by So Chi Ming. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1991. / Includes bibliographical references. / Acknowledgement --- p.i / Abstract --- p.ii / Chapter 1. --- Objectives of the Study --- p.1 / Chapter 2. --- Literature Review --- p.2 / Chapter 2.1 --- Heavy Metals in the Environment --- p.2 / Chapter 2.2 --- Heavy Metal Pollution in Hong Kong --- p.3 / Chapter 2.3 --- Chemistry and Toxicity of Copper in the Environment --- p.6 / Chapter 2.4 --- Conventional and Alternative Methods for Heavy Metal Removal --- p.10 / Chapter 2.5 --- Heavy Metal Removal by Microorganisms --- p.14 / Chapter 2.6 --- Factors Affecting Biosorption of Heavy Metals --- p.27 / Chapter 2.7 --- Applicability of Biosorbent in Heavy Metal Removal --- p.31 / Chapter 3. --- Materials and Methods --- p.36 / Chapter 3.1 --- Screening of Bacteria for Copper Removal Capacity --- p.36 / Chapter 3.1.1 --- Isolation of Bacteria from Activated Sludge --- p.36 / Chapter 3.1.2 --- Selection of Copper Resistant Bacteria from Water Samples --- p.37 / Chapter 3.1.3 --- Pre-screening of Bacteria for Copper Uptake --- p.37 / Chapter 3.1.4 --- Determination of Copper Removal Capacity of Selected Bacteria --- p.37 / Chapter 3.2 --- Effect of Culture Conditions on Copper Removal Capacity of Pseudomonas putida 5-X --- p.39 / Chapter 3.2.1 --- Effect of Nutrient Limitation --- p.39 / Chapter 3.2.2 --- Effect of Incubation Temperature and Culture Age --- p.41 / Chapter 3.3 --- Determination of Copper Uptake Mechanism of Pseudomonas putida 5-X --- p.41 / Chapter 3.3.1 --- Effect of Glucose and Sodium Azide on Copper Removal Capacity --- p.41 / Chapter 3.3.2 --- Transmission Electron Micrograph of Pseudomonas putida 5-X after Copper Uptake --- p.43 / Chapter 3.4 --- Effect of Pretreatment of Cells on Copper Removal Capacity of Pseudomonas putida 5-X --- p.43 / Chapter 3.5 --- Physico-chemical Characterization of Pseudomonas putida 5-X as Biosorbent for Copper Removal --- p.43 / Chapter 3.5.1 --- Determination of Copper Uptake Kinetics --- p.43 / Chapter 3.5.2 --- Determination of Freundlich Isotherm for Copper Uptake --- p.44 / Chapter 3.5.3 --- Effect of pH on Copper Removal Capacity --- p.44 / Chapter 3.5.4 --- Effect of Metal Ions on Copper Removal Capacity --- p.44 / Chapter 3.5.5 --- Effect of Anions on Copper Removal Capacity --- p.45 / Chapter 3.6 --- Copper Removal by Immobilized Cells of Pseudomonas putida 5-X --- p.45 / Chapter 3.6.1 --- Effect of Retention Time on Copper Removal Capacity of Immobilized Cells --- p.47 / Chapter 3.6.2 --- Efficiency of Copper Recovery from Immobilized Cells by Various Eluants --- p.47 / Chapter 3.6.3 --- Performance of Immobilized Cells on Multiple Copper Loading-elution Cycles --- p.48 / Chapter 3.6.4 --- Treatments of Effluent from an Electroplating Factory by Immobilized Cells --- p.48 / Chapter 4. --- Results --- p.49 / Chapter 4.1 --- Screening of Bacteria for Copper Removal Capacity --- p.49 / Chapter 4.2 --- Effect of Culture Conditions on Copper Removal Capacity of Pseudomonas putida 5-X --- p.49 / Chapter 4.2.1 --- Effect of Nutrient Limitation --- p.49 / Chapter 4.2.2 --- Effect of Incubation Temperature and Culture Age --- p.52 / Chapter 4.3 --- Determination of Copper Uptake Mechanism of Pseudomonas putida 5-X --- p.52 / Chapter 4.3.1 --- Effect of Glucose and Sodium Azide on Copper Removal Capacity --- p.52 / Chapter 4.3.2 --- Transmission Electron Micrograph of Pseudomonas putida 5-X after Copper Uptake --- p.52 / Chapter 4.4 --- Effect of Pretreatment of Cells on Copper Removal Capacity of Pseudomonas putida 5-X --- p.56 / Chapter 4.5 --- Physico-chemical Characterization of Pseudomonas putida 5-X as Biosorbent for Copper Removal --- p.56 / Chapter 4.5.1. --- Determination of Copper Uptake Kinetics --- p.56 / Chapter 4.5.2 --- Determination of Freundlich Isotherm for Copper Uptake --- p.56 / Chapter 4.5.3 --- Effect of pH on Copper Removal Capacity --- p.60 / Chapter 4.5.4 --- Effect of Metal Ions on Copper Removal Capacity --- p.60 / Chapter 4.5.5 --- Effect of Anions on Copper Removal Capacity --- p.60 / Chapter 4.6 --- Copper Removal by Immobilized Cells of Pseudomonas putida 5-X --- p.60 / Chapter 4.6.1 --- Copper Removal Capacity of Immobilized Cells and Breakthrough Curve for Copper Removal --- p.60 / Chapter 4.6.2 --- Effect of Retention Time on Copper Removal Capacity of Immobilized Cells --- p.65 / Chapter 4.6.3 --- Efficiency of Copper Recovery from Immobilized Cells by Various Eluants --- p.65 / Chapter 4.6.4 --- Performance of Immobilized Cells on Multiple Copper Loading-elution Cycles --- p.65 / Chapter 4.6.5 --- Treatment of Effluent from an Electroplating Factory by Immobilized Cells --- p.65 / Chapter 5. --- Discussion --- p.72 / Chapter 5.1 --- Screening of Bacteria for Copper Removal Capacity --- p.72 / Chapter 5.2 --- Effect