Ce travail porte sur la modélisation d'écoulements turbulents anisothermes dans des milieux macroporeux. Ce problème intéresse de nombreux domaines : échangeurs de chaleur, réacteurs nucléaires, canopées... Notre objectif est de modéliser des écoulements traversant une structure solide selon un approche multi-échelle. L'utilisation d'un opérateur de moyenne spatiale permet ainsi d'obtenir une description homogénéisée des écoulements, tandis que l'aspect turbulent est traité grâce à un opérateur de moyenne statistique. Au cours du processus de moyenne, une partie des informations sur l'état microscopique est perdue. Cela se traduit, à l'échelle macroscopique, par l'apparition de termes inconnus liés à la turbulence (contraintes de Reynolds) et à la présence de la matrice solide (dispersion). C'est sur ces termes de dispersion présents dans les équations macroscopiques de quantité de mouvement et de la température que porte notre travail. Nous proposons un modèle de dispersion thermique qui permet de prédire de façon satisfaisante l'évolution de la température moyenne du fluide pour des écoulements à l'équilibre hydraulique présentant de forts gradients de température ou de flux thermique à la paroi. De plus, un modèle macroscopique de température de paroi basé sur le modèle de température moyenne est dérivé. Il permet de prédire avec précision l'évolution de la température de paroi pour des écoulements hors équilibre thermique. Afin de pouvoir traiter aussi des cas hors équilibre hydraulique, un modèle macroscopique de turbulence est proposé. Une analyse physique détaillée des transferts énergétiques a montré que c'est l'énergie dispersive qui permet de caractériser le déséquilibre hydraulique. Un modèle de turbulence prenant en compte les déséquilibres d'énergie dispersive a donc été dérivé. Il permet de prédire de façon satisfaisante la dynamique d'établissement d'écoulements entrant dans des canaux et de fournir des conditions aux limites précises à la sortie des canaux. Enfin, nous proposons un modèle dynamique pour le tenseur de dispersion basé sur l'énergie dispersive et la dissipation associée. / This works deals with the modelling if anisothermal turbulent flows in macroporous media. This topic concerns many practical applications such as heat exchangers, nuclear reactors, canopies... Our aim is to model flows through porous matrices by means of a multi-scale approach. A macroscopic description of the flows is obtained thanks to a spatial average operator, while a statistical average operator is used to handle turbulence. The successive application of both filters leads to a loss of information. Therefore, at macroscopic scale, unknown contributions linked to turbulence (Reynolds stresses) and the presence of the solid matrix (dispersion) appear. We focus on dispersion terms. We propose a thermal dispersion model for hydrodynamically established flows. Mean temperature predictions obtained with this model are very accurate for channel flows with strong temperature and wall heat flux gradients. We also derive a wall temperature model based the mean temperature model. It gives good macroscopic results for thermally developping flows. In order to be able to simulate hydrodynamically developping flows, a turbulence model is needed. A two-scale analysis of energy transfers within the flow shows that the dynamic behaviour of unbalanced flows can be described using the dispersive kinetic energy. A turbulence model that accounts for dispersive energy is derived. It predicts very well the dynamics of a flows near a channel inlet and provides accurate boundary conditions for exit flows. Finally, a dynamic model based on the dispersive energy and its dissipation rate is proposed for the dispersion tensor.

