ELECTROCATALYTIC PROCESSING OF RENEWABLE BIOMASS-DERIVED COMPOUNDS FOR PRODUCTION OF CHEMICALS, FUELS AND ELECTRICITY

The dual problems of sustaining the fast growth of human society and preserving the environment for future generations urge us to shift our focus from exploiting fossil oils to researching and developing more affordable, reliable and clean energy sources. Human beings had a long history that depended on meeting our energy demands with plant biomass, and the modern biorefinery technologies realize the effective conversion of biomass to production of transportation fuels, bulk and fine chemicals so to alleviate our reliance on fossil fuel resources of declining supply. With the aim of replacing as much non-renewable carbon from fossil oils with renewable carbon from biomass as possible, innovative R&D activities must strive to enhance the current biorefinery process and secure our energy future. Much of my Ph.D. research effort is centered on the study of electrocatalytic conversion of biomass-derived compounds to produce value-added chemicals, biofuels and electrical energy on model electrocatalysts in AEM/PEM-based continuous flow electrolysis cell and fuel cell reactors. High electricity generation performance was obtained when glycerol or crude glycerol was employed as fuels in AEMFCs. The study on selective electrocatalytic oxidation of glycerol shows an electrode potential-regulated product distribution where tartronate and mesoxalate can be selectively produced with electrode potential switch. This finding then led to the development of AEMFCs with selective production of valuable tartronate or mesoxalate with high selectivity and yield and cogeneration of electricity. Reaction mechanisms of electrocatalytic oxidation of ethylene glycol and 1,2-propanediol were further elucidated by means of an on-line sample collection technique and DFT modeling. Besides electro-oxidation of biorenewable alcohols to chemicals and electricity, electrocatalytic reduction of keto acids (e.g. levulinic acid) was also studied for upgrading biomass-based feedstock to biofuels while achieving renewable electricity storage. Meanwhile, ORR that is often coupled in AEMFCs on the cathode was investigated on non-PGM electrocatalyst with comparable activity to commercial Pt/C. The electro-biorefinery process could be coupled with traditional biorefinery operation and will play a significant role in our energy and chemical landscape.

SYSTEM DYNAMICS MODELING AS A QUANTITATIVE-QUALITATIVE FRAMEWORK FOR SUSTAINABLE WATER RESOURCES MANAGEMENT: INSIGHTS FOR WATER QUALITY POLICY IN THE GREAT LAKES REGION

Early water resources modeling efforts were aimed mostly at representing hydrologic processes, but the need for interdisciplinary studies has led to increasing complexity and integration of environmental, social, and economic functions. The gradual shift from merely employing engineering-based simulation models to applying more holistic frameworks is an indicator of promising changes in the traditional paradigm for the application of water resources models, supporting more sustainable management decisions. This dissertation contributes to application of a quantitative-qualitative framework for sustainable water resources management using system dynamics simulation, as well as environmental systems analysis techniques to provide insights for water quality management in the Great Lakes basin. The traditional linear thinking paradigm lacks the mental and organizational framework for sustainable development trajectories, and may lead to quick-fix solutions that fail to address key drivers of water resources problems. To facilitate holistic analysis of water resources systems, systems thinking seeks to understand interactions among the subsystems. System dynamics provides a suitable framework for operationalizing systems thinking and its application to water resources problems by offering useful qualitative tools such as causal loop diagrams (CLD), stock-and-flow diagrams (SFD), and system archetypes. The approach provides a high-level quantitative-qualitative modeling framework for "big-picture" understanding of water resources systems, stakeholder participation, policy analysis, and strategic decision making. While quantitative modeling using extensive computer simulations and optimization is still very important and needed for policy screening, qualitative system dynamics models can improve understanding of general trends and the root causes of problems, and thus promote sustainable water resources decision making. Within the system dynamics framework, a growth and underinvestment (G&U) system archetype governing Lake Allegan's eutrophication problem was hypothesized to explain the system's problematic behavior and identify policy leverage points for mitigation. A system dynamics simulation model was developed to characterize the lake's recovery from its hypereutrophic state and assess a number of proposed total maximum daily load (TMDL) reduction policies, including phosphorus load reductions from point sources (PS) and non-point sources (NPS). It was shown that, for a TMDL plan to be effective, it should be considered a component of a continuous sustainability process, which considers the functionality of dynamic feedback relationships between socio-economic growth, land use change, and environmental conditions. Furthermore, a high-level simulation-optimization framework was developed to guide watershed scale BMP implementation in the Kalamazoo watershed. Agricultural BMPs should be given priority in the watershed in order to facilitate cost-efficient attainment of the Lake Allegan's TP concentration target. However, without adequate support policies, agricultural BMP implementation may adversely affect the agricultural producers. Results from a case study of the Maumee River basin show that coordinated BMP implementation across upstream and downstream watersheds can significantly improve cost efficiency of TP load abatement.

