Orientador: Fabiano Tomazini da Conceição / Banca: Rodrigo Braga Moruzzi / Banca: Amauri Antonio Menegário / Resumo: Alguns elementos são considerados tóxicos, mesmo em baixas concentrações, causando diversos problemas de saúde pública. Dentre os metais tóxicos, o cádmio e chumbo possuem destaque, pois são amplamente utilizados em atividades industriais, podendo provocar contaminação do solo e de águas superficiais e subterrâneas. Diversas alternativas vêm sendo estudadas para a remoção destes metais. A indústria de aluminio gera um subproduto conhecido como lama vermelha, formado em larga escala necessitando de extensa área para sua disposição . Estudos vêm sendo feitos com o objetivo de reduzir a quantidade gerada de rejeitos por meio de tecnologias que possibilitem sua reutilização. Uma alternativa é o uso da lama vermelha como adsorvedor para tratamento de áreas contaminadas e efluentes líquidos, que quando ativada por tratamento térmico e químico tem apresentado aumento das propriedades de adsorção. Assim, na primeira etapa deste trabalho amostras de lama vermelha foram ativadas por tratamento térmico e químico, caracterizadas, obtidas as isotermas de adsorção, utilizando-se os modelos de Langmuir e Freundlich. Posteriormente, foram analisadas a influência de diferentes valores do pH e da temperatura na adsorção e obtidos o tempo de equilíbrio e cinética da reação da adsorção, permitindo quantificar o potencial de adsorção de cádmio e chumbo. A lama vermelha é um material argiloso, com mesosporos e cxom elevado teor alcalino, além de alta condutividade elétrica. Na maior parte dos casos estudados neste trabalho, as amostras foram melhores descritas pelo modelo de Freundlich, sendo que a alma vermelha ativada termicamente a 400ºC apresentou a melhor capacidade de adsorção, 0,96 m/mol/g de Cd2+ e 2,93 mmol/g de Pb2+. Em todos os casos, a maior eficiência de adsorção ocorreu em pH próximo a 7, o tempo de equilíbrio foi próximo a 420 minutos, a cinética da reação obedeceu melhor ao modelo de pseudo... / Abstract: Some elements are considered toxic, even in low concentrations, causing many public health problems. Among the toxic metals cadmium and lead have highlighted, as they are widely used in industrial activities, can cause contamination of soil and surface water and groundwater. Several alternatives are being studied for the removal of these metals. The aluminum industry generates a by-product known as red mud, formed large-scale requiring large area for your disposal. Studies have been made in order to reduce the amount of waste generated through technologies that will enables their reuse. An alternative is the use of red mud as adsorbent for treating contaminated liquids and waste areas, which when activated by heat and chemical treatment have shown increased adsorption properties. Thus, in the first step of this work red mud samples were activated by heat and chemical treatment, characterized the adsorption isotherms obtained using the Langmuir model and Freundlich. Subsequently, we analyzed the effect of different values of pH and temperature in the adsorption and obtained time balance and adsorption kinetics of the reaction, allowing to quantify the adsorption potential of cadmium and lead. The red mud is a clay material with mesoporous and high alkaline content, and high electrical conductivity. In most cases studied, the samples were best described by the Freundlich model, and the red mud thermally activated 400ºC showed the best adsortpion capacity 0.96 mmol/g Cd2+ and 2.93 mmol/g Pb2+. In all cases, the greater adsorption efficiency occurred at pH around 7, the equilibration time was close to 420 minutes, the reaction kinetics followed best to the pseudo second order model and endothermic reaction occurred / Mestre

