As atividades industriais e de mineração, juntamente com o uso inadequado de fertilizantes e pesticidas, tem contribuído para o aumento da contaminação do solo, cursos d\'água e lençol freático por elementos tóxicos. A procura pelo desenvolvimento de soluções tecnológicas tem aumentado para atender à legislação ambiental. Segundo a ABETRE, no Brasil, apenas 22% dos 2,9 milhões de toneladas de resíduos industriais perigosos produzidos nas últimas décadas recebem tratamento adequado, sendo os 78% restantes colocados indevidamente em lixões sem tratamento prévio. Vários métodos de remediação de solos contaminados são conhecidos, entre eles estão o isolamento, imobilização, redução da toxicidade, separação física e extração. Neste contexto, destaca-se a vermicompostagem que utiliza as minhocas para degradar a matéria orgânica recente, tonando-a um material quimicamente mais estabilizado, além de remover os elementos tóxicos do solo acumulando-os em seu organismo. Dentre outros benefícios dessa técnica, destacam-se a manutenção da fertilidade do solo e a grande aceitação pública por ser uma tecnologia verde. Este trabalho tem como objetivo determinar a relação entre as concentrações de elementos tóxicos (Cr, Cu e Pb) com o vermicomposto. É avaliada a adição do material adsorvente aos solos com o intuito de conhecer a capacidade de retenção deste material para posterior descontaminação de solos contaminados. Propriedades químicas, como: pH, teor de matéria orgânica, capacidade de troca catiônica, carbono orgânico total, e físicas: umidade e granulometria são estudadas. Conclui-se com este trabalho que o vermicomposto mostrou-se um excelente material adsorvente para as espécies metálicas estudadas, sendo a ordem de adsorção Pb2+ < Cu2+ < Cr3+. / Industrial and mining activities, as well as the inappropriate use of fertilizers and pesticides, have been contributing to the increase of the contamination of soils, watercourses and water tables by toxic elements. The search for the development of technological solutions has grown to comply with the environment legislation. According to ABETRE, only 22% of 2.9 million of tones of dangerous industrial residues, produced in Brazil, received an appropriate treatment in recent decades. The remaining 78% are thrown in dumps without previous treatment. Many methods of contaminated soil remediation are known, among them isolation, immobilization, toxicity reduction, physical separation and extraction. In this context, it stands out vermicomposting that uses worms to degrade the recent organic matter, which becomes a more chemically stabilized material, and this practice also removes accumulated toxic elements from soil. Among others benefits of this practice there are soil fertility maintenance and the acceptance of people as it is a green technology. This work aims at determining the relation between the concentration of toxic elements (Cr, Cu e Pb) and the vermicompost. The addition of the adsorptive material to soil is assessed by determining the retention capacity of this material for a later decontamination of soils. Both chemical (pH, organic matter content, cationic change capacity and total organic carbon) and physical properties (humidity and granulometry) have been studied. In this study, it was concluded that vermicompost proved to be an excellent adsorbent material to the studied metallic species, and the adsorption order was Pb2+ < Cu2+ < Cr3+.

As atividades industriais e de mineração, juntamente com o uso inadequado de fertilizantes e pesticidas, tem contribuído para o aumento da contaminação do solo, cursos d\'água e lençol freático por elementos tóxicos. A procura pelo desenvolvimento de soluções tecnológicas tem aumentado para atender à legislação ambiental. Segundo a ABETRE, no Brasil, apenas 22% dos 2,9 milhões de toneladas de resíduos industriais perigosos produzidos nas últimas décadas recebem tratamento adequado, sendo os 78% restantes colocados indevidamente em lixões sem tratamento prévio. Vários métodos de remediação de solos contaminados são conhecidos, entre eles estão o isolamento, imobilização, redução da toxicidade, separação física e extração. Neste contexto, destaca-se a vermicompostagem que utiliza as minhocas para degradar a matéria orgânica recente, tonando-a um material quimicamente mais estabilizado, além de remover os elementos tóxicos do solo acumulando-os em seu organismo. Dentre outros benefícios dessa técnica, destacam-se a manutenção da fertilidade do solo e a grande aceitação pública por ser uma tecnologia verde. Este trabalho tem como objetivo determinar a relação entre as concentrações de elementos tóxicos (Cr, Cu e Pb) com o vermicomposto. É avaliada a adição do material adsorvente aos solos com o intuito de conhecer a capacidade de retenção deste material para posterior descontaminação de solos contaminados. Propriedades químicas, como: pH, teor de