Made available in DSpace on 2015-04-13T12:17:09Z (GMT). No. of bitstreams: 1 benone.pdf: 1736781 bytes, checksum: 15d12331eaeb3efd6f6a7c41316fe723 (MD5) Previous issue date: 2013-04-24 / FAPEAM - Fundação de Amparo à Pesquisa do Estado do Amazonas / The improper disposal of solid waste generated several environmental problems, including contamination of soil, contamination of water resources and public health. In this context, this study was conducted at the disposal of municipal solid waste Humaita-AM due to concern with manure/leachate generated, therefore, potential sources of contamination. In this sense, the objective was to evaluate the environmental impacts in an area of waste disposal evaluating the physical and chemical soil quality content waste landfill (IQAR) and water quality index (IQA). Different studies have been conducted: 1) Evaluation of physical and chemical soil in three areas Mata Native (N), Field Natural (C) and area Arrangement (D), where soil samples were collected at different depths, which were subjected to analyzes to evaluate soil physical (texture, bulk density, soil resistance to root penetration), and evaluation of soil (organic matter, phosphorus, potassium, calcium, magnesium, aluminum, arsenic, cadmium, mercury, lead , chromium, nickel), 2) Determination of the Index of Quality of Landfill Waste (IQAR), were performed, a checklist of the features of the site, structural and operating municipal landfill. and 3) determination of physical, chemical and bacteriological index and water quality of bodies of water nearby landfill. Mediate the information generated in this study has shown that the nature of the silty soil is not suitable for solid waste disposal, and evaluation of physical attributes indicated higher compaction disposal area (D). The chemical evaluation enabled us to verify the low soil fertility in the three areas, in relation to heavy metals in the soil most of the elements studied were lower than the limits established by Cetesb (2005). The IQAR resulted in 1.43 which classifies it as a dump to open in inadequate conditions. The results of water analyzes found that heavy metals, coliform, total nitrogen, turbidity, color, total dissolved solids are according to the maximum allowed by CONAMA Resolution 357/05 for fresh water rivers of class 2. The Water Quality Index (IQA) at point P1 proved to be good with 65% at P2 and also proved to be good with 59%, studies have revealed the quality as good probably due to the influence of the area of solid waste disposal and mainly due to influence of solids and fecal coliform. / A disposição inadequada de resíduos sólidos urbanos gera vários problemas ambientais, incluindo riscos de contaminação dos solos, contaminação dos recursos hídricos e à saúde pública. Diante deste contexto, o presente estudo foi realizado na área de disposição de resíduos sólidos urbanos de Humaitá-AM, devido à preocupação com o chorume/lixiviado gerado, portanto, fontes potenciais de contaminação. Neste sentido, o objetivo foi avaliar os impactos ambientais em uma área de disposição de resíduos avaliando-se os atributos físicos e químicos do solo, índice da qualidade de aterros de resíduos (IQAR) e índice de qualidade da água (IQA). Foram realizados estudos diferenciados: 1) Avaliação dos atributos físicos e químicos do solo em três áreas: Mata Nativa (N), Campo Natural (C) e Área de Disposição (D), onde foram coletadas amostras de solos em diferentes profundidades, as quais foram submetidas às análises para avaliação física do solo (textura, densidade do solo, resistência do solo à penetração de raízes) e avaliação química do solo (matéria orgânica, fósforo, potássio, cálcio, magnésio, alumínio, arsênio, cádmio, mercúrio, chumbo, cromo, níquel); 2) Determinação do Índice da Qualidade de Aterros de Resíduos (IQAR): foi realizado um check list das características do local, estruturais e operacionais do lixão municipal; 3) Determinação dos parâmetros físicos, químicos e bacteriológicos e índice de qualidade da água dos corpos d águas nas proximidades do lixão. Mediante as informações geradas nesse trabalho foi possível verificar que a natureza siltosa do solo não é adequada para disposição de resíduos sólidos e a avaliação dos atributos físicos indicou maior compactação da área de disposição (D). A avaliação química possibilitou verificar a baixa fertilidade do solo nas três áreas, em relação aos metais pesados no solo, a maioria dos elementos estudados apresentou valores inferiores aos limites estabelecidos pela CETESB (2005). O IQAR resultou em 1,43 sendo classificado como um lixão a céu aberto em condições inadequadas. Os resultados das análises de água constataram que os metais pesados, coliformes, nitrogênio total, turbidez, cor, sólidos totais dissolvidos encontram-se de acordo com os valores máximos permitidos pela Resolução do CONAMA 357/05 para rios de águas doce de classe 2. O Índice de Qualidade da Água no ponto P1 mostrou-se boa com 65 % e no ponto P2 mostrou-se também boa com 59 %, os estudos revelaram a qualidade como boa provavelmente devido à influência da área de disposição de resíduos sólidos e principalmente devido à influência dos sólidos totais e coliformes termotolerantes.

