Processes that take place in the Earth’s mantle are not accessible to direct observation. Natural samples of mantle material that have been transported to the surface as xenoliths provide useful information on phase relations and compositions of phases at the pressure and temperature conditions of each rock fragment. In the past, considerable effort has been devoted by petrologists to investigate upper mantle processes experimentally. Results of high temperatures, high pressure experiments have provided insight into lower crust-upper mantle phase relations as a function of temperature, pressure and composition. However, the attainment of equilibrium in these experiments, especially in complex systems, may be very difficult to test rigorously. Furthermore, experimental results may also require extrapolation to different pressures, temperatures or bulk compositions. More recently, thermodynamic modeling has proved to be a very powerful approach to this problem, allowing the deciphering the physicochemical conditions at which mantle processes occur. On the other hand, a comprehensive thermodynamic model to investigate lower crust-upper mantle phase assemblages in complex systems does not exist. ¶ In this study, a new thermodynamic model to describe phase equilibria between silicate and/or oxide crystalline phases has been derived. For every solution phase the molar Gibbs free energy is given by the sum of contributions from the energy of the end-members, ideal mixing on sites, and excess site mixing terms. It is here argued that the end-member term of the Gibbs free energy for complex solid solution phases (e.g. pyroxene, spinel) has not previously been treated in the most appropriate manner. As an example, the correct expression of this term for a pyroxene solution in a general (Na-Ca-Mg-Fe2+-Al-Cr-Fe3+-Si-Ti) system is presented and the principle underlying its formulation for any complex solution phase is elucidated.¶ Based on the thermodynamic model an algorithm to compute lower crust-upper mantle phase equilibria for subsolidus mineral assemblages as a function of composition, temperature and pressure has been developed. Included in the algorithm is a new way to represent the total Gibbs free energy for any multi-phase complex system. At any given temperature and pressure a closed multi-phase system is at its equilibrium condition when the chemical composition of the phases present in the system and the number of moles of each are such that the Gibbs free energy of the system reaches its minimum value. From a mathematical point of view, the determination of equilibrium phase assemblages can, in short, be defined as a constrained minimization problem. To solve the Gibbs free energy minimization problem a ‘Feasible Iterate Sequential Quadratic Programming’ method (FSQP) is employed. The system’s Gibbs free energy is minimized under several different linear and non-linear constraints. The algorithm, coded as a highly flexible FORTRAN computer program (named ‘Gib’), has been set up, at the moment, to perform equilibrium calculations in NaO-CaO-MgO-FeO-Al2O3-Cr2O3-Fe2O3- SiO2-TiO2 systems. However, the program is designed in a way that any other oxide component could be easily added.¶ To accurately forward model phase equilibria compositions using ‘Gib’, a precise estimation of the thermodynamic data for mineral end-members and of the solution parameters that will be adopted in the computation is needed. As a result, the value of these parameters had to be derived/refined for every solution phase in the investigated systems. A computer program (called ‘GibInv’) has been set up, and its implementation is here described in detail, that allows the simultaneous refinement of any of the end-member and mixing parameters. Derivation of internally consistent thermodynamic data is obtained by making use of the Bayesian technique. The program, after being successfully tested in a synthetic case, is initially applied to pyroxene assemblages in the system CaO-MgO-FeO-Al2O3-SiO2 (i.e. CMFAS) and in its constituent subsystems. Preliminary results are presented.¶ The new thermodynamic model is then applied to assemblages of Ca-Mg-Fe olivines and to assemblages of coexisting pyroxenes (orthopyroxene, low Ca- and high Ca clinopyroxene; two or three depending on T-P-bulk composition conditions), in CMFAS system and subsystems. Olivine and pyroxene solid solution and end-member parameters are refined, in part using ‘GibInv’ and in part on a ‘trial and error’ basis, and, when necessary, new parameters are derived. Olivine/pyroxene phase relations within such systems and their subsystems are calculated over a wide range of temperatures and pressures and compare very favorably with experimental constraints.

