Graphite Furnace Atomic Absorption Spectroscopy (GFAA) and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) are two primary means of analyzing metals at the elemental level. Both techniques are widely accepted as tools for basic research. Each technique is performed differently and has its own distinct advantages as well as disadvantages. The choice of which technique to employ is determined by the needs of the analysis and the limitations of the instrumental technique.The idea to merge the two techniques was originallydeveloped by the research group of Dr. Michael W. Blades of the University of British Columbia, Vancouver, in 1989, who successfully demonstrated a "mini" plasma within a graphite furnace. The goal of the research was to design a device that would combine the advantages of both techniques and hopefully eliminate or minimize the unfavorable characteristics of each technique.The sustaining of a "mini" plasma has been demonstrated by this group. Although the end result was similar to that of Blades' group, the method of achieving the plasma was such that the "new" instrument could easily be mounted onto the furnace via a small Interface/Power Coupling device. The advantages of this system are: existing GFAA instruments can be used; modification of the furnace and RF supply is minimal; RF electronics can be remotely located; removal of the interface device is quickly achieved; and sample introduction, through the use of an autosampler, can be facilitated with small modification.Background spectra were acquired using helium, argon, and a mixture of argon/helium. It was found that all the plasmas have highly structured backgrounds and demonstrate the potential for many analysis regions. Two methods of sample introduction were used in acquiring the line emission of magnesium: injection through the sample inlet port to the furnace and end window injection. Inlet port injection suffers from a loss of sensitivity, when compared to end cap injection, but is more easily performed. / Department of Chemistry

Thesis (M.Sc.)(Hons) -- University of Western Sydney, 2005. / "A thesis presented to the University of Western Sydney in fulfilment of the requirements for the degree of Master of Science (Honours) Physics" Bibliography: leaves 101-108.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-04-27T19:32:31Z No. of bitstreams: 1 nairadasilvacampos.pdf: 1434649 bytes, checksum: 00b45610353851eacfdaa6cc731c0976 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-05-02T01:06:50Z (GMT) No. of bitstreams: 1 nairadasilvacampos.pdf: 1434649 bytes, checksum: 00b45610353851eacfdaa6cc731c0976 (MD5) / Made available in DSpace on 2016-05-02T01:06:50Z (GMT). No. of bitstreams: 1 nairadasilvacampos.pdf: 1434649 bytes, checksum: 00b45610353851eacfdaa6cc731c0976 (MD5) Previous issue date: 2016-02-26 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Este trabalho descreve a determinação dos teores totais de chumbo e ferro em amostras de carne de frango comercializadas na cidade de Juiz de Fora, Brasil. Além do teor total, determinado nos cortes coração, coxa, fígado, moela, peito e sobrecoxa, os teores bioacessíveis de ferro nos cortes de fígado e peito após cocção em panela de ferro também foram determinados. Os teores dos analitos foram determinados por espectrometria de absorção atômica. Os teores de chumbo total foram determinados por atomização em forno de grafite após dois métodos de preparo de amostra: mineralização ácida assistida por microondas empregando soluções diluídas de ácido e solubilização em meio alcalino utilizando o reagente TMAH®. Em ambos os métodos de preparo não foi possível quantificar o analito, pois os teores encontrados estavam abaixo do limite de quantificação. Todavia, os sinais de absorbância integrada, os limites de detecção (Meio ácido: 0,097 μg kg-1 e Meio alcalino: 0,099 μg kg-1) e quantificação (Meio ácido: 0,32 e Meio alcalino: 0,33 μg kg-1) e a massa característica (Meio ácido: 10 e Meio alcalino: 13 pg) obtidos para o chumbo após os dois preparos apresentaram a mesma ordem de grandeza. Assim, o preparo em meio alcalino apresenta-se como uma boa alternativa às digestões ácidas por apresentar maior frequência analítica e se adequar a análises de rotina. Ambos os métodos para o chumbo foram avaliados em termos de precisão, com desvios menores que 15 %, em termos de exatidão por meio de ensaios de adição e recuperação, apresentando faixas entre 83 e 110 % de recuperação. Os teores de ferro total e bioacessível foram determinados por atomização em chama após mineralização ácida e simulação in vitro da digestão gastrointestinal, respectivamente. Os cortes de vísceras cruas apresentaram um teor total de ferro maior que os das amostras de músculo, com uma