Experimental analysis of soil and dust stabilizers for controlling displacement of contaminated soils by wind tunnel experiments

During the remediation of burial grounds at the US Department of Energy's (DOE's) Hanford Site in Washington State, the dispersion of contaminated soil particles and dust is an issue that is faced by site workers on a daily basis. This contamination problem is even more of a concern when one takes into account the semi-arid characteristics of the region where the site is located. To mitigate this problem, workers at the site use a variety of engineered methods to minimize the dispersion of contaminated soil and dust (i.e. use of water and/or suppression agents that stabilizes the soil prior to soil excavation, segregation, and removal activities). A primary contributor to the dispersion of contaminated soil and dust is wind soil erosion. The erosion process occurs when the wind speed exceeds a certain threshold value which depends on a number of factors including wind force loading, particle size, surface soil moisture, and the geometry of the soil. Thus under these circumstances, the mobility of contaminated soil and generation and dispersion of particulate matter are significantly influenced by these parameters. This dependence of soil and dust movement on threshold shear velocity, fixative dilution and/or application rates, soil moisture content, and soil geometry were studied for Hanford's sandy soil through a series of wind tunnel experiments, laboratory experiments and theoretical analysis. In addition, the behavior of plutonium (Pu) powder contamination in the soil was studied by introducing a Pu simulant (cerium oxide). The results showed that soil dispersion and PM10 concentrations decreased with increasing soil moisture. Also, it was shown that the mobility of the soil was affected by increasing wind velocity. It was demonstrated that the use of fixative products greatly decreased the amount of soil and PM10 concentrations when exposed to varying wind conditions. In addition, it was shown that geometry of the soil sample affected the velocity profile and calculation of roughness surface coefficient when comparing round and flat soil samples. Finally, threshold shear velocities were calculated for soil with flat surface and their dependency on surface soil moisture was demonstrated. A theoretical framework was developed to explain these dependencies.

Weak strangeness changing semi-leptonic process

We have obtained total and differential cross sections for the strangeness changing charged current weak reaction ν L + p → Λ(Σ0) + L+ using standard dipole form factors, where L stands for an electron, muon, or tau lepton, and L + stands for an positron, anti-muon or anti-tau lepton. We calculated these reactions from near threshold few hundred MeV to 8 GeV of incoming neutrino energy and obtained the contributions of the various form factors to the total and differential cross sections. We did this in support of possible experiments which might be carried out by the MINERνA collaboration at Fermilab. The calculation is phenomenologically based and makes use of SU(3) relations to obtain the standard vector current form factors and data from Λ beta decay to obtain the axial current form factor. We also made estimates for the contributions of the pseudoscalar form factor and for the F E and FS form factors to the total and differential cross sections. We discuss our results and consider under what circumstances we might extract the various form factors. In particular we wish to test the SU(3) assumptions made in determining all the form factors over a range of q2 values. Recently new form factors were obtained from recoil proton measurements in electron-proton electromagnetic scattering at Jefferson Lab. We thus calculated the contributions of the individual form factors to the total and differential cross sections for this new set of form factors. We found that the differential and total cross sections for Λ production change only slightly between the two sets of form factors but that the differential and total cross sections change substantially for Σ 0 production. We discuss the possibility of distinguishing between the two cases for the experiments planned by the MINERνA Collaboration. We also undertook the calculation for the inverse reaction e − + p → Λ + νe for a polarized outgoing Λ which might be performed at Jefferson Lab, and provided additional analysis of the contributions of the individual form factors to the differential cross sections for this case. ^

Headspace analysis of smokeless powders: Development of mass calibration methods using microdrop printing for chromatographic and ion mobility spectrometric detection