Natural attenuation refers to the observed reduction in contaminant concentration via natural processes as contaminants migrate from the source into environmental media. Assessment of the dimensions of contaminant plumes and prediction of their fate requires predictions of the rate of dissolution of contaminants from residual non-aqueous-phase liquids (NAPLs) into the aquifer and the rate of contaminant removal through biodegradation. The available techniques to estimate these parameters do not characterize their confidence intervals by accounting for their relationships to uncertainty in source geometry and hydraulic conductivity distribution. The central idea in this thesis is to develop a flexible modeling approach for characterization of uncertainty in residual NAPL dissolution rate and first-order biodegradation rate by tailoring the estimation of these parameters to distributions of uncertainty in source size and hydraulic conductivity field. The first development in this thesis is related to a distance function approach that characterizes the uncertainty in the areal limits of the source zones. Implementation of the approach for a given monitoring well arrangement results in a unique uncertainty band that meets the requirements of unbiasedness and fairness of the calibrated probabilities. The second development in this thesis is related to a probabilistic model for characterization of uncertainty in the 3D localized distribution of residual NAPL in a real site. A categorical variable is defined based on the available CPT-UVIF data, while secondary data based on soil texture and groundwater table elevation are also incorporated into the model. A cross-validation study shows the importance of incorporation of secondary data in improving the prediction of contaminated and uncontaminated locations. The third development in this thesis is related to the implementation of a Monte Carlo type inverse modeling to develop a screening model used to characterize the confidence intervals in the NAPL dissolution rate and first-order biodegradation rate. The development of the model is based on sequential self-calibration approach, distance-function approach and a gradient-based optimization. It is shown that tailoring the estimation of the transport parameters to joint realizations of source geometry and transmissivity field can effectively reduce the uncertainties in the predicted state variables.

Crustal deformation can be the result of volcanic and tectonic activity such as fault dislocation and magma intrusion. The crustal deformation may precede and/or succeed the earthquake occurrence and eruption. Mitigating the associated hazard, continuous monitoring of the crustal deformation accordingly has become an important task for geo-observatories and fast response systems. Due to highly non-linear behavior of the crustal deformation fields in time and space, which are not always measurable using conventional geodetic methods (e.g., Leveling), innovative techniques of monitoring and analysis are required. In this thesis I describe novel methods to improve the ability for precise and accurate mapping the spatiotemporal surface deformation field using multi acquisitions of satellite radar data. Furthermore, to better understand the source of such spatiotemporal deformation fields, I present novel static and time dependent model inversion approaches. Almost any interferograms include areas where the signal decorrelates and is distorted by atmospheric delay. In this thesis I detail new analysis methods to reduce the limitations of conventional InSAR, by combining the benefits of advanced InSAR methods such as the permanent scatterer InSAR (PSI) and the small baseline subsets (SBAS) with a wavelet based data filtering scheme. This novel InSAR time series methodology is applied, for instance, to monitor the non-linear deformation processes at Hawaii Island. The radar phase change at Hawaii is found to be due to intrusions, eruptions, earthquakes and flank movement processes and superimposed by significant environmental artifacts (e.g., atmospheric). The deformation field, I obtained using the new InSAR analysis method, is in good agreement with continuous GPS data. This provides an accurate spatiotemporal deformation field at Hawaii, which allows time dependent source modeling. Conventional source modeling methods usually deal with static deformation field, while retrieving the dynamics of the source requires more sophisticated time dependent optimization approaches. This problem I address by combining Monte Carlo based optimization approaches with a Kalman Filter, which provides the model parameters of the deformation source consistent in time. I found there are numerous deformation sources at Hawaii Island which are spatiotemporally interacting, such as volcano inflation is associated to changes in the rifting behavior, and temporally linked to silent earthquakes. I applied these new methods to other