WATER RESOURCES, HEALTH, AND THE SUSTAINABILITY OF INTERVENTIONS TO ACHIEVE WATER AND SANITATION TARGETS OF THE MILLENNIUM DEVELOPMENT GOALS IN A CHANGING WORLD

This dissertation addresses sustainability of rapid provision of safe water and sanitation required to meet the Millennium Development Goals. Review of health-related literature and global statistics demonstrates engineers' role in achieving the MDGs. This review is followed by analyses relating to social, environmental, and health aspects of meeting MDG targets. Analysis of national indicators showed that inadequate investment, poor or nonexistent policies and governance are challenges to global sanitation coverage in addition to lack of financial resources and gender disparity. Although water availability was not found to be a challenge globally, geospatial analysis demonstrated that water availability is a potentially significant barrier for up to 46 million people living in urban areas and relying on already degraded water resources for environmental income. A daily water balance model incorporating the National Resources Conservation Services curve number method in Bolivian watersheds showed that local water stress is linked to climate change because of reduced recharge. Agricultural expansion in the region slightly exacerbates recharge reductions. Although runoff changes will range from -17% to 14%, recharge rates will decrease under all climate scenarios evaluated (-14% to -27%). Increasing sewer coverage may place stress on the readily accessible natural springs, but increased demand can be sustained if other sources of water supply are developed. This analysis provides a method for hydrological analysis in data scarce regions. Data required for the model were either obtained from publicly available data products or by conducting field work using low-cost methods feasible for local participants. Lastly, a methodology was developed to evaluate public health impacts of increased household water access resulting from domestic rainwater harvesting, incorporating knowledge of water requirements of sanitation and hygiene technologies. In 37 West African cities, domestic rainwater harvesting has the potential to reduce diarrheal disease burden by 9%, if implemented alone with 400 L storage. If implemented in conjunction with point of use treatment, this reduction could increase to 16%. The methodology will contribute to cost-effectiveness evaluations of interventions as well as evaluations of potential disease burden resulting from reduced water supply, such as reductions observed in the Bolivian communities.

Sustainable Energy Production in the United States: Life Cycle Assessment of Biofuels and Bioenergy

