The ability of natural zeolite and synthetic ion-exchange resin for ammonia removal from aqueous solution was studied through batch experiments. The results showed that both zeolite and ion-exchange resin were effective (up to 87% of removal) in eliminating ammonia from aqueous solution. Factorial design and response surface methodology were applied to evaluate and optimize the effects of pH, dose, contact time, temperature and initial ammonia concentration. Low pH condition was preferred with the optimum pH found to be 6 for both zeolite and ion-exchange resin. High dose generated high removal rate and low exchange capacity. Results of factorial design and response surface methodology showed that temperature was not a significant parameter. The model prediction was in good agreement with observed data (R2 = 0.969 for zeolite and R2 = 0.957 for resin, respectively). For zeolite, the optimum Qe was 22.90 mg/g achieved at pH=7 and initial ammonia concentration of 3000 mg/L. For ion-exchange resin, Qe of 28.78 mg/g was achieved at pH=6 and initial TAN concentration of 3000 mg/L. The reaction kinetics for both of them followed the Pseudo-second order kinetic model (R2=0.998 and R2=0.999, respectively). Equilibrium data were fitted to Langmuir and Freundlich isotherm models with Freundlich model providing a slightly better predication for zeolite (R2=0.992) and Langmuir providing more accurate prediction for ion-exchange resin (R2=0.996). The ion-exchange resin can be completely regenerated by 2N H2SO4.

The application of Ultrasound (US) irradiation to remove ammonia nitrogen from aqueous solutions, including synthetic solution and landfill leachate, at 20 kHz was investigated in this thesis. Batch experiments were carried out using two synthetic solutions with initial ammonia concentrations of 3000 and 5000 mg TAN/L in addition to two leachates from new and old landfills. The results of testing showed that US irradiation is an effective treatment technology for the removal of aqueous ammonia. More specifically, it was found that increasing sonication time and pH increased ammonia removal. The maximum observed removal of ammonia was 87.4% at a pH of 11 and sonication time of 25 minutes. Also, it was found that volatilization of ammonia to the atmosphere accounted for 0-7% of removal, the thermal effect of US accounted for 21.1-52.7%, and the non-thermal effect of US accounted for 44.5-78.8% (depending on pH and sonication time). Results of factorial design and response surface methodology showed that pH, energy output (kJ), and the interaction between the two were significant parameters. The predicted two factor interaction (2FI) model was in close agreement to the observed data (R2 = 0.94) and produced an optimum ammonia removal of 87% at a pH of 10.9 and energy output of 94.8 kJ. Analysis of variance tests showed that there were no significant differences in the percent removal of ammonia due to the non-thermal effects of US across all four solutions (synthetic and leachate) indicating that US irradiation is a non-selective treatment method for ammonia removal.

Current prices and demand for petroleum hydrocabons have generated an increase of oil spills around the country and the world. Health and environmental impacts associated to these organic pollutants represent a huge concern for the general public, leading the public and private sector to develop new technologies and methods to minimize or eliminate those risks. Ex-Situ bioremediation through biopiles, as a main remediation technique to treat a wide range of hydrocarbons, has been a topic of considerable research interest over the last years. It provides an economical and environmental solution to restore the environment to background levels. Nevertheless, successful bioremediation under cold climate conditions is of considerable concern in countries like Canada, as low temperatures can delay the rate of bioremediation of oil hydrocarbons, thus limiting the operation of soil treatment facilities to certain times of the year. Recent research has found out that bioremediation could be conducted even at low or cold temperatures with larger periods of times. And even more, the addition of petroleum degrading microorganisms (bioaugmentation) and nutrients or biosurfactants (biostimulation) could enhance the process in some cases. In the present study, a comprehensive assessment of bioaugmentation and biostimulation strategies for ex-situ bioremediation of petroleum contaminated soil under cold climate conditions is proposed. Field scale biopiles were constructed and subjected to different concentrations of commercial microbial consortia and mature compost, as bioaugmentation and biostimulation strategies, in a soil treatment facility at Moose Creek, Ontario over a period of 94 days (November 2012 to February 2013). Assessment and comparison of the biodegradation rates of total petroleum hydrocarbons (TPH) and their fractions were investigated. Furthermore, a response surface methodology (RSM) based on a factorial design to investigate and optimize the effects of the microbial consortia application rate and amount of compost on the TPH removal was also assessed. Results showed that biopiles inoculated with microbial consortia and amended with 10:1 soil to compost ratio under aerobic conditions performed the best, degrading 82% of total petroleum hydrocarbons (TPHs) with a first-order kinetic degradation rate of 0.016 d_1, under cold temperature conditions. The average removal efficiencies for TPHs after 94 days for control biopiles, with no amendments or with microbial consortia or compost only treatments were 48%, 55%, and 52%, respectively. Statistical analyses indicated a significant difference (p < 0.05) within and between the final measurements for TPHs and a significant difference between the treatment with combined effect, and the control biopiles. On the other hand, the modeling and optimization statistical analysis of the results showed that the microbial consortia application rate, compost amendment and their interactions have a significant effect on TPHs removal with a coefficient of determination (R2) of 0.88, indicating a high correlation between the observed and the predicted values for the model obtained. The optimum concentrations predicted via RSM were 4.1 ml m-3 for microbial consortia application rate, and 7% for compost amendment to obtain a maximum TPH removal of 90.7%. This research contributes to provide valuable knowledge to practitioners about cost-effective and existing strategies for ex-situ bioremediation under cold weather conditions.