While contaminated food products are known to be a leading source of exposure to potentially toxic elements (PTEs), for the general population, few studies have been carried out to examine PTEs levels in soils and plants in wet tropical regions such as Brazil. While the most commonly used index for estimating PTEs accumulation in vegetables and the subsequent exposure to humans who eat them is the bioconcentration factor (BCF) - the ratio between the concentration of metals in the edible portions of produce and their total concentration in soils - the BCF does not provide an adequate description of soil-to-plant metal transfers. A better understanding of such transfers requires information about the soil attributes that influence the availability of PTEs to plants. The state of São Paulo (SP) is the largest consumer of vegetables in Brazil, as well as the largest and most diversified producer. Studies are therefore needed on PTEs concentrations in soils and vegetables, in order to assess their quality under guidelines established by Brazilian legislation. It is likewise crucial to establish critical limits of these elements in soils, via models that assess risks to human health, based on data that reflect current conditions in the soils of São Paulo. The objectives in this study were: (i) to characterize and to evaluate the relations between the concentrations of Cd, Cu, Ni, Pb and Zn in soils and in vegetables from the \"Green Belt\" of the state of São Paulo, Brazil, taking the limits established by legislation into account; (ii) to develop empiric models to derive appropriate soil screening values and to provide an accurate risk assessment for tropical regions; (iii) to develop proposals for improved human health-based screening values for Cd, Cu, Ni, Pb and Zn in São Paulo soils, using soil - vegetable relations. With the exception of Cd, there was a positive correlation between pseudototais and bioavailable contents of PTEs. Cd and Pb content in plants, moreover, not significantly correlated with any of the variables studied. All models of random forests and trees were good predictors of results generated from a regression model and provided useful information about which covariates were important to forecast only for the zinc concentration in the plant. The soil-plant transfer models proposed in this study had a good performance and are useful for eight of the ten combinations (five metals versus two species). SP data combined with NL data for Cd in lettuce and for Ni and Zn in lettuce and in carrot when pH, organic carbon - OC and clay contents were included in the model. Including such soil properties results in improved relations between PTEs concentrations in soils and in vegetables to derive appropriate screening values for SP State. The model in which pH, OC and clay contents were included gave the most useful results with SP and NL data set combined for Cu, Pb, Zn in lettuce and for Cd and Cu in carrot. Our setup did not work for Ni and for Pb in carrot because the data models gave an inconsistent result and the combination of datasets did not or insufficiently improve the results. / Uma das principais vias de exposição de elementos potencialmente tóxicos (EPT) para a maioria da população é por meio da ingestão de alimentos, mas poucos são os estudos relacionados às concentrações de EPTs em solos e em vegetais de regiões tropicais úmidas, sobretudo no Brasil. O índice mais comumente utilizado para estimar o acúmulo de EPTs em vegetais e a subsequente exposição humana pelo consumo de vegetais é o fator de bioconcentração (BCF), que é a razão entre a concentração de metais em partes comestíveis de hortaliças e da concentração total do metal no solo. Porém, o BCF não descreve adequadamente a transferência solo-planta de metais. Assim, a utilização de relações envolvendo os principais atributos dos solos que influenciam a disponibilidade dos EPTs às plantas pode explicar com mais detalhe as relações solo-planta. O estado de São Paulo é o maior mercado consumidor, além de ser o maior e mais diversificado produtor olerícola no Brasil. Assim, são necessárias pesquisas referentes às concentrações de metais pesados em solos e hortaliças, para avaliação da qualidade dos mesmos em relação aos limites estabelecidos pela legislação. Os objetivos neste trabalho foram: (i) caracterizar e avaliar as relações solo-planta entre as concentrações de Cd, Cu, Ni, Pb e Zn em solos e olerícolas de folhas e raiz no estado de São Paulo, tendo em vista os limites estabelecidos pela legislação; (ii) desenvolver modelos empíricos para poder derivar adequados limites críticos do solo e fornecer uma avaliação de risco precisa para regiões tropicais; (iii) desenvolver propostas para melhorar os limites críticos baseados na saúde humana para Cd, Cu, Ni, Pb e Zn em solos de São Paulo, utilizando relações solo-planta adequadas para as condições tropicais. Com exceção do Cd, houve correlação positiva entre os teores pseudototais e biodisponíveis dos EPTs. Os teores de Cd e de Pb nas plantas, por outro lado, não correlacionaram significativamente com nenhuma das variáveis estudadas. Os modelos de florestas aleatórias e árvores foram bons preditores de resultados gerados a partir de um modelo de regressão e forneceram informações úteis sobre quais covariáveis foram importantes para previsão apenas para o teor de Zn na planta. A aplicação de modelos de transferência solo-planta proposto neste estudo tiveram bom desempenho e foram úteis para oito das dez combinações (cinco metais contra duas espécies). O conjunto de resultados de SP pode ser combinado com o da Holanda usando o modelo em que se incluem pH, teor de carbono orgânico - CO e teor de argila para Cd em alface e para Ni e Zn na alface e na cenoura. O modelo foi mais eficiente com os conjunto de resultados combinados para Cu, Pb, Zn, em alface e para Cd e Cu na cenoura. A abordagem não foi eficiente para Ni e para Pb em cenoura, com resultados incoerentes para os conjuntos de resultados combindados ou separados, para os quatro modelos testados.