Smokeless powder additives are usually detected by their extraction from post-blast residues or unburned powder particles followed by analysis using chromatographic techniques. This work presents the first comprehensive study of the detection of the volatile and semi-volatile additives of smokeless powders using solid phase microextraction (SPME) as a sampling and pre-concentration technique. Seventy smokeless powders were studied using laboratory based chromatography techniques and a field deployable ion mobility spectrometer (IMS). The detection of diphenylamine, ethyl and methyl centralite, 2,4-dinitrotoluene, diethyl and dibutyl phthalate by IMS to associate the presence of these compounds to smokeless powders is also reported for the first time. A previously reported SPME-IMS analytical approach facilitates rapid sub-nanogram detection of the vapor phase components of smokeless powders. A mass calibration procedure for the analytical techniques used in this study was developed. Precise and accurate mass delivery of analytes in picoliter volumes was achieved using a drop-on-demand inkjet printing method. Absolute mass detection limits determined using this method for the various analytes of interest ranged between 0.03–0.8 ng for the GC-MS and between 0.03–2 ng for the IMS. Mass response graphs generated for different detection techniques help in the determination of mass extracted from the headspace of each smokeless powder. The analyte mass present in the vapor phase was sufficient for a SPME fiber to extract most analytes at amounts above the detection limits of both chromatographic techniques and the ion mobility spectrometer. Analysis of the large number of smokeless powders revealed that diphenylamine was present in the headspace of 96% of the powders. Ethyl centralite was detected in 47% of the powders and 8% of the powders had methyl centralite available for detection from the headspace sampling of the powders by SPME. Nitroglycerin was the dominant peak present in the headspace of the double-based powders. 2,4-dinitrotoluene which is another important headspace component was detected in 44% of the powders. The powders therefore have more than one headspace component and the detection of a combination of these compounds is achievable by SPME-IMS leading to an association to the presence of smokeless powders.

Three essays on a longitudinal analysis of business start-ups using the Kauffman Firm Survey

This dissertation focused on the longitudinal analysis of business start-ups using three waves of data from the Kauffman Firm Survey. ^ The first essay used the data from years 2004-2008, and examined the simultaneous relationship between a firm's capital structure, human resource policies, and its impact on the level of innovation. The firm leverage was calculated as, debt divided by total financial resources. Index of employee well-being was determined by a set of nine dichotomous questions asked in the survey. A negative binomial fixed effects model was used to analyze the effect of employee well-being and leverage on the count data of patents and copyrights, which were used as a proxy for innovation. The paper demonstrated that employee well-being positively affects the firm's innovation, while a higher leverage ratio had a negative impact on the innovation. No significant relation was found between leverage and employee well-being.^ The second essay used the data from years 2004-2009, and inquired whether a higher entrepreneurial speed of learning is desirable, and whether there is a linkage between the speed of learning and growth rate of the firm. The change in the speed of learning was measured using a pooled OLS estimator in repeated cross-sections. There was evidence of a declining speed of learning over time, and it was concluded that a higher speed of learning is not necessarily a good thing, because speed of learning is contingent on the entrepreneur's initial knowledge, and the precision of the signals he receives from the market. Also, there was no reason to expect speed of learning to be related to the growth of the firm in one direction over another.^ The third essay used the data from years 2004-2010, and determined the timing of diversification activities by the business start-ups. It captured when a start-up diversified for the first time, and explored the association between an early diversification strategy adopted by a firm, and its survival rate. A semi-parametric Cox proportional hazard model was used to examine the survival pattern. The results demonstrated that firms diversifying at an early stage in their lives show a higher survival rate; however, this effect fades over time.^

Headspace Analysis of Smokeless Powders: Development of Mass Calibration Methods using Microdrop Printing for Chromatographic and Ion Mobility Spectrometric Detection

Smokeless powder additives are usually detected by their extraction from post-blast residues or unburned powder particles followed by analysis using chromatographic techniques. This work presents the first comprehensive study of the detection of the volatile and semi-volatile additives of smokeless powders using solid phase microextraction (SPME) as a sampling and pre-concentration technique. Seventy smokeless powders were studied using laboratory based chromatography techniques and a field deployable ion mobility spectrometer (IMS). The detection of diphenylamine, ethyl and methyl centralite, 2,4-dinitrotoluene, diethyl and dibutyl phthalate by IMS to associate the presence of these compounds to smokeless powders is also reported for the first time. A previously reported SPME-IMS analytical approach facilitates rapid sub-nanogram detection of the vapor phase components of smokeless powders. A mass calibration procedure for the analytical techniques used in this study was developed. Precise and accurate mass delivery of analytes in picoliter volumes was achieved using a drop-on-demand inkjet printing method. Absolute mass detection limits determined using this method for the various analytes of interest ranged between 0.03 - 0.8 ng for the GC-MS and between 0.03 - 2 ng for the IMS. Mass response graphs generated for different detection techniques help in the determination of mass extracted from the headspace of each smokeless powder. The analyte mass present in the vapor phase was sufficient for a SPME fiber to extract most analytes at amounts above the detection limits of both chromatographic techniques and the ion mobility spectrometer. Analysis of the large number of smokeless powders revealed that diphenylamine was present in the headspace of 96% of the powders. Ethyl centralite was detected in 47% of the powders and 8% of the powders had methyl centralite available for detection from the headspace sampling of the powders by SPME. Nitroglycerin was the dominant peak present in the headspace of the double-based powders. 2,4-dinitrotoluene which is another important headspace component was detected in 44% of the powders. The powders therefore have more than one headspace component and the detection of a combination of these compounds is achievable by SPME-IMS leading to an association to the presence of smokeless powders.

