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Chemometric analysis of full scan direct mass spectrometry data for the discrimination and source apportionment of atmospheric volatile organic compounds measured from a moving vehicle.Richards, Larissa Christine 30 August 2021 (has links)
Anthropogenic emissions into the troposphere can impact air quality, leading to poorer health outcomes in the affected areas. Volatile organic compounds (VOCs) are a group of chemical compounds, including some which are toxic, that are precursors in the formation of ground-level ozone and secondary organic aerosols. VOCs have a variety of sources, and the distribution of atmospheric VOCs differs significantly over time and space. Historically, the large number of chemical species present at low concentrations (parts-per-trillion to parts-per-billion by volume) have made VOCs difficult to measure in ambient air. However, with improvements in analytical instrumentation, these measurements are becoming more common place. Direct mass spectrometry (MS), such as membrane introduction mass spectrometry (MIMS) and proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) facilitate real-time, continuous measurements of VOCs in air, with full scan mass spectral data capturing changes in chemical composition with high temporal resolution. Operated on-road, mobilized direct MS has been used for quantitative mapping of VOCs at the neighborhood scale, but identifying VOC sources based on the observed mixture of molecules in the full scan MS dataset has yet to be explored. This dissertation describes the use of chemometric techniques to interrogate full scan MS data, and the progression from discriminating VOC samples of known chemical composition based on full scan MIMS data through to the apportionment of VOC sources measured continuously with a PTR-ToF-MS system operating in a moving vehicle. Lab‐constructed VOC samples of known chemical composition and concentration demonstrated the use of principal component analysis (PCA) to discriminate, and k-nearest neighbours to classify, samples based on normalized full scan MIMS data. Furthermore, multivariate curve resolution-alternating least squares (MCR-ALS) was used to resolve mixtures into molecular component contributions. PCA was also used to discriminate ‘real-world’ VOC mixtures (e.g., woodsmoke VOCs, headspace above aqueous hydrocarbon samples) of unknown chemical composition measured by MIMS. Using vehicle mounted MIMS and PTR-ToF-MS systems, full scan MS data of ambient atmospheric VOCs were collected and PCA was applied to the normalized full scan MS data. A supervised analysis performed PCA on samples collected near known VOC sources, while an unsupervised analysis using PCA followed by cluster analysis was used to identify groups in a continuous, time series PTR-ToF-MS dataset measured between Nanaimo and Crofton, British Columbia (BC). In both the supervised and unsupervised analysis, samples impacted by emissions from different sources (e.g., internal combustion engines, sawmills, composting facilities, pulp mills) were discriminated. With PCA, samples were discriminated based on differences in the observed full scan MS data, however real-world samples are often impacted by multiple VOC sources. MCR-weighted ALS (MCR-WALS) was applied to the continuous, time series PTR-ToF-MS data from three field campaigns on Vancouver Island, BC for source apportionment. Variable selection based on signal-to-noise ratios was used to reduce the mass list while retaining the observed m/z that capture changes in the mixture of VOCs measured, improving model results, and reducing computation time. Both point (e.g., anthropogenic hydrocarbon emissions, pulp mill emissions) and diffuse (e.g., VOCs from forest fire smoke) VOC sources were identified in the data, and were apportioned to determine their contributions to the measured samples. The data analyzed captured fine scale changes in the ambient VOCs present in the air, and geospatial maps of each individual source, and of the source apportionment were used to visualize the distribution of VOC sources across the sampling area. This work represents the first use of MCR-WALS to identify and apportion ambient VOC sources based on continuous PTR-ToF-MS data measured from a moving vehicle. The methods described can be applied to larger scale field campaigns for the source apportionment of VOCs across multiple days to capture diurnal and seasonal variations. Identifying spatial and temporal trends in the sources of VOCs at the regional scale can help to identify pollution ‘hot spots’ and inform evidence-based public policy for improving air quality. / Graduate / 2022-08-17
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Extension, Evaluation, and Validation of Load Based Testing for Residential and Commercial HVAC EquipmentParveen Dhillon (14203079) 02 December 2022 (has links)