Made available in DSpace on 2017-07-10T19:23:40Z (GMT). No. of bitstreams: 1 Ralpho.pdf: 2205542 bytes, checksum: 37ae4ee862cc62b72b5ed65409967739 (MD5) Previous issue date: 2013-05-17 / Collecting data on pesticide effects on the environment and several ecosystems is a slow and costly process. Therefore, significant research efforts have been focused on developing mathematical models to predict physical, chemical or biological properties of environmental interest. The soil sorption coefficient normalized to organic carbon content (Koc) is a physicochemical key parameter used in environmental risk assessments of substances released into the environment. Thus, several logKoc prediction models that use hydrophobic parameter (logP) or the logarithm of water solubility (logS) as descriptor have been reported in the last decades. Mostly, due to the lack of reliable experimental values of logP or logS, algorithms are used to calculate such properties. Despite the availability and easiness to access several algorithms for this purpose, scientific studies do not describe the procedure adopted to choose the algorithm used in quantitative structure-property relationship (QSPR) studies. Furthermore, the strong correlation between logP and logS prevents their application in the same mathematical equation obtained by multiple linear regression method. Since the sorption process of a chemical compound in soil is related both to its water solubility and its water/organic matter partition, it is expected models that are able to combine these two properties will can record more realistic results. This doctoral dissertation consists of two scientific papers. In the first one, a study was carried out to check the influence of choosing logP algorithm on logKoc modeling. Models were constructed to relate logKoc with logP according to different freeware algorithms. All models were assessed based on their statistic qualities and predictive power. The obtained results clearly showed that an arbitrary choice of the algorithm may not result in the best prediction model. On the other hand, a good choice can lead to obtaining simple models with statistic qualities and predictive power comparable to more complex models. The second paper aims at proposing an alternative approach for logKoc modeling, using simple descriptor of solubility, here referred as logarithm of corrected solubility by octanol/water partition (logSP). Thus, models were built with this descriptor and also with logP and logS conventional descriptors, which are isolated or associated with other explicative variables of easy physicochemical interpretation. The obtained models were validated and compared to other models previously published. The results showed that the use of logSP descriptor to replace the conventional ones led to obtaining simple models with statistic qualities and predictive power that are higher than other more complex models already found in literature. / A coleta de dados relativos aos danos causados pelos pesticidas sobre o meio ambiente e seus ecossistemas é lenta e onerosa. Desta maneira, grandes incentivos têm sido destinados às pesquisas que visam à construção de modelos matemáticos para predição de propriedades físicas, químicas ou biológicas de interesse ambiental. O coeficiente de sorção no solo normalizado para o conteúdo de carbono orgânico (Koc) é um importante parâmetro físico-químico utilizado nas avaliações de riscos ambientais das substâncias lançadas no meio ambiente. Assim, vários modelos para predição de logKoc, utilizando o parâmetro hidrofóbico (logP) ou o logaritmo da solubilidade em água (logS) como descritores, têm sido publicados nas últimas décadas. Muitas vezes, em virtude da ausência de valores experimentais confiáveis de logP ou logS, são usados algoritmos para o cálculo dessas propriedades. Apesar da disponibilidade e facilidade de acesso a diversos algoritmos para tal finalidade, os artigos científicos não descrevem o procedimento adotado para escolha do algoritmo usado nos estudos QSPR. Além disto, a forte correlação entre logP e logS impede que sejam usados em uma mesma equação obtida por regressão linear múltipla. Como o processo de sorção de um composto químico no solo está relacionado tanto com sua solubilidade em água como com sua partição água/matéria orgânica, espera-se que modelos que sejam capazes de combinar essas duas informações possam gerar resultados mais realistas. Este trabalho de tese é constituído de dois artigos. No primeiro artigo, foi feito um estudo para verificar a influência da escolha do algoritmo de logP na modelagem de logKoc. Foram construídos modelos que relacionam logKoc com logP a partir de diferentes algoritmos livres disponíveis. Todos os modelos foram avaliados quanto às suas qualidades estatísticas e poder de predição. Os resultados obtidos mostraram claramente que uma escolha arbitrária deste algoritmo pode não levar ao melhor modelo de predição. Por outro lado, uma boa escolha pode conduzir à obtenção de modelos simples com qualidades estatísticas e poder de predição comparáveis a de modelos mais complexos. No segundo artigo, o objetivo foi a proposição de uma abordagem alternativa para a modelagem de logKoc, utilizando um descritor simples de solubilidade, aqui designado como logaritmo da solubilidade corrigida pela partição octanol/água (logSP). Assim, foram construídos modelos com tal descritor e também com os descritores convencionais logP e logS, isolados ou associados com outras variáveis explicativas de fácil interpretação físico-química. Os modelos obtidos foram validados e comparados com outros modelos publicados anteriormente. Os resultados mostraram que o uso do descritor logSp em substituição aos descritores convencionais conduziu à obtenção de modelos simples com qualidades estatísticas e poder de predição superiores a de outros modelos mais complexos encontrados na literatura.

