Applications of capillary electrophoresis and mass spectrometry for the analysis of thiosalts

Thiosalt species are unstable, partially oxidized sulfur oxyanions formed in sulfur-rich environments but also during the flotation and milling of sulfidic minerals especially those containing pyrite (FeS₂) and pyrrhotite (Fe₍₁₋ₓ₎S, x = 0 to 0.2). Detecting and quantifying the major thiosalt species such as sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻), trithionate (S₃O₆²⁻), tetrathionate (S₄O₆²⁻) and higher polythionates (SₓO₆²⁻, where 3 ≤ x ≤ 10) in the milling process and in the treated tailings is important to understand how thiosalts are generated and provides insight into potential treatment. As these species are unstable, a fast and reliable analytical technique is required for their analysis. Three capillary zone electrophoresis (CZE) methods using indirect UV-vis detection were developed for the simultaneous separation and determination of five thiosalt anions: SO₄²⁻, S₂O₃²⁻, S₃O₆²⁻, S₄O₆²⁻ and S₅O₆²⁻. Both univariate and multivariate experimental design approaches were used to optimize the most critical factors (background electrolyte (BGE) and instrumental conditions) to achieve fast separation and quantitative analysis of the thiosalt species. The mathematically predicted responses for the multivariate experiments were in good agreement with the experimental results. Limits of detection (LODs) (S/N = 3) for the methods were between 0.09 and 0.34 μg/mL without a sample stacking technique and nearly four-fold increase in LODs with the application of field-amplified sample stacking. As direct analysis of thiosalts by mass spectrometry (MS) is limited by their low m/z values and detection in negative mode electrospray ionization (ESI), which is typically less sensitive than positive ESI, imidazolium-based (IP-L-Imid and IP-T-Imid) and phosphonium-based (IP-T-Phos) tricationic ion-pairing reagents were used to form stable high mass ions non-covalent +1 ion-pairs with these species for ESI-MS analysis and the association constants (Kassoc) determined for these ion-pairs. Kassoc values were between 6.85 × 10² M⁻¹ and 3.56 × 10⁵ M⁻¹ with the linear IP-L-Imid; 1.89 ×10³ M⁻¹ and 1.05 × 10⁵ M⁻¹ with the trigonal IP-T-Imid ion-pairs; and 7.51×10² M⁻¹ and 4.91× 10⁴ M⁻¹ with the trigonal IP-T-Phos ion-pairs. The highest formation constants were obtained for S₃O₆²⁻ and the imidazolium-based linear ion-pairing reagent (IP-L-Imid), whereas the lowest were for IP-L-Imid: SO₄²⁻ ion-pair.

Analysis of key predistribution schemes in wireless sensor networks

Combinatorial designs are used for designing key predistribution schemes that are applied to wireless sensor networks in communications. This helps in building a secure channel. Private-key cryptography helps to determine a common key between a pair of nodes in sensor networks. Wireless sensor networks using key predistribution schemes have many useful applications in military and civil operations. When designs are efficiently implemented on sensor networks, blocks with unique keys will be the result. One such implementation is a transversal design which follows the principle of simple key establishment. Analysis of designs and modeling the key schemes are the subjects of this project.

A postcolonial queer analysis of aboriginal queer clients' experiences of health care services in St. John's, Newfoundland

This thesis examines the gaps between health care services aimed at Aboriginal queer individuals living in St. John’s, Newfoundland and their health care needs. I used a multi-methods research design that includes interviews and demographic surveys, unobtrusive observation and qualitative content analysis. I conducted semi-structured interviews with institutional representatives from selected health related organizations – Eastern Health, Planned Parenthood Newfoundland and Labrador, the AIDS Committee of Newfoundland and Labrador, and St. John’s Native Friendship Center; as well as a transgender activist and three people who identify as Aboriginal and queer. I conducted observational research at two public seminars on Aboriginal people and health. Finally, I carried out qualitative content analysis of organizational reports and webpages of the selected community organizations. Using a postcolonial queer framework that analyzes how Newfoundland and Labrador’s colonial history is reflected in current health care realities I argue that the lack of appropriate services and culturally insensitive delivery of services reproduce the historical marginalization of an already vulnerable group.

