<p>Air pollutants pose a high risk for humans, and the environment, and this pollution is one of the major environmental problems facing modern society. Active air sampling is the technique that has been traditionally used to monitor nonpolar aromatic air pollutants. However, active high volume samplers (HiVols) require a power supply, maintenance and specialist operators, and the equipment is often expensive. Thus, there is a need to develop new, less complicated sampling techniques that can increase the monitoring frequency, the geographical distribution of the measurements, and the number of sites used in air monitoring programs. In the work underlying this thesis, the use of semipermeable membrane devices (SPMDs) as tools for monitoring gas phase concentrations of nonpolar aromatic compound was evaluated using the compound classes polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs) and nitrated PAHs (nitro-PAHs) as test compounds. </p><p>High wind-speeds increased the uptake and release in SPMDs of PAHs and PCBs with log K_OA values > 7.9, demonstrating that the uptake of most nonpolar aromatic compounds is controlled by the boundary layer at the membrane-air interface. The use of a metal umbrella to shelter the SPMDs decreased the uptake of PAHs and PCBs by 38 and 55 percent, respectively, at high wind/turbulence, and thus reduced the wind effect. Further, the use of performance reference compounds (PRCs) to assess the site effect of wind on the uptake in SPMDs reduced the between-site differences to less than 50 percent from as much as three times differences in uptake of PCBs and PAHs. However, analytical interferences reduced the precision of some PRCs, showing the importance of using robust analytical quality control.</p><p>SPMDs were shown to be efficient samplers of gas phase nonpolar aromatic compounds, and were able to determine local, continental and indoor spatial distributions of PAHs, alkyl- PAHs and nitro-PAHs. In addition, the use of the SPMDs, which do not require electricity, made sampling possible at remote/rural areas where the infrastructure was limited. SPMDs were also used to determine the source of PAH pollution, and different approaches were discussed. Finally, SPMDs were used to estimate the importance of the gas phase exposure route to the uptake of PAHs in plants. The results demonstrate that SPMDs have several advantages compared with HiVols, including integrative capacity over long times, reduced costs, and no need of special operators, maintenance or power supply for sampling. However, calibration data of SPMDs in air are limited, and spatial differences are often only semi-quantitatively determined by comparing amounts and profiles in the SPMDs, which have limited their use in air monitoring programs. In future work, it is therefore important that SPMDs are properly sheltered, PRCs are used in the sampling protocols, and that calibrated sampling rate data, or the SPMD-air partition data, of specific compounds are further developed to make determination of time weighted average (TWA) concentrations possible.</p>

En el dise��o de embutidos crudos curados enriquecidos en fibra alimentaria, es esencial la obtenci��n de ingredientes funcionales de elevada calidad, que puedan ser incorporados en la formulaci��n del embutido generando las menores modificaciones de las caracter��sticas f��sico-qu��micas y sensoriales del alimento. El principal objetivo de este trabajo consisti�� en optimizar la formulaci��n de un embutido crudo curado enriquecido en un concentrado de fibra alimentaria de zanahoria. La formulaci��n ��ptima debe proporcionar el contenido m��ximo de fibra alimentaria y producir los m��nimos cambios de calidad respecto al producto tradicional. Se ha propuesto una metodolog��a para optimizar ambos, la obtenci��n de un concentrado de fibra alimentaria de alta calidad y tambi��n la formulaci��n de un embutido crudo curado (sobrasada) enriquecido en fibra alimentaria. En primer lugar, se ha desarrollado un procedimiento que consiste en la modelizaci��n, simulaci��n y optimizaci��n del proceso de secado convectivo de zanahoria. El procedimiento de optimizaci��n no solo se refiere a la transferencia de materia, sino tambi��n se incluyen los criterios relacionados con los atributos de calidad del producto final. Una vez obtenido el ingrediente funcional de calidad, fue incorporado en la formulaci��n de la sobrasada. La cantidad ��ptima de concentrado de fibra alimentaria de zanahoria necesaria para obtener un embutido enriquecido de calidad se estim�� mediante el an��lisis de los efectos de la adici��n de fibra alimentaria de zanahoria en el proceso de maduraci��n-secado de sobrasada. / To design dry fermented sausages enriched in dietary fibre, it is essential to obtain high quality functional ingredients, which can be incorporated into sausage formulation with minor modifications of the physico-chemical and sensory properties of food. The main objective of this study was to optimize the formulation of a dry fermented sausage enriched with a dietary fibre concentrate from carrot. The optimal formulation should provide maximum dietary fibre content and produce minimal quality changes from the traditional product. A methodology has been proposed to optimize both the acquisition of a high quality fibre concentrate and also for the formulation of a