time of emplacement. The textural and mineralogic features of pyroxenite can be produced by the reaction 2( 1-X) CALCITE + AN_XAB_l-X = (1-X) NEPHELINE+ 2(1-X) WOLLASTONITE+ X ANORTHITE+ 2(1-X) CO₂. Plagioclase in pyroxenite has corroded margins and is rimmed by nepheline, suggestive of resorption by magma. Anorthite and wollastonite enter solid solution in titanaugite. For each mole of calcite dissolved, approximately one mole of clinopyroxene was crystallized. Thus the amount of limestone that may be assimilated is limited by the concentration of potential clinopyroxene in the magma. Wollastonite appears as a phase when magma has been depleted in iron and magnesium by crystallization of titanaugite. The predominance of mafic and ultramafic compositions among contaminated rocks and their restriction to a narrow zone along the intrusive contact provides little evidence for the generation of a significant volume of desilicated magma as a result of limestone assimilation.

Within 60 m of the intrusive contact with the gabbro, nodular chert in the Santa Elena Limestone reacted with the enveloping marble to form spherical nodules of high-temperature calc-silicate minerals. The phases wollastonite, rankinite, spurrite, tilleyite and calcite, form a series of sharply-bounded, concentric monomineralic and two-phase shells which record a step-wise decrease in silica content from the core of a nodule to its rim. Mineral zones in the nodules vary 'with distance from the gabbro as follows:

0-5 m CALCITE + SPURRITE + RANKINITE + WOLLASTONITE
5-16 m CALCITE + TILLEYITE ± SPURRITE + RANKINITE + WOLLASTONITE
16-31 m CALCITE + TILLEYITE + WOLLASTONITE
31-60 m CALCITE + WOLLASTONITE
60-plus CALCITE + QUARTZ

The mineral of a one-phase zone is compatible with the phases bounding it on either side but these phases are incompatible in the same volume of P-T-X_CO2.

Growth of a monomineralio zone is initiated by reaction between minerals of adjacent one-phase zones which become unstable with rising temperature to form a thin layer of a new single phase that separates the reactants and is compatible with both of them. Because the mineral of the new zone is in equilibrium with the phases at both of its contacts, gradients in the chemical potentials of the exchangeable components are established across it. Although zone boundaries mark discontinuities in the gradients of bulk composition, two-phase equilibria at the contacts demonstrate that the chemical potentials are continuous. Hence, Ca, Si and CO₂ were redistributed in the growing nodule by diffusion. A monomineralic zone grows at the expense of an adjacent zone by reaction between diffusing components and the mineral of the adjacent zone. Equilibria between two phases at zone boundaries buffers the chemical potentials of the diffusing species. Thus, within a monomineralic zone, the chemical potentials of the diffusing components are controlled external to the local assemblage by the two-phase equilibria at the zone boundaries.

Mineralogically zoned calc-silicate skarn occurs as a narrow band that separates pyroxenite and marble along the intrusive contact and forms a rim on marble xenoliths in gabbro. Skarn consists of melilite or idocrase pseudomorphs of melili te, one or two . stoichiometric calcsilicate phases and accessory Ti-Zr garnet, perovskite and magnetite. The sequence of mineral zones from pyroxenite to marble, defined by a characteristic calc-silicate, is wollastonite, rankinite, spurrite, calcite. Mineral assemblages of adjacent skarn zones are compatible and the set of zones in a skarn band defines a facies type, indicating that the different mineral assemblages represent different bulk compositions recrystallized under identical conditions. The number of phases in each zone is less than the number that might be expected to result from metamorphism of a general bulk composition under conditions of equilibrium, trivariant in P, T and u_CO2. The "special" bulk composition of each zone is controlled by reaction between phases of the zones bounding it on either side. The continuity of the gradients of composition of melilite and garnet solid solutions across the skarn is consistent with the local equilibrium hypothesis and verifies that diffusion was the mechanism of mass transport. The formula proportions of Ti and Zr in garnet from skarn vary antithetically with that of Si Which systematically decreases from pyroxenite to marble. The chemical potential of Si in each skarn zone was controlled by the coexisting stoichiometric calc-silicate phases in the assemblage. Thus the formula proportion of Si in garnet is a direct measure of the chemical potential of Si from point to point in skarn. Reaction between gabbroic magma saturated with plagioclase and clinopyroxene produced nepheline pyroxenite and melilite-wollastonite skarn. The calcsilicate zones result from reaction between calcite and wollastonite to form spurrite and rankinite.