An experimental geochemical characterization analysis of archaeological iron from the contact period of Newfoundland and Labrador

This research uses scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX) and inductively coupled plasma-mass spectrometry (ICP-MS) on cross-sections of iron artifacts sectioned from along shafts to determine the elemental constituents of a collection of Inuit and European artifacts from along the coast of Labrador. Hand-wrought iron nails from early historic period (16th – 18th centuries CE) Inuit sites in Labrador were originally manufactured by and acquired from early whalers and fishers of various European nationalities. The purpose of this research was to assess if the elements in different samples are sufficiently homogeneous to be viable for a provenience analysis to discern which Inuit nails were originally derived from which European groups; the Basque, English or French. The consistent relationships between the geochemical signatures of iron nails found in Inuit sites and historic nails derived from specific European groups could provide insights into the prevalence, activity and the nature of indigenous interactions of different European nationalities in the region over time. The results show that the methods applied to evaluate the geochemistry of the nails was not sufficient to detect meaningful patterns because the nails did not demonstrate the necessary degree of chemical uniformity among different samples in the same artifacts.

Dynamic fault tree analysis with PEWMA modeling of event rates and Bayesian updating of material balance parameters using MCMC

This research explores Bayesian updating as a tool for estimating parameters probabilistically by dynamic analysis of data sequences. Two distinct Bayesian updating methodologies are assessed. The first approach focuses on Bayesian updating of failure rates for primary events in fault trees. A Poisson Exponentially Moving Average (PEWMA) model is implemnented to carry out Bayesian updating of failure rates for individual primary events in the fault tree. To provide a basis for testing of the PEWMA model, a fault tree is developed based on the Texas City Refinery incident which occurred in 2005. A qualitative fault tree analysis is then carried out to obtain a logical expression for the top event. A dynamic Fault Tree analysis is carried out by evaluating the top event probability at each Bayesian updating step by Monte Carlo sampling from posterior failure rate distributions. It is demonstrated that PEWMA modeling is advantageous over conventional conjugate Poisson-Gamma updating techniques when failure data is collected over long time spans. The second approach focuses on Bayesian updating of parameters in non-linear forward models. Specifically, the technique is applied to the hydrocarbon material balance equation. In order to test the accuracy of the implemented Bayesian updating models, a synthetic data set is developed using the Eclipse reservoir simulator. Both structured grid and MCMC sampling based solution techniques are implemented and are shown to model the synthetic data set with good accuracy. Furthermore, a graphical analysis shows that the implemented MCMC model displays good convergence properties. A case study demonstrates that Likelihood variance affects the rate at which the posterior assimilates information from the measured data sequence. Error in the measured data significantly affects the accuracy of the posterior parameter distributions. Increasing the likelihood variance mitigates random measurement errors, but casuses the overall variance of the posterior to increase. Bayesian updating is shown to be advantageous over deterministic regression techniques as it allows for incorporation of prior belief and full modeling uncertainty over the parameter ranges. As such, the Bayesian approach to estimation of parameters in the material balance equation shows utility for incorporation into reservoir engineering workflows.

Integrated sensitivity analysis, calibration, and uncertainty propagation analysis approaches for supporting hydrological modeling