diferença de até 87 %. A exatidão e precisão do método foram avaliadas por ensaios de adição e recuperação e análise de material de referência certificado, com valores entre 91 e 110 % de recuperação e desvios menores que 5 %. As frações bioacessíveis em peito e fígado, após cocção em panela de ferro, foram de 23 e 56 %, respectivamente, indicando que o fígado é uma boa fonte de ferro. A Espectroscopia Raman foi utilizada para o monitoramento dos mecanismos de solubilização dos cortes de frango crus em meio alcalino. Os resultados indicam que o TMAH® atua na decomposição de compostos como aminoácidos, carboidratos, lipídios e proteínas, devido a mudanças do perfil espectral das amostras antes e após o tratamento. Estes dados indicam que este tipo de preparo pode ser empregado para extração de metais ligados exclusivamente a estes compostos. / This study describes the determination of total content of lead and iron in chicken meat samples commercialized in the city of Juiz de Fora, Brazil. In addition to the total content, determined in heart cuts, thigh, liver, gizzard, breast and drumstick, iron bioaccessible fraction in breast and liver cuts was determined after cooking in iron pot. The analytes levels were determined by atomic absorption spectrometry. The total lead content was determined by graphite furnace atomization after two sample preparation methods: microwave-assisted acid digestion, using dilute acid solutions and solubilization in an alkaline medium, using TMAH® reagent. In both preparation methods, it was not possible to quantify the analyte because the levels found were below the limit of quantification. However, the signals of integrated absorbance, limits of detection (Acid medium: 0.097 μg kg-1 and Alkaline medium: 0.099 μg kg-1) and quantification (Acid medium: 0.32 μg kg-1and Alkaline medium: 0.33 μg kg-1) and characteristic mass (Acid medium: 10 pg and Alkaline medium: 13 pg) obtained for the lead after two sample preparations showed the same order of magnitude, demonstrating that the sample preparation in alkaline medium is a good alternative to acid digestion due to its higher analytical frequency and also it suits the routine analysis. Both methods for lead were evaluated in terms of accuracy, with deviations smaller than 15%, and through addition to recovery tests, with ranges between 83 and 110%. The total and bioaccessible iron fractions were determined by flame atomization after acid mineralization and in vitro gastrointestinal digestion simulation method, respectively. The raw viscera cuts had total iron content larger than those of muscle samples with differences up to 87%. The accuracy and precision of the method were evaluated through recovery tests and analysis of certified reference material, with range between 91-110% of recovery and deviations less than 5%. The iron bioaccessible fractions in breast and liver after cooking in iron pot were 23% and 56%, respectively, which indicates that liver is a good source of iron. The Raman spectroscopy was used to monitor the mechanisms of solubilization of raw chicken cuts in alkaline medium. The results indicate that TMAH® acts in the decomposition of some compounds such as amino acids, carbohydrates, lipids and proteins, due to changes in the spectral profile of the samples before and after the treatment. These data indicate that this type of preparation can be used for the extraction of metals bound exclusively to these compounds.

Este trabalho teve por objetivo estudar a capacidade da remoção da camada de smear das paredes do canal radicular, pelas soluções de EDTA a 15%, ácido cítrico a 10%, citrato de sódio a 10%, vinagre de maçã, ácido acético a 5%, ácido málico a 5% e hipoclorito de sódio a 1% por meio da microscopia eletrônica de varredura e quantificar a concentração de ions cálcio presentes nessas soluções após suas utilizações, por meio da espectrofotometria de absorção atômica de chama. Utilizaram-se 42 dentes incisivos centrais superiores, nos quais se realizou a cirurgia de acesso, remoção de ombro cervical e desgaste compensatório. Aferiu-se o comprimento de trabalho com uma lima tipo K, diâmetro #10 introduzida no canal radicular de cada dente até ser visualizada no ápice, subtraindo-se um milímetro. Determinou-se também o diâmetro anatômico do canal do dente no comprimento de trabalho por meio da introdução de instrumentos tipo K da primeira série com diâmetros sucessivamente maiores, que foi anotado quando um dos instrumentos sofresse resistência ao ser retirado do comprimento de trabalho. Todos os dentes que apresentaram diâmetro anatômico do canal acima de 40 centésimos de milímetros foram descartados e repostos por outros. Desta forma, garantiu-se o desgaste de 20 centésimos de