This research proposes a novel Retrofit Design Approach based on process simulation and the Response Surface Methodology (RSM).Retrofit Design Approach comprises: 1) a diagnosis stage in which the variables are screened and promising variables to improve system performance are identified through a sensitivity analysis, 2) an evaluation stage in which RSM is applied to assess the impact of those promising variables and the most important factors are determined by building a reduced model from the process response behaviour, and 3) an optimisation stage to identify optimal conditions and performance of the system, subject to objective function and model constraints. All these stages are simulation-supported. The main advantages of the proposed Retrofit Design Approach using RSM are that the design method is able to handle a large industrial-scale design problem within a reasonable computational effort, to obtain valuable conceptual insights of design interactions and economic trade-off existed in the system, as well as to systematically identify cost-effective solutions by optimizing the reduced model based on the most important factors. This simplifies the pathway to achieve pseudo-optimal solutions, and simultaneously to understand techno-economic and system-wide impacts of key design variables and parameters. In order to demonstrate the applicability and robustness of the proposed design method, the proposed Retrofit Design Approach has been applied to two case studies which are based on existing gas processing processes. Steady-state process simulation using Aspen Plus TM® has been carried out and the simulation results agree well with the plant data. Reduced models for both cases studies have been obtained to represent the techno-economic behaviour of plants. Both the continuous and discrete design options are considered in the retrofitting of the plant, and the results showed that the Retrofit Design Approach is effective to provide reliable, cost-effective retrofit solutions which yield to improvements in the studied processes, not only economically (i.e. cost and product recovery), but also environmentally linked (i.e. CO₂ emissions and energy efficiency). The main retrofitting solutions identified are, for the first case, column pressure change, pump-around arrangement and additional turbo-expansion capacity, while for the second case, columns pressure change, trays efficiency, HEN retrofit arrangements (re-piping) and onsite utility generation schemes are considered. These promising sets of retrofit design options were further investigated to reflect implications of capital investment for the retrofit scenarios, and this portfolio of opportunities can be very useful for supporting decision-making procedure in practice. It is important to note that in some cases a cost-effective retrofit does not always require structural modifications. In conclusion, the proposed Retrofit Design Approach has been found to be a reliable approach to address the retrofit problem in the context of industrial applications.

The objective of this study is to identify the optimal designs of converging-diverging supersonic and hypersonic nozzles that perform at maximum uniformity of thermodynamic and flow-field properties with respect to their average values at the nozzle exit. Since this is a multi-objective design optimization problem, the design variables used are parameters defining the shape of the nozzle. This work presents how variation of such parameters can influence the nozzle exit flow non-uniformities. A Computational Fluid Dynamics (CFD) software package, ANSYS FLUENT, was used to simulate the compressible, viscous gas flow-field in forty nozzle shapes, including the heat transfer analysis. The results of two turbulence models, k-e and k-ω, were computed and compared. With the analysis results obtained, the Response Surface Methodology (RSM) was applied for the purpose of performing a multi-objective optimization. The optimization was performed with ModeFrontier software package using Kriging and Radial Basis Functions (RBF) response surfaces. Final Pareto optimal nozzle shapes were then analyzed with ANSYS FLUENT to confirm the accuracy of the optimization process.