An environmentally friendly, rapid and cost effective analytical procedure based on dispersive liquid-liquid microextraction was developed for the determination of six tetracyclines (TCs) in meat destined for human consumption. Meat extracts were analyzed for TCs using a sensitive and selective analytical technique, liquid chromatography tandem mass spectrometry. Various influencing factors on the extraction, separation and determination of TCs such as pH of mobile phases, type and volume of disperser solvent, type and volume of extraction solvent and sample pH were optimized. Validation parameters such as calibration function, limit of detection (LOD), limit of quantification (LOQ), detection capability (CCα), decision limit (CCβ), accuracy and precision were established according to EU commission decision 2002/657/EC. Linearity in the range of 25-200 μg kg-1 was obtained with regression coefficients ranging from 0.9991 to 0.9998. Recoveries of spiked blank muscle samples at three levels (i.e. 50, 100 and 150 μg kg-1) ranged from 80 to 101% and reproducibility was between 2 and 7%. The LODs and LOQs ranged from 2.22 to 3.59 μg kg-1 and from 7.38 to 11.49 μg kg-1 respectively. The CCα ranged from 105 to 111 μg kg-1 while CCβ ranged from 107 to 122 μg kg-1. The proposed method compared well with the dispersive solid phase extraction method and was successfully applied to the determination of TCs in meat samples. Some of the thirty bovine muscle samples obtained from local abattoirs and butcheries were found to contain two tetracycline antibiotics residues (chlortetracycline and oxytetracycline) with oxytetracycline being the most commonly detected. The concentration levels of the TC residues detected in the eleven bovine muscle samples were between 12.4 and 68.9 μg kg-1, levels that are lower than the European Union set maximum residue level (MRL) of 100 μg kg-1 hence the meat was fit for human consumption. / Chemistry / M. Sc. (Chemistry)

The aim of the present investigation is to improve the geotechnical properties of dispersive soil by reducing their dispersivity after elucidating the important mechanisms controlling the dispersivity of the soils. Dispersive soils have unique properties, which under certain conditions deflocculate and are rapidly eroded and carried away by water flow. These soils are found extensively in the United States, Australia, Greece, India, Latin America, South Africa and Thailand. The mechanism of dispersivity of soils is a subject matter of great interest for geotechnical engineers. In the earlier days clays were considered to be non erosive and highly resistant to water erosion. However, recently it was found that highly erosive clay soils do exist in nature. Apart from clayey soil, dispersivity is also observed in silty soils. The tendency of the clays to disperse or deflocculate depends upon the mineralogy and soil chemistry and also on the dissolved salts in the pore water and the eroding water. Such natural dispersive soils are problematic for geotechnical engineers. They are clayey soils which are highly susceptible to erosion in nature and contain a high percentage of exchangeable sodium ions, (Na+). It is considered that the soil dispersivity is mainly due to the presence of exchangeable sodium present in the structure. When dispersive clay soil is immersed in water, the clay fraction behaves like single-grained particles; that is, the clay particles have a minimum of electrochemical attraction and fail to closely adhere to, or bond with, other soil particles. This implies that the attractive forces are less than the repulsive forces thus leading to deflocculation (in saturated condition).This weakens the aggregates in the soil causing structural collapse. Such erosion may start in a drying crack, settlement crack, hydraulic fracture crack, or other channel of high permeability in a soil mass. Total failure of slopes in natural deposits is initiated by dispersion of clay particles along cracks, fissures and root holes, accelerated by seepage water. For dispersive clay soils to erode, a concentrated leakage channel such as a crack (even a very small crack) must exist through an earth embankment. Erosion of the walls of the channel then occurs along the entire length at the same time. Many slope and earth dam failures have occurred due to the presence of dispersive soils. Unlike erosion in cohesionless soils, erosion in dispersive clay is not a result of seepage through the pores of clay mass. However, the role of type of clay and its Cation exchange capacity in the dispersion of soil is not well understood. Data on the presence, properties, and tests for identification of dispersive clays is scarce. Hence, an attempt is made, in this thesis, to develop reliable methods to identify these soils and understand the extent of their dispersivity as well as to develop methods to control their dispersivity. The present study deals with the characterization of a local dispersive soil collected from southern part of Karnataka State. This study has focused on comprehensive tests to assess the dispersivity of the soils by different methods and to methods to improve geotechnical properties by reducing the dispersivity of the soil. An attempt is made to reduce the dispersivity of soil by using calcium based stabilizers such as lime, cement and fly ash. The mechanism of improvement in reducing the dispersivity of the soil with calcium based stabilizers has been studied. One of the important mechanism by which the dispersivity of the soil is reduced is by inducing cementation of soil particles. The differences in effectiveness of different additives are due to their differences in abilities to produce cementitious compounds. Although all the additives increased the strength of the soil and reduced the dispersivity of the soil, cement was found to significantly reduce the dispersivity of