milímetros no terço apical. A técnica utilizada foi a Free Tip Preparation (PECORA et al. 2002) até que um instrumento de diâmetro #60 e taper .04 percorresse todo o comprimento de trabalho. Utilizou-se a solução de hipoclorito de sódio a 1,0% durante todo o preparo biomecânico. Os dentes tiveram seus canais radiculares lavados com 20 mililitros de água deionizada para a remoção de possíveis raspas de dentina soltas no interior do canal radicular. Após o término do preparo biomecânico, os dentes foram divididos aleatoriamente em 7 grupos de 6 dentes cada, de acordo com a substância química utilizada para a irrigação final, a saber: G1 - solução de EDTA a 15,0%; G2 - solução de ácido cítrico a 10,0%; G3 - solução de citrato de sódio a 10,0%; G4 - vinagre de maçã; G5 - solução de ácido acético a 5,0%; G6 - solução de ácido málico a 5,0% e G7 - sem irrigação final (controle negativo). O tempo de permanência das soluções nos canais radiculares foi de 5 minutos. Os dentes foram clivados no sentido vestíbulo-palatino e encaminhados para a microscopia eletrônica de varredura, em que se obtiveram fotomicrografias com o aumento de 1000 vezes. As soluções coletadas foram encaminhadas para a análise química, realizada com um espectrofotômetro de absorção atômica de chama. Concluiu-se que o EDTA a 15% e o ácido cítrico a 10% são eficientes para a remoção da camada de smear. O vinagre de maçã, o citrato de sódio a 10%, os ácidos acético e málico a 5% e o hipoclorito de sódio não foram eficientes para a mesma finalidade. O EDTA a 15% apresentou a maior concentração de ions cálcio em solução; o ácido cítrico a 10% ficou na segunda posição e a terceira foi ocupada pelo vinagre de maçã e os ácidos acético e málico a 5%. A menor concentração de íons cálcio foi encontrada no citrato de sódio a 10%. / This study evaluated the smear layer removal capacity of 15% EDTA, 10% citric acid, 10% sodium citrate, apple vinegar, 5% acetic acid and 1% sodium hypochlorite using scanning electron microscopy and flame atomic absorption spectrophotometry. Forty two central superior incisives were used. On these teeth, it were accomplished the access surgery, removal of cervical shoulder and compensatory wear. The working length was checked with a #10 K-type file that was introduced in the radicular canal of each tooth until be visualized at the apex, then a millimeter was subtracted. The anatomical diameter of the canal in the working length was also determined through the introduction of K-type instruments of the first series with successively larger diameters. The anatomical diameter of the radicular canal was notated when one of the instruments showed resistance to be removed from the working length. All the teeth that presented the canal diameter in the working length above 40 hundredths millimeters were discarded and replaced by other. This way, it was obtained a standard wear of 20 hundredths millimeters in the apical third. The Free Tip Preparation technique (PECORA et al. 2002) was used until a #60- diameter instrument and .04 taper reached the entire working length. The 1.0% sodium hypoclorite solution was used during biomechanical preparation. The teeth had their radicular canals washed with 20 milliliters of deionized water, using Milli-Q® water purification system, for removal of possible dentine chips presented inside the root canal. After the biomechanical preparation, the teeth were randomly divided into 7 groups of 6 teeth each: group 1: teeth with final irrigation with 15% EDTA solution, group 2: teeth with final irrigation with 10%citric acid solution, group 3: final irrigation with 10% sodium citrate solution, group 4: final irrigation with apple vinegar, group 5: final irrigation with 5% acetic acid solution, group 6: final irrigation with 5% maleic acid solution and group 7: teeth only instrument and irrigated with sodium hypochlorite, without final irrigation. Each solution remained 5 minutes in the radicular canal. The cleavage of teeth was done in buccal-palatine direction and they were subjected to the scanning electron microscopy and photographed at 1000X. The collected solutions were submitted to chemical analysis through flame atomic absorption spectrophotometry. It was concluded that 15% EDTA and 10% citric acid, used for 5 minutes, are effective in removing the smear layer. The apple vinegar, 10% sodium citrate, 5% acetic and maleic acids and sodium hypochlorite were not effective in removing the smear layer from root canal. 15% EDTA presented a higher concentration of calcium ions in solution, followed by 10% citric acid. Intermediary results were observed by apple vinegar, 5% acetic and maleic acids, and the inferior concentration of calcium ions was obtained with the 10% sodium citrate.