of Culture Conditions on Copper Removal Capacity of Pseudomonas putida 5-X --- p.73 / Chapter 5.2.1 --- Effect of Nutrient Limitation --- p.73 / Chapter 5.2.2 --- Effect of Incubation Temperature and Culture Age --- p.74 / Chapter 5.3 --- Determination of Copper Uptake Mechanism of Pseudomonas putida 5-X --- p.75 / Chapter 5.3.1 --- Effect of Glucose and Sodium Azide on Copper Removal Capacity --- p.75 / Chapter 5.3.2 --- Transmission Electron Micrograph of Pseudomonas putida 5-X after Copper Uptake --- p.75 / Chapter 5.4 --- Effect of Pretreatment of Cells on Copper Removal Capacity of Pseudomonas putida 5-X --- p.76 / Chapter 5.5 --- Physico-chemical Characterization of Pseudomonas putida 5-X as Biosorbent for Copper Removal --- p.77 / Chapter 5.5.1 --- Copper Uptake Kinetics --- p.77 / Chapter 5.5.2 --- Freundlich Isotherm for Copper Uptake --- p.78 / Chapter 5.5.3 --- Effect of pH on Copper Removal Capacity --- p.78 / Chapter 5.5.4 --- Effect of Metal Ions on Copper Removal Capacity --- p.79 / Chapter 5.5.5 --- Effect of Anions on Copper Removal Capacity --- p.80 / Chapter 5.6 --- Copper Removal by Immobilized Cells of Pseudomonas putida 5-X --- p.80 / Chapter 5.6.1 --- Copper Removal Capacity of Immobilized Cells and Breakthrough Curve for Copper Removal --- p.80 / Chapter 5.6.2 --- Effect of Retention Time on Copper Removal Capacity of Immobilized Cells --- p.82 / Chapter 5.6.3 --- Efficiency of Copper Recovery from Immobilized Cells by Various Eluants --- p.82 / Chapter 5.6.4 --- Performance of Immobilized Cells on Multiple Copper Loading-elution Cycles 的 --- p.83 / Chapter 5.6.5 --- Treatment of Effluent from an Electroplating Factory by Immobilized Cells --- p.84 / Chapter 6. --- Conclusion --- p.85 / Chapter 7. --- Summary --- p.87 / Chapter 8. --- References --- p.89

by Ngar, Yuen-ngor. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1993. / Includes bibliographical references (leaves 186-196). / Chapter Chapter 1 --- Introduction Page / Chapter 1.1 --- Sludge as a waste problem --- p.1 / Chapter 1.2 --- The degraded geological environment of Hong Kong --- p.2 / Chapter 1.3 --- Use of weathered granitic material and sand as planting media --- p.3 / Chapter 1.4 --- Need of soil improvement material --- p.4 / Chapter 1.5 --- Potential for land application of sewage sludge --- p.5 / Chapter 1.6 --- Objectives of study --- p.6 / Chapter 1.7 --- Significance of study --- p.6 / Chapter Chapter 2 --- Literature Review / Chapter 2.1 --- Soil organic amendment for vegetation establishment --- p.9 / Chapter 2.2 --- Types and properties of sewage sludge --- p.10 / Chapter 2.3 --- Guidelines for land application of sludge --- p.12 / Chapter 2.3.1 --- Cation exchange capacity --- p.13 / Chapter 2.3.2 --- Zinc equivalent concept --- p.14 / Chapter 2.4 --- Effects of sludge on soil chemical and physical properties --- p.15 / Chapter 2.4.1 --- Chemical properties --- p.15 / Chapter 2.4.2 --- Physical properties --- p.18 / Chapter 2.5 --- Effects of sludge application on vegetation --- p.19 / Chapter 2.5.1 --- Germination --- p.19 / Chapter 2.5.2 --- Grass growth --- p.20 / Chapter 2.6.1 --- Choice of heavy metals for study --- p.21 / Chapter 2.6.2 --- Factors governing heavy metal availability --- p.25 / Chapter 2.6.3 --- Effects of lime on sludge-amended soil and the heavy metal availability --- p.26 / Chapter 2.6.4 --- Assessing available sludge-borne heavy metals --- p.27 / Chapter Chapter 3 --- Germination and seedling growth of bermudagrass in sludge-amended sand and CDG / Chapter 3 .1 --- Introduction --- p.30 / Chapter 3.2 --- Experimental design --- p.31 / Chapter 3.3 --- Experimental results --- p.34 / Chapter 3.3.1 --- Seed germination --- p.34 / Chapter 3.3.2 --- Seedlings and biomass growth --- p.35 / Chapter 3.3.3 --- DTPA-Extractable heavy metals --- p.39 / Chapter 3.3.4 --- Total heavy metals in plant tissue --- p.44 / Chapter 3.3.5 --- Chemical properties of the soil substrates --- p.49 / Chapter 3.4 --- Discussion --- p.54 / Chapter 3.4.1 --- Germination --- p.54 / Chapter 3.4.2 --- Nutrient effect --- p.56 / Chapter 3.4.3 --- Heavy metal availability from substrates --- p.59 / Chapter 3.4.4 --- Heavy metal uptake by the seedlings --- p.61 / Chapter 3.4.4.1 --- Metal uptake efficiency --- p.61 / Chapter 3.4.4.2 --- Amount of heavy metal uptake --- p.63 / Chapter 3.4.5 --- Textural characteristics --- p.66 / Chapter 3.5 --- Conclusions --- p.67 / Chapter Chapter 4 --- Growth and heavy metal uptake by bermudagrass grown in sludge-amended substrates / Chapter 4.1 --- Introduction --- p.70 / Chapter 4.2 --- Experimental design --- p.71 / Chapter 4.3 --- Results --- p.74 / Chapter 4.3.1 --- Biomass growth --- p.74 / Chapter 4.3.2 --- Heavy metal content of plant tissues --- p.82 / Chapter 4.3.2.1 --- Heavy metal content of the shoot --- p.83 / Chapter 4.3.2.2 --- Heavy metal content of the root --- p.89 / Chapter 4.3.3 --- Comparing the heavy metal levels in the shoot and root portions --- p.93 / Chapter 4.3.4 --- DTPA-extractable heavy metal content in soil substrates --- p.94 / Chapter 4.3.5 --- Chemical properties of the substrates --- p.100 / Chapter 4.4 --- Discussion --- p.103 / Chapter 4.4.1 --- Shoot biomass (First clipping) --- p.104 / Chapter 4.4.2 --- Shoot biomass (Second clipping) --- p.105 / Chapter 4.4.3 --- Shoot biomass ratio between the two clippings --- p.107 / Chapter 4.4.4 --- Total shoot biomass --- p.108 / Chapter 4.4.5 --- Root biomass and root: shoot ratios --- p.112 / Chapter 4.4.5.1 --- Nutrient effect --- p.113 / Chapter 4.4.5.2 --- Heavy metal phytotoxicity --- p.115 / Chapter 4.4.6 --- Total biomass production --- p.117 / Chapter 4.5 --- Conclusions --- p.118 / Chapter Chapter 5 --- Effect of lime on the growth and heavy metal uptake of bermudagrass in sludge-amended substrates / Chapter 5.1 --- Introduction --- p.121 / Chapter 5.2 --- Experimental design --- p.123 / Chapter 5.3 --- Results --- p.125 / Chapter 5.3.1 --- Biomass growth --- p.126 / Chapter 5.3.2 --- DTPA-extractable heavy metals --- p.133 / Chapter 5.3.3 --- Heavy metal uptake by the shoot portion --- p.138 / Chapter 5.3.4 --- Heavy metal uptake by the root portion --- p.147 / Chapter 5.3.5 --- Comparing metal uptake between shoot and root portions --- p.151 / Chapter 5.3.6 --- Chemical properties of substrates --- p.155 / Chapter 5.4 --- Discussion --- p.157 / Chapter 5.4.1 --- Effect of sludge and lime treatments on pH --- p.158 / Chapter 5.4.2 --- Patterns of DTPA-extractable metals and plant uptake --- p.159 / Chapter 5.4.2.1 --- Variation of heavy metal levels with liming rates --- p.160 / Chapter 5.4.2.2 --- Variation of heavy metal levels with sludge loading rates --- p.161 / Chapter 5.4.2.3 --- Bermudagrass as metal accumulator --- p.162 / Chapter 5.4.3 --- Metal uptake by the root and shoot --- p.162 / Chapter 5.4.3.1 --- Antagonistic interactions --- p.163 / Chapter 5.4.3.2 --- Parititioning of heavy metals in shoot and root --- p.163 / Chapter 5.4.4 --- Poor biomass growth --- p.166 / Chapter 5.4.4.1 --- Heavy metal toxicity --- p.166 / Chapter 5.4.4.2 --- Effect of poor soil conditions --- p.167 / Chapter 5.5 --- Conclusions --- p.177 / Chapter Chapter 6 --- Conclusions / Chapter 6.1 --- Summary of findings --- p.179 / Chapter 6.2 --- Implications of the study --- p.180 / Chapter 6.3 --- Limitations --- p.182 / Chapter 6.4 --- Suggestions for further studies --- p.184 / References --- p.186 / Appendix

P1B-type ATPases transport a number of monovalent and divalent heavy metals (Cu+, Cu2+, Ag+, Zn2+, Cd2+, Pb2+ and Co+2) across biological membranes. These ATPases are found in archea, bacteria and eukaryotes and are one of the key elements required for maintaining metal homeostasis. Plants have an unusually high number of P1B-type ATPases with distinct metal selectivity compared to other eukaryotes that usually have one or two Cu+-ATPases. Higher plants are the only eukaryotes where Zn2+-ATPases have been identified. Towards understanding the physiological roles of plant Zn2+-ATPases, we characterized Arabidopsis thaliana HMA2. We expressed HMA2 in yeast and measured the metal dependent ATPase activity in membranes. We showed that HMA2 is a Zn2+-ATPase that is also activated by Cd2+. Zn2+ transport determinations showed that this enzyme drives the efflux of metal from the cytoplasm. Analysis of HMA2 mRNA levels showed that the enzyme is present in all plant organs. We analyzed the effect of removal of HMA2 full-length transcript in whole plants by gene knock out. Although hma2 mutants did not show a different visible phenotype from the wild type plants, we observed increased levels of Zn2+ or Cd2+. The observed phenotype of hma2 mutants and plasma membrane location of HMA2, mainly in vasculature (Hussain et al., 2004), indicates that this ATPase might have a central role in Zn2+ uploading into the phloem. P1B-type ATPases have cytoplasmic regulatory metal binding domains (MBDs) in addition to transmembrane metal binding sites (TMBDs). Plant Zn2+-ATPases have distinct sequences in both their N- and C-termini that might contribute to novel metal binding sites. These ATPases contain long C-terminal sequences rich in CC dipeptides and His repeats. Removal of the C-terminus (C-MBD) of HMA2 leads to a 50% reduction in the enzyme turnover suggesting a regulatory role for this domain. Atomic Absorption Spectroscopy (AAS) analysis showed that Zn2+ binds to C-MBD with a stoichiometry of three (3 Zn/C-MBD). Chemical modification studies and Zn K-edge X-ray Absorption Spectroscopy (XAS) of Zn-C-MBD showed that Zn2+ is likely coordinated by His in two sites and the third site slightly differs from the others