A oxidação lipídica é uma das causas mais importantes que levam à perda das qualidades nutricionais e sensoriais dos alimentos que possuem lipídios em sua composição, diminuindo assim sua vida de útil e provocando rejeição por parte dos consumidores. Considerando estes aspectos, a indústria de alimentos faz o uso de compostos antioxidantes, capazes de retardar a oxidação. A maioria dos antioxidantes utilizados atualmente é de origem sintética, que apresentam restrições quanto ao seu uso em alimentos que variam de país para país. Tais restrições fundamentam-se em aspectos relacionados ao impacto dos antioxidantes sintéticos sobre a saúde do consumidor. Em consequência, na última década ocorreu um aumento considerável no número de pesquisas que abordam uso de antioxidantes obtidos de fontes naturais em alimentos, a fim de identificar fontes promissoras desses compostos. Com esse objetivo, o presente trabalho avaliou a atividade antioxidante de extratos hidroalcoólicos de duas amostras de frutos de murtilla (Ugni molinae Turcz.), silvestre e a cultivar melhorada 14-4, por meio da aplicação de testes in vitro e em sistema modelo a base de óleo de soja. A aplicação da Metodologia de Superfície de Resposta permitiu a seleção da melhor condição operacional para a produção de extratos hidroalcoólicos a partir dos frutos desidratados. A condição que apresentou maior eficiência para recuperação dos compostos fenólicos foi o emprego de etanol 49,5% (v/v) a temperatura de 30ºC, sendo que para a murtilla silvestre o teor foi de 18,39 mg GAE/ g matéria seca e 26,14 mg GAE/ g matéria seca para a cultivar 14-4. As análises de ABTS e DDPH foram realizadas nos extratos produzidos nas condições otimizadas e os resultados obtidos foram 471?mol TEAC/g matéria seca de murtilla silvestre e 881,84 ?mol TEAC/g matéria seca de murtilla 14-4 para o ABTS e 229,59 ?mol TEAC/g matéria seca de murtilla silvestre e 403 ?mol TEAC/g matéria seca de murtilla 14-4 para o DPPH. Análise cromatográfica em fase gasosa acoplada a detector de massas foi realizada visando a identificação dos compostos presentes nos extratos, após derivatização das amostras. Foram identificados componentes como quercetina, epicatequina, ácido gálico, ácido benzoico e ácido hidrocafeico, que possuem atividade antioxidante comprovada. Os extratos potencialmente antioxidantes foram aplicados em sistema modelo (50, 100, 150 e 200 mg kg-1) com óleo insaturado (óleo refinado de soja, sem adição de antioxidantes sintéticos) em condições aceleradas: Teste de estufa (Schaal Oven Test) e Rancimat. No teste de Estufa e no Rancimat as concentrações que apresentaram melhor poder antioxidante foram a de 150 e 200 mg kg-1 para as duas amostras de extratos de frutos de murtilla analisadas. Os resultados de análise sensorial com provadores treinados demonstraram que não houve diferenças estatisticamente significativas entre as concentrações dos extratos adicionados ao óleo de soja submetido à oxidação em estufa, sendo que o TBHQ demonstrou a melhor aceitação. Contudo, considerando as observações feitas pelos provadores é possível afirmar que após as 96 horas de estufa, o odor de ranço foi mascarado pelo odor agradável do extrato dos frutos. / Lipid oxidation is one of the most important causes that promote the loss of nutritional and sensory qualities of foods containing lipids in their composition, thus decreasing their shelf life and causing rejection by consumers. Considering theses aspects, the food industry uses antioxidant compounds that are able to inhibit or retard oxidation. However most of antioxidants currently used are synthetic, with restrictions as to its use in lipid-based foods that vary from country to country. Such restrictions are based on aspects related to the impact of synthetic antioxidants on consumer\'s health. Due to this, in the last decade there was an increase in the number of researches that focuses on using natural sources of antioxidants, such as vegetables, fruits, among others, in food, in order to identify potential sources of antioxidants. With this objective, the present study evaluated the antioxidant activity of hydroalcoholic extracts of two varieties of murtilla\'s fruits (Ugni molinae Turcz.), wild and 14-4, through the application of in vitro assays and in a model system based on soybean oil. The application of response surfaces methodology allowed the selection of the optimal operating condition for the production of hydroethanolic extracts from dried fruit. The total phenolic compounds were determined for evaluation of extracts\' antioxidant activity and adjustment of mathematical models. The condition with the highest phenolic content was extracted using ethanol 49,5% (v/v) and temperature at 30°C, the content for the wild murtilla was 18,39 mg GAE/g dry matter and 26,14 mg GAE/g dry sample for 14-4. The ABTS and DDPH analyses were proceeded with selected optimization extracts and the results were 471?mol TEAC/g dry sample of wild murtilla and 881,84 ?mol TEAC/g dry sample of 14-4 murtilla for ABTS and 229,59 ?mol TEAC/g dry sample of wild murtilla and 403 ?mol TEAC/g dry sample of 14-4 murtilla for DDPH. The analysis by gas chromatography-mass detector was performed for the identification of compounds presents in the extracts after derivatization of the samples. Were identified compounds as quercetin, epicatechin, gallic acid, benzoic acid and hidrocafeico that have proven antioxidant activity. The extracts potentially antioxidants were applied to the model system in increasing doses (50, 100, 150 and 200 mg kg-1) with unsaturated oil (refined soybean oil without addition of synthetic antioxidants) under accelerated conditions: Oven Test (Schaal Oven Test) and Rancimat. Concentrations that better presented antioxidant power were 150 and 200 mg kg-1for both of murtilla samples. Sensory results showed that there was no statistically significant difference among the concentrations of the extracts, and TBHQ showed a better acceptance by the trained panel. However, considering the comments made by the tasters is possible to affirm that after 96 hours of oven, the rancid odor is masked by the pleasant odor of the fruit.