THE ASSESSMENT OF INFLUENCE OF ZINC IONS AND ECHINACEA PURPUREA (L.) MOENCH FOR MICE INTOXICATED BY CADMIUM IONS Abstract Background. Cadmium (Cd), a well-known environmental hazard, exerts a number of toxic effects in organism. It disturbs the activity of biochemical systems of cells. Accumulation of cadmium depends on the amount of essential trace elements, including zinc. Echinacea purpurea (L.) Moench (EP) can modify its influence. The aim of the study was to assess the influence of ions of cadmium, zinc, and EP on organism in experimental model of mice. The objectives of the scientific work were as follows: 1. To evaluate the accumulation of cadmium in the internal organs of experimental mice after acute and chronic intraperitoneal and per oral intoxication. 2. To assess morphological changes in liver tissue, mitotic and apoptotic activity of liver cells after the intoxication by cadmium ions of different duration and dose. 3. To assess the effect of zinc ions to the accumulation of cadmium in the internal organs and to the mitotic and apoptotic activity of liver cells in the organism of mice intoxicated by cadmium. 4. To evaluate the effect of EP to accumulation of cadmium in internal organs, mitotic and apoptotic activity of liver cells after the chronic intraperitoneal and per oral intoxication by cadmium ions. The scientific novelty of the study. This work makes our knowledge about mechanisms and outcomes of acute and chronic exposure to cadmium deeper. The... [to full text]

Este trabalho teve por objetivo estudar a capacidade da remoção da camada de smear das paredes do canal radicular, pelas soluções de EDTA a 15%, ácido cítrico a 10%, citrato de sódio a 10%, vinagre de maçã, ácido acético a 5%, ácido málico a 5% e hipoclorito de sódio a 1% por meio da microscopia eletrônica de varredura e quantificar a concentração de ions cálcio presentes nessas soluções após suas utilizações, por meio da espectrofotometria de absorção atômica de chama. Utilizaram-se 42 dentes incisivos centrais superiores, nos quais se realizou a cirurgia de acesso, remoção de ombro cervical e desgaste compensatório. Aferiu-se o comprimento de trabalho com uma lima tipo K, diâmetro #10 introduzida no canal radicular de cada dente até ser visualizada no ápice, subtraindo-se um milímetro. Determinou-se também o diâmetro anatômico do canal do dente no comprimento de trabalho por meio da introdução de instrumentos tipo K da primeira série com diâmetros sucessivamente maiores, que foi anotado quando um dos instrumentos sofresse resistência ao ser retirado do comprimento de trabalho. Todos os dentes que apresentaram diâmetro anatômico do canal acima de 40 centésimos de milímetros foram descartados e repostos por outros. Desta forma, garantiu-se o desgaste de 20 centésimos de milímetros no terço apical. A técnica utilizada foi a Free Tip Preparation (PECORA et al. 2002) até que um instrumento de diâmetro #60 e taper .04 percorresse todo o comprimento de trabalho. Utilizou-se a solução de hipoclorito de sódio a 1,0% durante todo o preparo biomecânico. Os dentes tiveram seus canais radiculares lavados com 20 mililitros de água deionizada para a remoção de possíveis raspas de dentina soltas no interior do canal radicular. Após o término do preparo biomecânico, os dentes foram divididos aleatoriamente em 7 grupos de 6 dentes cada, de acordo com a substância química utilizada para a irrigação final, a saber: G1 - solução de EDTA a 15,0%; G2 - solução de ácido cítrico a 10,0%; G3 - solução de citrato de sódio a 10,0%; G4 - vinagre de maçã; G5 - solução de ácido acético a 5,0%; G6 - solução de ácido málico a 5,0% e G7 - sem irrigação final (controle negativo). O tempo de permanência das soluções nos canais radiculares foi de 5 minutos. Os dentes foram clivados no sentido vestíbulo-palatino e encaminhados para a microscopia eletrônica de varredura, em que se obtiveram fotomicrografias com o aumento de 1000 vezes. As soluções coletadas foram encaminhadas para a análise química, realizada com um espectrofotômetro de absorção atômica de chama. Concluiu-se que o EDTA a 15% e o ácido cítrico a 10% são eficientes para a remoção da camada de smear. O vinagre de maçã, o citrato de sódio a 10%, os ácidos acético e málico a 5% e o hipoclorito de sódio não foram