<p>With rising temperatures, urbanization, population growth, improving economic wellbeing, decarbonization and electrification efforts, the demand for space cooling and heating equipment is continuously increasing around the world. To counteract the effect of rising demand for air conditioners and heat pumps on total energy consumption, peak electricity demand, and emissions, it is crucial to promote the development and market penetration of energy-efficient systems. Establishing minimum energy performance standards (MEPS), energy labeling and utility programs are some of the effective and tested methods for achieving this goal. The technical basis for these energy efficiency standards is a testing and rating procedure for estimating equipment seasonal performance from laboratory tests. Although the current rating procedures provide standardized metrics to compare different equipment performances, they fail to appropriately characterize the field representative performance of systems by not considering the effects of: 1) test unit embedded controls, thermostat, and realistic interactions with the building load and dynamics; 2) different climate zones and building types; and 3) and other integrated accessories for improving energy efficiency such as economizer for rooftop units (RTUs). Therefore, current approaches for performance ratings neither incentives the development and implementation of improved system and control designs nor consumers with a metric that represents the advanced systems' actual energy savings. To address this, a load-based testing methodology that enables dynamic performance evaluation of equipment with its integrated controls, thermostat, and other accessories was recently proposed. The test methodology is based on the concept of emulating the response of a representative building conditioned by the test unit in a test lab using a virtual building model. </p>
<p>In this work, the proposed load-based testing methodology was further extended, evaluated, and validated for residential heat pumps to integrate it into next-generation energy efficiency testing and rating procedures and to serve as a tool for engineers to develop and validate improved control algorithms in a laboratory setting. Further, a load-based testing method for evaluating the dynamic performance of RTUs with integrated economizers was also developed and demonstrated.</p>
<p>A load-based testing approach previously developed for residential cooling equipment is extended for heat pump heating-mode and demonstrated for a variable-speed system. The heat pump's typical dynamic behaviors are captured along with controller imperfections that aren't reflected in current testing approaches. Further, a comprehensive comparison was performed between the proposed load-based testing approach to the current steady-state testing approach in the U.S., AHRI 210/240, based on performance evaluation of three residential variable-speed heat pumps to understand the differences and their significance for the next-generation rating procedure. For cooling mode, steady-state testing estimates higher seasonal performance, but for heating mode, the steady-state testing approach estimates higher seasonal performance for warmer climates and is comparable for colder climates. The load-based testing methodology was validated by comparing the laboratory performance of a heat pump to that of a residential building in a controlled environment. The virtual building modeling approach for building loads and thermal dynamics effectively captured these characteristics of the house. The heat pump's cycling rate response with run-time fraction, which represents the unit's overall dynamic response, matched well between lab load-based tests and house tests. The test unit's COP difference for cooling and heating tests was within 3% between the two facilities, except for 9% in 95°F and 6% in 104°F cooling dry-coil test intervals. To evaluate the applicability of the developed load-based testing methodology as next-generation rating standards, its repeatability and reproducibility were assessed based on multiple heat pump round-robin tests conducted in two labs. Overall, reasonable to good repeatability was observed in load-based test results in both labs, however, poor reproducibility was observed except for one heat pump heating mode results. A root cause analysis of the observed differences along with recommendations for a next-generation rating approach are presented. This work aided in the development of a CSA (Canadian Standards Association) standard EXP07:19 and its subsequent revision for equipment rating based on load-based testing.</p>
<p>The application of the load-based testing methodology as a tool for the development and evaluation of a residential heat pump controller design was demonstrated. Further, a load-based testing methodology was developed and demonstrated for the dynamic performance evaluation of RTUs with integrated economizers in a test laboratory setting. Recommendations for future work to further develop and improve the repeatability, reproducibility, and representativeness of the load-based testing and rating approach for residential and commercial air conditioners and heat pumps are summarized at the end of the dissertation. </p>
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Novel Applications of Optical Diffraction Tomography: On-chip Microscopy and Detection of Invisibility CloaksDíaz Fernández, Francisco Javier 21 January 2022 (has links)
