Dissertations / Theses on the topic 'Freundlich Isotherm'

Discharge of colored effluents without decoloration originated from textile industries may cause serious problems in the receiving environments. In this study, natural materials that are basaltic tephra and clinoptilolite were used to remove various dyestuffs used in the textile industry. Those materials are cheap and available in large quantities in Turkey. The investigation of adsorption of basic, acidic and reactive dyes on these materials is the objective of this study. During preliminary experiments it was seen that adsorption equilibrium was reached in about 2 days. In adsorption experiments, in order to obtain adsorption isotherms, a fixed amount of adsorbent and 100 mL dye solutions of different concentrations were placed in glass bottles which were shaken at 200 rpm and 25±
2oC for 2 days. Then, samples were filtered and the equilibrium concentrations of dyestuffs in the solutions were determined by using spectrophotometer at appropriate wavelength corresponding to the maximum absorbency. After equilibrium concentrations of the solutions were obtained, Langmuir and Freundlich adsorption isotherm constants were calculated for the adsorbents used in this study. The removal efficiencies for cationic basic dyes are higher than those for anionic acidic and reactive dyes with the natural materials. Therefore, modification of surface properties of natural materials with a cationic surfactant was considered to increase the removal efficiencies of those for anionic dyes. After modification of the surface properties, adsorption capacities of adsorbents for anionic dyes were higher than those of natural materials. Finally, the adsorption capacity of activated carbon for the same dyes was determined to compare with that of natural and modified materials. The results showed that the adsorption of dyes on adsorbents used in this study fitted nicely the Langmuir Isotherm Equations.

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The agricultural sector has great influence in Brazilian economy. Furthermore, agricultural yield has been associated with pesticides application during crop cycle, which atrazine is applied for example, since it can cause environmental contamination when it does not reach its target. Thus, there are some essential and imperative options that can minimize contamination and negative impacts during agricultural practices. So, present study aimed at evaluating the ability of three biochars in atrazine adsorption. Therefore, three biochars produced from bamboo culm were used, whose species is Phyllostachys aurea, and temperature ranged at 350 ºC, 450 ºC and 550 ºC. The three studied biochars were named as BE350, BE450 and BE550. They were characterized based on their physical and chemical properties by elemental analysis, characterization of functional groups (Infrared Spectroscopy Fourier Transform - FTIR), surfaces morphology evaluation (Scanning Electron Microscopy - SEM) as well as specific surface area (ASEBET) and porosity. A kinetic study was carried out to determine the equilibrium period of adsorption process and the kinetic mechanism that controls such process. Langmuir and Freundlich isotherms were also modeled during this trial. Atrazine determination, after the adsorption test, was carried out by High Performance Liquid Chromatography (HPLC). The obtained analyses showed that the adsorption capacity of biochars decreased in the following order: BE 450> BE 350 > BE 550, and such capacity has been associated with the physical and chemical characteristics of biochars. The three studied biochars are well represented by the kinetic model of pseudo-second order. At last, all biochars have shown high affinity to adsorb atrazine; however, the biochar that was produced at 450 ºC has shown the highest adsorption capacity.
O setor agrícola possui grande destaque na economia brasileira, a produção agrícola está associada ao uso de pesticidas durante o ciclo das culturas, como é o caso da atrazina, que pode causar a contaminação do ambiente, quando não atinge seu alvo. Sendo assim, alternativas que minimizem as contaminações e impactos negativos da prática agrícola são essenciais e urgentes. Desta forma, o presente estudo teve por objetivo avaliar a capacidade de três biocarvões, em adsorver o herbicida atrazina. Para tanto, foram utilizados três biocarvões, produzidos a partir do colmo de bambu, da espécie Phyllostachys aurea à 350ºC, 450ºC e 550ºC, nomeados BE350, BE450 e BE550. Os biocarvões foram caracterizados quanto as propriedades físicas e químicas, por meio de análise elementar, caracterização de grupos funcionais (Espectroscopia de Infravermelho com Transformada de Fourier - FTIR), avaliação da morfologia das superfícies (Microscopia Eletrônica de Varredura - MEV), bem como, área superficial específica (ASEBET) e porosidade. Estudo cinético foi realizado, visando determinar o tempo de equilíbrio do processo de adsorção, bem como, o mecanismo cinético que controla o processo. Também foram modeladas isotermas de Langmuir e Freundlich. A determinação da atrazina, após os ensaios de adsorção, foi realizada por Cromatografia Líquida de Alta Performance (CLAE). As análises realizadas apontaram que a capacidade de adsorção dos biocarvões diminuiu na ordem de BE 450 > BE 350 > BE 550, e tal capacidade está associada às características físicas e químicas dos biocarvões. Os três biocarvões são bem representados pelo modelo cinético de pseudo-segunda ordem. Todos biocarvões exibiram elevada afinidade para a adsorção do herbicida atrazina, contudo, o biocarvão produzido à 450 ºC demonstra maior capacidade de adsorção

>Magister Scientiae - MSc
There are huge amount of natural clinoptilolite available in South Africa which can be utilised for wastewater treatment of ammonia and chromium if their characteristics are properly known. However, these deposits have not been well characterised but in this study, the untreated clinoptilolite materials were fully characterised using techniques such as SEM-EDS, HRTEM-SAED, XRD, XRF, FTIR and BET. After acid pretreatment with several extractions, the pretreated samples were again characterised using the above mentioned techniques. These pretreated materials were used for NH₄⁺ and Cr³⁺ adsorption of wastewater. The three natural South African clinoptilolite samples used in this study were from ECCA Holdings (ESC and EHC samples) and Pratley (PC sample) deposits obtained from Western Cape and KwaZulu-Natal Province respectively. This study revealed that the chemical composition and mineral phases of South African clinoptilolites vary considerably from site to site, even clinoptilolite mined from the same deposit sites. The XRD analyses showed that Pratley clinoptilolite (PC) was the most pure clinoptilolite sample (81.41 %) compared to the purity of EHC (67.88 %) and ESC (44.0 %) sample. The ECCA Holdings untreated clinoptilolite samples contained dense phases such as quartz which was not found in Pratley sample. Quartz was found to be the most dominant impurity in both ECCA Holding sample. The cation exchange capacity (CEC) of ESC, EHC and PC samples were found to be 1.23, 1.81 and 2.90 meq/g respectively and these results were compared to that of XRF analyses. The acid solutions of 0.02 and 1.0 M HCl were used to pretreat natural clinoptilolite to determine the optimum acid concentration and number of extractions required to fully replace the exchangeable cations. The pretreatment results showed that 0.02 M HCl was the optimum acid concentration for acid pretreatment of clinoptilolite samples. Between 7 and 22 extractions were required to remove Na⁺, K⁺, Ca²⁺ and Mg²⁺ without causing much dealumination of the framework. Sodium ion was found to be weakly bound cation in the clinoptilolite framework, since it could be completely exchanged by H⁺ after 7 extractions with 0.02 M HCl acid solution. Potassium ion was found to be strongly bound in the clinoptilolite framework since it could not be completely exchanged during the acid pretreatment process even after 22 extractions. The HRTEM-SAED and BET results showed that ESC, EHC and PC were all polycrystalline and microporous materials respectively. It was found that the adsorption capacity of the treated Pratley clinoptilolite sample was increased by 36 % for NH₄⁺ removal, compared to that of the untreated PC sample. The adsorption study results showed that the pretreatment of clinoptilolite samples using 150 mL volumes of 0.02 M HCl with 7 acid extractions at 25 °C for ESC pretreated and EHC pretreated. The pretreatment of PC sample at 22 extractions could remove high percentage of NH₄⁺ (98.11 %) within a short contact time of 10 min. The pretreated Pratley clinoptilolite sample was found to be the best NH₄⁺ adsorbent (98.11 % NH₄⁺ removal) compared to EHC treated (93.89 % NH₄⁺ removal) and ESC treated (75.00 % NH₄⁺ removal) clinoptilolite samples. However, acid-pretreated Pratley clinoptilolite did not sufficiently remove Cr³⁺ (16.10 %) from synthetic wastewater showing that it is not a good adsorbent for this particular metal ion removal. Despite several studies that have been conducted on clinoptilolite, no study has been carried out on the pretreatment and comparison of sorption capacity of different South African clinoptilolites for the removal of NH₄⁺ from wastewater. This study has been able improve on the acid-pretreatment procedure for clinoptilolite. This study demonstrated that it is not only the acid concentration that is important but also the number of extractions needed to remove all the exchangeable cations from the clinoptilolite framework. This study has also been able to prove that South African clinoptilolite can treated ammonia from wastewater.

