Dans ce travail, nous nous sommes intéressés à la synthèse et à la caractérisation de matériaux à base d'argiles naturelles en provenance d'Algérie et de Tunisie, pouvant être utilisés en tant que catalyseurs dans l'oxydation de polluants organiques par les réactions Fenton et photo-Fenton. Nous avons également optimisé les paramètres réactionnels (quantité de catalyseur, concentration en polluant...) dans le but d'améliorer les performances catalytiques de ces derniers. En effet, l'oxydation de polluants organiques récalcitrants par des réactions de type Fenton est considérée comme l'une des techniques les plus performantes parmi les procédés d'oxydation avancée (POA). Elle permet d'aboutir dans certains cas au stade ultime de l'oxydation qui est la minéralisation (transformation en CO₂ et H₂O). La caractérisation des argiles à l'état brut par différentes techniques physico-chimiques montre qu'en plus des matériaux argileux, il existe quelques oxydes métalliques dans toutes les argiles étudiées, avec des proportions plus ou moins variées. En particulier, la smectite a montré une contenance assez importante en fer. Les argiles synthétisés montrent une très bonne performance catalytique en un minimum de temps (2 heures de réaction). Le catalyseur à base de smectite calciné à 450°C et tamisé donne le meilleur rendement catalytique. Cette activité peut être expliquée par la forte teneur en fer ainsi qu'à la combinaison entre le choix de la taille des particules et la température de calcination de la smectite. La caractérisation de ce catalyseur a montré que ce matériau mésoporeux contenait une quantité de fer (III) stabilisée dans la structure par le fait de la calcination. / In this study, we are interested to the synthesis and charaterization of materials based on natural clays from Algeria and Tunisia, usable as catalysts in the oxidation of organic pollutants by the Fenton's and photo-Fenton's reaction. We have also optimized the reaction parameters (amount of catalyst, concentration of pollutant...) in order to improve the catalytic performance of these catalysts. Indeed, the oxidation of recalcitrant organic pollutants by Fenton-type reactions is regarded as one of the most effective method amongst the advanced oxidation process (AOPs). It can lead in some cases to the total mineralization of pollutants (conversion into CO₂ and H₂O). The caracterization of the raw clays various physicochemical methods shows that, in addiction to clay minerals, there are some metallic oxides in all studied clays, with varied proportions. Especially, smectite showed a fairly significant iron capacity. The synthesized clays show a good catalytic performance in minimum of time (2 hours of reaction). The smectite catalyst, sieved and calcined at 450°C gives the best performance. This activity can be explained by the high content of iron as well as the combination of the choice of particle size and the calcination temperature of the smectite. The caracterization of this catalyst, showed that this mesoporous material contains an amount of iron (III) stabilized in the structure by the fact of calcination.

Les sols stockent trois fois plus de carbone que l'atmosphère sous la forme d'un mélange de molécules, la matière organique des sols (MOS). Certaines de ces molécules sont présentes dans le sol depuis des centaines voire des milliers d'années. Trois mécanismes de protection sont utilisés pour expliquer cette persistance à long terme des matières organiques dans les sols : (i) la récalcitrance chimique, (ii) la protection physique dans les agrégats et (iii) la protection physicochimique par adsorption sur les surfaces minérales. Le but de ce projet de thèse est d’améliorer la compréhension de ces processus de protection et de leur importance relative. Mon projet de thèse utilise des échantillons permettant l'accès au carbone persistant : les jachères nues de longue durée (5 sites en Europe). Il s'agit de parcelles maintenues vierges de toute végétation dans lesquelles, au fur et à mesure de la biodégradation, la quantité totale de carbone diminue, entraînant un enrichissement relatif en carbone persistant. La première étude expérimentale de ce travail de thèse vise à tester l'efficacité des méthodes d'oxydation chimique. Les deux réactifs les plus couramment utilisés -l'hypochlorite de sodium NaOCl et le peroxyde d'hydrogène H2O2- ont été testés sur des échantillons de la plus longue jachère nue (Versailles). Il est conclu que les méthodes d'oxydation chimique n'arrivent pas à isoler efficacement un réservoir de carbone persistant à l'échelle du siècle.En termes de mécanismes de persistance, les résultats obtenus montrent que la récalcitrance chimique n'est pas le principal mécanisme de protection. En effet, sur la durée de la jachère nue, la composition chimique de la MOS, caractérisée par spectroscopie NEXAFS, ne présente que peu de changements. Un enrichissement en composés présentant des groupements acides carboxyliques est détecté pour tous les sites testés. Une étude poussée de la persistance spécifique du carbone pyrogénique des sols a aussi été réalisée, ces composés sont actuellement considérés cinq fois plus persistants que le carbone total. Les