the soil, compared to the other two additives lime and fly ash. Cement is more effective as sufficient cementitious compounds are produced on hydration without depending on their formation. A detailed review of literature on all aspects connected with the present study is given in Chapter 2. A comprehensive description of dispersive soils present worldwide has been brought out in this section. Based on this survey, the scope of the present investigation has been elaborated at the end of the chapter. To understand the reasons for dispersivity of the soil and to estimate its degree of dispersivity, it is essential to assess standard methods to characterize the soil. Chapter 3 presents a summary of material properties and testing programs. The results of geotechnical characterization of the soil, the index properties of the soilspecific gravity, sieve analysis, Atterberg’s limits are discussed in Chapter 4. The physico chemical characteristics play an important role in determining the amount of dispersivity of the soil. Dispersive soils have two main characteristics which define its dispersivity chemically. These are Sodium Adsorption Ratio (S.A.R) and Exchangeable Sodium Percentage (E.S.P). The two characteristics are determined from the Cation exchange capacity of the soil. Exchangeable Sodium Percentage is defined as the concentration of sodium ions present in the soil with respect to the Cat ion exchange capacity of the soil. And Sodium Adsorption Ratio is used to quantify the free salts present in the pore water. Since Atterberg’s limits and grain size analysis do not help in identifying dispersive soils or in quantifying its dispersivity, two other tests- Emerson Crumb test and double hydrometer test were carried out on the soil. Emerson crumb test is a simple way for identification of dispersive soils. In this test, a crumb of soil measuring about 1mm diameter is immersed in a beaker containing distilled water and the subsequent reaction is observed for 5 minutes. It is solely based on direct qualitative observations. Depending on the degree of turbidity of the cloud formed in the beaker, the soil is classified in one of the four levels of dispersion in accordance with ASTM-D6572. Since this test is mainly a qualitative test and does not help in quantifying the dispersivity, it cannot be depended upon completely in identifying a dispersive soil. Another test double hydrometer test, which helps in quantifying the dispersivity of the soil, was also conducted on the soil. This test involves in conducting the particle size distribution using the standard hydrometer test in which the soil specimen was dispersed in distilled water with a chemical dispersant. A parallel hydrometer test was conducted on another soil specimen, but without a chemical dispersant. The dispersing agent used for the experiment was sodium hexametaphosphate. The percent dispersion is the ratio of the dry mass of particles smaller than 0.005 mm diameter of the test without dispersing agent to the test with dispersing agent expressed as a percentage. The double hydrometer test was carried out according to Double Hydrometer Test (ASTM D4221). Apart from the conventional tests, attempts are made to consider shrinkage limit test and unconfined compression test to determine the dispersivity of the soil. For this purpose, the shrinkage limit of the soil was determined with and without dispersing agent. The initial shrinkage limit of the untreated soil reduced on treating it with dispersing agent, thus indicating that the soil had further dispersed on addition of dispersing agent. In order to carry out the unconfined compression strength, the maximum dry density and optimum moisture content was determined through the compaction test. The soil was then treated with dispersing agent and compacted at the optimum moisture content. The soil exhibited high degree of dispersion through the strength test. Hence it is necessary to stabilize the soil with additives. Detailed experimental program has been drawn to find methods to improve the geotechnical properties and to reduce the dispersivity of the soil. Chapter 5 presents the investigations carried out on the dispersive soil with lime. The importance of lime stabilization and the mechanism of lime stabilization have been discussed initially. Commercially obtained hydrated lime was used in the present study. The soil was treated with three different percentages of lime 3, 5 and 8. The curing period was varied from one day to twenty eight days. The effect of addition of lime on various properties of the soil such as pH, Atterberg’s limits, compaction test and unconfined compression test is elaborated in chapter 5. The pH of the soil was maximum on addition of 3% lime. On further addition, the pH decreased and remained constant. The liquid limit of the soil increased on adding 3% lime and decreased with further lime content. The compaction test conducted on the soil showed an increase in maximum dry density of the soil and reduction in optimum moisture content with 3% lime content. On further increase in the lime content, the soil showed a decrease in the maximum dry density and increase in optimum moisture content. The unconfined compressive strength of the soil also increased on increasing lime content upto 5%. The variation in strength of the soil with respect to curing period was also compared. Optimum lime content arrived at based on the above conducted tests was 3%. The effect of lime in reducing the dispersivity of the soil through shrinkage limit test and unconfined compression test is also presented in this chapter. Details of the efforts made on the soil with fly ash are presented in Chapter 6.The fly ash used for stabilization of Suddha soil was of Class F type. This type of fly ash contains low reactive silica and lime. The effect of varying fly ash content on the properties of Suddha soil by