dry fermented sausage (sobrassada) enriched in dietary fibre. First, a procedure comprised of mathematical modelling, simulation and optimization of the convective carrot drying process was developed. The optimization procedure was not only concerned with mass transfer but also included criteria related to quality attributes of the final product. Once the high quality functional ingredient was obtained, it was incorporated into the sobrassada formulation. The optimal amount of carrot dietary fibre concentrate necessary to obtain a high quality enriched sausage was estimated by analysing the effects of carrot dietary fibre addition to the ripening-drying process of sobrassada. / En el disseny d'embotits crus curats enriquits en fibra aliment��ria, ��s essencial l'obtenci�� d'ingredients funcionals d'elevada qualitat que puguin ser incorporats en la formulaci�� de l'embotit generant les menors modificacions de les caracter��stiques fisicoqu��miques i sensorials de l'aliment. El principal objectiu d'aquest treball va consistir a optimitzar la formulaci�� d'un embotit cru curat enriquit en un concentrat de fibra aliment��ria de pastanaga. La formulaci�� ��ptima ha de proporcionar el contingut m��xim de fibra aliment��ria i produir la menor quantitat possible de canvis qualitatius respecte al producte tradicional. S'ha proposat una metodologia per optimitzar ambd��s aspectes esmentats, l'obtenci�� d'un concentrat de fibra aliment��ria d'alta qualitat i tamb�� la formulaci�� d'un embotit cru curat (sobrassada) enriquit en fibra aliment��ria. En primer lloc, s'ha desenvolupat un procediment que consisteix en la modelitzaci��, simulaci�� i optimitzaci�� del proc��s d'assecatge convectiu de pastanaga. El procediment d'optimitzaci�� no nom��s fa refer��ncia a la transfer��ncia de mat��ria, sin�� que tamb�� inclou els criteris relacionats amb els atributs de qualitat del producte final. Una vegada obtingut l'ingredient funcional de qualitat, va ser incorporat en la formulaci�� de la sobrassada. La quantitat ��ptima de concentrat de fibra aliment��ria de pastanaga necess��ria per obtenir un embotit enriquit de qualitat es va estimar mitjan��ant l'an��lisi dels efectes de l'addici�� de fibra aliment��ria de pastanaga en el proc��s de maduraci��/assecat de sobrassada.

Air pollutants pose a high risk for humans, and the environment, and this pollution is one of the major environmental problems facing modern society. Active air sampling is the technique that has been traditionally used to monitor nonpolar aromatic air pollutants. However, active high volume samplers (HiVols) require a power supply, maintenance and specialist operators, and the equipment is often expensive. Thus, there is a need to develop new, less complicated sampling techniques that can increase the monitoring frequency, the geographical distribution of the measurements, and the number of sites used in air monitoring programs. In the work underlying this thesis, the use of semipermeable membrane devices (SPMDs) as tools for monitoring gas phase concentrations of nonpolar aromatic compound was evaluated using the compound classes polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs) and nitrated PAHs (nitro-PAHs) as test compounds. High wind-speeds increased the uptake and release in SPMDs of PAHs and PCBs with log KOA values &gt; 7.9, demonstrating that the uptake of most nonpolar aromatic compounds is controlled by the boundary layer at the membrane-air interface. The use of a metal umbrella to shelter the SPMDs decreased the uptake of PAHs and PCBs by 38 and 55 percent, respectively, at high wind/turbulence, and thus reduced the wind effect. Further, the use of performance reference compounds (PRCs) to assess the site effect of wind on the uptake in SPMDs reduced the between-site differences to less than 50 percent from as much as three times differences in uptake of PCBs and PAHs. However, analytical interferences reduced the precision of some PRCs, showing the importance of using robust analytical quality control. SPMDs were shown to be efficient samplers of gas phase nonpolar aromatic compounds, and were able to determine local, continental and indoor spatial distributions of PAHs, alkyl- PAHs and nitro-PAHs. In addition, the use of the SPMDs, which do not require electricity, made sampling possible at remote/rural areas where the infrastructure was limited. SPMDs were also used to determine the source of PAH pollution, and different approaches were discussed. Finally, SPMDs were used to estimate the importance of the gas phase exposure route to the uptake of PAHs in plants. The results demonstrate that SPMDs have several advantages compared with HiVols, including integrative capacity over long times, reduced costs, and no need of special operators, maintenance or power supply for sampling. However, calibration data of SPMDs in air are limited, and spatial differences are often only semi-quantitatively determined by comparing amounts and profiles in the SPMDs, which have limited their use in air monitoring programs. In future work, it is therefore important that SPMDs are properly sheltered, PRCs are used in the sampling protocols, and that calibrated sampling rate data, or the SPMD-air partition data, of specific compounds are further developed to make determination of time weighted average (TWA) concentrations possible.