involving a Cys together with three His. All plant Zn2+-ATPases lack the typical CXXC signature sequences observed in Cu+-ATPases and some bacterial Zn2+-ATPases N-terminus metal binding domains (N-MBDs). Instead, these have conserved CCXXE sequences. Truncation of HMA2 N-MBD results in a 50% decrease in enzyme Vmax suggesting that N-MBD is also a regulatory domain. The results indicate that the N-MBD binds Zn2+ with a stoichiometry of one (1 Zn/N-MBD). Metal binding analysis of individual N-MBD mutants Cys17Ala, Cys18Ala and Glu21Ala/Cys prevented Zn+2 binding to HMA2 N-MBD suggesting the involvement of all these residues in metal coordination. ATPase activity measurements with HMA2 carrying the mutations Cys17Ala, Cys18Ala and Glu21Ala/Cys showed a reduction in the enzyme activity similar to that observed the truncated protein indicating that the enzyme activity reduction observed in the N-terminus truncated forms of the enzyme is related to the removal of the metal binding capability. Summaryzing, these studies show the central role of HMA2 in plant Zn2+ homeostasis. They also describe the mechanism and direction of Zn2+ transport. Finally, they establish the presence of novel metal binding domains in the cytoplasmic portion of the enzyme. Metal binding to these domains is required for full enzymatic activity.

Penicillium ochro-chloron (ATCC strain # 36741), a filamentous fungus with the capability for removing copper ions from aqueous solutions, was studied as a possible biological trap (biotrap) for remediation of heavy metal contaminants in industrial wastewaters. This research demonstrated that in shake flasks the fungus removed copper from surrogate wastewater with 100mg/L copper contamination by as much as 99%. These results did not translate to the bioreactor configuration of a packed bed column, as channeling occurred through the bed, shown by conductivity tracer studies. A fluidized bed configuration was studied and resulted in copper removal of 97%, with a capacity of 149 mg[Cu]/g dry weight biomass, under the conditions of 50% dissolved oxygen. For dissolved oxygen concentrations below the critical oxygen concentration for the fungus (20% saturation) there was minimal copper removal. Mixing studies in the fluidized bed reactor showed that the system was diffusion limited. Mathematical modeling using first order kinetics associated with diffusion limited reactions resulted in rate constants for Cu 2+ uptake of approximately 0.031 h -1 , which were dependent on the dissolved oxygen concentration. Modeling of the reaction with a second order kinetic equation showed that there are possibly factors regulating copper uptake besides oxygen. Electron microscopy showed that in some instances the copper removed was retained as large porous spherical extracellular precipitates. Energy Dispersive X-ray (EDX) analysis has shown similar complexes to be copper phosphate precipitates (Crusberg, 1994). Removal of heavy metal contaminants from wastewater discharge is a necessity for many industries, due to environmental concerns and federal regulations. The use of a biological system for the removal and recycling of heavy metals could prove more economical than currently used physio-chemical processes.

Discharge of metal containing effluents into water has been a cause of major concern. Traditional treatment methods are proving to be ineffective and expensive. Chitosan was studied as a potential biosorbent due to its positive charge and relatively low cost. The study involves evaluating the metal binding performance of chitosan in a polymer enhanced diafiltration (PEDF) system which uses an ultrafiltration membrane to retain the chitosan which, in turn, binds the metal, thereby preventing passage into the permeate stream. Conditions for binding such as pH, concentration of polymer and chromium were studied. Optimal performance was obtained when the system was operated at pH values lower then the pKa of chitosan i.e. 6.3. Using 6 g/L chitosan at pH 4.0, chromium concentration was reduced to less than 1mg/L from a feed concentration of 20 mg/L. Equilibrium dialysis experiments were done to study the kinetics of binding and the uptake of metal per gram of polymer. Rheological measurements demonstrated that in the presence of 1-100 mM chromate, chitosan was found to be slightly shear-thickening at low concentrations such as 4 g/L and 6 g/L whereas it was slightly shear-thinning at higher concentrations like 12 g/L and 20 g/L This suggests that neutralization of chromium anions is due to the interaction of multiple chitosan molecules. This result is consistent with the relatively stiff nature of the polysaccharide. Overall, this study suggests that some modification of the native polymer would be required to improve uptake and make it an industrially workable process.