Resumo: O objetivo do presente trabalho foi avaliar a agressividade de ratos expostos concomitantemente ao cádmio (Cd) e ao estresse por imobilização (EI). Ratos Wistar, machos, provenientes do Biotério Central da Unesp, foram divididos em 2 grupos experimentais: A- animais intrusos (sem tratamento) e B- animais residentes, os quais receberam um dos seguintes tratamentos: acetato de sódio (controle); acetato de cádmio (solução a 50 ppm de Cd na água de beber); submetidos ao estresse por imobilização (30 minutos, 3 vezes ao dia, 5 dias por semana, durante 4 semanas); expostos ao Cd e concomitantemente submetidos ao estresse por imobilização. O comportamento de agressividade dos animais residentes foi avaliado ao final da última semana do experimento, baseando-se no paradigma do animal intruso/residente, segundo os seguintes parâmetros: número total de ataques (NTA), tempo de latência para a 1º mordida (TLM), tempo total de manifestações de ataques (TTMA) e escore de agressão composta (EAC). Após a avaliação do comportamento de agressividade, o sangue e o cérebro dos animais foram coletados para dosagem de Cd por espectrometria de absorção atômica. O nível de cádmio no sangue não se alterou, mas no cérebro foi aumentado. Observou-se que exposição ao Cd ou estresse por imobilização sozinhos, não modificaram o NTA, TLM, TTMA ou EAC, porém, exposição ao Cd e EI concomitantemente aumentou significantemente o NTA, TTMA e o EAC. Esses resultados sugerem que exposição dos ratos à baixa dose de Cd associado ao estresse por imobilização pode causar interação e provocar aumento da agressividade dos animais. Um possível papel da serotonina (5-HT) e nível aumentado de cádmio no cérebro, como mecanismos responsáveis pela agressividade anormal observada, é discutido. / Abstract: The aim of this study was to assess the aggressiveness in rats concomitantly exposed to cadmium (Cd) and stress by immobilization (EI). Male Wistar rats, 70 days old, from the Biotério Central - UNESP, Botucatu - SP, were allocated into 2 experimental groups: A-intruder animals (without treatment) and B-resident animals, which received one of the following treatments: sodium acetate (control); Cadmium acetate (50 ppm Cd in drinking water); stress by immobilization (30 min, three times per day, five days per week, during four weeks); Cd exposure and concomitant stress by immobilization. The aggressive behavior of resident rats was evaluated at the end of the last experimental week based on the intruder/resident animal paradigm, according to the following parameters: total number of attacks (TNA), latent time for the first bite (LTB), total time of attack manifestations (TTAM), and composed aggression score (CAS). After aggressive behavior assessement, blood and brains were collected to determine Cd through atomic absorption spectrometry. Cd level was not altered in the blood but increased in the brain. Cd exposure or EI, alone, did not modify TNA, LTB, TTAM or CAS but Cd exposure and EI, concomitantly, increased significantly TNA, TTAM and CAS. These results suggest that rat exposure to low Cd level associated with stress by immobilization may lead to interaction with consequent increased animal aggressiveness. A possible paper of serotonin (5-HT) and increased brain Cd levels as responsible mechanisms by the observed abnormal aggressiveness is discussed. / Orientador: José Ricardo de Arruda Miranda / Coorientador: Antonio Francisco Godinho / Banca: Ethel Lourenzi Novelli / Banca: João Lauro Viana de Camargo / Mestre