[ES] La tomografía por difracción surge para mejorar las técnicas de imagen al considerar la naturaleza ondulatoria de la luz. Mientras que los primeros sistemas de imagen médica se basaban únicamente en fuentes sin difracción, este enfoque consigue mejorar la reconstrucción del índice de refracción de los objetos, lo que permite, por ejemplo, el estudio de estructuras subcelulares. Del mismo modo, la demanda de redes de telecomunicaciones cada vez más rápidas y seguras ha propiciado la aparición de la fotónica. Hace dos décadas, la combinación de estos dos campos dio lugar a los primeros sistemas de tomografía por difracción óptica (ODT), los cuáles han evolucionado rápidamente durante este siglo. En esta tesis, presentamos dos nuevas aplicaciones de la ODT. La primera está relacionada con el concepto del microscopio tomográfico de fase (TPM), una versión de la ODT que permite el estudio de células aisladas, con muchas aplicaciones biomédicas, como el diagnóstico y la prognosis del cáncer. Sin embargo, los sistemas TPM actuales son caros, pesados y complejos. Para resolver estos problemas, proponemos el concepto de TPM en chip. Con este fin, diseñamos una hoja de ruta hacia el primer dispositivo tomográfico integrado en el marco de la tecnología lab-on-a-chip (LoC), y desarrollamos los primeros pasos para ello: 1) Hasta ahora, sólo se han utilizado detectores planos para obtener los mapas de índice de refracción de los objetos estudiados en TPM, basados en la detección del campo difractado hacia delante. Sin embargo, los principios físicos fundamentales indican que medir también el campo difractado hacia detrás debería mejorar la resolución de las imágenes. Además, un detector plano no es la configuración óptima para el TPM en chip. En esta línea, hemos explorado la posibilidad de usar detectores circulares en este escenario, como una técnica más adecuada para las configuraciones en chip, demostrando al mismo tiempo que este enfoque proporciona una mejor resolución que el lineal. 2) Proponemos un esquema de TPM en chip basado en el uso de nanoantenas dieléctricas como fuente de luz y píxeles detectores ODT, y caracterizamos experimentalmente su comportamiento mediante microscopía óptica de campo cercano. En cuanto a la segunda aplicación, estudiamos el potencial de la ODT como nuevo paradigma en la detección de capas de invisibilidad realistas, una de las aplicaciones más importantes de los metamateriales. Hasta ahora, el scattering cross section (SCS) se ha utilizado como modelo de referencia para diseñar y observar la eficacia de estos dispositivos para ocultar objetos. En nuestro estudio, demostramos que la ODT puede detectar las capas de invisibilidad prácticas con una sensibilidad superior a la que ofrece el SCS, incluso a las frecuencias de trabajo óptimas. Además, es posible obtener una imagen representativa del tamaño y la forma de la capa, revelando claramente su existencia. Finalmente, se discuten las conclusiones extraídas de los resultados obtenidos. Además, se detallan las futuras líneas de trabajo para abordar los retos que no se han completado en esta tesis doctoral. / [CA] La tomografia per difracció sorgeix per millorar les tècniques d'imatge anteriors en considerar la naturalesa ondulatòria de la llum. Mentre que els primers sistemes d'imatge mèdica es basaven únicament en fonts sense difracció, aquest enfocament aconsegueix millorar la reconstrucció de l'índex de refracció dels objectes, la qual cosa permet, per exemple, l'estudi d'estructures subcelulars. De la mateixa manera, la demanda de xarxes de telecomunicacions cada vegada més ràpides i segures ha propiciat l'aparició de la fotònica. Fa dues dècades, la combinació d'aquests dos camps va portar als primers sistemes de tomografia per difracció òptica (ODT), els quals han evolucionat ràpidament durant aquest segle. En aquesta tesi, presentem dues noves aplicacions de la ODT. La primera està relacionada amb el concepte del microscopi tomogràfic de fase (TPM), una versió de la ODT que permet l'estudi de cèl·lules aïllades, amb moltes aplicacions en biomedicina, com el diagnòstic i prognosi del càncer. No obstant això, els sistemes TPM actuals són cars, pesats i complexos. Per resoldre aquests problemes, proposem el concepte de TPM en xip. Per fer-ho, dissenyem un full de ruta cap al primer dispositiu tomogràfic integrat en el marc de la tecnologia lab-on-a-chip (LoC), i desenvolupem els primers passos a aquest efecte: 1) Fins ara, només s'han utilitzat detectors plans per a obtindre els mapes d'índex de refracció dels objectes estudiats en TPM, basats en la detecció del camp difractat cap avant. No obstant això, els principis físics fonamentals indiquen que mesurar també el camp difractat cap endarrere hauria de millorar la resolució de les imatges. A més, un detector pla no és la configuració òptima per al TPM en xip. En aquesta línia, hem explorat la possibilitat d'usar detectors circulars en aquest escenari, com una tècnica més adequada per a les configuracions en xip, demostrant al mateix temps que aquest enfocament proporciona una millor resolució que el lineal. 