Lors que nous examinons numériquement des phénomènes multiphasiques suite à un accidentgrave dans le réacteur nucléaire, la dimension caractéristique des zones multi-fluides(non-réactifs et réactifs) s’avère beaucoup plus petite que celle du bâtiment réacteur, cequi fait la Simulation Numérique Directe de la configuration à peine réalisable. Autrement,nous proposons de considérer la zone de mélange multiphasique comme une interface infinimentfine. Puis, le solveur de Riemann réactif est inséré dans la Méthode des ÉquationsDiscrètes Réactives (RDEM) pour calculer le front de combustion à grande vitesse représentépar une interface discontinue. Une approche anti-diffusive est ensuite couplée avec laRDEM afin de précisément simuler des interfaces réactives. La robustesse et l’efficacité decette approche en calculant tant des interfaces multiphasiques que des écoulements réactifssont à la fois améliorées grâce à la méthode ici proposée : upwind downwind-controlled splitting(UDCS). UDCS est capable de résoudre précisément des interfaces avec les maillagesnon-structurés multidimensionnels, y compris des fronts réactifs de détonation et de déflagration. / When numerically investigating multiphase phenomena during severe accidents in a reactorsystem, characteristic lengths of the multi-fluid zone (non-reactive and reactive) are foundto be much smaller than the volume of the reactor containment, which makes the directmodeling of the configuration hardly achievable. Alternatively, we propose to consider thephysical multiphase mixture zone as an infinitely thin interface. Then, the reactive Riemannsolver is inserted into the Reactive Discrete Equations Method (RDEM) to compute highspeed combustion waves represented by discontinuous interfaces. An anti-diffusive approachis also coupled with RDEM to accurately simulate reactive interfaces. Increased robustnessand efficiency when computing both multiphase interfaces and reacting flows are achievedthanks to an original upwind downwind-controlled splitting method (UDCS). UDCS is capableof accurately solving interfaces on multi-dimensional unstructured meshes, includingreacting fronts for both deflagration and detonation configurations.