tectonic and volcanic terrains, most of which revealing the importance of associated or coupled deformation sources. The findings are 1) the relation between deep and shallow hydrothermal and magmatic sources underneath the Campi Flegrei volcano, 2) gravity-driven deformation at Damavand volcano, 3) fault interaction associated with the 2010 Haiti earthquake, 4) independent block wise flank motion at the Hilina Fault system, Kilauea, and 5) interaction between salt diapir and the 2005 Qeshm earthquake in southern Iran. This thesis, written in cumulative form including 9 manuscripts published or under review in peer reviewed journals, improves the techniques for InSAR time series analysis and source modeling and shows the mutual dependence between adjacent deformation sources. These findings allow more realistic estimation of the hazard associated with complex volcanic and tectonic systems. / Oberflächendeformationen können eine Folge von vulkanischen und tektonischen Aktivitäten sein, wie etwa Plattenverschiebungen oder Magmaintrusion. Die Deformation der Erdkruste kann einem Erdbeben oder einem Vulkanausbruch vorausgehen und/oder folgen. Um damit drohende Gefahren für den Menschen zu verringern, ist die kontinuierliche Beobachtung von Krustendeformationen eine wichtige Aufgabe für Erdobservatorien und Fast-Responce-Systems geworden. Auf Grund des starken nicht-linearen Verhaltens von Oberflächendeformationsgebiet in Zeit und Raum, die mit konventionellen Methoden nicht immer erfasst werden (z.B., Nivellements), sind innovative Beobachtungs- und Analysetechniken erforderlich. In dieser Dissertation beschreibe ich Methoden, welche durch Mehrfachbeobachtungen der Erdoberfläche nit satellitengestützem Radar eine präzise und akkurate Abbildung der raumzeitlichen Oberflächendeformationen ermöglichen. Um die Bildung und Entwicklung von solchen raumzeitlichen Deformationsgebieten besser zu verstehen, zeige ich weiterhin neuartige Ansätze zur statischen und zeitabhängigen Modellinversion. Radar-Interferogramme weisen häufig Gebiete auf, in denen das Phasensignal dekorreliert und durch atmosphärische Laufzeitverzögerung verzerrt ist. In dieser Arbeit beschreibe ich wie Probleme des konventionellen InSAR überwunden werden können, indem fortgeschrittene InSAR-Methoden, wie das Permanent Scatterer InSAR (PSI) und Small Baseline Subsets (SBAS), mit einer Wavelet-basierten Datenfilterung verknüpft werden. Diese neuartige Analyse von InSAR Zeitreihen wird angewendet, um zum Beispiel nicht-lineare Deformationsprozesse auf Hawaii zu überwachen. Radar-Phasenänderungen, gemessen auf der Pazifikinsel, beruhen auf Magmaintrusion, Vulkaneruption, Erdbeben und Flankenbewegungsprozessen, welche durch signifikante Artefakte (z.B. atmosphärische) überlagert werden. Mit Hilfe der neuen InSAR-Analyse wurde ein Deformationsgebiet ermittelt, welches eine gute Übereinstimmung mit kontinuierlich gemessenen GPS-Daten aufweist. Auf der Grundlage eines solchen, mit hoher Genauigkeit gemessenen, raumzeitlichen Deformationsgebiets wird für Hawaii eine zeitabhängige Modellierung der Deformationsquelle ermöglicht. Konventionelle Methoden zur Modellierung von Deformationsquellen arbeiten normalerweise mit statischen Daten der Deformationsgebiete. Doch um die Dynamik einer Deformationsquelle zu untersuchen, sind hoch entwickelte zeitabhängige Optimierungsansätze notwendig. Dieses Problem bin ich durch eine Kombination von Monte-Carlo-basierten Optimierungsansätzen mit Kalman-Filtern angegangen, womit zeitlich konsistente Modellparameter der Deformationquelle gefunden werden. Ich fand auf der Insel Hawaii mehrere, raumzeitlich interagierende Deformationsquellen, etwa Vulkaninflation verknüpft mit Kluftbildungen und Veränderungen in bestehenden Klüften sowie zeitliche Korrelationen mit stillen Erdbeben. Ich wendete die neuen Methoden auf weitere tektonisch und vulkanisch aktive Gebiete an, wo häufig die eine Interaktion der Deformationsquellen nachgewiesen werden konnte und ihrer bedeutung untersucht wurde. Die untersuchten Gebiete und Deformationsquellen sind 1) tiefe und oberflächliche hydrothermale und magmatische Quellen unterhalb des Campi Flegrei Vulkans, 2) gravitationsbedingte Deformationen am Damawand Vulkan, 3) Störungsdynamik in Verbindung mit dem Haiti Beben im Jahr 2010, 4) unabhängige blockweise Flankenbewegung an der Hilina Störungszone, und 5) der Einfluss eines Salzdiapirs auf das Qeshm Erdbeben im Süd-Iran im Jahr 2005. Diese Dissertation, geschrieben als kumulative Arbeit von neun Manuskripten, welche entweder veröffentlicht oder derzeit in Begutachtung bei ‘peer-review’ Zeitschriften sind, technische Verbesserungen zur Analyse von InSAR Zeitreihen vor sowie zur Modellierung von Deformationsquellen. Sie zeigt die gegenseitige Beeinflussung von benachbarten Deformationsquellen, und sie ermöglicht, realistischere Einschätzungen von Naturgefahren, die von komplexen vulkanischen und tektonischen Systemen ausgehen.