matéria orgânica, capacidade de troca catiônica, carbono orgânico total, e físicas: umidade e granulometria são estudadas. Conclui-se com este trabalho que o vermicomposto mostrou-se um excelente material adsorvente para as espécies metálicas estudadas, sendo a ordem de adsorção Pb2+ < Cu2+ < Cr3+. / Industrial and mining activities, as well as the inappropriate use of fertilizers and pesticides, have been contributing to the increase of the contamination of soils, watercourses and water tables by toxic elements. The search for the development of technological solutions has grown to comply with the environment legislation. According to ABETRE, only 22% of 2.9 million of tones of dangerous industrial residues, produced in Brazil, received an appropriate treatment in recent decades. The remaining 78% are thrown in dumps without previous treatment. Many methods of contaminated soil remediation are known, among them isolation, immobilization, toxicity reduction, physical separation and extraction. In this context, it stands out vermicomposting that uses worms to degrade the recent organic matter, which becomes a more chemically stabilized material, and this practice also removes accumulated toxic elements from soil. Among others benefits of this practice there are soil fertility maintenance and the acceptance of people as it is a green technology. This work aims at determining the relation between the concentration of toxic elements (Cr, Cu e Pb) and the vermicompost. The addition of the adsorptive material to soil is assessed by determining the retention capacity of this material for a later decontamination of soils. Both chemical (pH, organic matter content, cationic change capacity and total organic carbon) and physical properties (humidity and granulometry) have been studied. In this study, it was concluded that vermicompost proved to be an excellent adsorbent material to the studied metallic species, and the adsorption order was Pb2+ < Cu2+ < Cr3+.

Coal fly ash is a by-product of coal combustion that has drawn renewed public scrutiny due to the negative environmental impacts from accidental release of this waste material from storage facilities. Historically, the leaching of toxic elements from coal fly ash into the environment has always been a major environmental concern. Despite extensive efforts into the characterization of coal fly ash, effective models for the fate and transport of toxic fly ash constituents have remained lacking, making it difficult to perform accurate environmental impact assessment for coal fly ash. To close this critical knowledge gap, the overall objective of this study was to develop a predictive model for the leaching of toxic elements from fly ash particles. First, physical properties of coal fly ash were characterized to evaluate their contribution to elemental transport. Unburned carbon was shown to contribute to the sorption of arsenic to fly ash, which slowed the release of arsenic from fly ash. In parallel, leaching properties of various elements were determined to differentiate species of varying leaching capacities, demonstrating that the majority of toxic elements were not mobile under environmentally relevant conditions. Subsequently, a mechanistic model for the dissolution of fly ash elements was developed and validated with batch kinetics studies. Furthermore, elemental dissolution was integrated with hydrodynamic modeling to describe the leaching of toxic elements from fly ash in dry disposal facilities, which was validated by column studies. The mechanistic model developed and validated in this research represents the first such model that successfully characterized the complex processes underlying the release and transport of toxic elements in coal fly ash, providing a valuable tool to predict the environment impact of coal fly ash and develop more effective management practices for both the industry and regulators.

It is an ordinary practice to cover the areas after brown-coal mining with natural topsoil cover (topsoiling). Topsoiling is removal one topsoil from agricultural land, forest or area with vegetation and excavating to another place with poor organic matter content or in our case the brown-coal mining dumpsite. Advantages of topsoiling include higher organic matter and greater available water-holding capacity and nutrient content. Content of potentially toxic elements is very low. Ammonia nitrate (NH4NO3) extraction, BCR sequential analysis and aqua regia determination were applied in this study to prove that the proportion of bioavailable forms of PTE in reclaimed soils is also low. Amounts of potentially toxic elements were compared between different types of reclamation: an agricultural shown higher value for Pb and Cd, forestry has only one contaminant -- Cd. The research shows that toxicity of soil is low and has no dangerous influence for agricultural application.