varying the percentage of fly ash from 3 to 10 percentages is discussed in this chapter. The tests conducted on fly ash treated Suddha soil were pH test, compaction test, Atterberg’s limits and unconfined compression test with varying curing period. The fly ash treated Suddha soil was cured from one day to twenty eight days for the unconfined compressive strength analysis. The pH of the soil system increased with increasing percentage of fly ash. The increase in liquid limit was marginal on addition of fly ash. The maximum dry density of fly ash treated Suddha soil decreased continuously and the optimum moisture content of the treated soil increased with increasing fly ash content. The unconfined compressive strength of Suddha soil increased with increase in fly ash content upto 8% and then decreased for fly ash content of 10%. For all the percentages of fly ash added, the strength of the soil increased with increase in the curing period. The effect of fly ash in reducing the dispersivity of the soil was carried out using shrinkage limit and unconfined compression test. It was seen that on increasing the fly ash content, the soil treated with dispersing agent showed an increase in the shrinkage limit. Also, the same trend was observed for the unconfined compression strength to determine dispersivity. Optimum fly ash was determined as 8% with the help of all the tests conducted on the soil. Since the improvement in the properties of the soil with lime and fly ash was not very high, Cement was also considered as another additive used for stabilization of Suddha soil. It is known that soil with lesser amount of clay content will respond well with cement. The effect of cement addition on various properties of Suddha soil has been brought out in Chapter 7. It was found that addition of cement had positive effects on all the properties of Suddha soil. The pH of the soil increased for all the percentages of cement addition. The liquid limit of the soil increased on increasing the cement content. The shrinkage limit also showed a similar trend. The optimum moisture content of the soil decreased on increasing the cement content for Suddha soil and the maximum dry density increased for cement treated Suddha soil. The soil showed the maximum dry density at 8% cement content. The unconfined compression strength conducted on cement treated Suddha soil increased significantly for higher cement contents and also with curing period. Suddha soil when treated with 8% cement content exhibited maximum strength in comparison to other percentages. Also, the effect of cement in reducing the dispersivity of the soil was carried out using shrinkage limit and unconfined compression test. The shrinkage limit of the soil increased for all percentages of cement content, even in the presence of dispersing agent. Through the unconfined compression strength for dispersivity, it could be seen that 8% cement treated Suddha soil had the least dispersion. Optimum cement content was derived as 8% with the help of the tests conducted on the soil. A comparison of effect of all the additives on the strength of the soil as well as effect of the additives in reducing the dispersivity of the soil is discussed in Chapter 8. The effect of additives on the shrinkage limit of the soil with and without dispersing agent has been compared. The variation in shrinkage limit of the soil when treated with the additives was due to the different mechanisms involved in reducing the dispersivity by each additive. The effect on the unconfined compression strength of the soil treated with the additives with and without dispersing agent is also brought out in this chapter. It was noted that the dispersion exhibited through shrinkage limit test was lesser as compared to the percentage dispersivity exhibited through unconfined compression test. Hence it could be said that dispersion of the soil is due to loss of cohesion than volume change behavior. Also, the unconfined compression strength of the soils with respect to curing period is compared. The percentage dispersivity calculated through these tests is summarized and compared. With the help of this it could be said that to control the dispersivity of the soil, it is necessary to enhance the strength of the soil. The general summary and major conclusions drawn from the thesis are presented in Chapter 9.

Nous nous intéressons au contrôle non destructif par ultrasons des matériaux industriels. En pratique, les signaux réceptionnés par le transducteur ultrasonore sont analysés pour détecter les discontinuités de la pièce inspectée. L'analyse est néanmoins rendue difficile par l'acquisition numérique, les effets de la propagation ultrasonore et la superposition des échos lorsque les discontinuités sont proches. La déconvolution parcimonieuse est une méthode inverse qui permet d'aborder ce problème afin de localiser précisément les discontinuités. Ce procédé favorise les signaux parcimonieux, c'est à dire ne contenant qu'un faible nombre de discontinuités. Dans la littérature, la déconvolution est généralement abordée sous l'hypothèse d'un modèle invariant en fonction de la distance de propagation, modalité qui n'est pas appropriée ici car l'onde se déforme au cours de son parcours et en fonction des discontinuités rencontrées. Cette thèse développe un modèle et des méthodes associées qui visent à annuler les dégradations dues à l'instrumentation et à la propagation ultrasonore, tout en résolvant des problèmes de superposition d'échos. Le premier axe consiste à modéliser la formation du signal ultrasonore en y intégrant les phénomènes propres aux ultrasons. Cette partie permet de construire un modèle linéaire mais non invariant, prenant en compte l'atténuation et la dispersion. L'étape de modélisation est validée par des acquisitions avec des matériaux atténuants. La deuxième partie de cette thèse concerne le développement