Estudo de famílias wavelets para aplicação na análise em DOAS

Trace gases are important to our environment even though their presence comes only by ‘traces’, but their concentrations must be monitored, so any necessary interventions can be done at the right time. There are some lower and upper boundaries which produce nice conditions for our lives and then monitoring trace gases comes as an essential task nowadays to be accomplished by many techniques. One of them is the differential optical absorption spectroscopy (DOAS), which consists mathematically on a regression - the classical method uses least-squares - to retrieve the trace gases concentrations. In order to achieve better results, many works have tried out different techniques instead of the classical approach. Some have tried to preprocess the signals to be analyzed by a denoising procedure - e.g. discrete wavelet transform (DWT). This work presents a semi-empirical study to find out the most suitable DWT family to be used in this denoising. The search seeks among many well-known families the one to better remove the noise, keeping the original signal’s main features, then by decreasing the noise, the residual left after the regression is done decreases too. The analysis take account the wavelet decomposition level, the threshold to be applied on the detail coefficients and how to apply them - hard or soft thresholding. The signals used come from an open and online data base which contains characteristic signals from some trace gases usually studied.

Estudo de famílias wavelets para aplicação na análise em DOAS

Trace gases are important to our environment even though their presence comes only by ‘traces’, but their concentrations must be monitored, so any necessary interventions can be done at the right time. There are some lower and upper boundaries which produce nice conditions for our lives and then monitoring trace gases comes as an essential task nowadays to be accomplished by many techniques. One of them is the differential optical absorption spectroscopy (DOAS), which consists mathematically on a regression - the classical method uses least-squares - to retrieve the trace gases concentrations. In order to achieve better results, many works have tried out different techniques instead of the classical approach. Some have tried to preprocess the signals to be analyzed by a denoising procedure - e.g. discrete wavelet transform (DWT). This work presents a semi-empirical study to find out the most suitable DWT family to be used in this denoising. The search seeks among many well-known families the one to better remove the noise, keeping the original signal’s main features, then by decreasing the noise, the residual left after the regression is done decreases too. The analysis take account the wavelet decomposition level, the threshold to be applied on the detail coefficients and how to apply them - hard or soft thresholding. The signals used come from an open and online data base which contains characteristic signals from some trace gases usually studied.

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.

Semi-engineered earthquake-resistant structures: one-storey buildings built up with gabion-box walls

This thesis studies the static and seismic behavior of simple structures made with gabion box walls. The analysis was performed considering a one-story building with standard dimensions in plan (6m x 5m) and a lightweight timber roof. The main focus of the present investigation is to find the principals aspects of the seismic behavior of a one story building made with gabion box walls, in order to prevent a failure due to seismic actions and in this way help to reduce the seismic risk of developing countries where this natural disaster have a significant intensity. Regarding the gabion box wall, it has been performed some calculations and analysis in order to understand the static and dynamic behavior. From the static point of view, it has been performed a verification of the normal stress computing the normal stress that arrives at the base of the gabion wall and the corresponding capacity of the ground. Moreover, regarding the seismic analysis, it has been studied the in-plane and out-of-plane behavior. The most critical aspect was discovered to be the out-of-plane behavior, for which have been developed models considering the “rigid- no tension model” for masonry, finding a kinematically admissible multiplier that will create a collapse mechanism for the structure. Furthermore, it has been performed a FEM and DEM models to find the maximum displacement at the center of the wall, maximum tension stresses needed for calculating the steel connectors for joining consecutive gabions and the dimensions (length of the wall and distance between orthogonal walls or buttresses) of a geometrical configuration for the standard modulus of the structure, in order to ensure an adequate safety margin for earthquakes with a PGA around 0.4-0.5g. Using the results obtained before, it has been created some rules of thumb, that have to be satisfy in order to ensure a good behavior of these structure.