The successful performance of a hydrological model is usually challenged by the quality of the sensitivity analysis, calibration and uncertainty analysis carried out in the modeling exercise and subsequent simulation results. This is especially important under changing climatic conditions where there are more uncertainties associated with climate models and downscaling processes that increase the complexities of the hydrological modeling system. In response to these challenges and to improve the performance of the hydrological models under changing climatic conditions, this research proposed five new methods for supporting hydrological modeling. First, a design of experiment aided sensitivity analysis and parameterization (DOE-SAP) method was proposed to investigate the significant parameters and provide more reliable sensitivity analysis for improving parameterization during hydrological modeling. The better calibration results along with the advanced sensitivity analysis for significant parameters and their interactions were achieved in the case study. Second, a comprehensive uncertainty evaluation scheme was developed to evaluate three uncertainty analysis methods, the sequential uncertainty fitting version 2 (SUFI-2), generalized likelihood uncertainty estimation (GLUE) and Parameter solution (ParaSol) methods. The results showed that the SUFI-2 performed better than the other two methods based on calibration and uncertainty analysis results. The proposed evaluation scheme demonstrated that it is capable of selecting the most suitable uncertainty method for case studies. Third, a novel sequential multi-criteria based calibration and uncertainty analysis (SMC-CUA) method was proposed to improve the efficiency of calibration and uncertainty analysis and control the phenomenon of equifinality. The results showed that the SMC-CUA method was able to provide better uncertainty analysis results with high computational efficiency compared to the SUFI-2 and GLUE methods and control parameter uncertainty and the equifinality effect without sacrificing simulation performance. Fourth, an innovative response based statistical evaluation method (RESEM) was proposed for estimating the uncertainty propagated effects and providing long-term prediction for hydrological responses under changing climatic conditions. By using RESEM, the uncertainty propagated from statistical downscaling to hydrological modeling can be evaluated. Fifth, an integrated simulation-based evaluation system for uncertainty propagation analysis (ISES-UPA) was proposed for investigating the effects and contributions of different uncertainty components to the total propagated uncertainty from statistical downscaling. Using ISES-UPA, the uncertainty from statistical downscaling, uncertainty from hydrological modeling, and the total uncertainty from two uncertainty sources can be compared and quantified. The feasibility of all the methods has been tested using hypothetical and real-world case studies. The proposed methods can also be integrated as a hydrological modeling system to better support hydrological studies under changing climatic conditions. The results from the proposed integrated hydrological modeling system can be used as scientific references for decision makers to reduce the potential risk of damages caused by extreme events for long-term water resource management and planning.

Regional flood frequency analysis for Newfoundland and Labrador using the L-Moments index-flood method

The L-moments based index-flood procedure had been successfully applied for Regional Flood Frequency Analysis (RFFA) for the Island of Newfoundland in 2002 using data up to 1998. This thesis, however, considered both Labrador and the Island of Newfoundland using the L-Moments index-flood method with flood data up to 2013. For Labrador, the homogeneity test showed that Labrador can be treated as a single homogeneous region and the generalized extreme value (GEV) was found to be more robust than any other frequency distributions. The drainage area (DA) is the only significant variable for estimating the index-flood at ungauged sites in Labrador. In previous studies, the Island of Newfoundland has been considered as four homogeneous regions (A,B,C and D) as well as two Water Survey of Canada's Y and Z sub-regions. Homogeneous regions based on Y and Z was found to provide more accurate quantile estimates than those based on four homogeneous regions. Goodness-of-fit test results showed that the generalized extreme value (GEV) distribution is most suitable for the sub-regions; however, the three-parameter lognormal (LN3) gave a better performance in terms of robustness. The best fitting regional frequency distribution from 2002 has now been updated with the latest flood data, but quantile estimates with the new data were not very different from the previous study. Overall, in terms of quantile estimation, in both Labrador and the Island of Newfoundland, the index-flood procedure based on L-moments is highly recommended as it provided consistent and more accurate result than other techniques such as the regression on quantile technique that is currently used by the government.

Active suspension development based on energy analysis

This research focuses on developing active suspension optimal controllers for two linear and non-linear half-car models. A detailed comparison between quarter-car and half-car active suspension approaches is provided for improving two important scenarios in vehicle dynamics, i.e. ride quality and road holding. Having used a half-car vehicle model, heave and pitch motion are analyzed for those scenarios, with cargo mass as a variable. The governing equations of the system are analysed in a multi-energy domain package, i.e., 20-Sim. System equations are presented in the bond-graph language to facilitate calculation of energy usage. The results present optimum set of gains for both ride quality and road holding scenarios are the gains which has derived when maximum allowable cargo mass is considered for the vehicle. The energy implications of substituting passive suspension units with active ones are studied by considering not only the energy used by the actuator, but also the reduction in energy lost through the passive damper. Energy analysis showed less energy was dissipated in shock absorbers when either quarter-car or half-car controllers were used instead of passive suspension. It was seen that more energy could be saved by using half-car active controllers than the quarter-car ones. Results also proved that using active suspension units, whether quarter-car or half-car based, under those realistic limitations is energy-efficient and suggested.