de méthodes de déconvolution efficaces pour ce problème, reposant sur la minimisation d'un critère des moindres carrés pénalisé par la pseudo-norme L0. Nous avons développé des algorithmes d'optimisation spécifiques, prenant en compte, d'une part, un modèle de trains d'impulsions sur-échantillonné par rapport aux données, et d'autre part le caractère oscillant des formes d'onde ultrasonores. En utilisant des données synthétiques et expérimentales, ces algorithmes associés à un modèle direct adapté aboutissent à de meilleurs résultats comparés aux approches classiques pour un coût de calcul maîtrisé. Ces algorithmes sont finalement appliqués à des cas concrets de contrôle non destructif où ils démontrent leur efficacité. / This thesis deals with the ultrasonic non destructive testing of industrial parts. During real experiments, the signals received by the acoustic transducer are analyzed to detect the discontinuities of the part under test. This analysis can be a difficult task due to digital acquisition, propagation effects and echo overlapping if discontinuities are close. Sparse deconvolution is an inverse method that aims to estimate the precise positions of the discontinuities. The underlying hypothesis of this method is a sparse distribution of the solution, which means there are a few number of discontinuities. In the literature, deconvolution is addressed by a linear time-invariant model as a function of propagation distance, which in reality does not hold.The purpose of this thesis is therefore to develop a model and associated methods in order to cancel the effects of acquisition, propagation and echo overlapping. The first part is focused on the direct model development. In particular, we build a linear time-variant model that takes into account dispersive attenuation. This model is validated with experimental data acquired from attenuative materials. The second part of this work concerns the development of efficient sparse deconvolution algorithms, addressing the minimization of a least squares criterion penalized by a L0 pseudo-norm. Specific algorithms are developed for up-sampled deconvolution, and more robust exploration strategies are built for data containing oscillating waveforms. By using synthetic and experimental data, we show that the developed methods lead to better results compared to standard approaches for a competitive computation time. The proposed methods are then applied to real non destructive testing problems where they confirm their efficiency.

Ternary indium aluminum nitride (InXAl1-XN) semiconductor is an attractive material with a wide-range bandgap energy varied from ultraviolet (Eg(AlN): 6.2 eV) to near infrared (Eg(InN): 0.7 eV). With tuning composition, it can be widely used to many optoelectronic device applications. In this thesis, I have studied InXAl1-XN film deposited on Si (111) substrate using natural and isotopically enriched nitrogen as reactive gas by reactive magnetron sputter epitaxy (MSE). Four series of experiments were performed, which are I. InAlN presputtering, II. InAlN sputter deposition, III. InAlN direct deposition, and IV. InAlN direct deposition using isotopically enriched nitrogen. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDX). The θ-2θ XRD scan confirms that the designed composition x = 0.17 of InXAl1-XN film was obtained. TEM images shows that an amorphous interlayer with a thickness ranging from 1.2 nm to 1.5 nm was formed between Si substrate and InXAl1-XN film. However, high-resolution TEM shows that the interlayer actually contains partial crystalline structures. EDX line profile indicates that the chemical composition of the amorphous interlayer is silicon nitride (SiNX). By comparing d-spacing measurement of partial crystalline structures with EDX line profile, it reveals that partial SiNX crystal is formed in the interlayer. Nonetheless, the samples (IAD01, IAD02, IAD03, IAD04), grown without presputtering procedure, contain both crystalline SiNX and InXAl1-XN embedded in the amorphous interlayer. It means that SiNX and InXAl1-XN film can be directly grown on the substrate in the beginning of deposition. Moreover, the samples (IAD01, IAD03), quenched directly after deposition, have less crystalline structures in the interlayer then the samples (IAD02, IAD04), maintained at 800℃ for 20 min.

Integrable systems arise in nonlinear processes and, both in their classical and quantum version, have many applications in various fields of mathematics and physics, which makes them a very active research area. In this thesis, the problem of integrability of multidimensional equations, especially in three dimensions (3D), is explored. We investigate systems of differential, differential-difference and discrete equations, which are studied via a novel approach that was developed over the last few years. This approach, is essentially a perturbation technique based on the so called method of dispersive deformations of hydrodynamic reductions . This method is used to classify a variety of differential equations, including soliton equations and scalar higher-order quasilinear PDEs. As part of this research, the method is extended to differential-difference equations and consequently to purely discrete equations. The passage to discrete equations is important, since, in the case of multidimensional systems, there exist very few integrability criteria. Complete lists of various classes of integrable equations in three dimensions are provided, as well as partial results related to the theory of dispersive shock waves. A new definition of integrability, based on hydrodynamic reductions, is used throughout, which is a natural analogue of the generalized hodograph transform in higher dimensions. The definition is also justified by the fact that Lax pairs the most well-known integrability criteria are given for all classification results obtained.