Structural Analysis and Form-Finding of Mycelium-Based Monolithic Domes

As sustainability becomes an integral design driver for current civil structures, new materials and forms are investigated. The aim of this study is to investigate analytically and numerically the mechanical behavior of monolithic domes composed of mycological fungi. The study focuses on hemispherical and elliptical forms, as the most typical solution for domes. The influence of different types of loading, geometrical parameters, material properties and boundary conditions is investigated in this study. For the cases covered by the classical shell theory, a comparison between the analytical and the finite element solution is given. Two case studies regarding the dome of basilica of “San Luca” (Bologna, Italy) and the dome of sanctuary of “Vicoforte” (Vicoforte, Italy) are included. After the linear analysis under loading, buckling is also investigated as a critical type of failure through a parametric study using finite elements model. Since shells rely on their shape, form-found domes are also investigated and a comparison between the behavior of the form-found domes and the hemispherical domes under the linear and buckling analysis is conducted. From the analysis it emerges that form-finding can enhance the structural response of mycelium-based domes, although buckling becomes even more critical for their design. Furthermore, an optimal height to span ratio for the buckling of form-found domes is identified. This study highlights the importance of investigating appropriate forms for the design of novel biomaterial-based structures.

Converging evidence that common timing processes underlie temporal-order and simultaneity judgments: a model-based analysis

Perception of simultaneity and temporal order is studied with simultaneity judgment (SJ) and temporal-order judgment (TOJ) tasks. In the former, observers report whether presentation of two stimuli was subjectively simultaneous; in the latter, they report which stimulus was subjectively presented first. SJ and TOJ tasks typically give discrepant results, which has prompted the view that performance is mediated by different processes in each task. We looked at these discrepancies from a model that yields psychometric functions whose parameters characterize the timing, decisional, and response processes involved in SJ and TOJ tasks. We analyzed 12 data sets from published studies in which both tasks had been used in within-subjects designs, all of which had reported differences in performance across tasks. Fitting the model jointly to data from both tasks, we tested the hypothesis that common timing processes sustain simultaneity and temporal order judgments, with differences in performance arising from task-dependent decisional and response processes. The results supported this hypothesis, also showing that model psychometric functions account for aspects of SJ and TOJ data that classical analyses overlook. Implications for research on perception of simultaneity and temporal order are discussed.

Content-aware compression for big textual data analysis

A substantial amount of information on the Internet is present in the form of text. The value of this semi-structured and unstructured data has been widely acknowledged, with consequent scientific and commercial exploitation. The ever-increasing data production, however, pushes data analytic platforms to their limit. This thesis proposes techniques for more efficient textual big data analysis suitable for the Hadoop analytic platform. This research explores the direct processing of compressed textual data. The focus is on developing novel compression methods with a number of desirable properties to support text-based big data analysis in distributed environments. The novel contributions of this work include the following. Firstly, a Content-aware Partial Compression (CaPC) scheme is developed. CaPC makes a distinction between informational and functional content in which only the informational content is compressed. Thus, the compressed data is made transparent to existing software libraries which often rely on functional content to work. Secondly, a context-free bit-oriented compression scheme (Approximated Huffman Compression) based on the Huffman algorithm is developed. This uses a hybrid data structure that allows pattern searching in compressed data in linear time. Thirdly, several modern compression schemes have been extended so that the compressed data can be safely split with respect to logical data records in distributed file systems. Furthermore, an innovative two layer compression architecture is used, in which each compression layer is appropriate for the corresponding stage of data processing. Peripheral libraries are developed that seamlessly link the proposed compression schemes to existing analytic platforms and computational frameworks, and also make the use of the compressed data transparent to developers. The compression schemes have been evaluated for a number of standard MapReduce analysis tasks using a collection of real-world datasets. In comparison with existing solutions, they have shown substantial improvement in performance and significant reduction in system resource requirements.

Forces of agglomeration and dispersal in rural business networks: a social network analysis