O fósforo (P) é um nutriente essencial para o crescimento das plantas. Milhões de toneladas de P são aplicados aos solos anualmente. No entanto, apenas uma pequena fração do P aplicado com fertilizantes é aproveitada nas lavouras no ano de aplicação, bem como a eficácia do fertilizante fosfatado diminui com o tempo. Para melhorar a nossa compreensão dos mecanismos, a esta resposta do P no campo, este trabalho visa estudar a migração desse elemento em solos tropicais brasileiros (Latossolo vermelho e Latossolo amarelo) tratados com três tipos de fertilizantes: fosfato monoamônico (MAP), o polímero revestido de fosfato monoamônio (MAPP) e fosfato organomineral (OMP) em um experimento de placa de Petri. Fluorescência de Raios X por Reflexão Total (TXRF) foi usada para determinar o fluxo difusivo P a distâncias radiais diferentes (entre 0 e 7,5 mm, entre 7,5 e 13,5 mm, 13,5 e 25,5 mm e entre 25,5 e 43 mm) a partir do grânulo de fertilizante. As análises usando TXRF foram realizadas no Laboratório Nacional de Luz Síncrotron (LNLS), em Campinas, São Paulo, na linha de Fluorescência de Raios X (Beamline D09B). Depois de um período de cinco semanas, a concentração total de P, Ca e Al foram obtidas e comparadas analisando o tipo de solo/textura, o pH e o respectivo extrator de P, que nesse estudo foram usados o Mehlich 1 e água régia. De forma geral, concluiu-se que 80,0 % de fósforo proveniente dos fertilizantes usados nessa proposta ficaram concentrados em distâncias menores que 10 mm do ponto de aplicação dos fertilizantes, independentemente do tipo de solo, do pH e da respectiva textura. Em relação à utilização da técnica TXRF, o sistema foi eficiente, dentre outras características, na discriminação dos picos de fósforo dos picos de enxofre, principalmente nas amostras de solo usadas a partir da extração com Mehlich 1. Destaca-se isso, pois os raios X característicos desses elementos são muitos próximos. / Phosphorus is an essential nutrient for plant growth. Million of tones of P are applied to the soils annually. However, only a small fraction of the P applied with fertilizers is taken up by crops in the year of application, and the effectiveness of any residual P fertilizer declines with time. To improve our understanding of the mechanisms underlying this response to P in the field, this work aims to study the migration of this element in Brazilian tropical soils (red and yellow Oxisol) treated with three types of fertilizers: monoammonium phosphate (MAP), polymer coated monoammonium phosphate (MAPp) and Organomineral phosphate (OMP) in a Petri dish experiment. Total Reflection X-Ray Fluorescence (TXRF) was used to determine the P diffusive flux at different distances (0 - 7.5, 7.5 13.5, 13.5 25.5 and 25.5 43 mm) from granular fertilizer. TXRF analyses were performed at the X-Ray Fluorescence Beamline D09B at Brazilian National Synchrotron Light Laboratory (LNLS), in Campinas, São Paulo. After a period of five weeks, the total concentration of P, Ca and Al were obtained and compared by analyzing the type/soil texture, pH, and the respective extractor P, this study used the Mehlich 1 and aqua regia . In general, it was found that 80.0 % of phosphorus from the fertilizer used in this proposal were concentrated in distances smaller than 10 mm from the point of application of fertilizers , regardless of the soil type , pH, and its texture. Regarding the use of TXRF technique , the system was efficient , among other features , the breakdown of phosphorus peaks of the sulfur peaks , especially in the soil samples used from the extraction with Mehlich 1. It is noteworthy that, as the rays X characteristic of these elements are very close.

O desenvolvimento e aplicação de métodos analíticos na avaliação das concentrações de metais nas frações dissolvida e lábil na bacia do rio Piracicaba são de relevante importância para o estudo do comportamento químico-ambiental desses metais e para seu monitoramento, devido ao impacto das atividades antropogênicas nessa bacia. A técnica de difusão em filmes finos por gradiente de concentração (DGT, do inglês diffusive gradients in thin-films), é uma promissora ferramenta analítica de amostragem, pois permite pré-concentração, análise temporal, remoção de interferentes, avaliação lábil e amostragem in situ. A quantificação dos metais pelas técnicas de fluorescência de raios X dispersiva em energia por reflexão total (TXRF, total reflection X-ray fluorescence analysis) para amostras líquidas e da fluorescência de raios X dispersiva em energia (EDXRF, energy dispersive X-ray fluorescence) para amostras sólidas, mostram-se interessantes devido ao caráter multielementar, simultâneo e não destrutivo da análise. Neste trabalho avaliou-se a DGT para a determinação de Cr, Mn, Co, Ni, Cu, Zn e Pb em águas naturais, utilizando-se como agente ligante a membrana de celulose P 81 e como meio difusivo, o papel cromatográfico 3 MM. Calcularam-se os fatores de eluição e coeficientes de difusão para estes metais. Estudou-se o efeito da substância húmica, em diferentes concentrações, no desempenho da DGT para esses metais, e os resultados foram comparados e concordantes com as frações livre e a ligada à matéria orgânica, calculadas pelo programa Visual MINTEQ. Compararam-se o