Distributed Load Control in Multiphase Radial Networks

The current power grid is on the cusp of modernization due to the emergence of distributed generation and controllable loads, as well as renewable energy. On one hand, distributed and renewable generation is volatile and difficult to dispatch. On the other hand, controllable loads provide significant potential for compensating for the uncertainties. In a future grid where there are thousands or millions of controllable loads and a large portion of the generation comes from volatile sources like wind and solar, distributed control that shifts or reduces the power consumption of electric loads in a reliable and economic way would be highly valuable.

Load control needs to be conducted with network awareness. Otherwise, voltage violations and overloading of circuit devices are likely. To model these effects, network power flows and voltages have to be considered explicitly. However, the physical laws that determine power flows and voltages are nonlinear. Furthermore, while distributed generation and controllable loads are mostly located in distribution networks that are multiphase and radial, most of the power flow studies focus on single-phase networks.

This thesis focuses on distributed load control in multiphase radial distribution networks. In particular, we first study distributed load control without considering network constraints, and then consider network-aware distributed load control.

Distributed implementation of load control is the main challenge if network constraints can be ignored. In this case, we first ignore the uncertainties in renewable generation and load arrivals, and propose a distributed load control algorithm, Algorithm 1, that optimally schedules the deferrable loads to shape the net electricity demand. Deferrable loads refer to loads whose total energy consumption is fixed, but energy usage can be shifted over time in response to network conditions. Algorithm 1 is a distributed gradient decent algorithm, and empirically converges to optimal deferrable load schedules within 15 iterations.

We then extend Algorithm 1 to a real-time setup where deferrable loads arrive over time, and only imprecise predictions about future renewable generation and load are available at the time of decision making. The real-time algorithm Algorithm 2 is based on model-predictive control: Algorithm 2 uses updated predictions on renewable generation as the true values, and computes a pseudo load to simulate future deferrable load. The pseudo load consumes 0 power at the current time step, and its total energy consumption equals the expectation of future deferrable load total energy request.

Network constraints, e.g., transformer loading constraints and voltage regulation constraints, bring significant challenge to the load control problem since power flows and voltages are governed by nonlinear physical laws. Remarkably, distribution networks are usually multiphase and radial. Two approaches are explored to overcome this challenge: one based on convex relaxation and the other that seeks a locally optimal load schedule.

To explore the convex relaxation approach, a novel but equivalent power flow model, the branch flow model, is developed, and a semidefinite programming relaxation, called BFM-SDP, is obtained using the branch flow model. BFM-SDP is mathematically equivalent to a standard convex relaxation proposed in the literature, but numerically is much more stable. Empirical studies show that BFM-SDP is numerically exact for the IEEE 13-, 34-, 37-, 123-bus networks and a real-world 2065-bus network, while the standard convex relaxation is numerically exact for only two of these networks.

Theoretical guarantees on the exactness of convex relaxations are provided for two types of networks: single-phase radial alternative-current (AC) networks, and single-phase mesh direct-current (DC) networks. In particular, for single-phase radial AC networks, we prove that a second-order cone program (SOCP) relaxation is exact if voltage upper bounds are not binding; we also modify the optimal load control problem so that its SOCP relaxation is always exact. For single-phase mesh DC networks, we prove that an SOCP relaxation is exact if 1) voltage upper bounds are not binding, or 2) voltage upper bounds are uniform and power injection lower bounds are strictly negative; we also modify the optimal load control problem so that its SOCP relaxation is always exact.

To seek a locally optimal load schedule, a distributed gradient-decent algorithm, Algorithm 9, is proposed. The suboptimality gap of the algorithm is rigorously characterized and close to 0 for practical networks. Furthermore, unlike the convex relaxation approach, Algorithm 9 ensures a feasible solution. The gradients used in Algorithm 9 are estimated based on a linear approximation of the power flow, which is derived with the following assumptions: 1) line losses are negligible; and 2) voltages are reasonably balanced. Both assumptions are satisfied in practical distribution networks. Empirical results show that Algorithm 9 obtains 70+ times speed up over the convex relaxation approach, at the cost of a suboptimality within numerical precision.