Toxoplasma gondii est le parasite responsable de la toxoplasmose, une zoonose infectant l'Homme et les autres espèces endothermes. Les fermes d'élevage sont connues pour présenter de forts risques de transmission pour les hôtes et constituent des réservoirs de la contamination environnementale en milieu rural. Cette étude visait à identifier les facteurs modulant la circulation du parasite dans les fermes dans deux compartiments du cycle: les hôtes définitifs et le sol. Pour cela, la dynamique d'infection par T. gondii dans cinq populations de chats a été suivie et modélisée par des modèles de capture-marquage-recapture « multi-événements ». Ceux-ci ont montré que les taux d'expositions des chats à T. gondii varient entre fermes et que les taux d'infection sont plus élevés en automne-hiver que durant le reste de l'année. La distribution spatiale de la contamination environnementale par T. gondii a ensuite été évaluée dans six fermes par recherche d'ADN dans des prélèvements de sols, puis mise en relation avec le patron de dépôt des fèces par les chats. Malgré une large distribution de T. gondii dans les fermes, les sites de défécation des chats constituent des zones à fort risque de transmission. Le niveau de contamination dans ces sites est dépendant de leur localisation et des caractéristiques des chats qui les utilisent, tout deux influencés par la localisation du site d'alimentation des chats dans les fermes. Cette étude montre que les fermes peuvent présenter des disparités en termes d'exposition au parasite. A l'intérieur des fermes, le patron spatio-temporel de dépôt des fèces par les chats modulent les risques d'infection pour les hommes et les animaux. / Toxoplasma gondii is the protozoan parasite responsible for toxoplasmosis, a zoonosis infecting humans and other endothermic animals. Livestock farms are considered high-risk sites for T. gondii transmission to hosts and they represent reservoirs of environmental contamination in rural areas. The aim of this study was to investigate the infection dynamics of T. gondii in cat populations by surveying five dairy farms using multi-event capture–mark–recapture models. The results showed that the rates of T. gondii infection in cats varied between farms. Infection rates were higher in autumn and winter compared to the rest of the year. The spatial distribution of soil contaminated by T. gondii on six farms was assessed using quantitative PCR on soil samples and analyzed in relation to the spatio-temporal pattern of faeces deposition by cats. Although there was wide spatial distribution of T. gondii in the soil of the farms, cat defecation sites were revealed to be high-risk areas for T. gondii transmission. The level of contamination in these sites depended on their location and characteristics of cats that use them, which were both influenced by the location of the main cats feeding site in the farms. This study demonstrated that T. gondii exposure varies from one farm to another. Infection risk is also heterogeneous within a farm and is driven by the spatio-temporal pattern of deposition of cat faeces.

The enormous rate of increase in waste generation across the world is a serious threat to the future generation, if not handled properly, due to the creation of health hazards and global warming. This was awakened many engineers and researchers to find an appropriate solution for efficient management of waste. The land filling of the waste is the most widely adopted method for its disposal, whose efficiency mainly depends on the engineered barrier system in place. Though possessing many limitations, clay liner solely or along with Geo-membrane is often used to avoid ground and surface water contamination. The thickness of the liner of a given breakthrough time depends on the transport rates of the selected contaminants. To estimate the transport rate of any given contaminant, it is necessary to understand the different migration processes of contaminants through the liner material. It was observed from the literature that, the transport rate of contaminants mainly depends on Dispersion coefficient (D) and Distribution coefficient (K) which are the main contaminant transport parameters. The amount of contaminant transport through the liner system for a desired time period is thus estimated from these contaminant transport parameters using the Advection-Dispersion Equation (ADE). The unregulated open dumps are another cause of serious environmental problem, where the contaminants are free to migrate in any direction through the underground soil. The percolation rate and the accumulation of leachate increase during the rainy season, which picks up more contaminants from the waste and thus the threat of the leachate increases. The leachate normally migrates in vertical and lateral directions, causing contamination of ground and surface water resources, and hence, there is a need to estimate the transport rates of contaminants in the porous media. These transport rates are not only useful for designing barrier systems, but also useful to find a suitable remediation technique for the removal of contaminants from a contaminated site. Thus, determination of transport rate is very important in effective waste management systems. Most of the researchers have obtained the contaminant transport parameters through the column tests to simulate one dimensional flow. Often, it is a lengthy process and there is a need to find an easy and effective method of determining these parameters which can reduce the time and effort. Generally, the metallic contaminants such as Cadmium (Cd), Copper (Cu), Lead (Pb), Mercury (Hg), Nickel (Ni) and Zinc (Zn) which are most hazardous are considered for the contaminant migration studies. In the present study, the transport rates of two heavy metals Copper and Zinc through locally available Black Cotton soil and Red soil were studied. Column experiments were conducted to simulate the field conditions under two types of test conditions i.e., Constant and Decreasing source concentrations. For Black Cotton soil as the hydraulic conductivity was very less and was taking a long time for achieving complete breakthrough, the soil sectioning method