Made available in DSpace on 2014-10-09T12:54:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:28Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:54:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:28Z (GMT). No. of bitstreams: 0 / Neste trabalho foram determinados os elementos As, Br, Co, Cr, Cs, Fe, K, Na, Rb, Se e Zn presentes em cogumelos comestíveis adquiridos em grandes centros de compra (supermercados), mercados municipais da cidade de São Paulo e diretamente de produtores da região de Mogi das Cruzes, Suzano, Juquitiba e Mirandópolis. A técnica analítica empregada para a determinação dos elementos nos cogumelos comestíveis foi a Análise por Ativação com Nêutrons Instrumental (INAA). Foram adquiridas espécies dos gêneros Agaricus, Lentinus e Pleurotus no período de novembro de 2006 a março de 2007. Cerca de 150 a 200 mg das amostras de cogumelo liofilizado foram irradiadas em fluxo de nêutrons térmicos de 1012cm-2s-1 por 8 horas no reator nuclear de pesquisa IEA-R1 do IPEN/CNEN/SP. Para a validação da metodologia com relação à exatidão e à precisão foram analisados quatro materiais de referência: INCT-MPH-2 Mixed Polish Herbs e INCT-TL-1 Tea Leaves, NIST SRM 1577b Bovine Liver e Mushroom da IAEA. Foi verificada uma variação nas concentrações dos elementos determinados entre os diferentes gêneros. Em algumas amostras apresentaram o elemento arsênio, em baixas concentrações, possivelmente de uma contaminação no cultivo pelo uso de pesticidas nos substratos de onde os cogumelos retiram seus nutrientes. Os resultados mostram que as amostras das espécies de cogumelos analisadas podem ser consideradas como boa fonte nutricional, principalmente devido aos baixos teores de Na, sendo também uma boa fonte de K, Fe e Zn. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN/CNEN-SP

Philosophiae Doctor - PhD / Mine water poses a serious environmental challenge and contains elements such as Fe, Al, and Mn in potentially toxic concentrations. The major anion in mine water is sulphate. The complexity and diversity of mine water composition makes its treatment very expensive, and there is no “one-fits-all” treatment option available for mine water. Active treatment of mine water produces water with good quality but the processes are not sustainable because of the costs. Previous studies have shown that acid mine drainage can be treated with coal FA to produce better quality water. The use of coal FA, a waste material from coal fired power station and mine water would go a long way in achievement of sustainable treatment of mine water as per previous studies. In this study mine water and coal FA were characterized to determine their physiochemical properties. This study linked the modelling results obtained by using the Geochemist’s workbench (GWB) software to the results obtained during the actual treatment of Matla mine water and Rand Uranium mine water using coal FA and lime. The chemistry involved when Matla mine water and Rand Uranium mine water were treated with flocculants was also investigated. Lastly the chemistry and kinetics involved was investigated when mine water was treated with various ameliorants such as Matla coal FA, lime and/or Al(OH)3 using jet loop mixing or overhead stirring. Mine water from Matla coal mine had a pH of 8 and therefore was classified as neutral mine drainage (NMD). Rand Uranium mine water had a pH of less than 3 and therefore was classified as acid mine drainage (AMD). The concentration of sulphate, Na, Ca, Mg, B, Hg, Se and Cd ions in Matla mine water was 1475, 956, 70, 40, 15, 2.43, 1.12 and 0.005 mg/L respectively. The concentration of sulphate, Fe, Ca, Mn, Mg, Al, B, Cr, Pb, U, Cd, Se and As ions in Rand Uranium mine water was 4126, 896, 376, 282, 155, 27, 5.43, 3.15, 0.51, 0.29, 0.007, 0.06 and 0.006 mg/L respectively . These concentrations were above the target water quality range (TWQR) for potable water set by the Department of Water Affairs (DWA) and World Health Organization (WHO). The gross alpha radioactivity was 6.01 Bq/L and gross beta radioactivity was 6.05 Bq/L in Rand Uranium mine water.