Ce travail concerne le dopage par des ions actifs et/ou des nanoparticules (NPs) semi-conductrices de CdS et la caractérisation de xérogels de SiO2 poreux obtenus par voie sol-gel. Le but de cette étude est de contribuer à la compréhension de l'effet du dopage sur les propriétés structurales, texturales et optiques du matériau final. Nous avons montré par spectroscopie Raman et absorption-désorption d'azote que l'incorporation d'ions actifs, tels que Cd2+, Pb2+ ou Eu3+, modifie les cinétiques et les mécanismes de la gélification et la densification du réseau de SiO2. La nature même de ces modifications est fonction de la concentration en ions dopants. Dans le cas de l'ion Eu3+, l'analyse a été complétée par la spectroscopie d'émission utilisant cet ion comme sonde luminescente. Des xérogels de SiO2 ont aussi été post-dopés avec des NPs de CdS. La méthode consiste à diffuser dans la matrice poreuse une solution aqueuse contenant les précurseurs de cadmium et du soufre. Les NPs cristallisent ensuite in situ de manière homogène sous traitement thermique. Les spectroscopies d'absorption UV-visible, d'émission et d'excitation ont montré l'influence des niveaux pièges liés à des défauts de surface des NPs sur leurs propriétés optiques et ont mis en évidence un transfert d'énergie lors du co-dopage de SiO2 par CdS :Eu3+. Une deuxième technique de croissance cristalline a été utilisée. Elle consiste à irradier, par un faisceau laser pulsé, les matrices sol-gel contenant les précurseurs de CdS pour former localement des microstructures de NPs. Nous montrons notamment que l'absorption à deux photons permet d'envisager la structuration à l'échelle submicronique des NPs de CdS. / This work concerns the elaboration by sol-gel process and the characterization of porous SiO2 xerogels doped with active ions and/or with semiconducting nanoparticles of CdS. The aim of the study was to contribute to the comprehension of the doping effects on structural and optical properties of the final material. We showed by Raman spectroscopy and nitrogen absorption-desorption that the insertion of active ions, such as Cd2+, Pb2+ or Eu3+, changes the kinetics and the mechanisms of the gelation and densification of the network of SiO2. The choices of the pH and of the concentration of the doping ion have distinct effects on the kinetics. This study was completed by emission spectroscopy using Eu3+ ion as luminescent probe to describe the environment of this ion in the porous matrix. The SiO2 xerogels were post-doped with CdS nanoparticles. The post-doping technique consists in the diffusion of an aqueous solution containing cadmium and sulphur precursors in the porous matrix. The nanoparticles crystallize in situ by heat treatment. The nanoparticle size and their emission properties were determined by UVvisible absorption as well as emission and excitation spectroscopies. The results showed the influence on optical properties of trap levels introduced by the surface defects of nanoparticles and an enhancement of the Eu3+ emission in SiO2 xerogel co-doped with CdS :Eu3+. A second method for the formation of CdS nanoparticles was used. CdS microstructures were created locally by pulsed laser irradiation of sol-gel matrices containing the CdS precursors.

Cadmium sulphide (CdS) films were electrodeposited from an aqueous electrolytic solution onto indium tin oxide and fluorine doped tin oxide substrates, commonly used in photovoltaic applications. The CdS films were deposited for between 1 minute and 4 hours at temperatures ranging from 30°C to 90°C and a deposition potential of 600 mV with respect to a Ag/AgCI reference electrode. Some films were annealed in an argon atmosphere at temperatures of 300°C, 400°C and 460°C for 15 minutes and 30 minutes with and without CdCh2 treatment. The cleaning efficiency of the substrates by several solvents was determined using atomic force microscopy (AFM), surface roughness and scanning electron microscopy (SEM). It was found that the cleaning of the substrates could be monitored by the RMS roughness of the surfaces, and that the efficiency of the cleaning methods was substrate dependent. The microstructure, composition and optical properties of the films were determined using SEM, transmission electron microscopy, transmission electron diffraction, AFM, x-ray photoelectron spectroscopy (XPS), transmittance and Raman spectroscopy. All films, including those formed at the lowest deposition temperature of 30°C, were crystalline with the hexagonal (wurtzite) structure. At deposition temperatures ≤50°C the crystallites were extremely small as evidenced by broad diffraction rings and Raman peaks. At higher deposition temperatures (≥60°C) the deposition rate increased and the crystalline quality improved significantly. At the very early stages of deposition the deposits consisted of isolated, three-dimensional particles. Rapid lateral growth of these particles dominated the initial stages of deposition. Field emission SEM and AFM showed that ostensibly single particles consisted of agglomerates of elongated and plate-like grains with no preferred orientation. The final films had a columnar structure with good contact between the substrate and the film. XPS results showed that there was no significant compositional change in the deposition temperature range used and the films were all slightly cadmium rich. Carbon, oxygen and chlorine were detected mainly on the surface of the films. After annealing, the composition of the CdS films were close to stoichiometric once the surface layer had been removed. There was an improvement in the crystallinity of the films after annealing. / Thesis (PhD (Physics))--University of Pretoria, 2006. / Physics / unrestricted