Basic oxygen furnace (BOF) slag media were studied through a series of laboratory, modeling and field studies as a potential treatment material for use in on site wastewater disposal systems. Microsphere enumeration methodology was examined in a factorial experiment to evaluate the minimum density and minimum number of microspheres that should be counted to ensure accurate and precise estimations of concentration. The results suggest that to minimize variability at least 350 microspheres should be counted and a microsphere density of 25-40 microspheres field-1 is necessary. A review of existing methodologies for high-titer bacteriophage production was conducted and an amalgamation of existing methodologies was chosen that reliably achieves elevated concentration and ensures a purified suspension. A combination of batch and column studies was conducted to evaluate the removal of the bacteriophage, PRD-1, and virus-sized fluorescent microspheres by BOF media, and to delineate the relative contributions of the two principle attenuation processes, inactivation and attachment. In the batch studies, substantial removal of PRD-1 does not occur in the pH 7.6 and 9.5 suspensions, but at pH 11.4, removal of the virus was 2.1 log C/C0 day-1 for the first two days, followed by 0.124 log C/C0 day-1 over the subsequent 10 days. Two column studies were conducted after 60 and 300 days of saturation with artificial groundwater at a flow rate of 1 pore volume day-1 using two BOF mixtures. After 300 days of column saturation, microsphere concentrations approached input levels, indicating a removal of 0.1-0.2 log C/C0 and suggesting attachment processes were negligible. PRD-1 removal was more pronounced (1.0-1.5 log C/C0). The reduction of PRD-1 is likely the result of a combination of virus inactivation at elevated pH (10.6-11.4), and attachment processes. Geochemical factors controlling microsphere attachment were compared between the two sets of experiments after 60 and 300 days of column saturation. Differences in attachment efficiency may be due to higher influent DOC concentration in the second experiment, conversion of amorphous iron phases to more crystalline forms over time, reductive dissolution of preferable attachment sites on iron phases, or precipitation of calcite. Hydrus-1D, a one-dimensional numerical model, was used to quantify transport processes, inactivation and attachment/detachment, occurring in the column experiments by model inversion. Fitted microsphere breakthrough closely matched observed data, whereas PRD-1 breakthrough with realistic parameter values does not closely match the peaked nature of the observed curves. The model achieved improved fits for microsphere and PRD-1 breakthrough when both strongly- and weakly-binding sites are represented. A unique set of parameter estimates could not be determined because of overparameterization of the inverse modeling for the experimental systems. An alternative latrine incorporating BOF slag media was constructed in a periurban community located near São Paulo, Brazil. Pathogen indicator removal is approximately 4-5 orders of magnitude in less than one meter of vertical transport through the BOF slag media. In a control latrine, constructed with similar hydraulic characteristics and inert materials, comparable reductions in pathogenic indicators were observed over three meters of vertical transport.