2) Proposem un esquema de TPM en xip basat en l'ús de nanoantenes dielèctriques com a font de llum i píxels detectors ODT, i caracteritzem experimentalment el seu comportament en camp pròxim mitjançant microscòpia òptica de camp pròxim. Pel que fa a la segona aplicació, estudiem el potencial de la ODT com a nou paradigma en la detecció de capes d'invisibilitat realistes, una de les aplicacions més importants dels metamaterials. Fins ara, el scattering cross section (SCS) s'ha utilitzat com a model de referència per a dissenyar i observar l'eficàcia d'aquests dispositius per a ocultar objectes. En el nostre estudi, vam demostrar que la ODT pot detectar les capes d'invisibilitat pràctiques amb una sensibilitat superior a la que ofereix el SCS, fins i tot a les freqüències de treball òptimes. A més, és possible obtindre una imatge representativa de la grandària i la forma de la capa, revelant clarament la seua existència. Finalment, es discuteixen les conclusions extretes dels resultats obtinguts i es detallen les futures línies de treball per a abordar els reptes que no s'han completat en aquesta tesi doctoral. / [EN] Diffraction Tomography arises to improve previous imaging techniques by considering the wave nature of light. Whereas the first medical imaging systems relied only on non-diffracting sources, this approach results in an enhanced reconstruction of the object's refractive index distribution, allowing, for example, the study of subcellular structures. Likewise, the demand for increasingly faster and secure telecommunication networks led to the advent of photonics. Two decades ago, the combination of these two fields gave rise to the first optical diffraction tomography (ODT) systems, which have rapidly evolved during this century. In this thesis, we present two novel applications of ODT. The first one is related to the concept of tomographic phase microscopy (TPM), a version of ODT that enables the study of isolated cells, with many applications in biomedicine, such as the diagnosis and prognosis of cancer. Nevertheless, current TPM systems are expensive, heavy, and cumbersome. To solve these issues we propose the concept of on-chip TPM. For this purpose, we design a roadmap towards the first integrated tomographic device in the frame of lab-on-a-chip (LoC) technology and develop the first steps to this end: 1) Until now, only flat detectors have been used to obtain the refractive index maps of the objects studied in TPM, based on the detection of the forward scattering. However, fundamental physical principles indicate that measuring also the backscattered field should improve the resolution of the images. Moreover, a flat detector is not the optimal configuration for on-chip TPM. In this vein, we have explored the possibility of using circular detectors in this scenario as a more suitable technique for on-chip configurations, demonstrating at the same time that this approach provides a better resolution than the linear one. 2) We propose a TPM on-chip scheme based on the use of dielectric nanoantennas as the ODT light source and detector pixels, and experimentally characterize their near-field behavior via scanning near-field optical microscopy. As for the second application, we study the potential of ODT as a new paradigm in the detection of realistic invisibility cloaks, one of the most important applications of metamaterials. Up to now, the scattering cross section (SCS) has been used as the gold standard to design and observe the effectiveness of these devices in hiding objects. In our study, we show that ODT can detect practical invisibility cloaks with a higher sensitivity than that offered by the SCS, even at the optimal working frequencies. Moreover, it is possible to obtain an image depicting the size and shape of the cloak, clearly revealing their existence. Finally, the conclusions drawn from the obtained results are discussed. In addition, future lines of action to address the challenges that have not been completed in this doctoral thesis are detailed. / Díaz Fernández, FJ. (2021). Novel Applications of Optical Diffraction Tomography: On-chip Microscopy and Detection of Invisibility Cloaks [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/180125
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Charakterizace vlastností fotovoltaického systému / Characteristic of photovoltaic systemPokorný, Marek January 2011 (has links)
The aim of this work is informed first about photovoltaics universally, works to inform the photovoltaic panels and complete plants. The work also includes instructions on how to implement PVP in accordance with law. Another part is the rough draft of the photovoltaic power 30 kWp, which can be placed on the house, computation and calculation of investment and them profitable investments to time. Design is made in two separate forms of the Fronius Solar and Sunny Design, their outputs are compared. The practical part of this work cooperates with the company SOLARTEC Ltd. for experimental measurements of the photovoltaic system and develop a methodology for setting the properties of real solar systems in operation from the measured data then stored in a database. These data further evaluate and compare the similar operating conditions. This data will show as the course of production of electricity during the typical day in percentage terms, depending on the incident irradiance, cell temperature, angle of incident radiation, etc. We can compare what it looks like an ideal day in terms of production of photovoltaic power, with the other days. Further are in work mentioned histograms achievement panel behind classical day and behind all - time investigation.