Knowledge about dispersion is of utmost importance for understanding populations’ reaction to changes in the environment. Expansion of a population range brings with it both spatial sorting and over time, spatial selection. This means that dispersion rates increases over time at the expanding edge. Most studies have so far been performed on continuously expanding populations. This study aims to bring more knowledge about dispersal biology in dynamic systems. I studied dispersal traits in two permanent and two seasonal vegetation habitats of an isopod (Asellus aquaticus), for which differentiation between habitat types has previously been shown. I quantified differences in displacement (dispersal rate) and three morphological traits, head angle (body streamline) and leg of the third and seventh pair of legs. Isopods from the seasonal vegetation had higher displacement rates than animals from permanent vegetation. This inclines that mechanisms driving spatial selection in expanding population ranges also exist in dynamic systems. The more streamlined isopods found in seasonal sites further points towards spatial sorting by dispersion capability. Because no effect of permanence was found on leg length and there was no correlation between streamlining and displacement, the higher dispersion among animals from seasonal habitats most likely derives from behavioral differences.

O comportamento da condutividade induzida por radiação-X (RIC) em copolímeros P(VDF/TrFE) de razões molares 60/40 e 70/30 em suas fases ferroelétrica (temperatura ambiente) e paraelétrica (acima de 110°C), foi estudado para diferentes condições ambientais. Foi observado que a RIC depende fortemente sobre a conformação molecular do polímero. Variaram-se parâmetros experimentais como campo elétrico aplicado, taxa de dose, atmosfera ambiente e, principalmente a temperatura. Medidas auxiliares como correntes termoestimuladas, calorimetria diferencial, espectroscopias infravermelho, ressonância eletrônica paramagnética, difração de raios-X, etc..., deram contribuições no sentido de entender modificações estruturais e morfológicas do material devido à radiação. Para análise dos resultados da condutividade induzida (RIC), foi usado o modelo de transporte em meios dispersivos desenvolvido por Arkhipov e colaboradores. Por meio de ajustes teórico-experimentais obtivemos parâmetros importantes do material como, a mobilidade dos portadores gerados, o coeficiente de recombinação, o parâmetro dispersivo, bem como a energia de geração de pares. / The behavior of the radiation induced conductivity (RIC) by X-rays in P(VDF/TrFE) copolymers of 70:30 and 60:40 molar ratios, in their ferro and paraelectric phases, were studied in different environments. It was observed that the RIC depends strongly on the molecular conformation of the polymer. For the experiments several parameters were varied as the external applied field, the dose rate, the atmosphere and mainly the temperature. Auxiliar measurements as thermal stimulated currents, differential scanning calorimetry, EPR and IR spectroscopy, X-ray diffraction, etc..., were used in the sense to supply additional information about morphological and structural variations of the material due to the irradiation. For a complete analysis of the radiation induced conductivity results a dispersive transport model developed by Arkhipov et al was used. From the theoretical experimental fitting we obtained important parameters of the material: carrier mobility, recombination coefficient, dispersive parameter Q, as well as the pair-generation energy.