was used to get the depth versus concentration. The soil sectioning method involves the determination of pore water concentration of any given contaminant in different sections of the soil column. The depth versus concentration profile can serve as the same purpose as that of complete column test after breakthrough. The column experiments can be done only up to a relative concentration (C/C0) of about 0.2 instead of 0.8 or more. The soil samples were compacted to different densities to know the effect of density on transport parameters. The Black Cotton Soil samples were compacted to 0.76-0.97 times of maximum dry density and Red Soil samples were compacted to 0.81-0.98 times of maximum dry density. The samples were compacted to lesser densities to reduce the experimentation time. The transport parameters for field densities can be determined by setting „Forecast Trend Lines‟ to the density versus dispersion coefficient and density versus distribution coefficient plots. The contaminant transport was modeled by various methods i.e., Analytical, Semi-analytical, Explicit Finite Difference and Implicit Finite Difference methods. These models can be extended to predict the contaminant migration through soil liners constructed with similar soils. During the lifetime of a landfill, it may be subjected to both constant and decreasing source concentration conditions and thus the contaminant transport parameters determined by both constant and decreasing tests will be useful to estimate the optimum thickness of soil liner. The disposal of waste solutions and sludges by industries has led to problems with the contamination of both soil and groundwater. Much research work has not been carried out in the past for the remediation of contaminated soils in India. Thus an attempt has been made to study in detail the different remediation techniques on various contaminated soils. Three heavy metal contaminated soils were studied with two remediation techniques i.e., Soil washing and immobilization. As a case study, Zinc contaminated soil was collected from Hindustan Zinc Limited located near Udaipur in Rajasthan State, India and column leach tests were conducted on this soil with different leaching solutions to study the efficiency of the soil washing technique. The leaching solutions used for removing zinc from this soil were 0.1N HCl, 0.1N EDTA, 0.1N HCl+0.1N EDTA and 0.1N FeCl3. It was found that 0.1N FeCl3 was more efficient to remove zinc from this soil. The removal efficiency was also high with 0.1N HCl+0.1N EDTA solution. The transport rates were determined by matching the theoretical elution curves with experimental elution curves. The contaminant transport for column leach tests was modeled using analytical solution based on the Leaching Mass Ratio approach. These transport rates are useful to estimate the rate of treatment as well as the amount of flushing solution required to remove Zinc knowing the area of contamination and in-situ soil conditions. One of the potential sources of soil and ground water contamination with toxic metal ions is Effluent Treatment Plant sludge (ETP Sludge). The efficiency of soil washing technique was also studied on ETP Sludge using five leaching solutions i.e., distilled water, 0.1N HCl, 0.1N EDTA, 0.1N HCl+0.1N EDTA and 0.1N FeCl3. ETP sludge was collected at a filter press, KIADB industrial area, Doddaballapur, Bangalore. The removal efficiencies of these leaching solutions for removal of different metal ions (Copper, Zinc, Iron, Nickel, Cadmium, Lead and Chromium) were studied. The highest removal efficiencies were observed with 0.1N FeCl3 and 0.1N HCl+0.1N EDTA. The transport rates of different metals were determined which will be useful to estimate the quantity of leaching solution required in the field to remediate this sludge using soil washing technique. Even though soil washing technique is more effective than immobilization, for less permeable soil with more clay content, it is not a cost effective method. In such cases immobilization technique can be used to remediate the contaminated soil. The immobilized metals will not migrate through soil to groundwater and will not give adverse environmental hazards in their treated state. In the present study, immobilization technique was studied on two materials, (i) contaminated soil from open dump and (ii) ETP Sludge. The contaminated soil was collected from an open dump located at the Bingipura dumping yard, Bangalore and was tested for the presence of heavy metal ions. The efficiency of treatment to immobilize the metals was studied with different additives. The chemical agents with which can decrease the solubility product will be effective to immobilize the metal ions. The stabilizing agents used for treating these materials were lime water, NaOH and cement. These stabilizing agents were selected after preliminary batch tests. Since most of the heavy metals in soils become less mobile with increase in pH, the lime water / NaOH was added to the soil/sludge to adjust the pH of the mixture to 7.0, 8.5 and 10.0. The cement: soil ratios used were, 1:100 (pH=6. 8), 1:50 (pH=8. 1) and 1:25 (pH=9. 8) by weight. Leaching tests were conducted on the amended soils to know the long term efficiencies of the chemical agents for immobilizing the metal ions. The work carried out in this thesis is presented in different chapters as given below: For the design of the liner system, it is necessary to know the different contaminant transport processes, the determination of their rates and modeling. For remediation of contaminated soil, it is required to find the suitable remediation technique based on the amount and type of pollutants, the type of soil and other geological conditions. The detailed information about sources of heavy metals, effects of heavy metal contamination on health and the environment, contaminant transport processes, methods of determining transport rates, and different modeling techniques for contaminant transport are explained in Chapter 1. The Background information along with the scope and objectives of this study are presented in this chapter. The extensive review of literature related to column experiments, various