agente ligante e o meio difusivo à base de celulose, utilizados neste trabalho, com os à base de gel de poliacrilamida, empregando-se o complexante Chelex-100. Avaliou-se a homogeneidade da retenção dos analitos e do grupo ligante fosfato sobre a superfície do agente ligante. Nesses ensaios utilizaram-se soluções sintéticas contendo os analitos em pH 5,5 e força iônica 0,05 mol L-1 (ajustados com NaNO3). As determinações foram realizadas por TXRF e EDXRF. Avaliaram-se os acoplamentos DGT-SRTXRF e da DGT-EDXRF para a determinação da fração lábil de Cr, Mn, Co, Ni, Cu, Zn e Pb em amostras de água da bacia do rio Piracicaba, através de imersão em laboratório e in situ. Esses resultados foram comparados com as concentrações dissolvidas desses metais determinados pela técnica de fluorescência de raios X por reflexão total com excitação por luz síncrotron (SRTXRF, synchrotron radiation total reflection X-ray analysis). Os valores de concentrações de Mn, Cu e Zn nas frações dissolvida e lábil foram comparados com os valores máximos estabelecidos pela legislação brasileira Nas amostragens in situ, nos cinco pontos de coleta, as concentrações de Mn dissolvido e lábil foram maiores que a concentração total máxima permitida para esse elemento. Os elmentos Cr, Co, Ni e Pb, nas amostras coletadas, apresentaram-se abaixo do limite de detecção das técnicas SRTXRF (dissolvido), DGT-SRTXRF (lábil) e DGT-EDXRF (lábil). Os limites de detecção para o Cr, Mn, Co, Ni, Cu, Zn e Pb foram de 2,2 a 10 \'mü\'g L-1 na SRTXRF, de 0,21 a 3,6 \'mü\'g L-1 e de 7,2 a 24 \'mü\'g L-1 na DGT-SRTXRF e DGT-EDXRF, respectivamente / Analytical methods evaluation for metal dissolved and labile fractions determination in Piracicaba river basin is notable for metal-behavior studies in this environment as well as their monitoring due to anthropogenic activities. The diffusive gradients in thin films (DGT) is a promising sampling technique because of its pre-concentration, time-integrated, matrix interference removal, labile evaluation and in situ analytical features. The analytical techniques total reflection X-ray fluorescence (TXRF) for liquid samples and energy dispersive X-ray fluorescence (EDXRF) for solid samples analysis are advantageous due to simultaneous, multielemental and non-destructive characteristics. In this work, it was evaluated the DGT technique for Cr, Mn, Co, Ni, Cu, Zn and Pb determination in freshwater, using P 81 cellulose membrane as bind agent and 3 MM chromatographic paper as diffusive layer. Elution factors and diffusion coefficients were calculated for these metals. The humic acids effect on DGT performance was assessed and compared to free and humic acid bound metal fractions estimated by Visual MINTEQ software, in which agreement results were found. The paper-based DGT and gel-based one with Chelex-100 as bind agent were compared. The metal retention and phosphate group homogenization on P 81 membrane bind agent surface was studied. For these tests it was utilized a synthetic solution these metals containing with pH and ionic strength adjust to 5.5 and 0.05 mol L-1 (NaNO3), respectively. It was used the TXRF and EDXRF techniques for these metal quantifications. The DGT-SRTXRF and DGT-EDXRF were assessed in order to determine Cr, Mn, Co, Ni, Cu, Zn and Pb labile fractions in batch and in situ in Piracicaba river basin freshwater samples. These results were compared to their dissolved fractions by synchrotron radiation total reflection X-ray analysis, SRTXRF. The dissolved and labile Mn, Cu and Zn concentrations levels were compared to maximum allowed set by Brazilian legislation. The dissolved and labile Mn concentrations were higher than the maximum allowed in all five samples in situ sampling. Cr, Co, Ni, and Pb concentrations were lower than their limits of detection for dissolved fractions (SRTXRF) and labile ones (DGT-SRTXRF and DGT-EDXRF). The detection limits for Cr, Mn, Co, Ni, Cu, Zn and Pb were from 2.2 to 10 \'mü\'g L-1 for SRTXRF, from 0.21 to 3.6 \'mü\'g L-1 and from 7.2 to 24 \'mü\'g L-1 for DGT-SRTXRF and DGT-EDXRF, respectively

The topic of this diploma thesis is systems of energy efficient buildings with a focus on the building envelope. The first theoretical part describes the quantities that we consider when designing the building envelope. The second half of the theoretical part is with reference to the experimental part of the thesis focused on a special type of vertical perimeter structure, namely walls with live vegetation installed from the outside of the structure. The second, practical part of this work, deals with the design of heating and hot water supply for a multifunctional building. The design is elaborated in two variants - heating by means of radiators in the first variant and in the second variant by means of floor heating for residential units of the solved building. The third part define an experiment, which had the task of comparing the measured quantities on two types of vertical perimeter structures, namely a structure with growing greenery from the outside and an identical structure only without a layer of greenery. At the same time, the task was to check the possible influence of the applied greenery on heat losses, and thus the design of the heating system.