eficientes para a mesma finalidade. O EDTA a 15% apresentou a maior concentração de ions cálcio em solução; o ácido cítrico a 10% ficou na segunda posição e a terceira foi ocupada pelo vinagre de maçã e os ácidos acético e málico a 5%. A menor concentração de íons cálcio foi encontrada no citrato de sódio a 10%. / This study evaluated the smear layer removal capacity of 15% EDTA, 10% citric acid, 10% sodium citrate, apple vinegar, 5% acetic acid and 1% sodium hypochlorite using scanning electron microscopy and flame atomic absorption spectrophotometry. Forty two central superior incisives were used. On these teeth, it were accomplished the access surgery, removal of cervical shoulder and compensatory wear. The working length was checked with a #10 K-type file that was introduced in the radicular canal of each tooth until be visualized at the apex, then a millimeter was subtracted. The anatomical diameter of the canal in the working length was also determined through the introduction of K-type instruments of the first series with successively larger diameters. The anatomical diameter of the radicular canal was notated when one of the instruments showed resistance to be removed from the working length. All the teeth that presented the canal diameter in the working length above 40 hundredths millimeters were discarded and replaced by other. This way, it was obtained a standard wear of 20 hundredths millimeters in the apical third. The Free Tip Preparation technique (PECORA et al. 2002) was used until a #60- diameter instrument and .04 taper reached the entire working length. The 1.0% sodium hypoclorite solution was used during biomechanical preparation. The teeth had their radicular canals washed with 20 milliliters of deionized water, using Milli-Q® water purification system, for removal of possible dentine chips presented inside the root canal. After the biomechanical preparation, the teeth were randomly divided into 7 groups of 6 teeth each: group 1: teeth with final irrigation with 15% EDTA solution, group 2: teeth with final irrigation with 10%citric acid solution, group 3: final irrigation with 10% sodium citrate solution, group 4: final irrigation with apple vinegar, group 5: final irrigation with 5% acetic acid solution, group 6: final irrigation with 5% maleic acid solution and group 7: teeth only instrument and irrigated with sodium hypochlorite, without final irrigation. Each solution remained 5 minutes in the radicular canal. The cleavage of teeth was done in buccal-palatine direction and they were subjected to the scanning electron microscopy and photographed at 1000X. The collected solutions were submitted to chemical analysis through flame atomic absorption spectrophotometry. It was concluded that 15% EDTA and 10% citric acid, used for 5 minutes, are effective in removing the smear layer. The apple vinegar, 10% sodium citrate, 5% acetic and maleic acids and sodium hypochlorite were not effective in removing the smear layer from root canal. 15% EDTA presented a higher concentration of calcium ions in solution, followed by 10% citric acid. Intermediary results were observed by apple vinegar, 5% acetic and maleic acids, and the inferior concentration of calcium ions was obtained with the 10% sodium citrate.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho, a microextração líquido-líquido dispersiva em fase reversa (RPDLLME) assistida por vórtex é proposta no preparo de amostras de óleos para posterior determinação de espécies metálicas por espectrometria de absorção atômica com atomização por chama (F AAS). A RP-DLLME foi proposta usando 2- propanol e solução de ácido nítrico (HNO3) como solventes dispersor e extrator, respectivamente. Foram otimizados os seguintes parâmetros: tipo e volume de solvente dispersor, concentração ácida no solvente extrator e tempo de ultrassom. Sob condições otimizadas, 5 g das amostras foram aquecidas (a uma temperatura de 95 ± 5°C) durante 10 min, em seguida, adicionadas de 1 mL da mistura de solventes, 2-propanol e solução de HNO3 1% (v/v), submetidas a agitação em vórtex por 20 s e sonicadas em banho ultrassônico por 10 min. Após a RP-DLLME, o sobrenadante foi separado por centrifugação e as concentrações de Fe, Mg e Zn na fase extratora foram determinadas por F AAS. A