Hydrotalcite and thermally activated hydrotalcites were examined for their potential as methods for the removal of oxalate anions from Bayer Process liquors. Hydrotalcite was prepared and characterised by a number of methods, including X-ray diffraction, thermogravimetric analysis, nitrogen adsorption analysis and vibrational spectroscopy. Thermally activated hydrotalcites were prepared by a low temperature method and characterised using X-ray diffraction, nitrogen adsorption analysis and vibrational spectroscopy. Oxalate intercalated hydrotalcite was prepared by two methods and analysed with X-ray diffraction and for the first time thermogravimetric analysis, Raman spectroscopy and infrared emission spectroscopy. The adsorption of oxalate anions by hydrotalcite and thermally activated hydrotalcite was tested in a range of solutions using both batch and kinetic adsorption models.

Sorption of quaternary metal ions (Pb2+, Cu2+, Cd2+ and Zn2+) was carried out on lignite from the South Moravia. Following experiments were tested: kinetic sorption, dependence of sorption on pH, initial concentration, temperature, effect of electrolytes (KNO3 and NaCl) and desorption in deionized water. Sorption studies was carried out in quaternary mixtures and in the case of inicial concentration effect additional in a single-component solution. The batch sorption experiments was used. Sorption time was 24 hour, although concentration of ions was a near equilibrium after two hour. As the optimal pH was determined pH 5. The order of affinity by lignite was obtained Pb >> Cd > Zn > Cu for the sorption of metals in the single-component solution and the order was Pb > Cu > Zn > Cd for the sorption of mixture of metals. The maximum adsorptium capacities from single solutions were for Pb 97,82 mg/g, Cd 60,34 mg/g, Zn 49,88 mg/g and Cu 30,28 mg/g and in the case of ones from mixture solutions were for Pb 39,03 mg/g, Cu 25,94 mg/g, Zn 15,21 mg/g and Cd 5,18 mg/g. Experimental data have been analysed using Langmuir and Freundlich model. Thermodynamic values H°, S° and G° were calculated. Desorption test showed that desorption efficiency is 0–3 %. NaCl had the greatest influence on sorption from electrolytes. On the basis obtained results we can say that metals are binding to lignite in particular due to chemical interactions. Lignite is s suitable as a sorption material for metal ions especially in the field of low concentrations.