solutions to Advection-Dispersion Equation, and different remediation techniques to treat the contaminated soil, is also presented in this chapter. Chapter 2 gives detailed information about various materials and methods used in this study. The characteristics of soils used in the present study and preparation of different chemical solutions were explained. The experimental procedures of batch tests, column tests and soil sectioning to determine the contaminant transport parameters were given in detail. The experimental procedures that are required for assessing the efficiency of soil washing technique i.e., Batch leach tests and column leach tests were also explained. The laboratory assessment of immobilization efficiency through leaching test was explained briefly. The analytical and numerical solutions used for this study were discussed in detail. This chapter also includes a method of prediction of breakthrough curves from the incomplete column test data. The contaminant transport parameters of metal ion Copper in two locally available soils i.e., Black cotton soil and Red soil were determined by various techniques i.e., Analytical (using MATLAB v7 software), semi-analytical (using POLLUTE v7 software), Explicit Finite Difference Method with two software tools (MATLAB v7 and M.S.EXCEL 2010), Implicit Finite Difference method with three schemes (BTCS, UPWIND & CRANK NICOLSON) using two software tools (MATLAB v7 and M.S.EXCEL 2010). Modifications were done in the spreadsheet solution of non-reactive solute available from the literature to incorporate the retardation factor as the solutes used in this study are reactive in nature. These results are presented in Chapter 3. The contaminant transport parameters determined for different test conditions (constant and variable source concentrations) and for different densities of soil are reported in this chapter. Determination of transport rates corresponding to maximum dry density using trend lines and preparation of design charts to estimate the thickness of the liner are also discussed in this chapter. The contaminant transport parameters were also determined for metal ion Zinc in the same soils with the same techniques as that of Copper and the migration rates were compared for both the ions. These models and comparative results are presented Chapter 4. It was observed that with increase in density, the dispersion coefficient decreases and Distribution coefficient increases. It was also found that the dispersion coefficient of Black Cotton Soil was lower than that of Red Soil whereas the distribution coefficient of Black Cotton soil is much higher than that of Red Soil. Further, it was observed that the dispersion coefficient of Copper was less than that of Zinc whereas the distribution coefficient of Copper was higher than Zinc. The design of liner thickness, based on transport rates of Zinc is briefly discussed in this chapter. A case study has been explained for the remediation of Zinc contaminated sandy soil using soil washing technique. The undisturbed soil samples collected from four locations of waste disposal site of Hindustan Zinc Limited located near Udaipur in Rajasthan State of Western India were assessed to find the suitable leaching solution and number of pore volumes for the effective removal of Zinc from this soil. The chelates/ solvents used for this soil were 0.1N HCl, 0.1N EDTA, 0.1N HCl+0.1N EDTA and 0.1N FeCl3. The contaminant transport parameters were also determined from the column leach tests based on the Leaching Mass Ratio approach and the results are presented in Chapter 5. From the experimental study it was observed that 0.1N FeCl3 and 0.1N HCl+0.1N EDTA are the most suitable leaching solutions to treat this soil. The Chapter 6 contains the sludge analysis of an industrial ETP sludge, column leach test results of this sludge with different leaching solutions, removal efficiencies of different solutions used and the transport rates of different contaminants. The leaching solutions used for this sludge were distilled water, 0.1N HCl, 0.1N EDTA, 0.1N HCl+0.1N EDTA and 0.1N FeCl3. It was observed that 0.1N FeCl3 and 0.1N HCl+0.1N EDTA are the most suitable leaching solutions to treat this sludge. Other solutions have also removed the contaminants by more than 50%, but the number of pore volumes required to leach out the contaminants was high. The order of removal efficiencies of different solutions is presented below: 0.1N FeCl3 > 0.1N HCl + 0.1N EDTA > 0.1N EDTA > 0.1N HCl > distilled water. The transport rates of different contaminants (Cu, Zn, Cd, Fe, Ni, Pb and Cr) were determined using analytical solution and are presented in this chapter. These transport rates are useful to estimate the quantity of leaching solution required in the field to remediate the sludge using soil washing technique. A contaminated soil collected from an open dump site within Bangalore city and ETP Sludge were analyzed to know the efficiency of immobilization/ solidification technique of remediation using three chemical agents lime, NaOH and cement. The soil samples were mixed with different proportions of these chemicals to adjust the pH of the mixtures to 7.0, 8.5 and 10.0. Leaching tests were conducted on the modified soils to know the long term efficiency of these chemical agents to immobilize the contaminants and these results are discussed in Chapter7. The results showed that highest immobilization efficiencies can be achieved with lime for this contaminated soil and cement is the most suitable chemical agent to treat this sludge. The immobilization efficiencies of different stabilizing agents for various metals were studied and the results analyzed. The Chapter 8 includes the major observations and conclusions of the present research work which will be useful for Geotechnical and Geo-environmental engineers to estimate the transport rates of contaminants, to design the soil liners, to assess the efficiency of soil washing technique to remediate the contaminated soil, to estimate the quantity of leaching solution required in the field for soil washing and to find the suitable chemical agent for remediating the contaminated soil by immobilization technique.