Este trabalho objetivou estudar a síntese de zeólita NaA sob condições hidrotérmicas e aplicála na adsorção de metais pesados. Para a síntese de zeólita NaA, caulim do município de Ipixuna, Pará, foi calcinado a 700 °C por 3 horas para obtenção de metacaulim e usado como fonte de sílica e alumina. Para efeito de comparação, cloreto de alumínio e metassilicato de sódio também foram utilizados na síntese de zeólitas como precursores de Si e Al. A influência da alcalinidade na síntese dos produtos zeolíticos foi avaliada utilizando-se diferentes concentrações de NaOH. Todas as sínteses foram realizadas a 110 °C em autoclaves. Visando à compreensão da influência do tempo na quantidade e tipo de fase formada, foram realizadas sínteses com diferentes tempos de cristalização. Os produtos de reação foram caracterizados por difração de raios X, espectroscopia na região do infravermelho, análise termogravimétrica, análise térmica diferencial, microscopia eletrônica de varredura e adsorção de nitrogênio para cálculo de área específica pelo método BET. A amostra que apresentou maior proporção de zeólita NaA foi utilizada como adsorvente em soluções de Cu2+, Ni2+ e Cd2+ com concentrações iniciais de 25 a 400 mg/L. A concentração de equilíbrio desses metais, após remoção pela zeólita NaA, foi determinada por espectrofotometria de absorção atômica. Os resultados mostraram que o aumento da alcalinidade e do tempo de cristalização favoreceu a obtenção de sodalita, uma fase zeolítica concorrente à Zeólita A, nos produtos de síntese. A zeólita NaA provou ser um excelente adsorvente para remoção dos metais analisados, apresentando uma capacidade de adsorção máxima de aproximadamente 79, 65 e 32 mg/g para Cd2+, Cu2+ e Ni2+, respectivamente. O modelo de isoterma de adsorção que melhor descreveu a remoção de metais pela zeólita NaA foi o de Langmuir. / The aim of this work was to study the synthesis of zeolite NaA under hydrothermal conditions and use it as adsorbent of heavy metals. To synthesize zeolite NaA, kaolin from the city of Ipixuna, Pará, was calcined at 700 °C for 3 hours and used as source of silica and alumina. For comparison purposes, aluminum chloride and sodium metasilicate were also used in the synthesis of zeolites as precursors of Si and Al. The influence of alkalinity on the synthesis of the zeolitic products was evaluated using different NaOH concentrations. All the syntheses were performed at 110 °C by autoclaving. To understand the influence of time on the type and relative amount of the obtained phases, syntheses with different crystallization times were carried out. The reaction products were characterized by means of X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, thermal differential analysis, scanning electron microscopy and nitrogen adsorption for calculating surface area by the BET method. One of the samples, which exhibited the highest content of zeolite NaA, was used as adsorbent of Cu2+, Ni2+ and Cd2+ solutions with initial concentrations ranging from 25 to 400 mg/L. The equilibrium concentration of these heavy metals, after removal by zeolite NaA, was determined by atomic absorption spectrophotometry. The results showed that increasing alkalinity of the reaction medium led to the formation of sodalite, a concurrent zeolitic phase, in the products. Zeolite NaA turned out to be an excellent adsorbent for removing heavy metals, with an adsorption capacity of 79, 65 and 32 mg/g for Cu2+, Cd2+ and Ni2+, respectively. The Langmuir isotherm model was the most appropriate to describe the removal of metals by zeolite A.

Pênfigos são doenças bolhosas autoimunes com produção de autoanticorpos contra proteínas de adesão dos queratinócitos. A região nordeste (NE) do estado de São Paulo (ESP) é endêmica para o pênfigo foliáceo (PF) e pênfigo vulgar (PV). Metais pesados - chumbo (Pb), mercúrio (Hg), cobre (Cu) e zinco (Zn) - têm sido relacionados à autoimunidade e aos pênfigos. A possível contaminação do Aquífero Guarani e das bacias hidrográficas da região NE do ESP por metais pesados tem sido indagada. Objetivos. Avaliou-se: (i) cádmio (Cd), Pb, Cu, cromo (Cr), Hg, manganês (Mn) e Zn em amostras de água residencial em Ribeirão Preto (representando o Aquífero Guarani) e dos rios Pardo, Mogi-Guaçu e Sapucaí/Mirim; (ii) Pb, Cu e Zn em amostras de pacientes com PF, PV e controles; (iii) a exposição ocupacional ou por lazer às diferentes exposições aos metais pesados em pacientes e controles. Materiais e Métodos. A quantificação dos metais pesados em amostras de água, e de sangue total e de soro de 118 pacientes com pênfigo (56 PV; 62 PF) e de 135 controles foi realizada por Espectrofotometria de Absorção Atômica (com chama, forno de grafite e gerador de hidretos). Resultados. A análise do Cu (18,25 µg.L-1) no rio Sapucaí/Mirim e do Hg (0,24 µg.L-1) no rio Mogi-Guaçu mostrou valores acima da legislação vigente. Os resultados limnológicos caracterizaram a bacia do rio Mogi-Guaçu como impactada. As concentrações dos metais, em amostras de água de abastecimento urbano, apresentaram grande variação entre as residências. A concentração de Cu sanguíneo resultou maior no gênero feminino (111,9 g%; 94,5 g%). Em relação aos moradores, maiores concentrações de Zn (89,1 g%) foram observadas na cidade de Batatais, comparada a Ribeirão Preto (76,5 g%). Concentrações de Pb acima do valor de referência foram encontradas mais frequentemente no grupo PV em relação aos controles (31,1%; 15,7%, respectivamente). As concentrações de Zn foram menores entre PV e PF, comparados aos controles (75,4 g%; 80,1 g%; 83,4 g%, respectivamente). A análise multivariada mostrou maior concentração