A eutrofização acelerada dos mananciais superficiais, devido aos despejos de águas residuárias não tratadas, vem comprometendo a qualidade das águas utilizadas no abastecimento público. Como conseqüência desse processo, inúmeros registros de florações de cianobactérias são relatados em todo o mundo. Esses microrganismos são potenciais produtores de toxinas, as quais, presentes na água bruta que abastece uma Estação de Tratamento de Água (ETA), precisam ser removidas. As toxinas podem ter efeitos adversos à saúde, podendo causar danos hepatotóxicos, neurotóxicos e dermatotóxicos. A maioria das ETAs brasileiras tratam a água através do processo convencional de tratamento, compreendendo as etapas de coagulação, floculação, sedimentação, filtração e cloração. Esse tratamento é considerado eficiente para remover células de microrganismos, incluindo as cianobactérias. No entanto, suas toxinas não são afetadas, permanecendo na água tratada. Em função disso, alternativas de tratamento devem ser incorporadas ao tratamento convencional, visando remover a hepatotoxina microcistina a concentrações menores ou iguais a 1 μg.L-1, pois esse é o valor máximo permitido (VMP) pela Portaria nº 518/2004, do Ministério da Saúde, a qual define as diretrizes relativas ao controle e vigilância da qualidade da água para consumo humano. Nesse contexto, o objetivo do trabalho foi avaliar a eficiência do carvão ativado pulverizado (CAP), na remoção da cianotoxina microcistina presente na água utilizada para abastecimento público. Cinco amostras de CAP, produzidas a partir de madeira, osso, antracito e coco, foram caracterizadas e, para cada uma, determinadas as Isotermas de Freundlich. As Isotermas mostraram que os CAPs produzidos a partir da madeira apresentaram maior capacidade de remover microcistina. Os residuais de microcistina obtidos nestes ensaios foram ajustados ao modelo de decaimento logarítmico. Assim, para cada CAP, foi estabelecida uma equação geral do processo adsortivo, com a qual foi possível estabelecer dosagens de CAP, variando a concentração de microcistina inicial, para atingir uma concentração residual de 1 μg.L-1. A aplicabilidade da equação foi testada para uma amostra de CAP, em água natural, utilizando o coagulante policloreto de alumínio e concentrações iniciais de microcistina de 1, 10 e 100 μg.L-1. Os resultados mostraram que as dosagens de CAP calculadas foram suficientes para atingir o residual desejado. Além disso, através de ensaios de adsorção, em equipamento de jarros, foram simuladas as etapas de coagulação (utilizando coagulantes sulfato de alumínio e cloreto férrico), floculação, sedimentação e filtração do tratamento convencional para água natural acrescida de 100 μg.L-1 de microcistina. A aplicação do CAP foi realizada em dois pontos do tratamento (1) entrada da água bruta e (2) antes da aplicação do coagulante. A aplicação na entrada da água bruta possibilitou remoção da toxina abaixo do VMP, correspondendo à redução de, aproximadamente, 99% da concentração inicial de toxina. Já no ponto de aplicação antes do coagulante, não foi atingido o VMP. A partir dos estudos aqui realizados, concluiu-se que a melhor maneira de escolher o CAP para remoção de microcistina é a realização de ensaios específicos, como a Isoterma de Freundlich. Para uma remoção eficiente da toxina, o tratamento convencional mostra-se eficaz, desde que a etapa de adsorção seja incorporada ao tratamento.
The accelerated surface waters eutrophication, due to non treated residual waters discharges, has been harming the water quality utilized in the public supply. As a consequence of this process, countless records of cyanobacterias’ bloom are reported all over the world. These microorganisms potentially producers of toxins, which, when presented in the raw water that supplies the Water Treatment Plant (WTP), needs to be removed. The toxins can have harmfull effects to the health causing hepatotoxic, neurotoxic and dermatotoxic damage. Most of the Brazilian WTPs treat the water through the conventional water treatment process, covering the stages of coagulation, flocculation, sedimentation, filtering and chlorination. This treatment is considered efficient to remove microorganisms’ cells, including cyanobacterias. However its toxins are not affected, remaining in the treated water. Due to this fact, alternative treatment must be incorporated to the conventional one, trying to remove the microcystin hepatotoxin to concentrations lower or equal to 1 μg.L-1, the maximum allowed value (MAV) according to the Brazilian Ministry of Health Administrative Ruling 518/2004, which defines the rules related to the control and vigilance of the water quality for human consumption. In this context, the objective of the present work was to evaluate the efficiency of the powdered activated carbon’s (PAC), in the removal of the microcystin cyanotoxin present in the water for public supply. Five samples of PAC, made of wood, bone, antracite and coconut, were characterized and, for each one, were determined Freundlich adsorption isotherm . The isotherm showed that the PACs produced from wood presented the highest capacity of microcystin removal. The residuals of microcystin obtained in these tests were adjusted to the logarithmic decay model. Thus, for each PAC, it was established a general equation of the adsorptive process, in order to establish PAC dosages, varying the initial microcystin concentration, to achieve the residual concentration of 1 μg.L-1. The usage of this equation was tested for one sample of PAC, in natural water, using poly-aluminum chloride as a coagulant and the initial concentrations of microcystins of 1, 10 and 100 μg.L-1. The results showed that the dosage of PAC calculated was enough to achieve the desired residual. Besides this, through adsorptive tests, using jar’s equipments, were simulated the stages of coagulation (using alum sulphate and ferric chloride as coagulants), flocculation, sedimentation and filtering of the conventional treatment for natural water and with 100 μg.L-1 of microcystin added. The application of the PAC was performed in two points of the treatment: (1) entrance of the raw water and; (2) before the application of the coagulant. The application in the entrance of the raw water made possible the removal of the toxin under MAV, corresponding to a reduction of, approximately, 99% of the initial concentration of the toxin. Nevertheless, in the point of application before the coagulant, the MAV was not achieved. According to these studies, it was concluded that the best manner of choosing the PAC for microcystin removal is the realization of specific tests like a Freundlich isotherm. For an efficient removal of the toxin, the conventional treatment is efficient, once the adsorption stage is incorporated to the treatment.

In the context of increasing demand for potable water and the depletion of water resources, stormwater is a logical alternative. However, stormwater contains pollutants, among which metals are of particular interest due to their toxicity and persistence in the environment. Hence, it is imperative to remove toxic metals in stormwater to the levels prescribed by drinking water guidelines for potable use. Consequently, various techniques have been proposed, among which sorption using low cost sorbents is economically viable and environmentally benign in comparison to other techniques. However, sorbents show affinity towards certain toxic metals, which results in poor removal of other toxic metals. It was hypothesised in this study that a mixture of sorbents that have different metal affinity patterns can be used for the efficient removal of a range of toxic metals commonly found in stormwater. The performance of six sorbents in the sorption of Al, Cr, Cu, Pb, Ni, Zn and Cd, which are the toxic metals commonly found in urban stormwater, was investigated to select suitable sorbents for creating the mixtures. For this purpose, a multi criteria analytical protocol was developed using the decision making methods: PROMETHEE (Preference Ranking Organisation METHod for Enrichment Evaluations) and GAIA (Graphical Analysis for Interactive Assistance). Zeolite and seaweed were selected for the creation of trial mixtures based on their metal affinity pattern and the performance on predetermined selection criteria. The metal sorption mechanisms employed by seaweed and zeolite were defined using kinetics, isotherm and thermodynamics parameters, which were determined using the batch sorption experiments. Additionally, the kinetics rate-limiting steps were identified using an innovative approach using GAIA and Spearman correlation techniques developed as part of the study, to overcome the limitation in conventional graphical methods in predicting the degree of contribution of each kinetics step in limiting the overall metal removal rate. The sorption kinetics of zeolite was found to be primarily limited by intraparticle diffusion followed by the sorption reaction steps, which were governed mainly by the hydrated ionic diameter of metals. The isotherm study indicated that the metal sorption mechanism of zeolite was primarily of a physical nature. The thermodynamics study confirmed that the energetically favourable nature of sorption increased in the order of Zn < Cu < Cd < Ni < Pb < Cr < Al, which is in agreement with metal sorption affinity of zeolite. Hence, sorption thermodynamics has an influence on the metal sorption affinity of zeolite. On the other hand, the primary kinetics rate-limiting step of seaweed was the sorption reaction process followed by intraparticle diffusion. The boundary layer diffusion was also found to limit the metal sorption kinetics at low concentration. According to the sorption isotherm study, Cd, Pb, Cr and Al were sorbed by seaweed via ion exchange, whilst sorption of Ni occurred via physisorption. Furthermore, ionic bonding is responsible for the sorption of Zn. The thermodynamics study confirmed that sorption by seaweed was energetically favourable in the order of Zn < Cu < Cd < Cr . Al < Pb < Ni. However, this did not agree with the affinity series derived for seaweed suggesting a limited influence of sorption thermodynamics on metal affinity for seaweed. The investigation of zeolite-seaweed mixtures indicated that mixing sorbents have an effect on the kinetics rates and the sorption affinity. Additionally, the theoretical relationships were derived to predict the boundary layer diffusion rate, intraparticle diffusion rate, the sorption reaction rate and the enthalpy of mixtures based on that of individual sorbents. In general, low coefficient of determination (R2) for the relationships between theoretical and experimental data indicated that the relationships were not statistically significant. This was attributed to the heterogeneity of the properties of sorbents. Nevertheless, in relative terms, the intraparticle diffusion rate, sorption reaction rate and enthalpy of sorption had higher R2 values than the boundary layer diffusion rate suggesting that there was some relationship between the former set of parameters of mixtures and that of sorbents. The mixture, which contained 80% of zeolite and 20% of seaweed, showed similar affinity for the sorption of Cu, Ni, Cd, Cr and Al, which was attributed to approximately similar sorption enthalpy of the metal ions. Therefore, it was concluded that the seaweed-zeolite mixture can be used to obtain the same affinity for various metals present in a multi metal system provided the metal ions have similar enthalpy during sorption by the mixture.