O chumbo é um metal muito tóxico e que tem ampla distribuição pela sua grande utilidade. Mesmo a exposição a baixos níveis (que não causam sintomas de intoxicação aguda) de chumbo é associada a desordens cognitivas e neurológicas. O osso é considerado o melhor marcador de exposição a chumbo. No tecido ósseo, vários elementos estão presentes, e alguns deles poderiam ter sua concentração modificada pela exposição a chumbo. Testou-se a hipótese de que haja variações nos elementos Zn e Mg nas tíbias de animais expostos a chumbo (por técnica de química analítica convencional). Testou-se também se variações em microelementos poderiam ser detectadas por técnicas semiquantitativas nas tíbias de controles e animais expostos a chumbo. O objetivo deste projeto foi caracterizar em animais expostos ao chumbo desde a gestação e controles as concentrações deste elemento no osso (tíbia) de animais de 28 e 60 dias. Além do chumbo, investigamos também a concentração de 2 outros microelementos no osso: zinco e magnésio. As medidas quantitativas de chumbo foram feitas no sangue total coletado ao final dos períodos. As medidas quantitativas de chumbo, cálcio, zinco e magnésio foram realizadas a partir de soluções ácidas obtidas pela dissolução total do osso, sendo estas utilizadas para quantificar por Espectrometria de Absorção Atômica no modo chama ou com Forno e Grafite. Mandíbulas foram análisadas em Microscopia Eletrônica de Varredura e utilizando os acessórios Eletron Dispersive Spectroscopy para os elementos mais abundantes e Wavelenght dispersive Spectroscopy para investigar por análise semiquantitativa os mais abundantes elementos inorgânicos no osso destes animais, como forma de verificar se há variações nestes microelementos nos animais expostos a chumbo em comparação com controles. Como o chumbo se concentra na superfície do esmalte, também analisou-se o esmalte de primeiros molares inferiores, a fim de verificar se era visto o sinal do elemento chumbo nestes dentes. Foram usados ratos Wistar machos de 28 e 60 dias divididos em 2 grupos: C 28D (n=5) e Pb 28D (n=5) e, C 60D (n=12) e Pb 60D (n=17). Em todas as medidas de chumbo dos grupos controle as concentrações obtidas foram próximas ao limite de detecção, e houve sempre diferença estatisticamente significante (P<0.0001) quando os controles foram comparados aos grupos expostos a chumbo. As concentrações de chumbo obtidas no sangue de animais do grupo Pb 28D foi de 8,0 ug/dl (± 1.1) e no grupo Pb 60D foi de 7,2 ug/dl (± 0.89). Houve diferença estatisticamente significante entre as massas das tíbias (aferidas em balança e também a partir da quantidade de cálcio dissolvida em solução) do grupo C 60D (0,86 g ± 0,13) e Pb 60D (0,61 g ±0,11)(p=0.0004). As concentrações de chumbo detectadas nos ossos do grupo Pb 28D foi 8,02 (± 1,12) e no grupo Pb 60D foi de 43,3ug/g (± 13,26). Concentração de zinco no osso do grupo C 60D foi 0,22 mg/g e no grupo Pb 60D foi 0,22 mg/g (p>0.05). A concentração de magnésio no osso do grupo C 60D foi de 4,89 mg/g ± 0,74 e no grupo Pb 60D foi de 4,98mg/g ±0,79 (p>0.05). Os microelementos mais abundantes detectados nas tíbias contralaterais por Microscopia Eletrônica de varredura por EDS/WDS foram cálcio, fósforo, carbono, oxigênio, magnésio, sódio e potássio, não tendo sido detectadas variações nestes elementos entre os grupos controle e expostos a chumbo de 60 dias. O chumbo foi detectado apenas na região cervical dos dentes molares por MEV-EDS, e, nesta posição, apenas na forma de óxido de chumbo (deposição extrínseca) que pode ser útil para fins forenses ou de determinação de contaminação desconhecida. As conclusões deste estudo são: Houve diferença estatisticamente significante entre as massas de osso do grupo Pb 60D e C 60D. Mesmo não havendo diferença entre as concentrações de chumbo no sangue total de animais de 28 e 60 dias, houve quantidade de chumbo 5 vezes maior nos animais Pb 60D. Não houve diferenças nas concentrações de zinco e magnésio entre controles e animais expostos a chumbo. Os microelementos mais abundantes detectados nas tibias contralaterais por Microscopia Eletrônica de varredura por EDS/WDS foram cálcio, fósforo, carbono, oxigênio, magnésio, sódio e potássio, não tendo sido detectadas variações semi-quantitativas nestes elementos. O chumbo não foi detectado nem nos grupos controle ou expostos por MEV, e nos molares só foi detectada no grupo exposto como uma deposição extrínseca. / Lead is a highly toxic metal that is ubiquitous do to its great usefulness. Exposure to even low levels of lead (which do not cause symptoms of acute poisoning) is associated with cognitive and neurological disorders. Bone is considered the best marker of exposure to lead. Several chemical elements are found in bone, and some of them may have a different concentration or distribution due to exposure to lead. We tested the hypothesis that there are variations in the elements zinc and magnesium in the tibia of animals exposed to lead (being those elements determined by a conventional analytic chemistry technique). It was also tested whether variations in microelements