Basic oxygen furnace (BOF) slag media were studied through a series of laboratory, modeling and field studies as a potential treatment material for use in on site wastewater disposal systems. Microsphere enumeration methodology was examined in a factorial experiment to evaluate the minimum density and minimum number of microspheres that should be counted to ensure accurate and precise estimations of concentration. The results suggest that to minimize variability at least 350 microspheres should be counted and a microsphere density of 25-40 microspheres field-1 is necessary. A review of existing methodologies for high-titer bacteriophage production was conducted and an amalgamation of existing methodologies was chosen that reliably achieves elevated concentration and ensures a purified suspension. A combination of batch and column studies was conducted to evaluate the removal of the bacteriophage, PRD-1, and virus-sized fluorescent microspheres by BOF media, and to delineate the relative contributions of the two principle attenuation processes, inactivation and attachment. In the batch studies, substantial removal of PRD-1 does not occur in the pH 7.6 and 9.5 suspensions, but at pH 11.4, removal of the virus was 2.1 log C/C0 day-1 for the first two days, followed by 0.124 log C/C0 day-1 over the subsequent 10 days. Two column studies were conducted after 60 and 300 days of saturation with artificial groundwater at a flow rate of 1 pore volume day-1 using two BOF mixtures. After 300 days of column saturation, microsphere concentrations approached input levels, indicating a removal of 0.1-0.2 log C/C0 and suggesting attachment processes were negligible. PRD-1 removal was more pronounced (1.0-1.5 log C/C0). The reduction of PRD-1 is likely the result of a combination of virus inactivation at elevated pH (10.6-11.4), and attachment processes. Geochemical factors controlling microsphere attachment were compared between the two sets of experiments after 60 and 300 days of column saturation. Differences in attachment efficiency may be due to higher influent DOC concentration in the second experiment, conversion of amorphous iron phases to more crystalline forms over time, reductive dissolution of preferable attachment sites on iron phases, or precipitation of calcite. Hydrus-1D, a one-dimensional numerical model, was used to quantify transport processes, inactivation and attachment/detachment, occurring in the column experiments by model inversion. Fitted microsphere breakthrough closely matched observed data, whereas PRD-1 breakthrough with realistic parameter values does not closely match the peaked nature of the observed curves. The model achieved improved fits for microsphere and PRD-1 breakthrough when both strongly- and weakly-binding sites are represented. A unique set of parameter estimates could not be determined because of overparameterization of the inverse modeling for the experimental systems. An alternative latrine incorporating BOF slag media was constructed in a periurban community located near São Paulo, Brazil. Pathogen indicator removal is approximately 4-5 orders of magnitude in less than one meter of vertical transport through the BOF slag media. In a control latrine, constructed with similar hydraulic characteristics and inert materials, comparable reductions in pathogenic indicators were observed over three meters of vertical transport.

It is well known that the Preisach model is useful to approximate the effect of hysteresis behavior in smart materials, such as piezoactuators and Shape Memory Alloy(SMA) wire actuators. For tracking control, many researchers estimate a Preisach model and then compute its inverse model for hysteresis compensation. However, the inverse of its hysteresis behavior also shows hysteresis behavior. From this idea, the inverse model with Kransnoselskii-Pokrovskii(KP) model, a developed version of Preisach model, can be used directly for SMA position control and avoid the inverse operation. Also, we propose another method for the tracking control by approximating the inverse model using an orthogonal polynomial network. To estimate and update the weight parameters in both inverse models, a gradient-based learning algorithm is used. Finally, for the SMA position control, PID controller, adaptive controllers with KP model and adaptive nonlinear inverse model controller are compared experimentally.