do Pb para idosos e expostos aos metais. As variáveis idade, exposição a pesticidas, exposição ocupacional, zona rural, contato com rios e concentração de Zn foram as que mais influenciaram significativamente na incidência dos pênfigos na região endêmica. Conclusões. Os metais pesados nas amostras de água obedeceram à legislação vigente, exceto Cu no rio Sapucaí/Mirim e Hg no rio Mogi-Guaçu. A etiopatogênese dos pênfigos pode estar associada à presença de Pb e à deficiência de Zn em indivíduos geneticamente predispostos. / Pemphigus are autoimmune bullous diseases with production of autoantibodies against keratinocyte adhesion proteins. The Northeast (NE) of São Paulo (ESP) is endemic to foliaceus (PF) and pemphigus vulgaris (PV). Heavy metals - lead (Pb), mercury (Hg), copper (Cu) and zinc (Zn) - have been related to autoimmunity and pemphigus. The possible contamination of the Guarani Aquifer and river basins ESP NE region by heavy metals has been inquired. Objectives. Were evaluated: (i) cadmium (Cd), Pb, Cu, chromium (Cr), mercury, manganese (Mn) and Zn in residential water samples in Ribeirão Preto (representing the Guarani Aquifer) and Pardo rivers, Mogi Guaçu and Sapucai / Mirim; (ii) Pb, Cu and Zn in samples of patients with PF, PV and controls; (iii) occupational or leisure exposure at different exposures to heavy metals in patients and controls. Materials and methods. The quantification of heavy metals in water samples, and whole blood and serum of 118 patients with pemphigus (PV 56; 62 PF) and 135 controls was performed by Atomic Absorption Spectrophotometry. Results. The analysis of Cu (0.01825 mg L-1) in the river Sapucaí / Mirim and Hg (0.00024 mg L-1) in Mogi Guaçu showed values above the legislation. Limnological results characterized the basin of the Mogi-Guaçu as impacted. The metal concentrations in urban water supply samples showed great variation between households. The blood Cu concentration resulted higher in females (111.9 g%; 94.5 g%). Compared to residents, higher Zn concentrations (89.1g%%) were observed in the city of Batatais, compared to Ribeirão Preto (76.5 g%). Pb concentrations above the reference value were found more often in PV group compared to controls (31.1%; 15.7%, respectively). Zn concentrations were lower in PV and PF, compared to controls (75.4 g%; 80.1 g%; 83.4 g%, respectively). Multivariate analysis showed higher concentrations of Pb for the elderly and exposed to metals. The variables age, exposure to pesticides, occupational exposure, rural, contact rivers and concentration of Zn were the most significant influence on the incidence of pemphigus in the endemic region. Conclusions. Heavy metals in the water samples complied with current legislation, except Cu in the river Sapucaí / Hg at Mirim and Mogi-Guaçu. The etiopathogenesis of pemphigus may be associated with the presence of Pb and Zn deficiency in genetically predisposed individuals.

O Tietê é um importante rio para o estado de São Paulo, pois é considerado de grande potencial econômico, energético e de navegabilidade. A bacia do alto rio Tietê corresponde ao trecho da nascente em Salesópolis até o reservatório de Pirapora, passando pela região metropolitana de São Paulo. Por estar em uma região com grande pressão antrópica, o rio Tietê sofre grandes impactos ambientais associados ao lançamento de efluentes domésticos e industriais. Atualmente, um dos mais sérios problemas na área ambiental está relacionado à poluição química de natureza inorgânica em sedimentos fluviais, principalmente metais pesados. O presente estudo objetivou avaliar a distribuição dos principais metais pesados (Co, Cr, Cu, Zn, Cd, Ni e Pb) presentes nos sedimentos de fundo, em perfis de profundidade, nas estações de amostragem de Ponte Nova, Biritiba, Mogi das Cruzes e Pirapora ao longo da bacia do alto rio Tietê, identificando as ocorrências de origens naturais e antrópicas, levando em consideração diferentes critérios de toxicidade e biodisponibilidade. A determinação da concentração total dos metais de interesse, em perfil de profundidade, obtidas a partir do método da fusão alcalina permitiu avaliar os critérios de toxicidade considerando os valores-guia de qualidade de sedimentos VI, VP, PEL e TEL bem como os fatores de enriquecimento (EF) e índices de geo-acumulação (Igeo) tendo como base o fundo geoquímico natural regional. A avaliação da biodisponibilidade foi analisada para os metais pesados, de acordo com o processo da extração sequencial seletiva bem como pela relação entre sulfetos volatilizados após ataque ácido a frio (AVS) e extração simultânea de metais pesados (SEM). A origem da matéria orgânica presente no sedimento de fundo foi identificada através da comparação com parâmetros de referência em base isotópica (\'delta\' 13C). Em termos de toxicidade de metais pesados, foi observado que para a estação de Ponte Nova, próxima a nascente do rio Tietê, apenas o Cu esteve relacionado à contribuição antrópica, possivelmente associado ao controle de algas no reservatório. Já para a estação de amostragem em Biritiba, a maioria dos metais pesados estudados mostraram ter origem antrópica, devido às atividades agrícolas da região. Os sedimentos de fundo amostrados em Mogi das Cruzes e Pirapora indicaram fortes contaminações de metais pesados, como Cu, Cr e Zn associados essencialmente aos esgotos domésticos. Os demais aspectos de biodisponibilidade estudados indicaram contaminação de metais pesados em Pirapora, confirmando a toxicidade observada nos demais critérios avaliados. A origem da matéria orgânica, presente nos sedimentos de fundo do alto rio Tietê, mostrou ser para Ponte