résultats montrent que le carbone pyrogénique est moins persistant que prévu. En effet, le temps de résidence moyen du carbone pyrogénique obtenu par la méthode BPCA (116 ans) est seulement 1,6 fois supérieur à celui de la MOS (73 ans). L'étude du contrôle minéralogique de la persistance des MOS montre que les argiles contenant du potassium (illite) protègent moins de carbone que les argiles smectitiques. Le rapport C/N décroit avec le temps dans toutes les fractions argiles, ce qui prouve que les composés riches en azote sont préférentiellement préservés. Enfin, la présence de microagrégats dans la fraction grossière des argiles implique la coexistence de deux mécanismes de protection : la protection physique et la protection par adsorption sur les minéraux. / Soils store three times more carbon than the atmosphere, under the form of a complex mixture of molecules called soil organic matter (SOM). Some of these molecules have been standing in the soil for hundreds to thousands of years. Three main mechanisms are invoked to explain this long term carbon persistence in soils, (i) chemical recalcitrance, (ii) physical protection in aggregates and (iii) protection by adsorption on mineral surfaces. One of the major challenges in SOM science is to better understand the relative importance of each mechanism, that is the aim of this PhD project. Here, we use samples from by long term bare fallows (5 sites across Europe). These experimental plots have been kept free of vegetation by manual or chemical weeding for several decades and have been regularly sampled and stored. As the duration of the bare fallow increases, biodegradation occurs and samples get enriched in persistent carbon.First experiments consisted in testing the efficiency of chemical oxidations (two reagent were tested, sodium hypochlorite –NaOCl- and hydrogen peroxide –H2O2) on the longest bare fallow. We concluded that oxidation methods were not able to efficiently isolate a pool of persistent carbon at the centennial timescale. In terms of mechanisms of persistence, the obtained results show that chemical recalcitrance does not seem to be the major mechanism. Indeed, over the duration of the bare fallow, the chemical composition of SOM, as seen by synchrotron based NEXAFS spectroscopy, shows little changes. There is a consistent increase in carboxylics for all sites (12% increase on average) though it is significant for 2 out of the 4 selected sites. We also studied the particular persistence of soil pyrogenic carbon, which is thought to be at least five times more persistent than bulk SOM. Results show that pyrogenic carbon lacks long term persistence. Indeed the BPCA-estimated mean residence time of pyrogenic carbon (116 years) is on average 1.6 times longer than MRT for bulk SOM (73 years). Finally, the study of mineralogical control of the persistence of SOC showed that clay minerals containing potassium (illite) seemed to protect less carbon. As seen by NEXAFS-STXM, more mineral surfaces with very little SOM appear with the duration of bare fallow. C:N ratio decreased in all clay fractions, suggesting a preferential persistence of N-rich compounds. Presence of microaggregates in the coarser clay fraction led to the coexistence of two protection mechanisms: adsorption and physical protection.

Plates of ceramic samples to accompany a thesis studying the suitability of five clays from the vicinity of Denton, Texas for use in high-school ceramics classes. The abundance of natural clays in Denton County and throughout the state of Texas, the ease with which clays may be obtained, and the ease with which they may be refined for use provide almost unlimited teaching possibilities in high-school art classes. This study of five Denton County clays has proved informative in several respects. It has shown that within the vicinity of Denton there are clays that are suitable for high-school use. Although all these clays may be suitable for one technique of pottery making each may not be suitable for all techniques. Many clays may be used after refining by a simple, quick process without the use of expensive and complicated equipment. Simple glazes, which have an aesthetic as well as a utilitarian value, may be compounded to fit these clays.

No description available.

The purpose of this study is to determine the suitability of five clays from the vicinity of Denton, Texas for use in high-school ceramics classes. The abundance of natural clays in Denton County and throughout the state of Texas, the ease with which clays may be obtained, and the ease with which they may be refined for use provide almost unlimited teaching possibilities in high-school art classes. This study of five Denton County clays has proved informative in several respects. It has shown that within the vicinity of Denton there are clays that are suitable for high-school use. Although all these clays may be suitable for one technique of pottery making each may not be suitable for all techniques. Many clays may be used after refining by a simple, quick process without the use of expensive and complicated equipment. Simple glazes, which have an aesthetic as well as a utilitarian value, may be compounded to fit these clays.