The United States of America is making great efforts to transform the renewable and abundant biomass resources into cost-competitive, high-performance biofuels, bioproducts, and biopower. This is the key to increase domestic production of transportation fuels and renewable energy, and reduce greenhouse gas and other pollutant emissions. This dissertation focuses specifically on assessing the life cycle environmental impacts of biofuels and bioenergy produced from renewable feedstocks, such as lignocellulosic biomass, renewable oils and fats. The first part of the dissertation presents the life cycle greenhouse gas (GHG) emissions and energy demands of renewable diesel (RD) and hydroprocessed jet fuels (HRJ). The feedstocks include soybean, camelina, field pennycress, jatropha, algae, tallow and etc. Results show that RD and HRJ produced from these feedstocks reduce GHG emissions by over 50% compared to comparably performing petroleum fuels. Fossil energy requirements are also significantly reduced. The second part of this dissertation discusses the life cycle GHG emissions, energy demands and other environmental aspects of pyrolysis oil as well as pyrolysis oil derived biofuels and bioenergy. The feedstocks include waste materials such as sawmill residues, logging residues, sugarcane bagasse and corn stover, and short rotation forestry feedstocks such as hybrid poplar and willow. These LCA results show that as much as 98% GHG emission savings is possible relative to a petroleum heavy fuel oil. Life cycle GHG savings of 77 to 99% were estimated for power generation from pyrolysis oil combustion relative to fossil fuels combustion for electricity, depending on the biomass feedstock and combustion technologies used. Transportation fuels hydroprocessed from pyrolysis oil show over 60% of GHG reductions compared to petroleum gasoline and diesel. The energy required to produce pyrolysis oil and pyrolysis oil derived biofuels and bioelectricity are mainly from renewable biomass, as opposed to fossil energy. Other environmental benefits include human health, ecosystem quality and fossil resources. The third part of the dissertation addresses the direct land use change (dLUC) impact of forest based biofuels and bioenergy. An intensive harvest of aspen in Michigan is investigated to understand the GHG mitigation with biofuels and bioenergy production. The study shows that the intensive harvest of aspen in MI compared to business as usual (BAU) harvesting can produce 18.5 billion gallons of ethanol to blend with gasoline for the transport sector over the next 250 years, or 32.2 billion gallons of bio-oil by the fast pyrolysis process, which can be combusted to generate electricity or upgraded to gasoline and diesel. Intensive harvesting of these forests can result in carbon loss initially in the aspen forest, but eventually accumulates more carbon in the ecosystem, which translates to a CO2 credit from the dLUC impact. Time required for the forest-based biofuels to reach carbon neutrality is approximately 60 years. The last part of the dissertation describes the use of depolymerization model as a tool to understand the kinetic behavior of hemicellulose hydrolysis under dilute acid conditions. Experiments are carried out to measure the concentrations of xylose and xylooligomers during dilute acid hydrolysis of aspen. The experiment data are used to fine tune the parameters of the depolymerization model. The results show that the depolymerization model successfully predicts the xylose monomer profile in the reaction, however, it overestimates the concentrations of xylooligomers.

Interoperable Resource Brokering with Policy-based Provisioning and Job Allocation

The increasing needs for computational power in areas such as weather simulation, genomics or Internet applications have led to sharing of geographically distributed and heterogeneous resources from commercial data centers and scientific institutions. Research in the areas of utility, grid and cloud computing, together with improvements in network and hardware virtualization has resulted in methods to locate and use resources to rapidly provision virtual environments in a flexible manner, while lowering costs for consumers and providers. However, there is still a lack of methodologies to enable efficient and seamless sharing of resources among institutions. In this work, we concentrate in the problem of executing parallel scientific applications across distributed resources belonging to separate organizations. Our approach can be divided in three main points. First, we define and implement an interoperable grid protocol to distribute job workloads among partners with different middleware and execution resources. Second, we research and implement different policies for virtual resource provisioning and job-to-resource allocation, taking advantage of their cooperation to improve execution cost and performance. Third, we explore the consequences of on-demand provisioning and allocation in the problem of site-selection for the execution of parallel workloads, and propose new strategies to reduce job slowdown and overall cost.