Two concepts in rural economic development policy have been the focus of much research and policy action: the identification and support of clusters or networks of firms and the availability and adoption by rural businesses of Information and Communication Technologies (ICT). From a theoretical viewpoint these policies are based on two contrasting models, with clustering seen as a process of economic agglomeration, and ICT-mediated communication as a means of facilitating economic dispersion. The study’s conceptual framework is based on four interrelated elements: location, interaction, knowledge, and advantage, together with the concept of networks which is employed as an operationally and theoretically unifying concept. The research questions are developed in four successive categories: Policy, Theory, Networks, and Method. The questions are approached using a study of two contrasting groups of rural small businesses in West Cork, Ireland: (a) Speciality Foods, and (b) firms in Digital Products and Services. The study combines Social Network Analysis (SNA) with Qualitative Thematic Analysis, using data collected from semi-structured interviews with 58 owners or managers of these businesses. Data comprise relational network data on the firms’ connections to suppliers, customers, allies and competitors, together with linked qualitative data on how the firms established connections, and how tacit and codified knowledge was sourced and utilised. The research finds that the key characteristics identified in the cluster literature are evident in the sample of Speciality Food businesses, in relation to flows of tacit knowledge, social embedding, and the development of forms of social capital. In particular the research identified the presence of two distinct forms of collective social capital in this network, termed “community” and “reputation”. By contrast the sample of Digital Products and Services businesses does not have the form of a cluster, but matches more closely to dispersive models, or “chain” structures. Much of the economic and social structure of this set of firms is best explained in terms of “project organisation”, and by the operation of an individual rather than collective form of “reputation”. The rural setting in which these firms are located has resulted in their being service-centric, and consequently they rely on ICT-mediated communication in order to exchange tacit knowledge “at a distance”. It is this factor, rather than inputs of codified knowledge, that most strongly influences their operation and their need for availability and adoption of high quality communication technologies. Thus the findings have applicability in relation to theory in Economic Geography and to policy and practice in Rural Development. In addition the research contributes to methodological questions in SNA, and to methodological questions about the combination or mixing of quantitative and qualitative methods.

Développement et caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque

Ce projet de recherche mené en collaboration industrielle avec St-Jean Photochimie Inc. / PCAS Canada vise le développement et la caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque. La quête du récoltage des photons se situant dans le proche-infrarouge a été au centre des modifications structurales explorées afin d’augmenter l’efficacité de conversion des cellules solaires de type organique et à pigments photosensibles. Trois familles de composés intégrant le motif dipyrrométhène ont été synthétisées et caractérisées du point de vue spectroscopique, électrochimique, structural ainsi que par modélisation moléculaire afin d’établir des relations structures-propriétés. La première famille comporte six azadipyrrométhènes au potentiel de coordination tétradentate sur des centres métalliques. Le développement d’une nouvelle voie synthétique asymétrique combinée à l’utilisation d’une voie symétrique classique ont permis d’obtenir l’ensemble des combinaisons de substituants possibles sur les aryles proximaux incluant les noyaux 2-hydroxyphényle, 2-méthoxyphényle et 2- pyridyle. La modulation du maximum d’absorption dans le rouge a pu être faite entre 598 et 619 nm. De même, la présence de groupements méthoxyle ou hydroxyle augmente l’absorption dans le violet (~410 nm) tel que démontré par modélisation. La caractérisation électrochimique a montré que les dérivés tétradentates étaient en général moins stables aux processus redox que leur contre-parti bidentate. La deuxième famille comporte dix dérivés BODIPY fusionnés de façon asymétrique en position [b]. L’aryle proximal a été modifié de façon systématique afin de mieux comprendre l’impact des substituents riches en électron et de la fusion de cycles aromatiques. De plus, ces dérivés ont été mis en relation avec une vaste série de composés analogues. Les résultats empiriques ont montré que les propriétés optoélectroniques de la plateforme sont régies par le degré de communication électronique entre l’aryle proximal, le pyrrole sur lequel il est attaché et le noyau indolique adjacent à ce dernier. Les maximums d’absorption dans le rouge sont modulables entre 547 et 628 nm et la fluorescence des composés se situe dans le proche- infrarouge. L’un des composé s’est révélé souhaitable pour une utilisation en photovoltaïque ainsi qu’à titre de sonde à pH. La troisième famille comporte cinq complexes neutres de RuII basés sur des polypyridines et portant un ligand azadipyrrométhène cyclométalé. Les composés ont montré une forte absorption de photons dans la région de 600 à 800 nm (rouge à proche- infrarouge) et qui a pu être étendue au-delà de 1100 nm dans le cas des dérivés portant un ligand terpyridine. L’analyse des propriétés optoélectroniques de façon empirique et théorique a montré un impact significatif de la cyclométalation et ouvert la voie pour leur étude en tant que photosensibilisateurs en OPV et en DSSC. La capacité d’un des complexes à photo-injecter un électron dans la bande de conduction du semi-conducteur TiO2 a été démontré en collaboration avec le groupe du Pr Gerald J. Meyer à University of North Carolina at Chapel Hill, premier pas vers une utilisation dans les cellules solaires à pigments photosensibles. La stabilité des complexes en solution s’est toutefois avérée problématique et des pistes de solutions sont suggérées basées sur les connaissances acquises dans le cadre de cette thèse.