Soft soil deposits of coastal regions and lowland areas pose many geotechnical problems but it is indispensable to utilize these grounds to meet the growing demand for infrastructure with ever increasing urbanization and industrial development. Soft soils are generally associated with high compressibility and low strength characteristics which augment the risk of huge settlements and foundation failure. It is essential to understand the complex behaviour of the ground consisting of soft clays as construction and maintenance of infrastructure in these areas is challenging. Marine sediments mostly possess open microstructure irrespective of the differences in their mineral composition and sedimentation environment. Also this particular microstructure in marine sediments is generally accompanied by the presence of a great amount of organic residues and fragments of marine organisms. Formation of pyrite is also possible because of the presence of decomposable organic matter, dissolved sulfate and reactive iron minerals. These soils due to their inherent mineralogy and microstructure have high void ratios and consequently high water holding capacity which explains the reason for their low shear strength and high compressibility characteristics. And often the formation environment is conducive for incorporation of organic content in the soft clay deposits which further aggravates the problem. A complete characterization of the soil can enhance the understanding of soil behavior and therefore can play a crucial role in suggesting suitable and sustainable ground improvement method. Soft clay deposits of Kuttanad area in Kerala, India extending to varying depths below the ground level, present a challenge as a foundation soil due to low bearing capacity and high settlement. Geologically Kuttanad is considered as a recent sedimentary formation. In the geological past, the entire area was a part of the Arabian Sea. Presently Kuttanad area covers an area of about 1,100 km2. Many intriguing reports of distresses to structures founded on this soil are available. An over view of specific characteristics of soft clays along with the comprehensive description of soft clays from various parts of the world is presented in the introductory Chapter. Deep soil mixing and mass stabilization methods are found to be relatively advantageous in reducing differential settlements and in achieving expeditious construction. A more detailed review of literature on Kuttanad soil problems and various ground improvement methods adopted are presented. The different ground improvement techniques attempted are soil reinforcement, stone columns, preloading etc. Soil mixing can be relatively advantageous over the other conventional ground improvement methods. Laboratory studies carried out earlier with different binders such as cement, lime and lime fly ash combinations did not exhibit appreciable improvement in soil strength. It is reasoned that the lack of understanding of the soil characteristics is responsible for the limited success of these attempts. Based on the review of literature the detailed scope of the work is presented at the end of Chapter 1. The method of collection of the soil from Kuttanad region, methods adopted for characterization of soil, characteristics of various binders used and testing procedures adopted for assessing the geotechnical behavior with and without binders are described in Chapter 2. In order to characterize the soil for understanding its behaviour under different conditions as well as to gauge its response to different stabilizers, a detailed physico¬chemical, mineralogical, morphological and fabric studies are carried out and presented in Chapter 3. An attempt has been made to explain the role of components of soils such as organic substances, pyrite and sesquioxides for variations in its properties with change in water content. The high water holding capacity of the soil reflected in its Liquid limit along with relatively low plasticity characteristics of the soil has been explained as due to the presence of minerals such as metahalloysite and gibbsite, the flocculated fabric, porous organic matter and water filled diatom frustules (amorphous silica). Based on the study conducted on the plasticity characteristics of Kuttanad soil under different conditions of drying and treatment, it was brought about that the organic content plays a dominant role in particle cementation and aggregation causing a substantial reduction in plasticity upon drying. Further, the presence of minerals such as pyrite and iron oxides also account for the plasticity changes. The significant changes in soil properties upon drying have also been successfully explained in Chapter 4. Attempts made to stabilize the soil using conventional chemical stabilizers are described in Chapter 5. The effect of binders on the strength improvement of soil has been explained based on the changes occurring in the composition, fabric and physico-chemical characteristics of soil upon addition of the binders. Lack of strength development in soil with lime has been attributed to the inherent composition of the soil hindering the formation of pozzolanic compounds and unfavourable modification of the fabric. On the other hand the soil responded well to cement stabilisation. The influence of various parameters such as Water/Cement (W/C) ratio, Initial water content, curing period and additive dosage on the strength development of cement treated soil has been examined. Cement improved the strength of the soil by binding the soil particles without depending on the interaction with the soil. It was observed that the role of initial water content is insignificant and the strength improved with reducing W/C ratio. The dependence of strength development with cement addition on the fabric at different W/C ratios has been assessed. Also the role of other additives such as Lime, Sand, Fly Ash, Ground granulated blast furnace slag, Silica fume and Sodium silicate to enhance the strength of cement treated soil has been analysed in Chapter 5. It was shown that only Sodium Silicate (NS) along with cement meets with good success. The studies on the undrained shear strength and compressibility characteristics of cemented soil carried out to understand the strength and deformation behaviour of the cemented soil are presented in Chapter 6. It is clear from the compressibility characteristics of the cemented soil that there is a well defined yield stress demarcating the least compressible pre-yield zone and more compressible post yield zone. Generally the yield stress increases with reducing water cement ratio. It is interesting to note that the post yield compressibility of the cemented soil is controlled more by the fabric of soil than by cementation effect. The study on the undrained shear behavior of cemented soil revealed that the cohesion intercept and angle of internal friction increases with addition of cement. However the impact of cementation is reflected more as increase in cohesion intercept with increasing cement content. The uniqueness of failure envelope observed for the cemented soil irrespective of whether the confining stress is above or below the yield stress has been explained in detail. A case study on the performance of embankment founded on Kuttand soil improved with Deep mixed cement columns (DMCC) has been evaluated through numerical simulations using FLAC 2D and this forms the subject matter of Chapter 7. For this work the soil properties of the Kuttanad soil determined by experimental investigations have been used. The simulation results showed that the introduction of DMCC columns improved the factor of safety against failure and reduced settlements. This study clearly endorses the analysis and the results of the test carried out on Kuttanad soil. The final chapter summarizes the details of the work carried out which brings out the importance of characterization of the soil in terms of soil components, physico-chemical environment as well as the micro structure of the soil in predicting the behaviour of the soil in changing environment and to understand the stabilization response of the soil with different binders which intern helps to select appropriate binder and or binder combinations.