Work creativity as a dimension of job performance

To stay competitive, many employers are looking for creative and innovative employees to add value to their organization. However, current models of job performance overlook creative performance as an important criterion to measure in the workplace. The purpose of this dissertation is to conduct two separate but related studies on creative performance that aim to provide support that creative performance should be included in models of job performance, and ultimately included in performance evaluations in organizations. Study 1 is a meta-analysis on the relationship between creative performance and task performance, and the relationship between creative performance and organizational citizenship behavior (OCB). Overall, I found support for a medium to large corrected correlation for both the creative performance-task performance (ρ = .51) and creative performance-OCB (ρ = .49) relationships. Further, I also found that both rating-source and study location were significant moderators. Study 2 is a process model that includes creative performance alongside task performance and OCB as the outcome variables. I test a model in which both individual differences (specifically: conscientiousness, extraversion, proactive personality, and self-efficacy) and job characteristics (autonomy, feedback, and supervisor support) predict creative performance, task performance, and OCB through engagement as a mediator. In a sample of 299 employed individuals, I found that all the individual differences and job characteristics were positively correlated with all three performance criteria. I also looked at these relationships in a multiple regression framework and most of the individual differences and job characteristics still predicted the performance criteria. In the mediation analyses, I found support for engagement as a significant mediator of the individual differences-performance and job characteristics-performance relationships. Taken together, Study 1 and Study 2 support the notion that creative performance should be included in models of job performance. Implications for both researchers and practitioners alike are discussed.^

Integration of a Sedimentation Module to a Hydrologic Model and its Application to a Mercury TMDL Analysis

This research is part of continued efforts to correlate the hydrology of East Fork Poplar Creek (EFPC) and Bear Creek (BC) with the long term distribution of mercury within the overland, subsurface, and river sub-domains. The main objective of this study was to add a sedimentation module (ECO Lab) capable of simulating the reactive transport mercury exchange mechanisms within sediments and porewater throughout the watershed. The enhanced model was then applied to a Total Maximum Daily Load (TMDL) mercury analysis for EFPC. That application used historical precipitation, groundwater levels, river discharges, and mercury concentrations data that were retrieved from government databases and input to the model. The model was executed to reduce computational time, predict flow discharges, total mercury concentration, flow duration and mercury mass rate curves at key monitoring stations under various hydrological and environmental conditions and scenarios. The computational results provided insight on the relationship between discharges and mercury mass rate curves at various stations throughout EFPC, which is important to best understand and support the management mercury contamination and remediation efforts within EFPC.

Development of a Coupling Model for Fluid-Structure Interaction using the Mesh-free Finite Element Method and the Lattice Boltzmann Method

In the presented thesis work, the meshfree method with distance fields was coupled with the lattice Boltzmann method to obtain solutions of fluid-structure interaction problems. The thesis work involved development and implementation of numerical algorithms, data structure, and software. Numerical and computational properties of the coupling algorithm combining the meshfree method with distance fields and the lattice Boltzmann method were investigated. Convergence and accuracy of the methodology was validated by analytical solutions. The research was focused on fluid-structure interaction solutions in complex, mesh-resistant domains as both the lattice Boltzmann method and the meshfree method with distance fields are particularly adept in these situations. Furthermore, the fluid solution provided by the lattice Boltzmann method is massively scalable, allowing extensive use of cutting edge parallel computing resources to accelerate this phase of the solution process. The meshfree method with distance fields allows for exact satisfaction of boundary conditions making it possible to exactly capture the effects of the fluid field on the solid structure.

Testing and Expanding an Emotion-Centered Model of Workplace Aggression: The Moderating Effects of Perceived Intensity and Social Support in the Workplace

The purpose of this thesis was to examine the mediating effects of job-related negative emotions on the relationship between workplace aggression and outcomes. Additionally, the moderating effects of workplace social support and intensity of workplace aggression are considered. A total 321 of working individuals participated through an online survey. The results of this thesis suggest that job-related negative emotions are a mediator of the relationship between workplace aggression and outcomes, with full and partial mediation supported. Workplace social support was found to be a buffering variable in the relationship between workplace aggression and outcomes, regardless of the source of aggression (supervisor or co-worker) or the source of the social support. Finally, intensity of aggression was found to be a strong moderator of the relationship between workplace aggression and outcomes.