Earth-Abundant Zinc-IV-Nitride Semiconductors

This investigation is motivated by the need for new visible frequency direct bandgap semiconductor materials that are abundant and low-cost to meet the increasing demand for optoelectronic devices in applications such as solid state lighting and solar energy conversion. Proposed here is the utilization of zinc-IV-nitride materials, where group IV elements include silicon, germanium, and tin, as earth-abundant alternatives to the more common III-nitrides in optoelectronic devices. These compound semiconductors were synthesized under optimized conditions using reactive radio frequency magnetron sputter deposition. Single phase ZnSnN₂, having limited experimental accounts in literature, is validated by identification of the wurtzite-derived crystalline structure predicted by theory through X-ray and electron diffraction studies. With the addition of germanium, bandgap tunability of ZnSn_xGe_1-xN₂ alloys is demonstrated without observation of phase separation, giving these materials a distinct advantage over In_xGa_1-xN alloys. The accessible bandgaps range from 1.8 to 3.1 eV, which spans the majority of the visible spectrum. Electron densities, measured using the Hall effect, were found to be as high as 10²² cm⁻³ and indicate that the compounds are unintentionally degenerately doped. Given these high carrier concentrations, a Burstein-Moss shift is likely affecting the optical bandgap measurements. The discoveries made in this thesis suggest that with some improvements in material quality, zinc-IV-nitrides have the potential to enable cost-effective and scalable optoelectronic devices.

Single cell proteomics microchip to profile immune function, with applications in stem cell biology, translational disease mechanism study and clinical therapeutics monitoring

In response to infection or tissue dysfunction, immune cells develop into highly heterogeneous repertoires with diverse functions. Capturing the full spectrum of these functions requires analysis of large numbers of effector molecules from single cells. However, currently only 3-5 functional proteins can be measured from single cells. We developed a single cell functional proteomics approach that integrates a microchip platform with multiplex cell purification. This approach can quantitate 20 proteins from >5,000 phenotypically pure single cells simultaneously. With a 1-million fold miniaturization, the system can detect down to ~100 molecules and requires only ~104 cells. Single cell functional proteomic analysis finds broad applications in basic, translational and clinical studies. In the three studies conducted, it yielded critical insights for understanding clinical cancer immunotherapy, inflammatory bowel disease (IBD) mechanism and hematopoietic stem cell (HSC) biology.

To study phenotypically defined cell populations, single cell barcode microchips were coupled with upstream multiplex cell purification based on up to 11 parameters. Statistical algorithms were developed to process and model the high dimensional readouts. This analysis evaluates rare cells and is versatile for various cells and proteins. (1) We conducted an immune monitoring study of a phase 2 cancer cellular immunotherapy clinical trial that used T-cell receptor (TCR) transgenic T cells as major therapeutics to treat metastatic melanoma. We evaluated the functional proteome of 4 antigen-specific, phenotypically defined T cell populations from peripheral blood of 3 patients across 8 time points. (2) Natural killer (NK) cells can play a protective role in chronic inflammation and their surface receptor – killer immunoglobulin-like receptor (KIR) – has been identified as a risk factor of IBD. We compared the functional behavior of NK cells that had differential KIR expressions. These NK cells were retrieved from the blood of 12 patients with different genetic backgrounds. (3) HSCs are the progenitors of immune cells and are thought to have no immediate functional capacity against pathogen. However, recent studies identified expression of Toll-like receptors (TLRs) on HSCs. We studied the functional capacity of HSCs upon TLR activation. The comparison of HSCs from wild-type mice against those from genetics knock-out mouse models elucidates the responding signaling pathway.

In all three cases, we observed profound functional heterogeneity within phenotypically defined cells. Polyfunctional cells that conduct multiple functions also produce those proteins in large amounts. They dominate the immune response. In the cancer immunotherapy, the strong cytotoxic and antitumor functions from transgenic TCR T cells contributed to a ~30% tumor reduction immediately after the therapy. However, this infused immune response disappeared within 2-3 weeks. Later on, some patients gained a second antitumor response, consisted of the emergence of endogenous antitumor cytotoxic T cells and their production of multiple antitumor functions. These patients showed more effective long-term tumor control. In the IBD mechanism study, we noticed that, compared with others, NK cells expressing KIR2DL3 receptor secreted a large array of effector proteins, such as TNF-α, CCLs and CXCLs. The functions from these cells regulated disease-contributing cells and protected host tissues. Their existence correlated with IBD disease susceptibility. In the HSC study, the HSCs exhibited functional capacity by producing TNF-α, IL-6 and GM-CSF. TLR stimulation activated the NF-κB signaling in HSCs. Single cell functional proteome contains rich information that is independent from the genome and transcriptome. In all three cases, functional proteomic evaluation uncovered critical biological insights that would not be resolved otherwise. The integrated single cell functional proteomic analysis constructed a detail kinetic picture of the immune response that took place during the clinical cancer immunotherapy. It revealed concrete functional evidence that connected genetics to IBD disease susceptibility. Further, it provided predictors that correlated with clinical responses and pathogenic outcomes.