Il est bien connu que la synchronisation de l’activité oscillatoire dans les réseaux de neurones joue un rôle important dans le fonctionnement du cerveau et pour le traitement des informations données pas les neurones. Cette thèse porte sur l’analyse de l’activité de synchronisation en utilisant des outils et des méthodes issues de la théorie du contrôle et de la théorie de la stabilité. En particulier, deux modèles ont été étudiés pour décrire l’activité oscillatoire des réseaux de neurones : le modèle de Kuramoto et le modèle de Hindmarsh-Rose. Une partie de ce manuscript est consacrée à l’étude du modèle de Kuramoto, qui est un des systèmes les plus simples utilisé pour modéliser un réseau de neurones, avec une connexion complète (all-to-all). Il s’agit d’un modèle classique qui est utilisé comme une version simplifiée d’un réseau de neurones. Nous construisons un système linéaire qui conserve les informations sur les fréquences naturelles et sur les gains d’interconnexion du modèle original de Kuramoto. Les propriétés de stabilité de ce modèle sont ensuite analysées et nous montrons que les solutions de ce nouveau système linéaire convergent vers un cycle limite périodique et stable. Finalement, nous montrons que contraint au cycle limite, les dynamiques du système linéaire coïncident avec le modèle de Kuramoto. Dans une seconde partie, nous avons considéré un modèle de réseau de neurones plus proche de la réalité d’un point de vue biologique, mais qui est plus complexe que le modèle de Kuramoto. Plus précisément, nous avons utilisé le modèle de Hindmarsh-Rose pour décrire la dynamique de chaque neurone que nous avons interconnecté par un couplage diffusif (c’est à dire linéaire). A partir des propriétés de semi-passivité du modèle de Hindmarsh- Rose, nous avons analysé les propriétés de stabilité d’un réseau hétérogène de Rindmarsh-Rose. Nous avons également montré que ce réseau est pratiquement synchronisé pour une valeur suffisamment grande du gain d’interconnexion. D’autre part, nous avons caractérisé le comportement limite des neurones synchronisés et avons établi une approximation de ce comportement par une moyenne des dynamiques de tous les neurones. / It is widely recognized that rhythmic oscillatory activity in networks of neurons plays an important role in the brain functionning and a key role in processing neural information. This thesis is devoted to the analysis of this synchronized activity by using tools and methods issued from automatic control and stability theory. Two models are used to describe oscillatory activity of neural networks : Kuramoto model and network of Hindmarsh-Rose neurons. First, we consider Kuramoto model with complete (all-to-all) coupling, which is one of the simplest systems used to model neural network. For this model we construct an auxiliary linear system that preserves information on the natural frequencies and interconnection gains of the original Kuramoto model. Next, stability properties of this model are analyzed and we show that the solutions of the new linear system converge to a stable periodic limit cycle. Finally, we show that constrained to the limit cycle, dynamics of the linear system coincide with the original Kuramoto model. Second, a model for the network (population) with a better behavior, with respect to the Kuramoto model, from a biological point of view but more complex is considered. Particularly, we consider a network of diffusively coupled neurons where we use a Hindmarsh-Rose model to describe the dynamics of each individual neuron. Based on semi-passivity of individual Hindmarsh-Rose neurons, we analyse stability properties of a heterogeneous network of such neurons and show that network is practically synchronized for sufficient large values of interconnection gains. Moreover, we characterize the limiting synchronized behavior by using an averaging of all neuron dynamics.