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The intensification of the use of land for farming has caused great concern, mainly due to the impacts that these activities are causing the environment, particularly with regard to it s contamination by chemicals. The application of chemicals and waste ground and in several, or in plants in order to take agronomically solid waste, improve productivity and increase agricultural production has been growing in the practices of cultivation. The form of improper disposal of waste in the soil, without any control of dose and form of application, and without knowledge of their ability to assimilate the different soil types, possibly predisposing the occurrence of contamination and pollution along the profile these soils and may reach the water table and contaminate groundwater. This work aimed the analysis of the retention of some heavy metals in Ultisol, Oxisol Typic Acrustox, Quartzipsamment and Kandic Oxisol found in savannah soil of the Goiás. Heavy metals in tests were Cadmium (Cd+2), lead (Pb+2), copper (Cu+2), chromium (Cr+3 and Cr+6), nickel (Ni+2) and zinc (Zn+2). The sorption of the heavy metals in soil was evaluated by batch method and described by potential and linear models of the Freundlich isotherm. For the establishment of sorption isotherm were added in 5,0 cm3 of soil and 50,0 cm3 of solution containing the heavy metal being assessed with different concentrations within the limits acceptable soil. The potential and linear sorption isotherm submitted a good adjusted to describe the behavior of adsorption of heavy metals in different classes of soil studied. The detention of heavy metals in descending order was the Ultisol: Cr+3 > Cr+6 > Ni+2 > Zn+2 > Cu+2 > Pb+2 > Cd+2; Oxisol Typic Acrustox: Cr+3 > Cr+6 > Ni+2 > Cu+2 > Cd+2 > Zn+2 > Pb+2; Quartzipsamment: Cr+6 > Cr+3 > Cu+2 > Pb+2 > Ni+2 > Zn+2 > Cd+2; Kandic Oxisol: Cr+3 > Cr+6 > Pb+2 > Cu+2 > Zn+2 > Ni+2 > Cd+2. The Quartzipsamment presented a less retention metal comparison other classes of soil, and therefore more vulnerable to contamination of groundwater.
A intensificação do uso das terras para fins agropecuários tem causado grande preocupação, devido, principalmente, aos impactos que essas atividades vêm causando ao meio ambiente, sobretudo no que diz respeito à sua contaminação por substâncias químicas. A aplicação de produtos químicos e de resíduos diversos no solo e, ou, nas plantas, com o propósito de aproveitar agronomicamente resíduos sólidos, melhorar a produtividade e aumentar a produção agrícola, tem sido crescente nas práticas de cultivo. A forma inadequada de disposição de resíduos no solo, sem qualquer controle das doses e da forma de aplicação, e sem o conhecimento da capacidade de sua assimilação pelos diferentes tipos de solos, possivelmente, predispõem a ocorrência de contaminação e de poluição ao longo do perfil desses solos, podendo alcançar o lençol freático e contaminar as águas subterrâneas. Objetivou-se com este trabalho a análise da retenção de alguns metais pesados nas classes de solo Argissolo Vermelho Eutrófico, Latossolo Vermelho Acriférrico, Neossolo Quartzarênico e Nitossolo Vermelho Eutroférrico encontrados em áreas de cultivo do Estado de Goiás. Os metais tóxicos avaliados nos ensaios de sorção foram cádmio (Cd+2), chumbo (Pb+2), cobre (Cu+2), cromo (Cr+3 e Cr +6), níquel (Ni+2) e zinco (Zn+2). A sorção dos metais foi avaliada pelos modelos potencias e lineares da isoterma de Freundlich. Para o estabelecimento de isotermas de sorção foram adicionados em 5,0 cm3 de solo e 50,0 cm3 de solução contendo o metal tóxico a ser avaliado com diferentes concentrações, respeitando os limites aceitáveis. As isotermas de sorção potencial e linear apresentaram um bom ajuste para descrever o comportamento de adsorção dos metais tóxicos nas diferentes classes de solos estudadas. A sequência da retenção dos metais tóxicos em ordem decrescente foi, para o Argissolo Vermelho Eutrófico: Cr+3 > Cr+6 > Ni+2 > Zn+2 > Cu+2 > Pb+2 > Cd+2; Latossolo Vermelho Acriférrico: Cr+3 > Cr+6 > Ni+2 > Cu+2 > Cd+2 > Zn+2 > Pb+2; Neossolo Quartzarênico: Cr+6 > Cr+3 > Cu+2 > Pb+2 > Ni+2 > Zn+2 > Cd+2; Nitossolo Vermelho Eutroférrico: Cr+3 > Cr+6 > Pb+2 > Cu+2 > Zn+2 > Ni+2 > Cd+2. O Neossolo Quartzarênico apresentou uma menor retenção de metais em comparação às demais classes de solo, sendo, portanto, mais vulnerável à contaminação das águas subterrâneas.

The results of this study show that novel mesoporous carbons were obtained as inverse replica of SBA-15, HMS and MCM-41 silica templates, with a large pore diameter (2-4 nm), a BET surface area of 1867, 874 and 910 m2g –1 respectively for CA_SBA-15_LPG_105, CA_HMS_LPG_80 and CA_MCM- 41_LPG_80 with bimodal pore size distribution (PSD) in the mesopores range. The results obtained show that mesoporous carbon with graphitic structures can be synthesized via the LPG route.

The Diploma thesis deals with humic acids and their ability to adsorb metal ions on their surface. Humic acids are aromatic polycyclic compounds which contain carboxylic and fenolic functional groups on their sidechains. Thanks to these functional groups humic acids can form complexes with metal ions of different stability and assist the partial immobilization of pollutants in the nature. In this thesis, the sorption of Pb2+ and Zn2+ ions on humic acids was studied by relatively new electroanalytic method called galvanostatic stripping chronopotentiometry. Experimental data were described by Freundlich and Langmuir isotherms. The results show that the amount of examined metal ions increases with their increasing concentration. Furthermore it was determined that Pb2+ ions are adsorbed better on humic acids than Zn2+ ions. Both metals are adsorbed better from solution containing only one metal ion than in presence of four metals at the same time (Cd, Cu, Zn and Pb) where the sorption of these metals is not influenced by the presence of other metals.