Nova, Biritiba e Mogi das Cruzes composta por material litólico e plantas C3, enquanto que para Pirapora a origem da matéria orgânica foi essencialmente antrópica / The Tietê River is important for São Paulo state, because it is considered of great economic, energy and navigability potential. The Tiete River basin comprises its source in Salesópolis to the Pirapora reservoir, through the metropolitan region of São Paulo. Due to its location in a region with high human pressure the Tietê River has suffered countless environmental impacts associated with the release of domestic and industrial effluents. Currently, one of the most serious environmental problems in the area is related to the inorganic nature of river sediments, mainly heavy metals. This study aimed to evaluate the distribution of major heavy metals (Co, Cr, Cu, Zn, Cd, Ni and Pb) present in bottom sediments, in depth profiles, in the Ponte Nova Biritiba, Mogi das Cruzes Pirapora sampling stations along the basin of the upper Tietê River, identifying the occurrences of natural and anthropogenic sources, taking into account different criteria of toxicity and bioavailability. The determination of total concentration of metals of interest in depth profile obtained from the alkaline fusion method allowed to evaluate the toxicity criteria considering the sediment quality values guidelines VI, VP, TEL and PEL as well as the enrichment factors (EF) and geo-accumulation index (Igeo) based on the regional natural background levels. The assessment of bioavailability was analyzed for heavy metals, according to the sequential selective extraction process and the link between acid volatile sulfides (AVS) and simultaneously extracted heavy metals (SEM). The origin of organic matter in bottom sediment was identified by comparison with end-members based on isotopic (\'delta\' 13C). In terms of heavy metal toxicity has been observed that for the Ponte Nova station, near the Tietê River headwaters, only Cu was related to the anthropogenic contribution, possibly associated with the control of algae in the reservoir. For the Biritiba sampling station, most of the heavy metals showed to have anthropogenic origin, due to agricultural activities in the region. The bottom sediments sampled in Mogi das Cruzes and Pirapora indicated strong contamination of heavy metals such as Cu, Cr and Zn mainly associated with domestic sewage. Other aspects of bioavailability studies indicated contamination of heavy metals in Pirapora, confirming the toxicity observed in the other criteria. The origin of organic matter showed to be for Ponte Nova, Biritiba and Mogi das Cruzes composed of C3 plants and lithic material, while for Pirapora, the origin of organic matter was mainly anthropogenic.

The major concern of this work is the development of hierarchically porous structured zeolite composites for ion-exchange applications by deposition of a thin layer of zeolite on inexpensive porous supports which offers better efficiency in separation processes. The merits of utilization of zeolite composites in industrial applications are generally reducing mass transfer resistance and pressure drop. In addition to this they have advantages in the removal of metal ions from wastewater such as increasing the metals uptake and minimizing the volume of waste disposed especially after vitrification. This thesis presents results from a combination of experimental work and simulation study of experimental data to give isotherm and kinetic models. The experimental work shed light on the preparation of zeolite composites using zeolite X (Si/Al ~ 1.35) and clinoptilolite (Si/Al ~ 4.3), studying the performance of these composites on the removal of the Sr2+ and Mn2+ ions and then stabilization of waste materials resulting from the ion-exchange process. Clinoptilolite was hydrothermally synthesized to show the effect of non-framework cations on the removal process. The porous supports were diatomite which is naturally occurring silica and carbon which is obtained from Iraqi date stones by a thermal treatment conducted at 900°C. Coating the support surface with zeolites crystals was conducted in two different ways. The layer by layer approach, which has not previously been used, was used to prepare monolithic carbon clinoptilolite composite using a combination of sucrose/citric acid and zeolite. The other approach was modifying the support surface by ultrasonication in the presence of nanoparticles suspension prepared using ball mill to create nucleation sites and enhance the crystal attachment during hydrothermal treatment. Characterisation was implemented in each case using XRD, SEM, EDAX, TGA and BET method. Ion-exchange experimental results showed higher ion-exchange capacity obtained when the composites were used in comparison to pure zeolites, when a comparison is based on actual weight of zeolite used for removal of Sr2+ and Mn2+ ions. A study of encapsulation of ions showed that it is feasible to solidify the waste materials by vitrification and/or geopolymerization to eliminate leaching of ions to the environment. The simulation studies showed that the ion-exchange kinetic followed the pseudo second order kinetic model. This fitting indicates that the rate of ion-exchange process is controlled by a chemical reaction related to valence forces. The overall ion-exchange process is controlled by a combination of ion-exchange reaction, film diffusion and intra-particle diffusion. Moreover, the thermodynamic studies which were conducted under different temperatures revealed that the ion-exchange of Sr2+ and Mn2+ ions is practicable, spontaneous and endothermic.