calibração foi realizada por RPDLLME utilizando adição de padrões organometálicos em amostra de óleo vegetal previamente purificada. Os intervalos de calibração foram 0,05-0,50 μg g-1 , 0,01-0,10 μg g-1 e 0,02-0,20 μg g-1 para Fe, Mg e Zn respectivamente. Os valores de Limite de detecção (LOD) foram de 9 ng g-1 , 2 ng g-1 e 8 ng g-1 para Fe, Mg e Zn. Os valores de desvio padrão relativo (RSD) obtidos ficaram entre 1 e 11%. A comparação dos resultados obtidos pela metodologia proposta com os obtidos por diluição direta não apresentou diferença significativa de acordo com o teste T emparelhado e teste F. Os testes de recuperação apresentaram valores entre 81-110%, demonstrando a boa exatidão do método. O método proposto foi aplicado para a determinação de Fe, Mg e Zn em amostras de óleos vegetais de diferentes origens, e as concentrações obtidas foram da ordem de μg g-1 . / In this work, Vortex-assisted reverse-dispersive liquid-liquid dispersion (RP-DLLME) is proposed for the preparation of oil samples and for further determination of metal species by flame atomization (F AAS) atomic absorption spectrometry. RP-DLLME was proposed using 2-propanol and nitric acid solution (HNO3) as dispersant and extractor solvents, respectively. The following parameters were optimized: type and volume of dispersing solvent, acid concentration in the extracting solvent and ultrasonic time. Under optimized conditions, 5 g of the samples were heated (at a temperature of 95 ± 5 ° C) for 10 min, then added with 1 ml of the solvent mixture, 2- propanol and 1% HNO3 solution (v/v), vortexed for 20 sec if sonicated in an ultrasonic bath for 10 min. After RP-DLLME, the supernatant was separated by centrifugation and the concentrations of Fe, Mg and Zn in the extractive phase were determined by F AAS. Calibration was performed by RP-DLLME using addition of organometallic standards in previously purified vegetable oil sample. The calibration intervals were 0.05-0.50 μg g-1 , 0.01-0.10 μg g-1 and 0.02-0.20 μg g -1 for Fe, Mg and Zn respectively. The limit of detection (LOD) values were 9 ng g-1 , 2 ng g-1 and 8 ng g-1 for Fe, Mg and Zn. The relative standard deviation (RSD) values obtained were between 1 and 11%. The comparison of the results obtained by the proposed methodology with those obtained by direct dilution did not show a significant difference by paired test T and test F. The recovery tests showed values between 81-110%, demonstrating the good accuracy of the method. The proposed method was applied for the determination of Fe, Mg and Zn in samples of vegetable oils of different origins, and the concentrations obtained were of the order of μg g-1 .

Platinum nanoparticles pose a risk to environmental compartments. The aim of this diploma thesis is to conduct research on the influence of platinum nanoparticles in a wide range of concentrations on soil properties at different humidities. Specifically, it is about influencing the stability of water molecular bridges, the content of aliphatic crystallites, the retention capacity of water in the soil and the strength of water binding. Furthermore, the amount of nanoparticles sorbed on the soil was also measured. These indicators give us more information about the influence of platinum nanoparticles on evapotranspiration and soil deterioration. Methods of thermal analysis (differential scanning calorimetry) and optical methods (atomic absorption spectrometry) were used for these researches. The theoretical part of the work is devoted to a comprehensive introduction to platinum and its nanoparticles, as well as aqueous molecular bridges. It has been found that 200 nm platinum nanoparticles affect the strength of aqueous molecular bridges, have no effect on aliphatic crystallite content, have minimal effect on soil water retention, and that the water bond strength decreases due to platinum nanoparticles at high relative humidity. With 200 nm platinum nanoparticles, complete adsorption to soil occurs over the entire concentration range. With 3 nm nanoparticles, the soil is supersaturated at higher concentrations and larger amounts are not adsorbed. The results show that the larger the size of the platinum nanoparticles, the lower the negative effect on evapotranspiration and soil function itself.