Les processus de transfert de pesticide dans les sols sont encore mal connus. Avec l'objectif de mieux comprendre les mécanismes impliqués, des essais dans des colonnes remplies avec différents types de sols ont été effectués sous les conditions de saturation et de saturation partielle en eau. Des expériences avec un traceur ont été utilisées pour la caractérisation hydrodynamique du milieu. Les mécanismes d'interaction physicochimiques d'une molécule pesticide modèle, le pentachlorophenol (pcp) avec la matrice solide, sont observés par la comparaison des courbes de restitution du pesticide avec celles du traceur. Les résultats expérimentaux ont montré que les interactions du pcp avec le solide sont dépendants de la succession chronologique des expériences, de la vitesse moyenne d'écoulement, du profil de la teneur en eau dans la colonne, de la concentration en pcp, du ph et de la présence de sel dans la solution injectée. L'isotherme d'adsorption du pcp sur le sable suit le modèle de freundlich, et la restitution partielle est probablement due à une fixation irréversible du pcp ionisé ou non. Un modèle numérique, résolu à l'aide de la méthode des différences finies a été développé. Les descriptions des courbes de restitution des solutes obtenues sur un sable en condition de saturation en eau se sont avérées satisfaisantes. En revanche, le modèle n'a pas permis de décrire complètement les courbes d'élution résultantes de créneaux injectés dans la colonne de sable saturé en semence avec des bactéries, dans le sable partiellement saturé et dans le sol saturé

Orientador: Susanne Rath
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química
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Resumo: Antimicrobianos, entre eles as sulfonamidas, têm sido amplamente utilizados em medicina veterinária para fins terapêuticos e profiláticos. Uma vez excretados os fármacos e/ou metabólitos podem levar a contaminação do meio ambiente e estudos sobre o impacto ambiental ainda são escassos. Em adição, no Brasil, ainda não existe uma fiscalização de medicamentos veterinários. A não conformidade dos medicamentos reflete diretamente na saúde animal, como também é um tópico relevante quanto à segurança alimentar. Assim sendo, métodos foram desenvolvidos e validados para a determinação de sulfadiazina (SDZ), sulfadimetoxina (SDM) e sulfaquinoxalina (SQX) em medicamentos de uso veterinário por cromatografia líquida de alta eficiência associada a um detector de arranjo de fotodiodos (HPLC-DAD). Os resultados obtidos indicam a necessidade de controle de qualidade dos fármacos de uso veterinário comercializados no Brasil. Ainda, o trabalho estudou a sorção da SDZ, SDM e SQX em quatro solos característicos do Estado de São Paulo. Os estudos foram conduzidos conforme recomendação do Guia OECD 106. As sulfonamidas foram quantificadas nas soluções de solo por um método HPLC-DAD previamente validado. Os dados de adsorção/dessorção das sulfonamidas nos quatro solos foram ajustados com isotermas de Freundlich na forma linear ou logarítmica. Um fenômeno de histerese de adsorção/dessorção foi evidente em todos os solos. Os baixos valores do coeficiente de Freundlich (KF) obtidos sugerem fraca adsorção das sulfonamidas nos solos avaliados e, portanto, estas tendem a ser lixiviados e, por sua vez apresentam potencial para contaminar águas superficiais e subterrâneas
Abstract: Antimicrobials, including sulfonamides, have been widely used in veterinary medicine for therapeutic and prophylactic purposes. Once excreted, drugs and/or metabolites can contaminate the environment. Environmental impact studies are still scarce. In addition, in Brazil, there is no surveillance of veterinary medicines. The poor quality of drugs may reflect directly on animal health and is also a topic relevant to food safety. Therefore, methods were developed and validated for the determination of sulfadiazine (SDZ), sulfadimethoxine (SDM) and sulfaquinoxaline (SQX) in veterinary drugs, using high performance liquid chromatography coupled to a photodiode array detector (HPLC-DAD). The obtained results indicate the need for a quality control program of veterinary drugs comercialized in Brazil. Moreover, the present work aim studied the sorption of sulfonamides (SDZ, SDM and SQX) in four characteristic soils of the State of São Paulo. The studies were conducted as recommended by the OECD Guidelines 106. The sulfonamides were quantified in the soil solutions by a previously validated HPLC-DAD method. Adsorption/desorption data of sulfonamides in soils were fitted to Freundlich isotherms in the linear or logarithmic forms. A hysteresis of adsorption/desorption was evident in all four soils evaluated. The low values of the Freundlich coefficient (KF) obtained suggest weak adsorption of sulfonamides in soils, and therefore they tend to be leached and present high potential to contaminate surface and groundwater
Doutorado
Quimica Analitica
Doutora em Ciências