Successful aging at 100 years: the relevance of subjectivity and psychological resources

Very old individuals seem to present an admirable capacity to overcome adversities and adapt to the challenges of advanced age. However, studies focusing successful pattern of centenarians found that they may easily fail to be categorized as successful agers when objective criteria are applied. The present study examines if centenarians can be considered successful agers. Following Rowe and Kahn's successful aging model, the primary goal was to clarify whether centenarians are able to be successful agers according to objective and subjective criteria of no major disease and disability, high cognitive and physical functioning and engagement with life. The second goal was to investigate whether socio-demographic factors, psychological, social, and economic resources are related to objective and subjective successful aging profiles.

Digital literacy matters. Increasing workforce productivity through blended English language programmes

Current workplace demands newer forms of literacies that go beyond the ability to decode print. These involve not only competence to operate digital tools, but also the ability to create, represent, and share meaning in different modes and formats; ability to interact, collaborate and communicate effectively using digital tools, and engage critically with technology for developing one’s knowledge, skills, and full participation in civic, economic, and personal matters. This essay examines the application of the ecology of resources (EoR) model for delivering language learning outcomes (in this case, English) through blended classroom environments that use contextually available resources. The author proposes the implementation of the EoR model in blended learning environments to create authentic and sustainable learning environments for skilling courses. Applying the EoR model to Indian skilling instruction contexts, the article discusses how English language and technology literacy can be delivered using contextually available resources through a blended classroom environment. This would facilitate not only acquisition of language and digital literacy outcomes, but also consequent content literacy gain to a certain extent. This would ensure satisfactory achievement of not only communication/language literacy and technological literacy, but also active social participation, lifelong learning, and learner autonomy.

The potential of symbolic approximation. Disentangling the effects of approximation vs. calculation demands in nonsymbolic and symbolic representations.

Mathematical skills that we acquire during formal education mostly entail exact numerical processing. Besides this specifically human faculty, an additional system exists to represent and manipulate quantities in an approximate manner. We share this innate approximate number system (ANS) with other nonhuman animals and are able to use it to process large numerosities long before we can master the formal algorithms taught in school. Dehaene´s (1992) Triple Code Model (TCM) states that also after the onset of formal education, approximate processing is carried out in this analogue magnitude code no matter if the original problem was presented nonsymbolically or symbolically. Despite the wide acceptance of the model, most research only uses nonsymbolic tasks to assess ANS acuity. Due to this silent assumption that genuine approximation can only be tested with nonsymbolic presentations, up to now important implications in research domains of high practical relevance remain unclear, and existing potential is not fully exploited. For instance, it has been found that nonsymbolic approximation can predict math achievement one year later (Gilmore, McCarthy, & Spelke, 2010), that it is robust against the detrimental influence of learners´ socioeconomic status (SES), and that it is suited to foster performance in exact arithmetic in the short-term (Hyde, Khanum, & Spelke, 2014). We provided evidence that symbolic approximation might be equally and in some cases even better suited to generate predictions and foster more formal math skills independently of SES. In two longitudinal studies, we realized exact and approximate arithmetic tasks in both a nonsymbolic and a symbolic format. With first graders, we demonstrated that performance in symbolic approximation at the beginning of term was the only measure consistently not varying according to children´s SES, and among both approximate tasks it was the better predictor for math achievement at the end of first grade. In part, the strong connection seems to come about from mediation through ordinal skills. In two further experiments, we tested the suitability of both approximation formats to induce an arithmetic principle in elementary school children. We found that symbolic approximation was equally effective in making children exploit the additive law of commutativity in a subsequent formal task as a direct instruction. Nonsymbolic approximation on the other hand had no beneficial effect. The positive influence of the symbolic approximate induction was strongest in children just starting school and decreased with age. However, even third graders still profited from the induction. The results show that also symbolic problems can be processed as genuine approximation, but that beyond that they have their own specific value with regard to didactic-educational concerns. Our findings furthermore demonstrate that the two often con-founded factors ꞌformatꞌ and ꞌdemanded accuracyꞌ cannot be disentangled easily in first graders numerical understanding, but that children´s SES also influences existing interrelations between the different abilities tested here.