Tellurium and bismuth are non-biogenous elements, which can be accumulated in human body. The aim of this work is focused on the determination of these elements by the electrochemical hydride generation with non-membrane electrolytic cell with quartz tube - atomic absorption spectrometry. The first step of the work was to optimize parameters for the continuous setup measurements and to obtain its figures of merit. After this, the arrangement with most suitable conditions for determination of these elements was converted to the flow injection setup (FIA) and all experimental parameters were again optimized and its figures of merit were obtained. The conditions of hydride generation were studied for platinum, lead and silver cathodes with hydrochloric and sulphuric acids and their sodium salts as electrolytes. The optimizations of the FIA setup were performed on platinum cathode in hydrochloric acid for bismuth and on lead cathode in sulphuric acid for tellurium. The limit of detection achieved for the generation of tellurium hydride was 1.1 ppm with a linear range up to 20 ppm; for the bismuth hydride the limit of detection was 9.5 ppm and limit of linearity 50 ppm. Keywords Bismuth, tellurium, electrochemical hydride generation, atomic absorption spectroscopy, flow injection analysis

CAPES / Este estudo avaliou a qualidade das águas e dos sedimentos da sub-bacia do rio Barigüi, Região Metropolitana de Curitiba, em relação à presença, disponibilidade química e potencial tóxico de espécies químicas (Al, Fe, Ti, K, Ca, P, S, Zr, Mn, Zn, Sr, Cu, Nb, Y, Rb, Ni, Cr, Cd e Pb) majoritárias e traços. Sedimentos de bacias urbanas são matrizes ambientais complexas e multielementares, que se tornaram objeto de estudo de muitas pesquisas devido ao caráter ativo. Este compartimento intercambia espécies químicas com a coluna d’ água afetando sua qualidade, influenciando sua toxicidade e interferindo na biota aquática. As quatro campanhas de amostragem foram realizadas em três pontos de modo a cobrir regiões distintas da sub-bacia, sendo estas sujeitas a diversos impactos ambientais devido à urbanização e industrialização. Para a quantificação de espécies químicas nos sedimentos e na coluna d’água fez-se uso das técnicas instrumentais Espectrometria de Absorção Atômica com Atomizador Chama (FAAS) e Espectrometria de Fluorescência de Raios-X por Energia Dispersiva (EDXRF), segundo protocolos 3030B (APHA), 3050B (USEPA) e 200.2 (USEPA). Parâmetros acessórios tais como potencial redox, pH, amônia, fósforo total e ortofosfato, alcalinidade total e clorofila-a foram determinados nas amostras de águas. As amostras de água também foram caracterizadas por espectroscopia de absorção molecular e por espectroscopia de fluorescência molecular. Estabeleceu-se o estado de trofia das águas por meio do Índice de Estado Trófico IET e compararam-se os valores determinados com os valores regulamentadores da resolução 357 de 2005 do CONAMA. Os sedimentos passaram por análises térmicas (TGA/DSC), granulométricas, de umidade (%) e determinaram-se seus indicies geoquímicos de qualidade. Os resultados permitiram diferenciar as regiões estudadas, e observar que as amostras de águas e sedimentos sofrem influência da urbanização e industrialização como os principais responsáveis pelas cargas poluentes. Nesse sentido, o ponto amostral de Araucária encontra-se mais degradado em relação aos de Almirante Tamandaré e Santa Felicidade sobre a sub-bacia do rio Barigüi-PR, indicando a necessidade de ações de gestão ambiental sobre o sistema hídrico. / This study evaluated the water and sediment quality of the Barigui River sub-basin, Greater Curitiba, in terms of the presence, chemical availability, and toxic potential of common chemical species as well as trace elements. Urban basin sediments are complex multi-element environmental matrices and have become the subject of many studies because of their active character. These matrices interchange chemical species with the water column, which affects its quality, influences its toxicity, and interferes with aquatic life. Four sampling operations were completed at three different sites, subject to several environmental impacts due to urbanization and industrialization, in order to cover distinct regions of the sub-basin. For the quantification of chemical species in the sediments and water column, flame-atomizer atomic absorption spectroscopy (FAAS) and energy-dispersive X-ray fluorescence spectroscopy (EDXRF) techniques were used, according to protocol 3030B (APHA), 3050B (USEPA) and 200.2 (USEPA). Auxiliary parameters such as redox potential, pH, ammonia, total phosphorus and orthophosphate, total alkalinity, and chlorophyll a were determined for the water samples. The water samples were also characterized by molecular absorption spectroscopy and molecular fluorescence spectroscopy. The trophic state of the water was established using the trophic state index (TSI) and the determined values were compared with the regulatory values pertaining to CONAMA (2005) resolution 357. The sediments were subjected to thermal analysis (TGA/DSC), particle size and moisture content (%) estimation, and geochemical quality index determination. The results allowed us to differentiate between the studied regions and to conclude that the water and sediment samples are influenced by urbanization and industrialization, which are the main agents responsible for pollution. In this context, the Araucária sample was more degraded than those in Almirante Tamandaré and Santa Felicidade in the Barigui River sub-basin – PR, indicating the need for environmental management in this water system.