The biogeochemical cycling of oceanic dissolved cadmium (dCd) has been an active area of research for the past ~40 years, due in part to the close correlation with phosphate (PO4). The global Cd:PO4 relationship has led to the use of microfossil Cd/Ca as a paleoproxy for ocean circulation and nutrient utilization; however considerable spatial and temporal variability in the relationship - particularly in surface waters - limits the utility of the proxy. Understanding the global biogeochemical cycling of Cd is an active area of research; however the Arctic Ocean is largely omitted from global models due to lack of data. This work presents depth profiles of dCd and Cd/PO4 ratios from 18 individual stations in the Canadian Arctic, collected during the Canadian GEOTRACES cruises GN02 and GN03, which connect the Arctic Ocean to the North Atlantic through the Canadian Arctic Archipelago (CAA). Salinity-driven water mass stratification exerts a primary control on the spatial distribution of Cd in the region, with elevated dCd and high Cd/PO4 ratios (~0.37 pM/μM) associated with waters of Pacific-origin. The elevated dCd and Cd/PO4 ratios are used as a tracer of Pacific-origin waters, identifying the presence of Pacific-origin water through the CAA and into Baffin Bay. High surface Cd/PO4 ratios were observed across the transect, consistent with a general global increase in surface water Cd/PO4 with increasing latitude. The analysis of Cd and other bioactive trace metals (Mn, Fe, Ni, Cu, Zn and Pb) still presents considerable analytical challenges due to the high-risks of contamination, low concentrations and complex matrices. I present a novel multi-element analytical method, which combines the commercially-available seaFAST pico preconcentration system with ICP-MS/MS analysis. In this work, we demonstrate that ICP-MS/MS, which combines two mass-selecting quadrupoles separated by an octopole collision/reaction cell, effectively removes common interferences (ArO+ on 56Fe and MoO+ on Cd) when pressurized with O2 gas. Accurate and precise measurements of iv the consensus references standards SAFe S and SAFe D and the certified reference material NASS-6 are presented as validation of the method. This thesis presents a novel method for the analysis of trace / Graduate

The electronic g-tensor in halogen-doped cadmium sulfide has been measured at 1.7°K, and its dependence upon uniaxial pressures parallel and perpendicular to the c-axis has been investigated. A sample doped with iodine to a room temperature resistivity of ≈ 0.7Ω cm exhibited an anisotropic g-tensor with gǁ = 1.785 and g⊥ = 1.767. The anisotropy in a heavily bromine-doped sample [formula omitted] was the same, but gǁ was slightly larger, 1.789. When some of the cadmium is replaced by zinc, the alloy acquires properties intermediate between those of CdS and ZnS. This was shown to apply to the g-tensor by measuring it in CdS(10%Zn):I. It was found to have a smaller anisotropy and a larger absolute value than that of CdS:I, thus having changed towards that of ZnS. The pressuredependence of the g-tensor and the change in the optical bandgap under hydrostatic pressure could be reasonably well explained in terms of two deformation potential constants for the bandgap, D₁-C₁-C₃ ≈ 6.3 eV/unit strain and D₂-C₂-C₄ ≈ 1.8 eV/unit strain. It is therefore concluded that although the bandstructure of CdS is not sufficiently well known to predict the g-tensor correctly, the interaction of the conduction band with the valence bands appears to be dominant. Further experiments to study the conduction band edge are proposed. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