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
A informação sobre a adsorção de selênio (Se) em solos da região tropical é restrita e existem poucos parâmetros numéricos disponíveis para a definição de estratégias de remediação de áreas contaminadas. Os objetivos deste trabalho foram: avaliar a retenção de Se por amostras superficiais (0-0,2 m) de 30 solos representativos do Estado de São Paulo, pela quantificação de parâmetros de adsorção (Kd, Koc, Adsmáx, KL, Kf e n); gerar modelos de regressão e correlacionar os atributos químicos e físicos dos solos com os parâmetros de adsorção. Os experimentos de adsorção de Se foram conduzidos de acordo com o método “batch”. Isotermas de adsorção foram construídas a partir dos resultados experimentais e comparadas com as isotermas ajustadas pelos modelos de Langmuir e de Freundlich. A adsorção de Se foi representada por isotermas tipo L (exponencial) e tipo C (linear) e a equação de Langmuir ajustou melhor os resultados de adsorção de Se do que a isoterma de Freundlich. Os valores médios dos parâmetros de adsorção foram: Kd = 133 L kg-1, Koc = 2927 L kg-1, Adsmáx = 976 mg kg-1, KL = 0,04 L kg-1, Kf = 46 L kg-1 e n = 0,45. Os valores de Kd estiveram correlacionados principalmente com os teores de argila (r = 0,72*), enquanto Kf se correlacionou com teores de argila (r = 0,67***) e de óxidos de Fe livres (FeDCB; r = 0,69***) e amorfos (Feox; r = 0,56**). Os demais parâmetros de adsorção de Se não apresentaram relação causa-efeito com os atributos dos solos. Na análise conjunta, os teores de FeDCB explicaram 60% da variação dos valores de Kd e 50% da variabilidade de Kf, enquanto os teores de argila responderam por 52% da variação dos valores de KL.
Very limited information is available on selenium (Se) adsorption behavior in tropical soils and there are few numerical parameters related to the phenomena that can be used as references to take decisions on management strategies in contaminated areas. The objectives of this study were to evaluate Se adsorption in topsoil samples (0-0.2 m) from 30 representative soils of the State of São Paulo, Brazil, based on the quantitative adsorption parameters (Kd, Koc, Adsmax, KL, Kf and n) and on its correlation with chemical and physical soil attributes. Adsorption experiments were conducted according to batchwise method. Adsorption isotherms were elaborated from experimental results and compared with the isotherms fitted by Langmuir and Freundlich models. Selenium adsorption isotherms following L-type (exponential) and C-type (linear) pattern and Langmuir equation fitted well to the soil experimental results, when compared with Freundlich model. Arithmetic mean values for adsorption parameters were: Kd = 133 L kg-1; Koc = 2,927 L kg-1; Adsmáx = 976 mg kg-1; KL = 0.04 L kg-1; Kf = 46 L kg-1 and; n = 0.45. Distribution coefficient (Kd) was correlated with clay content (r = 0.72*), while Freundlich coefficient (Kf) was correlated with clay content (r = 0.67***) and with crystalline (r = 0.69***) and amorphous Fe oxyhydroxides (r = 0.56**). No consistent correlations were observed between soil attributes and Adsmaz, KL, n and Koc. In the joint analysis, crystalline Fe oxyhydroxides content explained 60% of the variation in Kd values and 50% of Kf variability, while clay content accounted for about 52% of the KL values.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico
Swine wastewater application into soil to reuse water on cropping provides the addition of total and dissolved organic matter to soil, which interferes in the dynamics of pesticides in soil. This study aims at evaluating the effects of total and dissolved organic matter application from two systems of swine wastewater, biodigestor and lagoon treatments, in alachlor sorption, desorption, leaching and formation of bound residues into soil. The batch method was used to test sorption and desorption and the results were presented in Freundlich isotherms. The evaluation of miscible displacement of alachlor, in soil treated with total and dissolved organic matter, was performed by disturbed soil columns, by monitoring the concentration of alachlor in leachate, total organic carbon and pH. Extraction and quantification of desorption, extractable and bound residues were carried out. After that, it was registered the chemical fractionation of humic substances in extracts containing organic matter of low molecular weight, humic acids and fulvic acids, which were characterized by infrared spectroscopy and total organic carbon concentration. The swine wastewater addition promoted greater sorption and desorption of alachlor compared to Control. The dissolved organic matter promoted less sorption of alachlor in soil when compared to total organic matter, resulting in an increased leaching of alachlor. The dissolved organic matter did not show desorption residues, only extractable ones. The highest amount of total organic carbon was in organic matter of low molecular weight, spectroscope characterized, by the presence of carboxylate anions, which are important in sorption process. The total organic matter has contributed to the emergence of new sorption sites in soil column and the solids present in its composition blocked the movement of pesticide, resulting in lower leaching of alachlor. The dissolved organic matter interacted with alachlor and / or competed with the sorption sites of soil, promoting greater losses by leaching of this herbicide.
A aplicação de água residuária de suinocultura ao solo como reúso de água na agricultura resulta na adição de matéria orgânica total e dissolvida, que interferem na dinâmica dos pesticidas no solo. Objetivou-se avaliar o efeito da aplicação de matéria orgânica total e dissolvida proveniente de dois sistemas de tratamento de água residuária de suinocultura, biodigestor e esterqueira, na adsorção, dessorção, lixiviação e formação de resíduos ligados de alaclor no solo. O método do equilíbrio foi utilizado para o teste de adsorção e dessorção e os resultados foram apresentados em isotermas de Freundlich. A avaliação do deslocamento miscível do alaclor no solo tratado com matéria orgânica total e dissolvida foi realizada por ensaios em colunas de solo deformado, monitorando-se a concentração de alaclor no lixiviado, teor de carbono orgânico total e pH. Realizou-se a extração e quantificação dos resíduos dessorvíveis, extraíves e ligados do solo. Na sequência, fez-se o fracionamento químico das substâncias húmicas em extratos contendo matéria orgânica de baixo peso molecular, ácidos húmicos e ácidos fúlvicos, que foram caracterizados por espectroscopia infravermelha e pela concentração de carbono orgânico total. A adição de água residuária de suinocultura promoveu maior adsorção e dessorção do alaclor comparado ao Controle. A matéria orgânica dissolvida promoveu menor adsorção de alaclor ao solo comparada à total, resultando em maior lixiviação. A matéria orgânica dissolvida não apresentou resíduos dessorvíveis, apenas extraíveis. A maior quantidade de carbono orgânico total esteve presente na matéria orgânica de baixo peso molecular, caracterizada espectroscopicamente, pela presença de ânions carboxilatos, importantes no processo de adsorção. A matéria orgânica total contribuiu com o surgimento de novos sítios de sorção na coluna de solo e os sólidos presentes em sua composição bloquearam a passagem do pesticida, resultando em menores perdas de alaclor por lixiviação. A matéria orgânica dissolvida interagiu com o alaclor e/ou competiu com os sítios sortivos do solo, promovendo maiores perdas deste herbicida por lixiviação.

L’objectif de cette thèse a consisté en la synthèse d’un polymère à empreinte moléculaire (MIP) permettant l’extraction du phosmet, un pesticide organophosphoré largement utilisé en oléiculture. La recherche du monomère fonctionnel (MF) disposant de la meilleure capacité à interagir de manière non-covalente avec le phosmet en présence du solvant porogène le plus approprié a été réalisée pour la toute première fois au moyen d’un capteur à acétylcholinestérase. Cette stratégie innovante a permis une meilleure compréhension des mécanismes cinétiques à l’œuvre lors de l’interaction MF-molécule cible. De par l’importance de son rôle dans la détermination de la structure d’un MIP, le choix d’un agent réticulant aux caractéristiques physico-chimiques adéquates a permis de sélectionner le meilleur MIP en s’appuyant sur l’étude des isothermes d’adsorption selon les modèles de Freundlich et Langmuir. La procédure d’extraction du phosmet selon la procédure MISPE (Molecularly Imprinted Solid Phase Extraction) a été effectuée par le biais d’une cartouche SPE dont la capacité a été évaluée à partir d’une solution standard. La validation du choix des réactifs de MIP sélectionnés a été confortée par la réalisation d’une expérience de réactivité croisée appliquée à une molécule analogue au phosmet. L’extraction du phosmet de l’huile d’olive a pu être effectuée avec succès selon un protocole d’extraction en flux inverse optimisé. Cette étude ouvre ainsi la voie à la recherche de nouvelles interactions MFs-molécules cibles au moyen de biocapteurs enzymatiques inhibant des composés toxiques tels que les herbicides, fongicides et autres pesticides
The objective of this thesis has been the synthesis of a molecularly imprinted polymer (MIP) for the extraction of phosmet, an organophosphorus pesticide widely used in olive growing. The search for the functional monomer (FM) having the best ability to interact non-covalently with phosmet in the presence of the most suitable pore-forming solvent was carried out for the first time by means of an acetylcholinesterase sensor. This innovative strategy allowed us to better understand the kinetic mechanisms of FM-template interaction. Because of the importance of its role in determining the structure of a MIP, the selection of a crosslinking agent with adequate physicochemical characteristics made it possible to select the best MIP, whose adsorption isotherms were studied according to Freundlich and Langmuir models. Extraction of phosmet using a Molecularly Imprinted Solid Phase Extraction (MISPE) procedure was carried out via an SPE cartridge, whose capacity was evaluated from a standard solution. The choice of reagents and experimental conditions were validated by carrying out selectivity assays using another organophosphorus insecticide. Extraction of phosmet from olive oil was successfully carried out according to an optimized reverse flow extraction protocol. This work opens new opportunities for studying new FM-template interactions by means of enzymatic biosensors capable of detecting other inhibitors such as herbicides, fungicides and other pesticides