La gestion au long terme des sédiments de dragage contaminés soulève le problème du devenir des éléments potentiellement toxiques contenus dans ces matrices. Les paramètres physicochimiques influencent la spéciation et la distribution des contaminants sur les différentes phases porteuses organiques ou minérales, ainsi lors de la gestion à terre des sédiments la modification de facteurs tels que l’aération, les cycles d’humectation/séchage et l’activité bactérienne va influencer les paramètres physico-chimiques et donc la spéciation des contaminants. Afin de préciser les mécanismes responsables de la mobilité des éléments potentiellement toxiques et d’estimer l’acceptabilité environnementale des sédiments de dragage en scénario de valorisation (p. ex. butte paysagère, remblai ou sous couche routière), l’étude a été axée sur trois principales étapes :I établir la caractérisation totale des sédiments (granulométrie, minéralogie, teneur en eau, composition de la phase solide, composition de l’eau interstitielle) et évaluer selon des procédures normaliséesl’influence de facteurs (pH, L/S, température…) sur la lixiviation des éléments et sur les mécanismes géochimiques mpliqués ; II développer un jeu de paramètres d’entrée pour le code géochimique ORCHESTRA selon des procédures normalisées (quantification des phases porteuses les plus réactives : argiles, carbonates, oxy-hydroxydes de fer ou d’aluminium et matière organique - acide fulviques et humiques) ; III modéliser et prédire les courbes de solubilité des éléments décrites lors des tests normalisés issus de l’étape (i) par l’intermédiaire du jeu de paramètres d’entrée défini dans l’étape II. Les tests de lixiviation et la réalisation de modèles sont des approches complémentaires, indispensables pour appréhender et préciser les mécanismes contrôlant la mobilité et la rétention des éléments. Les modélisations des tests de lixiviation dynamique en colonne sont très sensibles aux variations des paramètres d’entrée, c’est pourquoi les modèles pour les éléments majeurs doivent être le plus adéquats possible. En général, les prédictions pour Al, Ca, Cl, Fe, H2CO3, Mg, Si, SO4, Cu, Cr, MoO4 2- , Pb et Zn ont été proches des données expérimentales, ce qui a indiqué que les processus majoritaires contrôlant la solubilité des éléments ont été pris en compte. Par contre, les prédictions pour Ni et As n’ont pas été satisfaisantes, montrant que certains processus de rétention restent encore inconnus et qu’ils ne sont pas pris en compte par la base de données MINETEQ2A. Pour mieux décrire le comportement d'As, il semblerait intéressant d’intégrer, dans le module NiCA-Donan, la complexation potentielle d'As par la MON. / The long-term management of contaminated dredged sediments raises the problem of the fate of the potentially toxic element contained in these matrixes. The physico-chemical parameters influence the speciation and distribution of contaminants between organic or inorganic bearing phases, and the terrestrial management of sediment induces the modification of factors such as oxydation, wetting / drying cycles or bacterial activity that will influence the physico-chemical parameters and thus the contaminant speciation. In order to identify the main mechanisms responsible for the mobility ofpotentially toxic elements and to estimate the environmental acceptability of dredged sediment in valuation scenario (as hill landscape, road fill or undercoat), the study was organized following three main steps I characterizing the sediment (particle size, mineralogy, moisture content, solid phase and pore water composition) and evaluating factors (pH, L / S, temperature ...) that control the leaching of elements, according to standardized procedures, II developing a set of input parameters for the geochemical code ORCHESTRA according to standardized procedures (quantification of the most reactive carrier phases : clays, carbonates, oxyhydroxides of iron or aluminum and organic matter - fulvic and humic acid) III modeling and predicting the solubility curves of the elements described in the standardized tests from step (i) using the set of input parameters defined in step (ii). Leaching tests and implementation models are complementary approaches that are necessary to understand the mechanisms controlling the mobility and retention of elements. Modeling of column dynamic leaching tests is very sensitive to changes in input parameters, so the model for the major elements should be as adequate as possible. The obtained predictions for Al, Ca, Cl, Fe, H2CO3, Mg, Si, SO4 2-, Cu, Cr, MoO4 2-, Pb and Zn were close to the experimental data, which indicates that the main processes controlling the solubility of elements were taken into account. The predictions for Ni and As, however, were not satisfactory, showing that some retention processes are still unknown or were not taken into account by the database MINETEQ2A. A better description of As behavior would require to include inAs complexation by the MON in the module Nica-Donan.