Reconciling high-resolution geologic models to field production history is still a very time-consuming procedure. Recently streamline-based assisted and automatic history matching techniques, especially production data integration by “travel-time matching,” have shown great potential in this regard. But no systematic study was done to examine the merits of travel-time matching compared to more traditional amplitude matching for field-scale application. Besides, most applications were limited to two-phase water-oil flow because current streamline models are limited in their ability to incorporate highly compressible flow in a rigorous and computationally efficient manner. The purpose of this work is fourfold. First, we quantitatively investigated the nonlinearities in the inverse problems related to travel time, generalized travel time, and amplitude matching during production data integration and their impact on the solution and its convergence. Results show that the commonly used amplitude inversion can be orders of magnitude more nonlinear compared to the travel-time inversion. Both the travel-time and generalized travel time inversion (GTTI) are shown to be more robust and exhibit superior convergence characteristics. Second, the streamline-based assisted history matching was enhanced in two important aspects that significantly improve its efficiency and effectiveness. We utilize streamline-derived analytic sensitivities to determine the location and magnitude of the changes to improve the history match, and we use the iterative GTTI for model updating. Our approach leads to significant savings in time and manpower. Third, a novel approach to history matching finite-difference models that combines the efficiency of analytical sensitivity computation of the streamline models with the versatility of finite-difference simulation was developed. Use of finite-difference simulation can account for complex physics. Finally, we developed an approach to history matching three-phase flow using a novel compressible streamline formulation and streamline-derived analytic sensitivities. Streamline models were generalized to account for compressible flow by introducing a relative density of total fluids along streamlines and a density-dependent source term in the saturation equation. The analytical sensitivities are calculated based on the rigorous streamline formulation. The power and utility of our approaches have been demonstrated using both synthetic and field examples.

Knowledge of NOx (NO2 + NO) emissions is useful to understand processes affecting air quality and climate change. Emission inventories of surface NOx have high uncertainties. Satellite remote sensing has enabled measurements of trace gases in the atmosphere over a large regional and temporal scale. Inverse modeling of NO2 observations from satellites can be used to improve existing emissions inventories. This study seeks to understand the difference in two methods of inverse modeling: the mass balance approach and the adjoint approach using the GEOS-Chem chemical transport model and its adjoint. Using both synthetic satellite observations and those derived from the SCIAMACHY satellite instrument, this paper found that the performance of these two inversions was affected by pixel smearing and observational error. Smearing reduced the accuracy of the mass balance approach, while high observational error reduced the accuracy of the adjoint approach. However, both approaches improved the a priori emissions estimate.

No description available.

Seismic data have been established as a valuable source of information for the construction of reservoir simulation models, most commonly for determination of the modeled geologic structure, and also for population of static petrophysical properties (e.g. porosity, permeability). More recently, the availability of repeated seismic surveys over the time scale of years (i.e., 4D seismic) has shown promising results for the qualitative determination of changes in fluid phase distributions and pressure required for determination of areas of bypassed oil, swept volumes and pressure maintenance mechanisms. Quantitatively, and currently the state of the art in reservoir model characterization, 4D seismic data have proven distinctively useful for the calibration of geologic spatial variability which ultimately contributes to the improvement of reservoir development and management strategies. Among the limited variety of techniques for the integration of dynamic seismic data into reservoir models, streamline-based techniques have been demonstrated as one of the more efficient approaches as a result of their analytical sensitivity formulations. Although streamline techniques have been used in the past to integrate time-lapse seismic attributes, the applications were limited to the simplified modeling scenarios of two-phase fluid flow and invariant streamline geometry throughout the production schedule. This research builds upon and advances existing approaches to streamline-based seismic data integration for the inclusion of both production and seismic data under varying field conditions. The proposed approach integrates data from reservoirs under active reservoir management and the corresponding simulation models can be constrained using highly detailed or realistic schedules. Fundamentally, a new derivation of seismic sensitivities is proposed that is able to represent a complex reservoir evolution between consecutive seismic surveys. The approach is further extended to manage compositional reservoir simulation with dissolution effects and gravity-convective-driven flows which, in particular, are typical of CO2 transport behavior following injection into deep saline aquifers. As a final component of this research, the benefits of dynamic data integration on the determination of swept and drained volumes by injection and production, respectively, are investigated. Several synthetic and field reservoir modeling scenarios are used for an extensive demonstration of the efficacy and practical feasibility of the proposed developments.