Analysis of bio-derived platform chemicals in ionic liquid media by desorption/ionization mass spectrometry

In this work, desorption/ionization mass spectrometry was employed for the analysis of sugars and small platform chemicals that are common intermediates in biomass transformation reactions. Specifically, matrix-assisted laser desorption/ionization (MALDI) and desorption electrospray ionization (DESI) mass spectrometric techniques were employed as alternatives to traditional chromatographic methods. Ionic liquid matrices (ILMs) were designed based on traditional solid MALDI matrices (2,5-dihydroxybenzoic acid (DHB) and α-cyano-4-hydroxycinnamic acid (CHCA)) and 1,3-dialkylimidazolium ionic liquids ([BMIM]Cl, [EMIM]Cl, and [EMIM]OAc) that have been employed as reaction media for biomass transformation reactions such as the conversion of carbohydrates to valuable platform chemicals. Although two new ILMs were synthesized ([EMIM][DHB] and [EMIM][CHCA] from [EMIM]OAc), chloride-containing ILs did not react with matrices and resulted in mixtures of IL and matrix in solution. Compared to the parent solid matrices, much less matrix interference was observed in the low mass region of the mass spectrum (< 500 Da) using each of the IL-matrices. Furthermore, the formation of a true ILM (i.e. a new ion pair) does not appear to be necessary for analyte ionization. MALDI sample preparation techniques were optimized based on the compatibility with analyte, IL and matrix. ILMs and IL-matrix mixtures of DHB allowed for qualitative analysis of glucose, fructose, sucrose and N-acetyl-D-glucosamine. Analogous CHCA-containing ILMs did not result in appreciable analyte signals under similar conditions. Small platform compounds such as 5-hydroxymethylfurfural (HMF) and levulinic acid were not detected by direct analysis using MALDI-MS. Furthermore, sugar analyte signals were only detected at relatively high matrix:IL:analyte ratios (1:1:1) due to significant matrix and analyte suppression by the IL ions. Therefore, chemical modification of analytes with glycidyltrimethylammonium chloride (GTMA) was employed to extend this method to quantitative applications. Derivatization was accomplished in aqueous IL solutions with fair reaction efficiencies (36.9 – 48.4 % glucose conversion). Calibration curves of derivatized glucose-GTMA yielded good linearity in all solvent systems tested, with decreased % RSDs of analyte ion signals in IL solutions as compared to purely aqueous systems (1.2 – 7.2 % and 4.2 – 8.7 %, respectively). Derivatization resulted in a substantial increase in sensitivity for MALDI-MS analyses: glucose was reliably detected at IL:analyte ratios of 100:1 (as compared to 1:1 prior to derivatization). Screening of all test analytes resulted in appreciable analyte signals in MALDI-MS spectra, including both HMF and levulinic acid. Using appropriate internal standards, calibration curves were constructed and this method was employed for monitoring a model dehydration reaction of fructose to HMF in [BMIM]Cl. Calibration curves showed wide dynamic ranges (LOD – 100 ng fructose/μg [BMIM]Cl, LOD – 75 ng HMF/μg [BMIM]Cl) with correlation coefficients of 0.9973 (fructose) and 0.9931 (HMF). LODs were estimated from the calibration data to be 7.2 ng fructose/μg [BMIM]Cl and 7.5 ng HMF/μg [BMIM]Cl, however relatively high S/N ratios at these concentrations indicate that these values are likely overestimated. Application of this method allowed for the rapid acquisition of quantitative data without the need for prior separation of analyte and IL. Finally, small molecule platform chemicals HMF and levulinic acid were qualitatively analyzed by DESI-MS. Both HMF and levulinic acid were easily ionized and the corresponding molecular ions were easily detected in the presence of 10 – 100 times IL, without the need for chemical modification prior to analysis. DESI-MS analysis of ILs in positive and negative ion modes resulted in few ions in the low mass region, showing great potential for the analysis of small molecules in IL media.