Para avaliar a contaminação por mercúrio em peixes do Alto Pantanal, foram analisadas 74 amostras de peixes piscívoros das espécies Pseudoplatystoma fasciatum(cachara), Pirinanpus pirinanpu (barbado), Serrasalmus spp. (piranha), Pseudoplatystoma coruscans (pintado), Salminus maxillosus (dourado), Hemisorubin plathyrhynchos (jurupoca) e Surubin lima (jurupensém). Também foram analisadas amostras de sedimento e de material particulado em suspensão na água. As amostras foram coletadas no ano de 2000. As determinações de mercúrio total foram feitas por espectrometria de absorção atômica sem chama utilizando-se gerador de vapor frio VGA 77 da Varian® acoplado a um espectrômetro Varian® 220. As concentrações de mercúrio total nas amostras de peixe variaram de 0,02 ug/g (piranha) a 0,80 ug/g (cachara). As concentrações de mercúrio em piranhas variaram de 0,02 ug/g a 0,50 ug/g, com média de 0,16 ug/g +/- 0,12. A área CBA 2 (baías do rio Cuiabá, região próxima de Barão de Melgaço) foi a que teve as concentrações mais elevadas em relação às áreas BNG 1 (rio Bento Gomes, Poconé) (p=0,003), PAG 3 (rio Paraguai, Taiamã e Descalvado) (p=0,002) e PAG 5 (rio Paraguai, confluência com rio Cuiabá) (p<0,001), mas não houve diferença entre CBA 2 e PAG 4 (rio Canafisto, baía do Alegre e rio Alegre) . O teste de Spearman apontou correlação entre mercúrio em piranhas e mercúrio em material particulado em suspensão (r=0,561, p<0,001), e entre mercúrio em piranhas e mercúrio em sedimento da camada 0-2 cm; e não indicou correlações entre mercúrio em piranhas e mercúrio em sedimento da camada 0-10 cm, mercúrio em sedimento 0-10 cm e mercúrio em material particulado em suspensão, e mercúrio em sedimento 0-10 cm e concentração de matéria orgânica. As concentrações de mercúrio em peixes ficaram abaixo do limite máximo tolerável de mercúrio em peixes predadores, de 1 ug/g, estabelecido no Brasil. Em regiões não contaminadas, peixes de água doce apresentam teores de Hg de até 0,2 ug/g, 33% das amostras ficaram acima desse valor. Segundo a legislação brasileira, o pescado analisado não está impróprio para consumo humano, mas evidenciou-se um processo de contaminação que deve ser melhor estudado quanto aos fatores ambientais determinantes. É importante o monitoramento da região, já que estudos indicam que níveis abaixo de 1 ug/g já podem causar alterações importantes na saúde, dependendo da quantidade de pescado consumido. / In order to evaluate fish mercury contamination in Alto Pantanal region, Brazil, 74 samples of piscivorous fishes as Pseudoplatystoma fasciatum (cachara), Pirinanpus pirinanpu (barbado), Serrasalmus spp. (piranha), Pseudoplatystoma coruscans (pintado), Salminus maxillosus (dourado), Hemisorubin plathyrhynchos (jurupoca) and Surubin lima (jurupensém) were analysed in relation to total mercury. Sediment and suspended particulate matter samples were also analysed. The samples were collected in the year 2000. Total mercury concentrations were analysed by flameless atomic absorption spectrometry, with a spectrometer Varian® 220 and a cold vapor generation accessory VGA 77 Varian®. Total mercury concentrations in fish ranged from 0,02 ug/g (piranha) to 0,80 ug/g (cachara). Mercury concentrations in piranha ranged from 0,02 ug/g to 0,50 ug/g, with an average of 0,16 ug/g ± 0,12. CBA 2 area (baías from Cuiabá river, near Barão de Melgaço region) had higher concentrations than those of BNG 1 (Bento Gomes River, Poconé) (p=0,003), PAG 3 (Paraguai river, Taiamã e Descalvado) (p=0,002) and PAG 5 (confluence of Cuiabá and Paraguai rivers) (p<0,001), but there was no difference between CBA 2 and PAG 4 (Canafisto River, Baía do Alegre and Alegre River). Spearman Test showed correlation between values of mercury in piranha and mercury in suspended particulate matter (r=0,561, p<0,001) and between mercury in piranha and mercury in sediment of 0-2 cm deep. However, no statistical correlations were found between mercury in piranha and mercury in sediment of 0-10 cm deep; mercury in sediment 0-10 cm and mercury in suspended particulate matter; and between mercury in sediment 0-10 cm and organic matter load. Mercury concentrations in fish were all below the Brazilian mercury limit set for predators fish that is 1 ug/g w.w. Freshwater fishes from non contaminated areas have total mercury load up to 0,2 ug/g, 33% of fish samples had concentrations above this value. Despite the mercury concentrations were all below the Brazilian limit for a safe human consumption, a mercury contamination process is suggested. Thus, further research concerning environmental factors determining mercury contamination in Alto Pantanal region is needed. In addition, it is very important monitoring that region since previous surveys indicated that the ingestion of fish with a mercury content below 1.0 ug/g can cause important human health effects, depending on the amount of fish consumption.