A enzima lipoxigenase através da farinha integral de soja é amplamente utilizada na panificação com objetivos de branqueamento e melhora da reologia. Com base nesse pressuposto, o objetivo inicial deste estudo foi de observar a ação oxidante dessa enzima na presença de dois outros oxidantes (ácido ascórbico e peróxido de benzoíla) nas propriedades reológicas e sensoriais de pães. Sete misturas com diferentes combinações dos três compostos foram elaboradas utilizando-se um delineamento experimental do tipo \"centroide-simplex\", sendo aplicadas à farinha de trigo para o preparo de pães. A enzima apresentou sinergia com o ácido ascórbico na elasticidade da massa, sugerindo uma inter-relação bioquímica entre os dois compostos no fortalecimento da matriz protéica do glúten. A mesma sinergia entre a lipoxigenase da soja e o acido ascórbico foi observada na redução da tonalidade amarela dos pães medida instrumentalmente. A partir desses resultados, buscou-se avaliar a ação da enzima frente a variações tanto na força da farinha como no tempo de fermentação, reproduzindo as condições reais de processamento. Desta vez, um planejamento experimental do tipo Box-Behnken com três fatores (atividade da enzima, força da farinha e tempo de fermentação) em três níveis de variação, foi aplicado no preparo das amostras. Os resultados mostraram que a lipoxigenase da soja (fração 1) é uma enzima oxidante de ação rápida e seu efeito no branqueamento dos carotenóides da farinha de trigo exibiu interação positiva tanto com a força da farinha como o tempo de fermentação. Respostas reológicas e sensoriais decorrentes da ação conjunta de diferentes oxidantes e condições de processamento em pães foram pela primeira vez descritas através de modelos polinomiais com capacidade preditiva. / Soy lipoxygenase enzyme through soy flour is widely used in breadmaking for bleaching and rheological improvement. Based on this fact, the initial objective of this study was to observe the enzymes\' action in the presence of two other oxidants (ascorbic acid and benzoyl peroxide) in the rheological and sensory properties of breads. Seven mixtures with different combinations of the three compounds were prepared using a \"centroid-simplex\" design and applied to wheat flour for breadmaking. The enzyme showed synergism with ascorbic acid in the dough elasticity suggesting a biochemical interrelation between the two compounds in strengthening the gluten protein matrix. The same synergy between soy lipoxygenase and ascorbic acid was observed with the yellow hue reduction of breads measured instrumentally. From these results, the enzyme action was evaluated with wheat strength and proofing time variations reproducing real processing conditions. This time, a Box-Behnken experimental design with three factors (enzyme activity, wheat strength and proofing time), and three variation levels were applied in the sample preparation. The results showed that soy lipoxygenase (type 1) is a fast-acting oxidizing enzyme and its bleaching effect on wheat flour carotenoid exhibited a positive interaction with wheat strength and proofing time. Rheological and sensory results attributed to the combined action of the different oxidants and breadmaking conditions were for the first time described through polynomial models with predictive capacity.

The thesis gives overview of complex aerodynamic optimization approach applied to business-jet aircraft wing design. Response surface method (RSM) potential was explored particularly. The efficiency of RSM approach for CFD based aerodynamic optimization was demonstrated. Basic structural requirements were successfully integrated to optimization – real multidisciplinary problem was solved. Some methods for evaluation of forces distribution along wingspan were explored. Thesis was solving within the frame of 6th EU FP integrated project CESAR.

In this thesis, the design of experiment is studied. Firstly, a theoretic background in mathematical statistics necessary for understanding is built (chapter 2). The design of experiment is then presented in chapters 3 and 4. Chapter 3 is divided into several subchapters in which its brief history is provided as well as its complex theoretic description (basic principles, steps for planning, etc.). Chapter 4 deals with particular types of the design of experiment (Factorial experiments or Response surface design). Simple examples are provided to illustrate the theory in chapters 3 and 4. Last part of the thesis is strictly practical and focuses on an application of the theory for particular data sets and its evaluation (chapter 5).

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