Advanced thermal analysis of microelectronics using spreading resistance models

Thermal analysis of electronic devices is one of the most important steps for designing of modern devices. Precise thermal analysis is essential for designing an effective thermal management system of modern electronic devices such as batteries, LEDs, microelectronics, ICs, circuit boards, semiconductors and heat spreaders. For having a precise thermal analysis, the temperature profile and thermal spreading resistance of the device should be calculated by considering the geometry, property and boundary conditions. Thermal spreading resistance occurs when heat enters through a portion of a surface and flows by conduction. It is the primary source of thermal resistance when heat flows from a tiny heat source to a thin and wide heat spreader. In this thesis, analytical models for modeling the temperature behavior and thermal resistance in some common geometries of microelectronic devices such as heat channels and heat tubes are investigated. Different boundary conditions for the system are considered. Along the source plane, a combination of discretely specified heat flux, specified temperatures and adiabatic condition are studied. Along the walls of the system, adiabatic or convective cooling boundary conditions are assumed. Along the sink plane, convective cooling with constant or variable heat transfer coefficient are considered. Also, the effect of orthotropic properties is discussed. This thesis contains nine chapters. Chapter one is the introduction and shows the concepts of thermal spreading resistance besides the originality and importance of the work. Chapter two reviews the literatures on the thermal spreading resistance in the past fifty years with a focus on the recent advances. In chapters three and four, thermal resistance of a twodimensional flux channel with non-uniform convection coefficient in the heat sink plane is studied. The non-uniform convection is modeled by using two functions than can simulate a wide variety of different heat sink configurations. In chapter five, a non-symmetrical flux channel with different heat transfer coefficient along the right and left edges and sink plane is analytically modeled. Due to the edge cooling and non-symmetry, the eigenvalues of the system are defined using the heat transfer coefficient on both edges and for satisfying the orthogonality condition, a normalized function is calculated. In chapter six, thermal behavior of two-dimensional rectangular flux channel with arbitrary boundary conditions on the source plane is presented. The boundary condition along the source plane can be a combination of the first kind boundary condition (Dirichlet or prescribed temperature) and the second kind boundary condition (Neumann or prescribed heat flux). The proposed solution can be used for modeling the flux channels with numerous different source plane boundary conditions without any limitations in the number and position of heat sources. In chapter seven, temperature profile of a circular flux tube with discretely specified boundary conditions along the source plane is presented. Also, the effect of orthotropic properties are discussed. In chapter 8, a three-dimensional rectangular flux channel with a non-uniform heat convection along the heat sink plane is analytically modeled. In chapter nine, a summary of the achievements is presented and some systems are proposed for the future studies. It is worth mentioning that all the models and case studies in the thesis are compared with the Finite Element Method (FEM).

Dynamic safety analysis of managed pressure drilling operations

The exploration and development of oil and gas reserves located in harsh offshore environments are characterized with high risk. Some of these reserves would be uneconomical if produced using conventional drilling technology due to increased drilling problems and prolonged non-productive time. Seeking new ways to reduce drilling cost and minimize risks has led to the development of Managed Pressure Drilling techniques. Managed pressure drilling methods address the drawbacks of conventional overbalanced and underbalanced drilling techniques. As managed pressure drilling techniques are evolving, there are many unanswered questions related to safety and operating pressure regimes. Quantitative risk assessment techniques are often used to answer these questions. Quantitative risk assessment is conducted for the various stages of drilling operations – drilling ahead, tripping operation, casing and cementing. A diagnostic model for analyzing the rotating control device, the main component of managed pressure drilling techniques, is also studied. The logic concept of Noisy-OR is explored to capture the unique relationship between casing and cementing operations in leading to well integrity failure as well as its usage to model the critical components of constant bottom-hole pressure drilling technique of managed pressure drilling during tripping operation. Relevant safety functions and inherent safety principles are utilized to improve well integrity operations. Loss function modelling approach to enable dynamic consequence analysis is adopted to study blowout risk for real-time decision making. The aggregation of the blowout loss categories, comprising: production, asset, human health, environmental response and reputation losses leads to risk estimation using dynamically determined probability of occurrence. Lastly, various sub-models developed for the stages/sub-operations of drilling operations and the consequence modelling approach are integrated for a holistic risk analysis of drilling operations.