For widespread use of biochar in agriculture and horticulture, it must be ensured that application will neither adversely affect soil and plants, nor exceed legislated contaminant concentrations. The most relevant groups of contaminants in biochar are potentially toxic elements (PTEs), polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOC). In this thesis, the concentrations of these groups of contaminants were analysed in 90 different biochars produced by slow pyrolysis. Subsequently, the concentrations were compared to legislation/guideline threshold values and linked to production conditions. The risk these contaminants pose to plant growth was also assessed, to give recommendations on production of safe biochar. PTEs can neither be formed nor destroyed, which means their presence in biochar is predominantly determined by feedstock type. However, significant levels of Cr, Fe and Ni were introduced into biochar from the furnace steel, whilst PTEs with low boiling points, such as As, Cd and Zn, partially evaporated during pyrolysis. PTEs were not responsible for phytotoxic effects observed for PTE-rich biochars despite biochar’s exceedance of available and total PTE threshold values for soil and soil amendments. Although initial tests were promising, the risk that PTE-rich biochars as amendment for soil and growing media pose, needs further investigation. The PAH concentration in biochar was markedly reduced by increasing carrier gas flow rate, and the type of feedstock also influenced the PAH content. However, there was no clear dependence of pyrolysis temperature on PAH concentrations, which was attributed to PAHs being increasingly formed and evaporated at higher pyrolysis temperatures. Ultimately, condensation of pyrolysis vapours and deposition on biochar was identified as the main risk for biochar contamination with PAHs, as this resulted in elevated concentrations of high-risk, higher molecular weight PAHs. Weaknesses in the pyrolysis unit design, such as cold zones, resulted in elevated concentrations of VOCs, as well as PAHs, in biochar. Comparing concentrations and phytotoxic potential of both compound groups, it was concluded that observed toxic effects were much more likely caused by VOCs in biochars containing both contaminants. Overall, formation of VOCs and PAHs cannot be prevented, but their presence in biochar resulting from retention and deposition can be minimised.

Submitted by Claudia Rocha (claudia.rocha@udesc.br) on 2018-03-08T15:04:26Z No. of bitstreams: 1 PGCS17MA165.pdf: 672855 bytes, checksum: 96c8cbad495c26a671647f8e66eb4fea (MD5) / Made available in DSpace on 2018-03-08T15:04:26Z (GMT). No. of bitstreams: 1 PGCS17MA165.pdf: 672855 bytes, checksum: 96c8cbad495c26a671647f8e66eb4fea (MD5) Previous issue date: 2017-02-17 / Capes / The aim of this work was to quantify the acidic and soluble contents of the essential elements Ca, Mg, N, Cu, Mn and Zn of the toxic elements Al, Cd and Pb in four brands of yerba mate marketed in the city of Lages- SC. Samples of yerba mate (Ilex paraguariensis St. Hill.) Were commercially purchased from supermarkets in the city of Lages, SC. Four brands of commercial yerba mate were selected. All samples have the same date of manufacture, March 2016. The grinding is type PN-1. The samples were oven dried at 65 C ° for 24 h, crushed and sieved in 2 mm mesh. For the total content, the nitro-perchloric digestion was used according to the Manual of Methods of Tissue Analysis used in Embrapa and for the total N, content the sulfur digestion method was used. Infusion was weighed 1.5 g of yerba mate to 10 ml of deionized water, with contact time of 10 minutes, at temperatures of 70, 80 and 90 °C. The quantification of the elements was performed in ICP-OES. On average, the highest levels obtained for all infused elements were at 70 ° C. The nutrients Ca, Mg, N, Cu, Mn and Zn were transferred to the chimarrão. The levels of infused Cd are above the maximum values allowed by the legislation for infusions. However, for Pb content, only the M4 mark is above permitted / Esse trabalho teve como objetivo quantificar os teores via digestão ácida e solúveis em infusão dos elementos essenciais Ca, Mg, N, Cu, Mn e Zn dos elementos tóxicos Al, Cd e Pb em quatro marcas de erva-mate comercializadas na cidade de Lages-SC. As amostras de ervamate (Ilex paraguariensis St. Hill.) foram adquiridas comercialmente em supermercados da cidade de Lages, SC. foram selecionadas quatro marcas de erva-mate comerciais. Todas as amostras, possuem a mesma data de fabricação, mês de março de 2016. A moagem é do tipo PN-1. As amostras foram secas em estufa à 65 C° por 24 h, trituradas e peneiradas em malha 2mm. Para o teor total utilizou-se a digestão nitro-perclórica, de acordo com o Manual de Métodos de Análises de Tecidos utilizados na Embrapa e para o teor total de N, foi utilizado o método de digestão sulfúrica. Para a infusão foi pesado 1,5 g de erva-mate para 10 ml de água deionizada, com tempo de contato de 10 minutos, em temperaturas de 70 ,80 e 90 °C. A quantificação dos elementos foi realizada em ICP-OES. Em média os maiores teores obtidos para todos os elementos em infusão foi a 70 °C. Os nutrientes Ca, Mg, N, Cu, Mn e Zn foram transferidos para o chimarrão. Os teores de Cd em infusão encontram-se acima dos valores máximo permitidos pela legislação para infusões. Entretanto para teor Pb, apenas a marca M4 encontra-se acima do permitido