O presente trabalho trata da preparação e da caracterização de sistemas contendo tetrassulfoftalocianinas de Co(II) (CoPcTs) e Fe(III) (FePcTs) intercaladas ou somente adsorvidas externamente em matrizes de hidróxidos duplos lamelares (HDLs). Foram sintetizados materiais com composições variadas e empregando-se diferentes métodos de síntese visando, principalmente, o isolamento de materiais com microporosidade intracristalina e/ou com um baixo grau de agregação da ftalocianina. Técnicas de caracterização textural (difração de raios-X e medidas de área superficial) e espectroscópicas (vibracional na região do infravermelho, eletrônica no UV/visível, ressonância paramagnética eletrônica e absorção de raios-X), além das análises elementar (C, H, N e metais) e termogravimétrica foram utilizadas para a caracterização dos sólidos sintetizados. Avaliaram-se os materiais como catalisadores na reação de oxidação do 2,6-di-terc-butilfenol e do catecol, utilizando O2ou H2O2 como oxidantes. Nos materiais isolados contendo a CoPcTs intercalada em HDLs com composição MgxAl (x = 2, 3 e 4) e ZnxAl (x = 4 e 5), a ftalocianina está orientada perpendicularmente às lamelas do HDL, independentemente do método de síntese e da composição dos HDLs utilizados. Adicionalmente, constatou-se que a CoPcTs intercalada está altamente agregada e que os materiais não possuem microporosidade. Porém, a diminuição da densidade de carga do HDL provoca uma pequena diminuição na agregação da CoPcTs. Sob determinada condição sintética, a CoPcTs intercalada nos HDLs ZnxAl sofre o processo de enxertia através dos grupos sulfônicos. Quando testados como catalisadores na oxidação do 2,6-di-terc-butilfenol, os materiais contendo a CoPcTs intercalada e enxertada apresentaram reatividade inexpressiva, que pode ser devida ao acesso restrito do substrato ao sítio ativo na região interlamelar. Estudos de adsorção da FePcTs em HDLs MgxAl na forma carbonato, investigados por espectroscopia eletrônica UV/Visível in situ, mostraram uma elevada tendência de agregação da ftalocianina na superfície dos HDLs. Os espectros eletrônicos indicaram também que diferentes espécies derivadas da FePcTs são formadas durante o processo de adsorção nos HDLs e que a densidade de carga influencia o tipo de espécie adsorvida: há predominância de um dímero do tipo µ-oxo nos HDLs Mg2Al e Mg3Al e do dímero (FePcTs)2 no HDL Mg4Al. Os espectros de absorção de raios-X (XANES) da FePcTs adsorvida nos HDLs MgxAl mostraram que as espécies adsorvidas apresentam geometria piramidal de base quadrada (C4v) e/ou octaédrica (Oh), corroborando com os dados de espectroscopia no UV/Visível. Já os espectros de ressonância paramagnética eletrônica mostraram que a ftalocianina de Fe(III) quando adsorvida nos HDLs gera uma mistura de espécies com configuração de baixo spin e alto spin e, também, elevada distorção rômbica. A FePcTs adsorvida nos HDLs MgxAl apresentou estabilidade e reatividade catalítica superior quando comparada com a ftalocianina livre na oxidação dos fenóis. A ftalocianina adsorvida na superfície externa do HDL deve favorecer o acesso do substrato ao sítio ativo. Uma correlação entre os estudos de adsorção e os resultados dos testes catalíticos mostrou que a espécie dimérica do tipo µ-oxo pode ser a espécie mais ativa na oxidação dos fenóis. Nestes sistemas, as camadas positivas do HDL devem provocar um enfraquecimento da ligação O-H do fenol, facilitando a sua desprotonação (uma das etapas do mecanismo de oxidação). Este último efeito pareceu atuante, pois foram observadas reatividades crescentes dos catalisadores