Puget Sound’s MARS (Media Asset Retrieval System) Digital Library

The MARS (Media Asset Retrieval System) Project is a collaboration between public broadcasters, libraries and schools in the Puget Sound region to assess the needs of their constituents and pool resources to develop solutions to meet those needs. The Project’s ultimate goal is to create a digital online resource that will provide access to content produced by public broadcasters and libraries. The MARS Project is funded by a grant from the Corporation for Public Broadcasting (CPB) Television Future Fund. Convergence ConsortiumThe Convergence Consortium is a model for community collaboration, including representatives from public broadcasting, libraries and schools in the Puget Sound region. They meet regularly to consider collaborative efforts that will be mutually beneficial to their institutions and constituents. Specifically, the archives of public broadcasters have been identified as significant resources that can be accessed through libraries and used by schools, and integrated with text and photographic archives from other partners.Using the work-centered framework, we collected data through interviews with nine engineers and observation of their searching while they performed their regular, job-related searches on the Web. The framework was used to analyze the data on two levels: 1) the activities and organizational relationships and constrains of work domains, and 2) users’ cognitive and social activities and their subjective preferences during searching.

Les influences de la socialisation des genres sur l’expérience d’hommes ayant assuré des soins palliatifs de fin de vie à domicile pour leur conjointe atteinte d’un cancer en phase terminale

Notre étude a comme objectif de mieux comprendre comment la socialisation des hommes se manifeste dans le rôle de conjoints proches aidants à domicile, pour une conjointe atteinte d’un cancer à l’étape pré-terminale et terminale. Elle s’inscrit en tant que recherche exploratoire et compréhensive, d’orientation constructiviste. Le modèle de Schulz et de Cantor ont inspiré l’analyse des résultats. Douze hommes ont été rencontrés lors d’entrevues semi-dirigées. L’âge des répondants a permis d’avoir un échantillon d’hommes représentatif de deux générations différentes, soit celle des vétérans (1922-1945) et celle des baby-boomers (1946-1964). Selon leur génération, ils ont été exposés de façon plus ou moins importante aux valeurs et aux prescriptions sociales en ce qui concerne les genres. Il semble que ce soit le fait d’être informé, plutôt que le niveau d’éducation, qui a une influence sur le contexte de soins en procurant aux conjoints soignants les outils nécessaires pour mieux répondre aux demandes des soins. Il apparaît que les hommes qui ont conservé le modèle traditionnel du partage des tâches ont eu plus de difficultés à assurer le vie domestique de la maison. Les réseaux formels ont suppléé au manque de ressources familiales et au manque de connaissances des répondants. L’amour, le désir d’offrir les meilleurs soins et la fidélité à leur engagement sont des motifs à la base de la prise en charge. Les hommes plus jeunes n’ont pas hésité à quitter leur travail pour prendre soin. Ils n’ont pas exprimé de craintes quant à leur masculinité. Quant aux plus âgés à la retraite, ils auraient été hésitants à quitter leur travail pour soigner si la situation s’était présentée. Retenons que les hommes sont en mesure d’assumer ce qui doit être fait, mais à leur manière, c’est-à-dire en y apportant ce qu’ils ont à offrir en tant qu’homme.

Entrepreneurship: a long way to go

Entrepreneurship education has emerged as one popular research domain in academic fields given its aim at enhancing and developing certain entrepreneurial qualities of undergraduates that change their state of behavior, even their entrepreneurial inclination and finally may result in the formation of new businesses as well as new job opportunities. This study attempts to investigate the Colombian student´s entrepreneurial qualities and the influence of entrepreneurial education during their studies.