Performing "Up The Shore": a stylistic analysis of Newfoundland Irish English vowels in the Ferryland dinner theatre

This study is a variationist sociolinguistic analysis of two speech styles, performance and interview, of a dinner theatre troupe in Ferryland on the Southern Shore of Newfoundland. Five actors and ten of their characters are analyzed to test if their vowels change across styles. The study adopts a variationist framework with a Community of Practice model, drawing on Bell’s audience and referee design to argue that the performers’ stage conventions and identity construction are influenced by a third person referee: the Idealized Authentic Newfoundlander (IAN). Under this view the goal of the performer is to both communicate with and entertain the audience, which requires different tactics when speaking. These tactics manifest phonetically and are discussed in a quantitative, statistical analysis of the acoustic measurements of the vowel tokens [variables FACE, KIT, LOT/PALM and GOAT lexical sets with Newfoundland Irish English (NIE) variants] and a qualitative discussion.

The mosses of Terra Nova National Park, Eastern Newfoundland, a bryofloristic analysis and interpretation

The known moss flora of Terra Nova National Park, eastern Newfoundland, comp~ises 210 species. Eighty-two percent of the moss species occurring in Terra Nova are widespread or widespread-sporadic in Newfoundland. Other Newfoundland distributional elements present in the Terra Nova moss flora are the northwestern, southern, southeastern, and disjunct elements, but four of the mosses occurring in Terra Nova appear to belong to a previously unrecognized northeastern element of the Newfoundland flora. The majority (70.9%) of Terra Nova's mosses are of boreal affinity and are widely distributed in the North American coniferous forest belt. An additional 10.5 percent of the Terra Nova mosses are cosmopolitan while 9.5 percent are temperate and 4.8 percent are arctic-montane species. The remaining 4.3 percent of the mosses are of montane affinity, and disjunct between eastern and western North America. In Terra Nova, temperate species at their northern limit are concentrated in balsam fir stands, while arctic-montane species are restricted to exposed cliffs, scree slopes, and coastal exposures. Montane species are largely confined to exposed or freshwater habitats. Inability to tolerate high summer temperatures limits the distributions of both arctic-montane and montane species. In Terra Nova, species of differing phytogeographic affinities co-occur on cliffs and scree slopes. The microhabitat relationships of five selected species from such habitats were evaluated by Discriminant Functions Analysis and Multiple Regression Analysis. The five mosses have distinct and different microhabitats on cliffs and scree slopes in Terra Nova, and abundance of all but one is associated with variation in at least one microhabitat variable. Micro-distribution of Grimmia torquata, an arctic-montane species at its southern limit, appears to be deterJ]lined by sensitivity to high summer temperatures. Both southern mosses at their northern limit (Aulacomnium androgynum, Isothecium myosuroides) appear to be limited by water availability and, possibly, by low winter temperatures. The two species whose distributions extend both north and south or the study area (Encalypta procera, Eurhynchium pulchellum) show no clear relationship with microclimate. Dispersal factors have played a significant role in the development of the Terra Nova moss flora. Compared to the most likely colonizing source (i .e. the rest of the island of Newfoundland), species with small diaspores have colonized the study area to a proportionately much greater extent than have species with large diaspores. Hierarchical log-linear analysis indicates that this is so for all affinity groups present in Terra Nova. The apparent dispersal effects emphasize the comparatively recent glaciation of the area, and may also have been enhanced by anthropogenic influences. The restriction of some species to specific habitats, or to narrowly defined microhabitats, appears to strengthen selection for easily dispersed taxa.