Resumo: A informação sobre a adsorção de selênio (Se) em solos da região tropical é restrita e existem poucos parâmetros numéricos disponíveis para a definição de estratégias de remediação de áreas contaminadas. Os objetivos deste trabalho foram: avaliar a retenção de Se por amostras superficiais (0-0,2 m) de 30 solos representativos do Estado de São Paulo, pela quantificação de parâmetros de adsorção (Kd, Koc, Adsmáx, KL, Kf e n); gerar modelos de regressão e correlacionar os atributos químicos e físicos dos solos com os parâmetros de adsorção. Os experimentos de adsorção de Se foram conduzidos de acordo com o método "batch". Isotermas de adsorção foram construídas a partir dos resultados experimentais e comparadas com as isotermas ajustadas pelos modelos de Langmuir e de Freundlich. A adsorção de Se foi representada por isotermas tipo L (exponencial) e tipo C (linear) e a equação de Langmuir ajustou melhor os resultados de adsorção de Se do que a isoterma de Freundlich. Os valores médios dos parâmetros de adsorção foram: Kd = 133 L kg-1, Koc = 2927 L kg-1, Adsmáx = 976 mg kg-1, KL = 0,04 L kg-1, Kf = 46 L kg-1 e n = 0,45. Os valores de Kd estiveram correlacionados principalmente com os teores de argila (r = 0,72*), enquanto Kf se correlacionou com teores de argila (r = 0,67***) e de óxidos de Fe livres (FeDCB; r = 0,69***) e amorfos (Feox; r = 0,56**). Os demais parâmetros de adsorção de Se não apresentaram relação causa-efeito com os atributos dos solos. Na análise conjunta, os teores de FeDCB explicaram 60% da variação dos valores de Kd e 50% da variabilidade de Kf, enquanto os teores de argila responderam por 52% da variação dos valores de KL.
Abstract: Very limited information is available on selenium (Se) adsorption behavior in tropical soils and there are few numerical parameters related to the phenomena that can be used as references to take decisions on management strategies in contaminated areas. The objectives of this study were to evaluate Se adsorption in topsoil samples (0-0.2 m) from 30 representative soils of the State of São Paulo, Brazil, based on the quantitative adsorption parameters (Kd, Koc, Adsmax, KL, Kf and n) and on its correlation with chemical and physical soil attributes. Adsorption experiments were conducted according to batchwise method. Adsorption isotherms were elaborated from experimental results and compared with the isotherms fitted by Langmuir and Freundlich models. Selenium adsorption isotherms following L-type (exponential) and C-type (linear) pattern and Langmuir equation fitted well to the soil experimental results, when compared with Freundlich model. Arithmetic mean values for adsorption parameters were: Kd = 133 L kg-1; Koc = 2,927 L kg-1; Adsmáx = 976 mg kg-1; KL = 0.04 L kg-1; Kf = 46 L kg-1 and; n = 0.45. Distribution coefficient (Kd) was correlated with clay content (r = 0.72*), while Freundlich coefficient (Kf) was correlated with clay content (r = 0.67***) and with crystalline (r = 0.69***) and amorphous Fe oxyhydroxides (r = 0.56**). No consistent correlations were observed between soil attributes and Adsmaz, KL, n and Koc. In the joint analysis, crystalline Fe oxyhydroxides content explained 60% of the variation in Kd values and 50% of Kf variability, while clay content accounted for about 52% of the KL values.
Orientador: Wanderley Jose de Melo
Coorientador: Márcio Roberto Soares
Banca: Mara Cristina Pessoa da Cruz
Banca: José Carlos Casagrande
Mestre

To improve the adsorption capacity of polyacrylonitrile (PAN) fibres, hydrophilic amidoxime fibres were prepared by subsequent conversion of the cyano groups to an amidoxime group by reacting with hydroxylamine at 80°
C at an optimum amidoximation time of 2 hrs. The amidoxime fibre was hydrolyzed/alkali treated in a solution of sodium hydroxide to enhance or improve the adsorption properties. This was followed by characterization of the amidoxime and hydrolyzed fibres using Scanning electron microscopy (SEM)
Fourier transform Infrared Spectroscopy (FTIR) and exchange capacity (cationic and anionic). SEM showed that the hydrolysis process made the surface of Amidoxime fibre rougher than that of Polyacrylonitrile fibre. FTIR revealed that the hydrolyzed Amidoxime fibres contained conjugated imine (-C=N-) sequences. Functionalization enhanced the sorption of amidoxime fibres by an increase of 20 % in the cationic exchange capacity. This was achieved by the part conversion of the cyano groups into the carboxylic acid groups. The fibres showed faster kinetics largely due the available exchange sites on the surface of the fibres hence the equilibration was achieved much quicker.

Este trabalho contempla a utilização dos modelos de Langmuir, Freundlich, Sips, Redlich- Petersen, Toth, Dubinin–Radushkevich e Tempkin para análise de isotérmicas de adsorção de compostos fenólicos, amitriptilina e fluoxetina em carvões ativados e negros de fumo em fase líquida, obtidas pelo Grupo de Investigação de Química de Superfícies e Materiais da Universidade de Évora. Foi utilizado o ajuste não linear aos dados experimentais usando o software Solver do MS Excel. Para a avaliação da aplicabilidade dos modelos foram usadas as funções de erro, coeficiente de determinação, soma dos erros quadrados, média do erro relativo, desvio padrão percentual de Marquardt, função de erro fracionada hibrida, soma dos erros absolutos, chi-quadrado, raíz quadrada da média do erro e média percentual dos erros. Os modelos que apresentaram melhor ajuste foram os modelos de Sips, Freundlich, Toth e Langmuir observando-se para estes modelos as melhores correlações e minimização das funções de erro; ### Abstract: Title: Study of the Application of Various Models and Methodologies in the Analysis of Adsorption from the Liquid Phase. Isotherm adsorption models of Langmuir, Freundlich, Sips, Redlich-Petersen, Toth, Dubinin– Radushkevich and Tempkin were used to analyse isotherms of adsorption of phenolic compounds, amitriptyline and fluoxetine on activated carbons and carbon blacks from the liquid phase. The samples were obtained by the Surface & Materials Chemistry Group from University of Évora. The non-linear form of the models were used and fitted to the data using Solver from the MS Excel software. Several error functions were used, such as the Coefficient of Determination, the Sum of Squares of Errors, the Average Relative Error, the Marquardt’s Percent Standard Deviation, the Hybrid Fractional Error Function, the Sum of Absolute Errors, the Nonlinear Chi-square Test, the Residual Root Mean Square Error and the Average Percentage Errors. Sips, Freundlich, Toth and Langmuir models were considered to be the best-fitting, as they gave the best correlation and minimization of the error functions of the data.