à medida que se aumentava a densidade de carga do HDL. Estes resultados indicaram que existe um efeito cooperativo nos HDLs MgxAl contendo a FePcTs adsorvida, mostrando que o HDL não atua como um suporte inerte nos processos estudados. / The present work describes the preparation and characterization of materials containing Co(II) and Fe(III) tetrasulfonated phthalocyanines (CoPcTs and FePcTs, respectively) intercalated or adsorbed on layered double hydroxides (LDHs). Different compositions and synthetic methods were used to isolate materials with microporosity and/or the phthalocyanine in a low aggregation degree. X-ray diffraction analysis, surface area measurements, spectroscopic techniques (infrared, UV/visible and X-ray absorption), elemental analysis and thermogravimetry were used to characterize the solids. The materials were tested as catalysts in the 2,6-di-terc-butilfenol and catechol oxidation, using O2 or H2O2 as oxidants. In the materials prepared by intercalation of the CoPcTs in MgxAl (x = 2, 3 and 4) and ZnxAl (x = 4 and 5) LDHs, the phthalocyanine is perpendicularly orientated related to the LDH layers, regardless of synthetic method or LDH composition used. In addition, it was observed that the intercalated phthalocyanine is aggregated and the solids do not have microporous. However, the aggregation degree of the phthalocyanine is slightly lower when the LDH charge density decreases. Under a particular synthetic conditions the CoPcTs intercalated in the LDH ZnxAl is grafted through the sulfonic groups. Catalytic tests uisng this material in the 2,6-di-terc-butilfenol oxidation showed a neglectful reactivity, which confirms the aggregation of the intercalated CoPcTs, thus avoiding that the substrate accesses the reactive center. In an adsorption study carried by monitoring in situ the FePcTs UV/Vis electronic spectra during its addition to LDH suspensions, a strong tendency of aggregation was observed for the FePcTs. In addition, different FePcTs species are formed during the adsorption process on the LDHs, which is influenced by the LDH charge density: the µ-oxo complex is the main species adsorbed on the Mg2Al and Mg3Al LDHs, whereas for Mg4Al the non oxo-bridged dimeric complex prevailed. X-ray absorption spectra (XANES) of the adsorbed FePcTs on the MgxAl LDHs showed that the species present a square-pyramidal (C4v) and/or an octahedral (Oh) symmetry, in agreement with the UV/visible spectroscopic data. EPR spectra of these samples showed that the FePcTs adsorbed on the LDHs leads to a mixture of Fe(III) high and low spin species along with a strong rhombic distortion. The FePcTs adsorbed on the MgxAl LDHs showed an enhanced catalytic activity and longevity in the phenols oxidation compared to the homogeneous counterpart. The phthalocyanine on the LDH external surfaces allows the access of the substrate to the reactive metal center. A correlation between the adsorption study and the catalytic tests pointed that the FePcTs µ-oxo complex may be the active species in the oxidation of phenols. Furthermore, the positive charge of LDH layers may weaken the O-H bonding in the phenol molecules making them more easily ionized (one step of the phenol oxidation mechanism). This feature seems to be effective because higher activities of the catalysts were observed along with increasing charge density of the LDHs. These results indicated that a cooperative effect takes place in the materials containing the FePcTs adsorbed on the MgxAl LDHs, showing that LDH do not act as an inert support in the studied catalytic reactions.