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Evaluation of a Novel Biochemistry Course-Based Undergraduate Research Experience (CURE)Stefan M Irby (6326255) 15 May 2019 (has links)
<p>Course-based Undergraduate Research Experiences (CUREs) have been described in a range of educational contexts. Although various learning objectives, termed anticipated learning outcomes (ALOs) in this project, have been proposed, processes for identifying them may not be rigorous or well-documented, which can lead to inappropriate assessment and speculation about what students actually learn from CUREs. Additionally, evaluation of CUREs has primarily relied on student and instructor perception data rather than more reliable measures of learning.This dissertation investigated a novel biochemistry laboratory curriculum for a Course-based Undergraduate Research Experience (CURE) known as the Biochemistry Authentic Scientific Inquiry Lab (BASIL). Students participating in this CURE use a combination of computational and biochemical wet-lab techniques to elucidate the function of proteins of known structure but unknown function. The goal of the project was to evaluate the efficacy of the BASIL CURE curriculum for developing students’ research abilities across implementations. Towards achieving this goal, we addressed the following four research questions (RQs): <b>RQ1</b>) How can ALOs be rigorously identified for the BASIL CURE; <b>RQ2</b>) How can the identified ALOs be used to develop a matrix that characterizes the BASIL CURE; <b>RQ3</b>) What are students’ perceptions of their knowledge, confidence and competence regarding their abilities to perform the top-rated ALOs for this CURE; <b>RQ4</b>) What are appropriate assessments for student achievement of the identified ALOs and what is the nature of student learning, and related difficulties, developed by students during the BASIL CURE? To address these RQs, this project focused on the development and use of qualitative and quantitative methods guided by constructivism and situated cognition theoretical frameworks. Data was collected using a range of instruments including, content analysis, Qualtrics surveys, open-ended questions and interviews, in order to identify ALOs and to determine student learning for the BASIL CURE. Analysis of the qualitative data was through inductive coding guided by the concept-reasoning-mode (CRM) model and the assessment triangle, while analysis of quantitative data was done by using standard statistical techniques (e.g. conducting a parried t-test and effect size). The results led to the development of a novel method for identifying ALOs, namely a process for identifying course-based undergraduate research abilities (PICURA; RQ1; Irby, Pelaez, & Anderson 2018b). Application of PICURA to the BASIL CURE resulted in the identification and rating by instructors of a wide range of ALOs, termed course-based undergraduate research abilities (CURAs), which were formulated into a matrix (RQs 2; Irby, Pelaez, & Anderson, 2018a,). The matrix was, in turn, used to characterize the BASIL CURE and to inform the design of student assessments aimed at evaluating student development of the identified CURAs (RQs 4; Irby, Pelaez, & Anderson, 2018a). Preliminary findings from implementation of the open-ended assessments in a small case study of students, revealed a range of student competencies for selected top-rated CURAs as well as evidence for student difficulties (RQ4). In this way we were able to confirm that students are developing some of the ALOs as actual learning outcomes which we term VLOs or verified learning outcomes. In addition, a participant perception indicator (PPI) survey was used to gauge students’ perceptions of their gains in knowledge, experience, and confidence during the BASIL CURE and, therefore, to inform which CURAs should be specifically targeted for assessment in specific BASIL implementations (RQ3;). These results indicate that, across implementations of the CURE, students perceived significant gains with large effect sizes in their knowledge, experience, and confidence for items on the PPI survey (RQ3;). In our view, the results of this dissertation will make important contributions to the CURE literature, as well as to the biochemistry education and assessment literature in general. More specifically, it will significantly improve understanding of the nature of student learning from CUREs and how to identify ALOs and design assessments that reveal what students actually learn from such CUREs - an area where there has been a dearth of available knowledge in the past. The outcomes of this dissertation could also help instructors and administrators identify and align assessments with the actual features of a CURE (or courses in general), use the identified CURAs to ensure the material fits departmental or university needs, and evaluate the benefits of students participating in these innovative curricula. Future research will focus on expanding the development and validation of assessments so that practitioners can better evaluate the efficacy of their CUREs for developing the research competencies of their undergraduate students and continue to render improvements to their curricula.</p>
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