This thesis is focused on the degree of soil contamination with heavy metals in urban area of Brno. Samples were collected in three periods from October 2009 to March 2010, to represent different seasons and their impact on the concentration of heavy metals in examined soil. Ten locations was chosen, each with different level of concentration, starting with busy traffic area where the concentration of means was high continuing to areas located around habitation or parks. As result four elements were determined in every sample: Cu, Cd, Hg and Pb. Presence of copper and lead were detected by flame atomic absortion spectroscopy (F-AAS) and, cadmium by the help of electrothermal atomic absortion spectroscopy (ET-AAS). For the determination of mercury was used advanced mercury analyzer (AMA).

This thesis is focused on the assessment of contamination of non-agricultural soils of selected locations in Ostrava of hazardous metals. Selection of locations was based on the stationary pollution source REZZO1. Total 36 collected samples from 12 locations in three times periods between July 2010 and March 2011 that each collection represented a different time period for characteristic emissions conditions. The risk of metals mercury, cadmium, lead, copper and chromium were determined by atomic absorption spectrometry (F AAS, ET AAS, AMA 254).The influence of the distance of locations from stationary sources of REZZO1 on the extent of soil contamination by selected metals was confirmed.

No description available.

Afin d'établir l'impact et le risque lié aux fertilisants chimiques depuis leur fabrication jusqu'à leur amendement sur la contamination des sols par les éléments traces métalliques, une étude de leur mobilité et leur transfert s'avère nécessaire. L'objectif de ce travail de thèse était d'évaluer la source de contamination du sol par les éléments traces autour de l'industrie des fertilisants chimiques et suivre l'évolution temporelle de la mobilité et du transfert de ces éléments dans un profil du sol agricole amendé par des engrais phosphatés du type simple superphosphate (SSP) ou du phosphogypse. Pour cela nous avons utilisé des techniques permettant la caractérisation structurale et minéralogique des sols collectés comme la diffraction des rayons X et la microscopie électronique. Puis une caractérisation chimique des sols collectés concernant la concentration totale des éléments traces et des éléments majeurs a été établie. Comme la mobilité n'est pas stable au cours du temps dépendant de plusieurs paramètres physico-chimiques comme le pH, le potentiel redox, la teneur en matière organique, une extraction séquentielle a été adoptée le long de l'étude au cours du temps et dans le profil du sol amendé jusqu'à une profondeur de 55 cm. En outre, l'absorption des éléments traces par les plantes cultivées sur le terrain agricole amendé par les engrais ou le phosphogypse a été analysée au cours du temps afin d'évaluer le risque lié à la chaîne alimentaire et plus particulièrement la chaîne alimentaire humaine induisant des effets négatifs sur la santé. Une comparaison entre l'application du phosphogypse et celle des engrais a été mise en évidence à la finalité de ce travail / To determine the impact and risk of chemical fertilizers, from their manufacture to their amendment, on soil contamination by trace metals, the study of their mobility and transfer would be necessary. The objective of this work was to evaluate the source of soil contamination by trace elements around the industry of chemical fertilizers, and to follow the temporal evolution of mobility and transfer of these elements in the profile of agricultural soil amended by superphosphate (SSP) fertilizers or phosphogypsum. To achieve our objective, we used techniques allowing the determination of structural and mineralogical characterization of collected soil samples, such as X-ray diffraction and electron microscopy. Chemical characterization related to the total concentration of trace and major elements of collected soils was established. As mobility was unstable over time, depending on several physico-chemical parameters such as pH, redox potential, and organic matter content, a sequential extraction was adopted throughout the study over time in the amended soil profile to a depth of 55 cm. In addition, the absorption of trace elements by agricultural crops cultivated over land amended with fertilizer or phosphogypsum was analyzed over time to assess the risk of their transfer to the food chain, especially the human food chain, imposing health hazards. A comparison between the effects of the application of phosphogypsum and phosphate fertilizer was carried out in concluding this work