Made available in DSpace on 2017-07-25T19:30:02Z (GMT). No. of bitstreams: 1 Andre Carlos Auler.pdf: 1218277 bytes, checksum: aedcd75095720ba4b41e7ad48e647731 (MD5) Previous issue date: 2014-07-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Liming is the practice used to correct soil acidity and its reaction is dependent on the mode of application of the lime. The addition of lime to the soil with the tilling is an alternative for increasing his reaction. However, tillage alters its structure and processes occurring in it. The aim of this study was to evaluate the influence of liming of liming in three modes of application of limestone (on the surface, incorporated with plowing and harrowing and subsoiling and disking) on the physico-hydrical attributes of a Dystrudept. For this, an experiment was installed in the field with banded design, with treatments in a factorial arrangement (3 × 2). Treatments formed from the combination of two rates of lime (0 and 15 Mg ha-1) and three modes of application of limestone (on the surface, incorporate with plowing and harrowing and subsoiling and harrowing). Undisturbed and disturbed soil samples were collected at 0-0.10 and 0.10-0.20 m layers between plant rows of corn 18 months after installation of the experiment. The water-dispersed clay (WDC), flocculation degree (FD), bulk density (BD), total porosity (TP), water retention curves, pore size distribution curve, particle size and soil chemical properties were determined order to diagnose the effects of liming the soil studied. Liming effects on the physico-hydrical attributes of the soil were restricted to 0-0.10 m layer. The WDC and the FD were influenced by tillage, but not by liming. When liming was performed on the surface, there was a reduction of the DB and increased TP. In all modes of application of limestone, liming increased water retention and altered the distribution of pores. To conclude, the changes in physico-hydrical attributes of the soil were mostly due to the increase of pH and replacement of aluminum by calcium and magnesium in the exchange complex. / A calagem é a prática empregada na correção da acidez do solo e sua reação depende do modo de aplicação do corretivo. A incorporação de calcário com o revolvimento do solo é uma alternativa para o aumento da reação. Porém, a mobilização do solo altera a sua estrutura e os processos que nela ocorrem. O objetivo deste trabalho foi avaliar a influência da calagem em três modos de aplicação do calcário (na superfície, incorporada com aração e gradagem e com subsolagem e gradagem) nos atributos físico-hídricos de um CAMBISSOLO HÁPLICO Alumínico. Para isso, instalou-se um experimento em campo com delineamento em faixas, com tratamentos em arranjo fatorial (3 × 2). Os tratamentos constituíam-se da combinação de duas doses de calcário (0 e 15 Mg ha-1) e três modos de aplicação do calcário (na superfície, incorporado com aração e gradagem e subsolagem e gradagem). Amostras indeformadas e deformadas de solo nas camadas 0-0,10 e 0,10-0,20 m foram coletadas nas entrelinhas da cultura do milho 18 meses após a instalação do experimento. Foram avaliados os teores de argila dispersa em água (ADA), grau de floculação (GF), densidade do solo (Ds), porosidade total (Pt), curvas de retenção de água, curva de distribuição de poros, granulometria e atributos químicos do solo. Os efeitos da calagem sobre os atributos físico-hídricos do solo foram restritos à camada 0-0,10 m. A ADA e o GF foram influenciados pelo modo de aplicação do calcário, mas não pela calagem. Quando a calagem foi realizada na superfície, ocorreu redução da DS e aumento da Pt. Em todos os modos de aplicação do calcário, a calagem aumentou a retenção de água e alterou a distribuição de poros. Concluiu-se que as alterações nos atributos físico-hídricos do solo foram em sua maioria decorrentes do aumento do pH e da substituição do alumínio por cálcio e magnésio no complexo de troca.

A extensa utilização de pesticidas na agricultura moderna tem contribuído para um aumento na contaminação do meio ambiente. Os Hidróxidos Duplos Lamelares (HDLs) ou argilas aniônicas, apresentam uma estrutura lamelar na qual uma variedade de ânions podem ser intercalados entre as lamelas através de interações eletrostáticas. Estes materiais lamelares podem ser utilizados em processos de adsorção/sorção e como suporte para a liberação lenta de compostos químicos. Assim, os principais objetivos deste trabalho foram: o estudo da sorção de ânions orgânicos de herbicidas ácidos 2,4-D, MCPA e Picloram utilizados na agricultura nacional, pela regeneração de HDLs de Mg-Al-CO3 calcinado e por troca aniônica em HDLs de Mg-Al-Cl. Para isso foram investigados a cinética do processo de sorção, além da determinação das isotermas em dois valores diferentes de pH. Assim, estes herbicidas foram intercalados em HDLs de Mg-Al, utilizando dois métodos de síntese indireta: regeneração do material calcinado e troca aniônica em solução, além do método de síntese direta por coprecipitação, sendo os materiais devidamente caracterizados. Todos os materiais obtidos, intercalados com cada um dos herbicidas, foram utilizados para o estudo da cinética de liberação dos mesmos em água. Os materiais obtidos por regeneração contendo cada um dos três herbicidas foram utilizados também no estudo da lixiviação em colunas de solo e no estudo de bio-ensaio com plantas, para testar a eficiência dos HDLs como suportes na