could be detected by semiquantitative microanalysis in tibias of controls and animals exposed to lead. The objective of this project was to determine the concentration of lead in bone (tibia) of animals exposed to lead from pregnancy to day 28 and day 60. Besides lead, zinc and magnesium were also determined. Lead was also determined in whole blood collected at the end of the 2 time points. Quantitative measurements of lead, calcium, zinc and magnesium have been made in solutions obtained by dissolution of the bone by Atomic Absorption Spectrometry using flame or Graphite Furnace. Tibias were analyzed by scanning electron microscopy using the accessories Electron Dispersive Spectroscopy and Wavelength dispersive Spectroscopy for semiquantitative analysis of inorganic elements in the bone and molars of these animals. Lower molars were also analyzed by these means. Male Wistar rats aged 28 and 60 days were used in these study. In both these ages there were animals in the control (C 28D, n = 5 and C 60D, n=12) and lead exposed group (Pb 28D, n = 5 and Pb 60D, n = 17). Lead concentrations found in control groups were close to the detection limit, and there was always statistically significant differences (P <0.0001) when control groups were compared with those exposed to lead. Blood lead of groups Pb 28D and Pb 60D was 8.0 ug/dl (± 1.1) and 7.2 ug/dl (± 0.89), respectively. There was a statistically significant difference between the masses of the tibia (measured in balance and also from the amount of calcium dissolved in solution): C 60D showing 0.86 g (± 0.13 g) and 0.61 g (± 0, 11) of the Pb 60D group (p = 0.0004). Lead concentrations increased five times when the Pb 28D group was compared with the Pb 60D (8.02 and 43.3 ug/g)(p<0.0001). Zinc concentrations were not different in the C 60D (0.22 mg/g) and in the Pb 60D group (0.22 mg/g)(p>0.05). Magnesium concentrations were 4.89 mg/g in the C 60D and 4.98 mg/g in the Pb 60D (p>0.05). The most abundant trace elements detected in the contralateral tibiae by SEM-EDS/WDS were calcium, phosphorus, carbon, oxygen, magnesium, sodium and potassium and no variations in these elements were detected between the control and lead exposed groups. Lead was detected only in the cervical region of molar teeth of the lead exposed groups by SEM-EDS. This finding revealed lead in the lead oxide (extrinsic deposition) which may be useful for forensic purposes or for determining unknown contaminations. Conclusions: There was a statistically significant difference between the bone masses of the Pb 60D and C 60D groups. While there is no difference between lead concentrations in whole blood of animals 28 and 60 days, the amount of lead was 5 times higher in animals Pb 60D. There were no differences in the concentrations of zinc and magnesium between controls and lead exposed animals. The most abundant trace elements detected in the contralateral tibiae by SEM-EDS/WDS were calcium, phosphorus, carbon, oxygen, magnesium, sodium and potassium, and no semi-quantitative variations in these elements were detected in relation to exposure to lead. Lead was not detected either in control or exposed groups by SEM, and in molars it was only detected in the exposed group as an extrinsic deposition.

O contínuo Tempo Randon Walk desenvolvido por Scher e Montroll é generalizado a fim de incluir as transições de taxas de espaço e o tempo. Tomando o limite contínuo, no passeio de equações aleatórias, uma equação geral de uma carga espacial transportada é obtida. A equivalência entre hopping e transporte através de estados expandidos com armadilhas é mostrado para realizar no espaço uma carga caso. Uma análise dos transportes um processo com dois processos simultâneos condução, por um armadilhagem e alargado a outros estados e por hopping através de armadilhas, é realizada. O Método Substituição Funcional (EFM) é introduzida a fim de obter resultados semi-markofian de Markofian soluções. Soluções específicas são obtidas em campo caso o alto e aproximadas queridos no espaço cobrar caso. Uma aproximação analítica de solução para o potencial superficial de decadência de uma sólida com armadilhas cobrado pela Corona é dada pela utilização do FSM. / The continuous Time Randon Walk developed by Scher and Montroll is generalized in order t o include space and time transitions rates. Taking the continuum limit in the random walk equations a general equation for space charge transport is obtained. The equivalence between hopping and transport via extended states with traps is shown to hold in the space charge case. An analysis of a transport process with two simultaneous conduction process, one by trapping and extended states and the other by hopping via traps, is carried out. The Functional Substitution Method (FSM) is introduced in order to get semi-markofian results from Markofian solutions. Specific exact solutions are obtained in the high field case and approximated ones in the space charge case. An approximated analytical solution for the superficial potential decay of a solid with traps charged by Corona is given by use of FSM.