Na atualidade estudos direcionados para a avaliação do risco químico e do impacto ambiental produzidos por compostos químicos de uso intensivo, como agrotóxicos, petroquímicos e fármacos, vêm ganhando importância por elucidarem as implicações ao meio ambiente e à saúde pública decorrentes deste uso pela sociedade moderna de forma a estabelecer parâmetros restritivos para suas aplicações, evitando-se danos posteriores. Este Estudo compreendeu as observações de sorção e de interação do antibiótico de uso animal e agrícola oxitetraciclina (OTC) com solos brasileiros e ácidos húmicos (AH) extraídos de solos, tendo-se como objetivos gerais comprovar a sorção aos solos e aos AH e verificar a influência da matéria orgânica (MO) e do pH sobre a sorção, definindo quais os mecanismos moleculares de interação envolvidos, cabendo destacar que as tetraciclinas são uma das principais classes de antibióticos utilizadas na pecuária brasileira, tanto para tratamento de enfermidades quanto como Antibióticos Promotores de Crescimento (APC), além de serem freqüentemente aplicados na agricultura para controle de fungos e bactérias. Utilizou-se a Cromatografia Líquida de Alta Eficiência (CLAE) para a coleta de dados quantitativos que permitiram a construção de isotermas de sorção solo-OTC em pH 4,8 e AH-OTC em três valores de pH (3,1, 4,8 e 8,3) para a comprovação da sorção e da influência do conteúdo de MO no primeiro caso, e na sorção aos AH, para o segundo caso. Os solos foram caracterizados conforme procedimento padrão da EMBRAPA, enquanto que os AH foram caracterizados segundo procedimentos recomendados pela literatura por meio das técnicas instrumentais de Análise Elementar, Absorção na Região do Infravermelho Médio, Ressonância Magnética Nuclear e Ressonância Paramagnética Eletrônica. Foram utilizadas as técnicas espectroscópicas de Absorção na Região do Infravermelho (Próximo e Médio) e Absorção e Fluorescência na Região do UV-Visível, para a avaliação dos possíveis mecanismos de interação envolvidos, como ligação de hidrogênio, interação hidrofóbica e transferência de elétrons. A isoterma de Freundlich apresentou-se como um modelo matemático adequado para a verificação da sorção solos-OTC e AH-OTC, a partir da aplicação de um método cromatográfico adequado, comprovando a sorção para os dois casos, bem como o efeito do conteúdo de MO dos solos e do pH do meio sobre a capacidade e a intensidade da sorção, a qual foi quantificada como de capacidade de sorção inferior em comparação a dados obtidos em clima temperado e de alta capacidade de sorção quando comparada à legislação ambiental brasileira. Foi observado que a OTC interagiu com os AH em uma larga faixa de valores de pH, indo de 3,1 a 8,3. Contudo, o meio no qual foi possível observar de uma forma mais acentuada a interação entre AH e OTC foi o meio básico (pH 8,2), sendo notado a existência de mecanismos de interação associados e dependentes do pH do meio, como: ligação de hidrogênio, interação hidrofóbica e transferência de prótons. / At present further studies on the risk assessment of chemical and environmental impact produced by chemical-intensive, such as pesticides, petrochemicals and pharmaceuticals, have gained importance for elucidating the implications for the environment and public health arising from this use by modern society to establish restrictive parameters for their applications, avoiding further damage. This Study comprised observations of sorption and interaction of antibiotic for animal and agriculture use oxytetracycline (OTC) with brazilian soils and humic acids (HA) extracted from soil, having as objectives to prove the general sorption to soils and the AH and the influence of organic matter (OM) and pH on the sorption, which define the molecular mechanisms of interaction involved, highlighting that tetracyclines are a major classes of antibiotics used in the brazilian cattle industry, both for treatment of diseases such as antibiotic growth promoters (AGP), and frequently also applied in agriculture to control fungi and bacteria. The High Performance Liquid Chromatography (HPLC) was used to collect quantitative data that allowed the construction of sorption isotherms soils-OTC in pH 4.8 and AH-OTC in three pH values (3.1, 4, 8 and 8.3) for proof of sorption and the influence of OM content in the first case, and sorption to AH, for the second case. The soils were characterized as standard procedure of EMBRAPA, while AH were characterized according to procedures recommended by the literature by means of instrumental techniques for Elemental Analysis, Absorption in the Region of the Middle Infrared, Nuclear Magnetic Resonance and Electron Paramagnetic Resonance. The Spectroscopic Absorption in the Infrared Region (Middle) and Fluorescence and Absorption in the Region and the UV-Visible were used for the evaluation of interaction mechanisms involved, such as hydrogen bonding, hydrophobic interactions and electron transfer. The Freundlich isotherm was presented as a mathematical model suitable for the verification of soils-OTC sorption and AH-OTC sorption from the application of a chromatographic method that is suitable, proving the sorption for the two cases as well as the effect of OM content of soils and the pH on the capacity and sorption intensity, which was quantified as the lower sorption capacity in comparison with data from temperate and high sorption capacity when compared to Brazilian environmental legislation. It was observed that the OTC interacted with the HA in a wide range of pH values, ranging from 3.1 to 8.3. However, the way in which it was possible to observe a more pronounced interaction between HA and OTC was the basic medium (pH 8.2), and noted the existence of mechanisms of interaction associated and dependent on pH, such as: link hydrogen, hydrophobic interaction and proton transfer.