liberação lenta dos herbicidas. A partir do estudo da cinética do processo de sorção dos ânions orgânicos presentes em solução utilizando HDLs de Mg-Al contendo cloreto ou carbonato após a calcinação, observou-se que a remoção dos ânions ocorreu através dos processos de troca aniônica no caso do HDL contendo cloreto, ou de regeneração da estrutura lamelar no caso do HDL calcinado. A intercalação dos ânions orgânicos na posição vertical foi verificada no processo de adsorção/sorção, e se mostrou dependente da concentração do herbicida em solução. O HDL calcinado apresentou a maior eficiência na remoção dos ânions da solução. Os herbicidas suportados em HDLs, apresentaram uma liberação em água mais lenta do que os mesmos em sua forma livre, e não se mostrou dependente do método de preparação da matriz utilizada. Os resultados dos estudos de lixiviação utilizando como matriz o HDL obtido por regeneração, demonstraram que os HDLs são bons suportes para os herbicidas pois apresentaram uma liberação lenta do ingrediente ativo, principlamente para o herbicida Picloram. O bio-ensaio mostrou que a forma de liberação dos herbicidas suportados foi eficiente no controle da germinação das sementes de plantas em aplicações pré-emergenciais. / The extensive use of pesticides in modern agriculture has been contributing to an increase in environmental contamination. Layered Double Hydroxides (LDHs), or anionic clays, bear a layered structure, and a variety of anions can be intercalated between these layers through electrostatic interactions. These layered materials can be used in adsorption/sorption processes and in the slow release of chemical compounds. So this work aims at studing the sorption of the acid herbicides bearing organic anions 2,4-D, MCPA and Picloram, used in national agriculture, through regeneration of calcined Mg-Al-CO3 LDH and anion exchange of Mg-Al-Cl ? LDH. For this purpose, the kinetics of the sorption process was investigated, and the determination of isotherms in two different pH values was carried out. The herbicides were intercalated in Mg-Al ? LDH using two indirect synthesis methods: regeneration of the calcined material and anion exchange in solution; besides the direct synthesis method by coprecipitation. The obtained materials were properly characterized. All the obtained materials, intercalated with each of the herbicides, were used in a kinetic release study in water. The materials obtained by regeneration were also used in a leaching and in a bioassay study, to test the efficiency of LDHs as supports for the slow release of herbicides. From the kinetic sorption process of the organic anions in solution using Mg-Al ? LDH containing chloride or carbonate after calcination, it was observed that the removal of anions occurred through an anionic exchange process in the case of the LDH containing chloride, or through regeneration of the layered structure in the case of the calcined LDH. The intercalation of organic anions in a vertical position was observed in the adsorption/sorption process, and it was shown to be dependent on the herbicide concentration in solution. The calcined LDH was the most efficient for removal of anions in solution. The herbicides supported on LDHs, presented a slower release in water than the same compounds in their free form, and the release behavior was not dependent on the methodology used for the preparation of the matrix. Leaching study results using the LDH obtained by regeneration as matrix demonstrated a slow release of the active ingredient, mainly for the Picloram herbicide. The bioassay showed that the release behavior of the supported herbicides was efficient in the control of plant seeds germination at preemergence applications.

O presente trabalho trata da preparação e da caracterização de sistemas contendo tetrassulfoftalocianinas de Co(II) (CoPcTs) e Fe(III) (FePcTs) intercaladas ou somente adsorvidas externamente em matrizes de hidróxidos duplos lamelares (HDLs). Foram sintetizados materiais com composições variadas e empregando-se diferentes métodos de síntese visando, principalmente, o isolamento de materiais com microporosidade intracristalina e/ou com um baixo grau de agregação da ftalocianina. Técnicas de caracterização textural (difração de raios-X e medidas de área superficial) e espectroscópicas (vibracional na região do infravermelho, eletrônica no UV/visível, ressonância paramagnética eletrônica e absorção de raios-X), além das análises elementar (C, H, N e metais) e termogravimétrica foram utilizadas para a caracterização dos sólidos sintetizados. Avaliaram-se os materiais como catalisadores na reação de oxidação do 2,6-di-terc-butilfenol e do catecol, utilizando O2ou H2O2 como oxidantes. Nos materiais isolados contendo a CoPcTs intercalada em HDLs com composição MgxAl (x = 2, 3 e 4) e ZnxAl (x = 4 e 5), a ftalocianina está orientada perpendicularmente às lamelas do HDL, independentemente do método de síntese e da composição dos HDLs utilizados. Adicionalmente, constatou-se que a CoPcTs intercalada está altamente agregada e que os materiais não possuem microporosidade. Porém, a diminuição da densidade de carga do HDL provoca uma pequena diminuição na agregação da CoPcTs. Sob determinada condição sintética, a CoPcTs intercalada nos HDLs ZnxAl sofre o processo de enxertia através dos grupos sulfônicos. Quando testados como catalisadores na oxidação do 2,6-di-terc-butilfenol, os materiais contendo a CoPcTs