Magister Scientiae (Biodiversity and Conservation Biology) - MSc (Biodiv and Cons Biol) / The demand for better quality produce by consumers is on the increase, as higher heavy metal concentrations pose a problem in agriculture. They result in decreased yield and unsuitable food for human consumption. This brings about a negative economic effect as such products become unprofitable on the domestic or export markets thus affecting productivity of farms.Four heavy metals (Cd, Cu, Pb and Zn) have been shown to be a problem in the farming areas in Cape Town. Pot and field studies were carried out on the effects and concentrations of cadmium and lead on Phaseolus vulgaris. Field studies included collecting plant samples from the Joostenbergvlakte/ Kraaifontein farming areas and measuring the heavy metal concentrations within the different organs of the plants. Pot experiments were carried out, where Phaseolus vulgaris var. Contender were grown and then heavy metals were administered to these plants together with two heavy metal mitigation techniques, precipitation with phosphate and mobilisation with EDTA to see if they were successful in combating heavy metal pollution.Samples taken from farms in the Joostenbergvlakte/ Kraaifontein area revealed that cadmium, lead and zinc concentrations were higher than the legal standard in the edible fruits. In the pot experiment, results revealed that cadmium reduced the chlorophyll index as well as the shoot fresh mass and changes in mineral uptake were seen. Lead did not affect growth or the chlorophyll index. The high cadmium treatment resulted in a marked increase in sodium concentration in the shoots. The phosphate treatments and EDTA treatments both resulted in increased cadmium concentrations in the roots and shoots. The higher phosphate and lead treatments also reduced lead concentrations in the roots. Low phosphate and the EDTA treatments increased the shoot sodium concentrations.

An innovative approach for the removal of heavy metal ions such as Pb2+ and Cd2+ from aqueous solution was evaluated. It was established that alkaline filtration, which is in essence the combination of alkaline precipitation and membrane filtration, could drastically increase both the efficiency and completeness of Pb2+ or Cd2+ ions removal, producing water whose metal concentration satisfying drinking water standard from a simulation wastewater containing 5 ppm or more Pb2+ or Cd2+ ions. Filtration with three different membranes, including microfiltration (MF), ultrafiltration (UF), and nanofiltration (NF) membranes, were studied at three different pH levels, i.e., 7.0, 8.5, and 10, in terms of metal ion rejection, flux, and permeate pH and at varied dissolved inorganic carbon (DIC) concentration. Increasing the pH of the feed in the tested range would lead to the decrease of metal ion concentration in permeate while flux was in general unaffected. When the feed pH was 10, the Pb2+ concentration in permeate was below 10 ppb regardless of the DIC concentration and membrane for filtration. The effects of DIC concentration were significant but complex. It was found that MF, UF, NF could all effectively reject Pb2+ ions at pH 8.5 and pH 10 although only NF was charged. A hypothesis was proposed to explain the mechanism of alkaline filtration based on experimental data.

The present study was designed to test the effect of ethanol on cadmium accumulation in tissues of pregnant rats and their offspring. Starting 10 days before mating and continuing until parturition, ethanol (10% v/v) was present in the drinking water of half the rats. Cadmium chloride (CdCl2; 50 ppm) was present in the water of half the rats (± ethanol) from the first day after mating until parturition. On the day of parturition cadmium accumulated to a moderate level in bone (7.3 μg/g tissue, wet weight; this and other values, P < 0.05 vs. control), liver (12.9 μg/g) and kidney (13.0 μg/g) of dams, while the brain had only a low level of cadmium (0.45 μg/g). In offspring at 6 weeks cadmium accumulated in high amounts in the brain (34.0 μg/g), bone (15.9 μg), kidney (78.2 μg/g) and particularly the liver (227.3 μg/g). Ethanol, given simultaneously with cadmium, inhibited cadmium accumulation in brain (1.8 μg/g), bone (3.28 μg/g) and kidney (61.3 μg/g), but enhanced cadmium accumulation in liver (408.7 μg/g). At 12 weeks there were only residual levels of cadmium in all tissues of offspring. These findings demonstrate an interaction between 2 known teratogenic agents, with ethanol conferring protection of the brain from cadmium accumulation. The nature of this interaction is not known, but is likely to be related to ethanol induction of metallothionein in the liver and placenta.

No description available.