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A contaminação dos solos por metais pesados tem sido um problema crescente ao meio ambiente e à saúde das pessoas em função da alta toxicidade, razão por que a ciência busca alternativas que possam impedir ou pelo menos minimizar os efeitos poluidores desses metais ou, ainda, remediar os ambientes já contaminados. Assim, vários estudos utilizando matérias adsorventes estão sendo conduzidos como forma de reduzir os efeitos poluidores desses metais. E importante conhecer o processo de adsorção de metais pesados por minerais de argila, uma vez que estes são capazes de imobilizar referidos metais. No presente trabalho avaliou-se, através de três experimentos, a capacidade da bentonita na remediação de solos contaminados com zinco e cobre. O primeiro experimento consistiu no estudo da adsorção desses metais pela bentonita, em pH 4; 5 e 6, utilizando-se os modelos matemáticos de Langmuir e Freundlich. A partir de experimentos tipo "batch" foram elaboradas isotermas de adsorção com quantidades crescentes de zinco e cobre (5; 10; 20; 30; 50; 100; 150 e 200 mg L"1); o segundo experimento consistiu no estudo da mobilidade de zinco e cobre em colunas de lixiviação, preparadas com solo e doses crescentes de bentonita (0; 30 e 60 t ha"1). Os parâmetros de transporte foram calculados através do modelo computacional DISP. No último experimento avaliou-se, em casa de vegetação, o efeito das doses de zinco e cobre (50; 250 e 450 mg kg"1) e de bentonita (0; 30 e 60 t ha"1), adicionados ao solo, na produção de fitomassa e composição mineral do feijoeiro. Terminado o experimento (65 dias), foram determinadas as concentrações do zinco e do cobre nas partes aéreas e nas raízes das plantas e no solo das unidades experimentais, cujos resultados permitiram concluir que a incorporação de bentonita ao solo aumentou a adsorção do zinco e do cobre e que esta adsorção é dependente do pH da solução; que os modelos de Langmuir e Freundlich se apresentaram adequados para descrever a adsorção desses metais; que o tamanho das partículas da bentonita não influenciou na adsorção e a incorporação de bentonita ao solo contribuiu para diminuir a concentração e o acúmulo dos metais zinco e cobre, nas plantas de feijão-macassar.
The contamination of soil by heavy metais has been a growing problem to the environment and to the people's health in function of their toxicity, that has induced the science to search alternatives to prevent, or at least, minimize the pollutant effects of those metais or still, remediate the already polluted environment. Thus, several studies using sorbent materiais are conducted aiming to reduce the pollution problems produced by the excess of heavy metais. It is important to know the process of adsorption of heavy metais by clay minerais, because these are capable to immobilize such metais. The present study was carried out aiming, through three experiments, to evaluate the ability of the bentonite clay on the remediation of soils contaminated with zinc and copper. The fírst experiment consisted in studying the adsorption of these metais by bentonite at pH 4; 5 and 6, using the mathematical models of Langmuir and Freundlich. Adsorption isotherms were elaborated from batch adsorption assays, with increasing zinc and copper concentrations (5; 10; 20; 30; 50; 100; 150 and 200 mg L"1); the second experiment consisted in studying the zinc and copper mobility through leaching columns, prepared with soil and increasing bentonite leveis (0; 30 and 601 ha"1). The transport parameters were calculated using the computer model DISP. Finally, a greenhouse experiment was conducted to evaluate the effects of zinc and copper (50; 250 and 450mg kg"1) and bentonite (0; 30 and 60 t ha"1) added to the soil, on the phytomass production and mineral composition of a bean plant (Vigna unguiculata.h). At the end of the experiment (65 days) the phytomass and the content of zinc and copper in the aerial part, in the roots and in the soil were determined. It was observed that the adsorption of the elements increased with the bentonite application being dependent of the pH of the solution; the two studied models are appropriate to describe the zinc and copper adsorption for the bentonite; the granulometric size of the bentonite does not influence the metais adsorption and that the application of bentonite to the soil contributed to the decrease the concentration and accumulation of the heavy metais in the bean plant.

The work described in this thesis focuses on the effects that adsorption processes on catalytic surfaces pose in controlling key steps that can affect and control reaction pathways. To that, the development of Nuclear Magnetic Resonance (NMR) relaxometry methods and the comparison with traditional catalytic was performed with a series of C5 and C6 unsaturated hydrocarbons on two different alumina supports, γ- and θ-Al2O3. The developed techniques were applied in the study of liquid phase selective hydrogenation of citral on 5% Pt/SiO2. Infrared (IR) spectroscopy, volumetric adsorption isotherms, dynamic isotherms via a Tapered Element Oscillating Microbalance (TEOM), temperature programmed desorption (TPD) as well as 13C T1 NMR and 1H 2D T1-T2 relaxometry methods were employed. Energies of adsorption as a function of coverage were obtained via adsorption isotherms and the particular surface adsorbate interactions were described with IR spectroscopy. For example, 1-pentyne showed the strongest interaction with the alumina (94 kJ mol-1) while 1-pentene presented a weaker interaction (46 kJ mol-1) on θ-Al2O3. Desorption energies obtained from TPD ranged 85 – 130 kJ mol-1, irrespective of the adsorbate. Reactivity of the aluminas was captured with TPD, TEOM and NMR relaxometry. Interaction of adsorbates with hydrocarbon occurred predominantly on weak adsorption sites. 13C NMR T1 relaxometry provided in addition atom-specific adsorbate-adsorbent interaction strengths, showing the molecular geometry of adsorption, and applied in co adsorption measurements. The selective hydrogenation of citral as a model α,β-unsaturated aldehyde and the effect of different solvents on the activity and product distribution was studied at 298 and 373 K. A series of polar protic, polar aprotic and non polar solvents was investigated. Results showed higher initial reaction rates in non polar solvents but higher selectivities towards desired products on polar protic solvents. Solvent used also affected by product formation. The strong variations in reaction rates and selectivities reported were related with adsorbate catalyst interactions, as well as solvent reactant interactions. For example, adsorption isotherms showed that ethanol notably reduced the adsorption capacity of citral as compared with hexane, related with the rate differences observed. ATR-IR measurements indicated solvent citral interactions were solely present in polar protic solvents in line with higher yields of geraniol and nerol. Finally, 13C T1 NMR and 1H 2D T1-T2 correlation experiments determined that the geometry of adsorption of citral, influenced by solvent, affected product selectivity, and that product adsorption affected selectivity and deactivation.