intercalada e enxertada apresentaram reatividade inexpressiva, que pode ser devida ao acesso restrito do substrato ao sítio ativo na região interlamelar. Estudos de adsorção da FePcTs em HDLs MgxAl na forma carbonato, investigados por espectroscopia eletrônica UV/Visível in situ, mostraram uma elevada tendência de agregação da ftalocianina na superfície dos HDLs. Os espectros eletrônicos indicaram também que diferentes espécies derivadas da FePcTs são formadas durante o processo de adsorção nos HDLs e que a densidade de carga influencia o tipo de espécie adsorvida: há predominância de um dímero do tipo µ-oxo nos HDLs Mg2Al e Mg3Al e do dímero (FePcTs)2 no HDL Mg4Al. Os espectros de absorção de raios-X (XANES) da FePcTs adsorvida nos HDLs MgxAl mostraram que as espécies adsorvidas apresentam geometria piramidal de base quadrada (C4v) e/ou octaédrica (Oh), corroborando com os dados de espectroscopia no UV/Visível. Já os espectros de ressonância paramagnética eletrônica mostraram que a ftalocianina de Fe(III) quando adsorvida nos HDLs gera uma mistura de espécies com configuração de baixo spin e alto spin e, também, elevada distorção rômbica. A FePcTs adsorvida nos HDLs MgxAl apresentou estabilidade e reatividade catalítica superior quando comparada com a ftalocianina livre na oxidação dos fenóis. A ftalocianina adsorvida na superfície externa do HDL deve favorecer o acesso do substrato ao sítio ativo. Uma correlação entre os estudos de adsorção e os resultados dos testes catalíticos mostrou que a espécie dimérica do tipo µ-oxo pode ser a espécie mais ativa na oxidação dos fenóis. Nestes sistemas, as camadas positivas do HDL devem provocar um enfraquecimento da ligação O-H do fenol, facilitando a sua desprotonação (uma das etapas do mecanismo de oxidação). Este último efeito pareceu atuante, pois foram observadas reatividades crescentes dos catalisadores à medida que se aumentava a densidade de carga do HDL. Estes resultados indicaram que existe um efeito cooperativo nos HDLs MgxAl contendo a FePcTs adsorvida, mostrando que o HDL não atua como um suporte inerte nos processos estudados. / The present work describes the preparation and characterization of materials containing Co(II) and Fe(III) tetrasulfonated phthalocyanines (CoPcTs and FePcTs, respectively) intercalated or adsorbed on layered double hydroxides (LDHs). Different compositions and synthetic methods were used to isolate materials with microporosity and/or the phthalocyanine in a low aggregation degree. X-ray diffraction analysis, surface area measurements, spectroscopic techniques (infrared, UV/visible and X-ray absorption), elemental analysis and thermogravimetry were used to characterize the solids. The materials were tested as catalysts in the 2,6-di-terc-butilfenol and catechol oxidation, using O2 or H2O2 as oxidants. In the materials prepared by intercalation of the CoPcTs in MgxAl (x = 2, 3 and 4) and ZnxAl (x = 4 and 5) LDHs, the phthalocyanine is perpendicularly orientated related to the LDH layers, regardless of synthetic method or LDH composition used. In addition, it was observed that the intercalated phthalocyanine is aggregated and the solids do not have microporous. However, the aggregation degree of the phthalocyanine is slightly lower when the LDH charge density decreases. Under a particular synthetic conditions the CoPcTs intercalated in the LDH ZnxAl is grafted through the sulfonic groups. Catalytic tests uisng this material in the 2,6-di-terc-butilfenol oxidation showed a neglectful reactivity, which confirms the aggregation of the intercalated CoPcTs, thus avoiding that the substrate accesses the reactive center. In an adsorption study carried by monitoring in situ the FePcTs UV/Vis electronic spectra during its addition to LDH suspensions, a strong tendency of aggregation was observed for the FePcTs. In addition, different FePcTs species are formed during the adsorption process on the LDHs, which is influenced by the LDH charge density: the µ-oxo complex is the main species adsorbed on the Mg2Al and Mg3Al LDHs, whereas for Mg4Al the non oxo-bridged dimeric complex prevailed. X-ray absorption spectra (XANES) of the adsorbed FePcTs on the MgxAl LDHs showed that the species present a square-pyramidal (C4v) and/or an octahedral (Oh) symmetry, in agreement with the UV/visible spectroscopic data. EPR spectra of these samples showed that the FePcTs adsorbed on the LDHs leads to a mixture of Fe(III) high and low spin species along with a strong rhombic distortion. The FePcTs adsorbed on the MgxAl LDHs showed an enhanced catalytic activity and longevity in the phenols oxidation compared to the homogeneous counterpart. The phthalocyanine on the LDH external surfaces allows the access of the substrate to the reactive metal center. A correlation between the adsorption study and the catalytic tests pointed that the FePcTs µ-oxo complex may be the active species in the oxidation of phenols. Furthermore, the positive charge of LDH layers may weaken the O-H bonding in the phenol molecules making them more easily ionized (one step of the phenol oxidation mechanism). This feature seems to be effective because higher activities of the catalysts were observed along with increasing charge density of the LDHs. These results indicated that a cooperative effect takes place in the materials containing the FePcTs adsorbed on the MgxAl LDHs, showing that LDH do not act as an inert support in the studied catalytic reactions.